TW202108727A - Photosensitive adhesive composition dryfilm and method for manufacturing multilayer board - Google Patents

Abstract

Provided is a photosensitive adhesive composition capable of realizing high bonding strength when bonding a first member and a second member. The photosensitive adhesive composition contains: a carboxyl group-containing resin (A), a photopolymerization initiator (B), and a photopolymerizable compound (C). The photosensitive adhesive composition is used for bonding a first member 1 and a second member 2 through a first adhesive layer 11 and a second adhesive layer 12 by preparing the first adhesive layer 11 and the second adhesive layer 12 on the first member 1 and the second member 2, respectively, and overlapping the first adhesive layer 11 and the second adhesive layer 12 to bond them.

Description

Photosensitive adhesive composition, dry film, and manufacturing method of multilayer substrate

The present invention relates to a photosensitive adhesive composition, a dry film containing the photosensitive adhesive composition, and a method for manufacturing a multilayer substrate having a layer containing a cured product of the photosensitive adhesive composition.

With the demand for higher performance of electronic equipment, multilayer printed circuit boards are being developed. One method of multi-layering a printed wiring board is a method of joining two members through an adhesive.

For example, Patent Document 1 (International Publication No. 2011/071107) discloses a photosensitive composition that has adhesiveness after the photo-curing reaction and pattern formation, and discloses that the photosensitive adhesive composition is used to bond the substrates to each other. Sticky.

However, although the photosensitive adhesive composition of Patent Document 1 can bond members such as glass substrates to each other, it is difficult to necessarily obtain sufficient bonding strength.

The object of the present invention is to provide a method for manufacturing a photosensitive adhesive composition, a dry film, and a multilayer substrate, which can achieve high bonding strength when joining two members.

One aspect of the photosensitive adhesive composition of the present invention contains a carboxyl group-containing resin (A), a photopolymerization initiator (B), and a photopolymerizable compound (C). The photosensitive adhesive composition is used to make a first adhesive layer and a second adhesive layer on the first member and the second member, respectively, and overlap the first adhesive layer and the second adhesive layer to make them adhere. The first member and the second member are joined through the first adhesive layer and the second adhesive layer.

One aspect of the dry film of the present invention includes the dried product of the photosensitive adhesive composition.

In one aspect of the method for manufacturing a multilayer substrate of the present invention, a first adhesive layer and a second adhesive layer are formed on the first member and the second member from the photosensitive adhesive composition or the dry film, respectively. The first adhesive layer and the second adhesive layer are overlapped to make them adhere, and the first member and the second member are joined through the first adhesive layer and the second adhesive layer. [effect]

With the photosensitive adhesive composition and dry film of one aspect of the present invention, high bonding strength can be achieved when bonding the first member and the second member.

According to the manufacturing method of one aspect of a multilayer substrate of the present invention, a multilayer substrate with high bonding strength between members can be obtained.

Hereinafter, embodiments of the present invention will be described. In addition, 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 "acrylate" and "methacrylate".

The photosensitive adhesive composition of this embodiment contains a carboxyl group-containing resin (A), a photopolymerization initiator (B), and a photopolymerizable compound (C). The photosensitive adhesive composition is used to make a first adhesive layer 11 and a second adhesive layer 12 on the first member 1 and the second member 2, respectively, and overlap the first adhesive layer 11 and the second adhesive layer 12 To make it adhere, the first member 1 and the second member 2 are joined through the first adhesive layer 11 and the second adhesive layer 12.

According to this embodiment, the first adhesive layer 11 and the second adhesive layer 12 are made from the photosensitive adhesive composition as described above, and the first member 1 and the second adhesive layer 12 are connected through the first adhesive layer 11 and the second adhesive layer 12 The two members 2 are joined, and the high joint strength between the first member 1 and the second member 2 can be easily achieved. Furthermore, hereinafter, the layer composed of the first adhesive layer 11 and the second adhesive layer 12 is sometimes referred to as the bonding layer 13. The first adhesive layer 11 and the second adhesive layer 12 are used in the first adhesive layer 11 When overlapping with the second adhesive layer 12 to join the first member 1 and the second member 2, it is interposed between the first member 1 and the second member 2. In addition, at least one of the first member 1 and the second member 2 may be a printed wiring board provided with an insulating layer and conductor lines superimposed on the insulating layer, and may also be provided with a support base made of a resin material or the like. Metal-clad laminates of metal foils such as copper foil and other metal foils superimposed on a supporting base material. More specific examples of the first member 1 and the second member 2 will be described later.

In particular, the photosensitive adhesive composition of the present embodiment, even if the first adhesive layer 11 and the second adhesive layer 12 formed on the first member 1 and the second member 2 are irradiated with light such as ultraviolet rays. After exposure and curing, the first member 1 and the second member 2 are adhered through the first adhesive layer 11 and the second adhesive layer 12, and the high bonding strength of the first member 1 and the second member 2 can still be achieved .

In addition, in this embodiment, after exposing the photosensitive adhesive composition, development can be performed using an alkaline solution or the like. Therefore, the photosensitive adhesive composition of the present embodiment can impart an appropriate pattern to the first adhesive layer 11 and the second adhesive layer 12 by the photolithography method. At this time, the first member 1 and the second member 2 can be joined through the first adhesive layer 11 and the second adhesive layer 12 having appropriate patterns, and high joining strength can be achieved. Therefore, the bonding layer 13 having a high-definition pattern can also be produced from the photosensitive adhesive composition.

The first adhesive layer 11 and the second adhesive layer 12 formed from the photosensitive adhesive composition of this embodiment have high adhesiveness, and can impart high bonding strength when the first member 1 and the second member 2 are joined. Although the reason is not clear, we speculate that it is due to the following reasons.

We think the reason is that if the photosensitive adhesive composition of this embodiment contains a carboxyl group-containing resin (A), a photopolymerization initiator (B), and a photopolymerizable compound (C), it is irradiated with ultraviolet rays, etc. When the first member 1 and the first adhesive layer 11, and the second member 2 and the second adhesive layer 12 have been strongly adhered, respectively, the adhesive layers can be joined to each other. In addition, we believe that the reason is that the first adhesive layer 11 and the second adhesive layer 12 formed by the photosensitive adhesive composition, even in a photocured state, can still maintain a strong density between the adhesive layers. Combine the strength to join.

According to the photosensitive adhesive composition of the present embodiment, even if it is a substrate formed by laminating dozens of layers of the first member 1 and the second member 2, for example, the first member 1 and the second member 2 are alternately laminated by 10 The laminated substrate can still be formed by forming the first adhesive layer 11 and the second adhesive layer 12 on the first member 1 and the second member 2, respectively, and the first adhesive layer 11 and the second adhesive layer 12 are adhered to each other.接层13。 Bonding layer 13. Thereby, for example, a multilayer substrate having a larger number of layers than 20 layers or more can be produced. Therefore, the photosensitive adhesive composition of the present embodiment can be suitably used for bonding multilayer substrates to each other to produce substrates with more layers.

The components which can be contained in the photosensitive adhesive composition of this embodiment are demonstrated in detail.

The carboxyl group-containing resin (A) has a carboxyl group. The carboxyl group-containing resin (A) preferably has an ethylenically unsaturated group. The carboxyl group-containing resin (A) has an ethylenically unsaturated group, and the photosensitive adhesive composition containing the carboxyl group-containing resin (A) has photoreactivity. Therefore, the carboxyl group-containing resin (A) can impart photosensitivity, specifically, ultraviolet curability to the photosensitive adhesive composition.

The carboxyl group-containing resin (A) preferably contains a carboxyl group-containing resin having an aromatic ring. The carboxyl group-containing resin (A) contains an aromatic ring, that is, it can impart high heat resistance and insulation reliability to the cured product of the photosensitive adhesive composition containing the carboxyl group-containing resin (A). The carboxyl group-containing resin (A) is more preferably a carboxyl group-containing resin having a polycyclic aromatic ring of any one of a biphenyl skeleton, a naphthalene skeleton, a sulphur skeleton and an anthracene skeleton. The carboxyl group-containing resin (A) contains any polycyclic aromatic ring among biphenyl skeleton, naphthalene skeleton, anthracene skeleton, and anthracene skeleton, that is, it can harden the photosensitive adhesive composition containing carboxyl group-containing resin (A) The material gives higher heat resistance and insulation reliability. The carboxyl group-containing resin (A) is more preferably a carboxyl group-containing resin having a bisphenol sulfonate skeleton. The carboxyl group-containing resin (A) contains a bisphenol sulfonate skeleton, which is capable of imparting higher heat resistance and insulation reliability to the cured product of the photosensitive adhesive composition containing the carboxyl group-containing resin (A).

The carboxyl group-containing resin (A) preferably contains a carboxyl group-containing resin (A1) having a bisphenol sulfonate skeleton described below. The carboxyl group-containing resin (A1) is, for example, a reaction product of a specific intermediate and an acid anhydride (a3), and the specific intermediate is an epoxy compound (a1) having a bisphenol skeleton represented by the following formula (1) and containing A reaction product of unsaturated carboxylic acid (a2-1) and carboxylic acid (a2). In the formula (1), R ₁ to R ₈ are each independently hydrogen, an alkyl group having 1 to 5 carbon atoms, or halogen. The carboxyl group-containing resin (A1) is synthesized in the following manner: an epoxy compound (a1) having a bisphenol sulfide skeleton (S1) represented by the following formula (1) and an unsaturated group-containing carboxylic acid (a2-1) After the carboxylic acid (a2) of) is reacted, the intermediate thus obtained is reacted with the acid anhydride (a3).

In the formula (1), R ₁ to R ₈ are each independently hydrogen, an alkyl group having 1 to 5 carbon atoms, or halogen. In other words, in formula (1), R ₁ to R ₈ may each be hydrogen, or may be an alkyl group having 1 to 5 carbon atoms, or halogen. The reason is that even if the hydrogen in the aromatic ring is replaced by a low-molecular-weight alkyl or halogen, it will not adversely affect the physical properties of the carboxyl-containing resin (A1). On the contrary, it sometimes increases the carboxyl-containing resin ( A1) The heat resistance or flame retardancy of the cured product of the photosensitive adhesive composition.

When the carboxyl group-containing resin (A1) has a bisphenol sulfide skeleton represented by the formula (1), the carboxyl group-containing resin (A1) preferably has at least one alkyl group. In this case, it is possible to further reduce the dielectric loss tangent of the cured product layer including the cured product of the photosensitive adhesive composition. For example, in formula (1), _{at least one of R 1} to R _{8 is} preferably an alkyl group having 1 to 5 carbon atoms.

The carboxyl group-containing resin (A1) has a bisphenol skeleton represented by formula (1) derived from the epoxy compound (a1), that is, it can impart high heat resistance and insulation reliability to the cured product of the photosensitive adhesive composition. In addition, the carboxyl group-containing resin (A1) has a carboxyl group derived from the acid anhydride (a3), that is, it can impart excellent developability to the photosensitive adhesive composition. In addition, the photosensitive adhesive composition contains an epoxy resin, that is, it can impart thermosetting properties to the photosensitive adhesive composition.

The carboxyl group-containing resin (A1) can be synthesized in the manner described below, for example. In order to synthesize the carboxyl group-containing resin (A1), first, at least a part of the epoxy group (see formula (2)) of the epoxy compound (a1) is combined with a carboxylic acid containing an unsaturated group-containing carboxylic acid (a2-1) (a2) The reaction proceeds to synthesize an intermediate. The synthesis of the intermediate is defined as the first reaction. The intermediate has a structure (S3) represented by the following formula (3), and this structure (S3) is produced by a ring-opening addition reaction of an epoxy group and a carboxylic acid (a2). In other words, the intermediate has a secondary hydroxyl group in the structure (S3), and the secondary hydroxyl group is produced by the ring-opening addition reaction of the epoxy group and the carboxylic acid (a2). In formula (3), A is a carboxylic acid residue. This A contains an unsaturated group-containing carboxylic acid residue.

Next, the secondary hydroxyl group of the intermediate is reacted with acid anhydride (a3). Thereby, the carboxyl group-containing resin (A1) can be synthesized. The reaction of the intermediate and acid anhydride (a3) is defined as the second reaction. The acid anhydride (a3) can include acid monoanhydride and acid dianhydride. The so-called acid-anhydride refers to a compound with one acid anhydride group, which is formed by dehydration and condensation of two carboxyl groups in one molecule. The so-called acid dianhydride refers to a compound having two acid anhydride groups, which are formed by dehydration and condensation of four carboxyl groups in one molecule.

The acid anhydride (a3) may contain at least one of acid dianhydride (a3-2) and acid monoanhydride (a3-1). When the acid anhydride (a3) contains the acid monoanhydride (a3-1), the carboxyl group-containing resin (A1) has: a bisphenol skeleton (S1) represented by the formula (1), and a bisphenol skeleton (S1) represented by the following formula (4) Structure (S4).

The structure (S4) is produced in the following manner: the secondary hydroxyl group in the structure (S3) of the intermediate reacts with the acid anhydride group in the acid monoanhydride (a3-1). In formula (4), A is a carboxylic acid residue, and B is an acid monoanhydride residue. This A contains an unsaturated group-containing carboxylic acid residue.

When the acid anhydride (a3) contains the acid dianhydride (a3-2), the carboxyl group-containing resin (A1) has: a bisphenol phenol skeleton (S1) represented by the formula (1), and a bisphenol skeleton (S1) represented by the following formula (5) Structure (S5).

The structure (S5) is produced in the following way: the two acid anhydride groups in the acid dianhydride (a3-2) react with the two secondary hydroxyl groups in the intermediate respectively. In other words, the structure (S5) is produced in the following manner: the acid dianhydride (a3-2) crosslinks two secondary hydroxyl groups with each other. Furthermore, there may be situations in which two secondary hydroxyl groups existing in one molecule of the intermediate cross-link each other; and, two secondary hydroxyl groups respectively existing in two molecules of the intermediate cross-link each other. United. If the two secondary hydroxyl groups in the two molecules of the intermediate are cross-linked with each other, the molecular weight will increase. In formula (5), A is a carboxylic acid residue, and D is an acid dianhydride residue. This A contains unsaturated carboxylic acid residues.

The secondary hydroxyl group in the intermediate can be reacted with acid anhydride (a3) to obtain carboxyl group-containing resin (A1). When the acid anhydride (a3) contains acid dianhydride (a3-2) and acid monoanhydride (a3-1), part of the secondary hydroxyl group in the intermediate is reacted with acid dianhydride (a3-2), and The other part of the secondary hydroxyl group in the intermediate is reacted with acid monoanhydride (a3-1). Thereby, the carboxyl group-containing resin (A1) can be synthesized. At this time, the carboxyl group-containing resin (A1) has a bisphenol sulfide skeleton (S1), a structure (S4), and a structure (S5).

The carboxyl group-containing resin (A1) can also further have a structure (S6) represented by the following formula (6). The structure (S6) is produced in the following manner: only one of the two acid anhydride groups in the acid dianhydride (a3-2) reacts with the secondary hydroxyl group in the intermediate. In formula (6), A is a carboxylic acid residue, and D is an acid dianhydride residue. This A contains unsaturated carboxylic acid residues.

When a part of the epoxy group in the epoxy compound (a1) during the synthesis of the intermediate remains in the unreacted state, the carboxyl group-containing resin (A1) can also have the structure (S2) represented by the formula (2) Namely epoxy group. In addition, when a part of the structure (S3) in the intermediate remains in the unreacted state, the carboxyl group-containing resin (A1) can also have the structure (S3).

When acid anhydride (a3) contains acid dianhydride (a3-2), optimize the reaction conditions when synthesizing carboxyl-containing resin (A1), and reduce the structure (S2) and structure of carboxyl-containing resin (A1) The number of (S6), or most of the structure (S2) and the structure (S6) are removed from the carboxyl group-containing resin (A1).

As mentioned above, the carboxyl group-containing resin (A1) has a bisphenol skeleton (S1), and when the acid anhydride (a3) contains an acid monoanhydride (a3-1), it can have a structure (S4), and when the acid anhydride (a3) contains an acid In the case of dianhydride (a3-2), it can have structure (S5). In addition, when the acid anhydride (a3) contains the acid monoanhydride (a3-1), the carboxyl group-containing resin (A1) may have at least one of the structure (S2) and the structure (S3). In addition, when the acid anhydride (a3) contains the acid dianhydride (a3-2), the carboxyl group-containing resin (A1) may have at least one of the structure (S2) and the structure (S6). In addition, when the acid anhydride (a3) contains the acid monoanhydride (a3-1) and the acid dianhydride (a3-2), the carboxyl group-containing resin (A1) sometimes has the structure (S2), the structure (S3), and the structure ( At least one of 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) sometimes has a structure produced in the following manner: The secondary hydroxyl group in the epoxy compound (a1) reacts with the acid anhydride (a3).

Furthermore, the structure of the above-mentioned carboxyl-containing resin (A1) is a reasonable analogy based on common technical knowledge. In reality, the structure of the carboxyl-containing resin (A1) cannot be identified by analysis. The reason is as follows. When the epoxy compound (a1) itself has a secondary hydroxyl group (for example, when n=1 or more in the formula (7)), the structure of the carboxyl-containing resin (A1) will be due to the secondary hydroxyl group in the epoxy compound (a1). The number has changed drastically. In addition, when the intermediate is reacted with acid dianhydride (a3-2), as described above, there may be the following situation: two secondary hydroxyl groups existing in one molecule of the intermediate will use acid dianhydride (a3- 2) for cross-linking; and, the two secondary hydroxyl groups respectively existing in the two molecules of the intermediate are cross-linked with acid dianhydride (a3-2). Therefore, the finally obtained carboxyl group-containing resin (A1) will contain a plurality of molecules with mutually different structures, and even if the carboxyl group-containing resin (A1) is analyzed, its structure cannot be identified.

Since the carboxyl group-containing resin (A1) has an ethylenically unsaturated group derived from the unsaturated group-containing carboxylic acid (a2-1), it has photoreactivity. Therefore, the carboxyl group-containing resin (A1) can impart photosensitivity (specifically, ultraviolet curability) to the photosensitive adhesive composition. In addition, since the carboxyl group-containing resin (A1) has a carboxyl group derived from the acid anhydride (a3), it can impart developability to the photosensitive adhesive composition by an alkaline aqueous solution containing an alkali metal salt and At least one of alkali metal hydroxides. Also, when the acid anhydride (a3) contains the acid dianhydride (a3-2), the molecular weight of the carboxyl group-containing resin (A1) depends on the number of crosslinking by the acid dianhydride (a3-2). Therefore, it is possible to obtain a carboxyl group-containing resin (A1) whose acid value and molecular weight have been appropriately adjusted. When acid anhydride (a3) contains acid dianhydride (a3-2) and acid monoanhydride (a3-1), control the amount of acid dianhydride (a3-2) and acid monoanhydride (a3-1), and acid monoanhydride (a3-1) The amount of the acid dianhydride (a3-2), that is, the carboxyl group-containing resin (A1) of which the desired molecular weight and acid value can be easily obtained.

The weight average molecular weight of the carboxyl group-containing resin (A1) is preferably 700 or more and 10,000 or less. If the weight average molecular weight is 700 or more, the adhesion of the film formed by the photosensitive adhesive composition will be more suppressed, and the insulation reliability and plating resistance of the cured product will be more improved. In addition, if the weight average molecular weight is 10,000 or less, the developability of the photosensitive adhesive composition with an alkaline aqueous solution is particularly improved. The weight average molecular weight is more preferably 900 or more and 8000 or less, particularly preferably 1000 or more and 5000 or less.

The solid acid value of the carboxyl group-containing resin (A1) is preferably 60 mgKOH/g or more and 140 mgKOH/g or less. In this case, the developability of the photosensitive adhesive composition is particularly improved. The solid content acid value is preferably 80 mgKOH/g or more and 135 mgKOH/g or less, and more preferably 90 mgKOH/g or more and 130 mgKOH/g or less.

Preferably, the polydispersity (polydispersity index) of the carboxyl group-containing resin (A1) is 1.0 or more and 4.8 or less. In this case, it is possible to ensure good insulation reliability and plating resistance (such as whitening resistance during electroless nickel plating/gold processing) of the cured product formed by the photosensitive adhesive composition, while facing photosensitive adhesion The agent composition imparts excellent developability. It is more preferable that the polydispersity of the carboxyl group-containing resin (A1) is 1.1 or more and 4.0 or less, and it is still more preferable that it is 1.1 or more and 2.8 or less. In addition, the polydispersity is the value (Mw/Mn) of the ratio of the weight average molecular weight (Mw) of the carboxyl group-containing resin (A1) to the number average molecular weight (Mn).

The weight average molecular weight (Mw) of the carboxyl group-containing resin (A1) is calculated from the result of molecular weight measurement obtained by gel permeation chromatography. The molecular weight measurement by gel permeation chromatography can be performed under the following conditions, for example. GPC device: SHODEX SYSTEM 11 manufactured by Showa Denko Corporation; Column: 4 pieces of SHODEX KF-800P, KF-005, KF-003, KF-001 in series; Mobile phase: THF; Flow rate: 1 mL/min; Column temperature: 45℃; Detector: refractive index (RI); Conversion: Polystyrene.

The raw materials of the carboxyl group-containing resin (A1) and the reaction conditions when synthesizing the carboxyl group-containing resin (A1) are explained in detail.

The epoxy compound (a1) has a structure (S7) represented by the following formula (7), for example. In formula (7), n is, for example, a number of 0 or more and 20 or less. In order to make the molecular weight of the carboxyl group-containing resin (A1) an appropriate value, it is particularly preferable that the average of n is 0 or more and 1 or less. If the average of n is in the range of 0 or more and 1 or less, especially when the acid anhydride (a3) contains the acid dianhydride (a3-2), it is easy to suppress the molecular weight due to the addition of the acid dianhydride (a3-2) Increase in excess.

The carboxylic acid (a2) contains an unsaturated group-containing carboxylic acid (a2-1). The carboxylic acid (a2) may contain only the unsaturated group-containing carboxylic acid (a2-1). Alternatively, the carboxylic acid (a2) may include an unsaturated group-containing carboxylic acid (a2-1) and a carboxylic acid other than the unsaturated group-containing carboxylic acid (a2-1).

The unsaturated group-containing carboxylic acid (a2-1) can contain, for example, a compound having only one ethylenically unsaturated group in one molecule. More specifically, the unsaturated group-containing carboxylic acid (a2-1) can contain, for example, at least one compound selected from the group consisting of acrylic acid, methacrylic acid, ω-carboxy-polycaprolactone Ester (n≒2) monoacrylate, crotonic acid, cinnamic acid, 2-propenyloxyethyl succinic acid, 2-methacryloyloxyethyl succinic acid, 2-propenyloxyethyl o-benzene Dicarboxylic acid, 2-methacryloxyethyl phthalic acid, 2-acryloxypropyl phthalic acid, 2-methacryloxypropyl phthalic acid, 2-acrylic acid Oxyethyl maleic acid, 2-methacryloyloxyethyl maleic acid, β-carboxyethyl acrylate, 2-acryloyloxyethyl tetrahydrophthalic acid, 2-methacrylic acid Oxyethyltetrahydrophthalic acid, 2-propenyloxyethylhexahydrophthalic acid, and 2-methacryloyloxyethylhexahydrophthalic acid. Preferably, the unsaturated group-containing carboxylic acid (a2-1) contains acrylic acid.

The carboxylic acid (a2) may include a polybasic acid (a2-2). The polybasic acid (a2-2) is an acid in which two or more hydrogen atoms can be substituted with metal atoms in one molecule. The polybasic acid (a2-2) preferably has two or more carboxyl groups. At this time, the epoxy compound (a1) reacts with both the unsaturated group-containing carboxylic acid (a2-1) and the polybasic acid (a2-2). The polybasic acid (a2-2) crosslinks the epoxy groups present in the two molecules of the epoxy compound (a1), that is, an increase in molecular weight can be obtained. Thereby, the adhesion of the film formed of the photosensitive adhesive composition can be further suppressed, and the insulation reliability and plating resistance of the cured product can be further improved.

The polybasic acid (a2-2) preferably contains a dicarboxylic acid. The polybasic acid (a2-2) can contain, for example, one or more compounds selected from the group consisting of 4-cyclohexene-1,2-dicarboxylic acid, oxalic acid, malonic acid, succinic acid, and glutaric acid. Diacid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid. Preferably, the polybasic acid (a2-2) contains 4-cyclohexene-1,2-dicarboxylic acid.

When the epoxy compound (a1) and the carboxylic acid (a2) are reacted, an appropriate method can be adopted. For example, the carboxylic acid (a2) is added to the solvent solution of the epoxy compound (a1), and the thermal polymerization inhibitor and the catalyst are further added as needed and stirred and mixed to obtain a reactive solution. The reaction of this reactive solution at a temperature of preferably 60°C or higher and 150°C or lower, particularly preferably 80°C or higher and 120°C or lower, by a conventional method, can obtain an intermediate. At this time, the solvent can 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, Acetate esters such as butyl acetate, cellulose acetate, butyl cellulose acetate, carbitol acetate, butyl carbitol acetate, and propylene glycol monomethyl ether acetate; and , Dialkyl glycol ethers. The thermal polymerization inhibitor contains, for example, at least one of hydroquinone and hydroquinone monomethyl ether. The catalyst can contain, for example, at least one component selected from the group consisting of: tertiary amines such as benzyldimethylamine and triethylamine; trimethylbenzylammonium chloride, chloride Quaternary ammonium salts such as methyl triethyl ammonium; triphenyl phosphine; and, triphenyl antimony.

Preferably, the catalyst contains triphenylphosphine in particular. In other words, it is preferable to react the epoxy compound (a1) with the carboxylic acid (a2) in the presence of triphenylphosphine. At this time, the epoxy group in the epoxy compound (a1) and the carboxylic acid (a2) can be particularly promoted to undergo a ring-opening addition reaction, and a reaction rate of 95% or more, 97% or more, or almost 100% can be achieved ( Conversion rate). Therefore, the intermediate having the structure (S3) can be obtained in a high yield. In addition, ion migration is suppressed in the layer containing the cured product of the photosensitive adhesive composition, and the insulation reliability of the layer is further improved.

When the epoxy compound (a1) is reacted with the carboxylic acid (a2), the amount of the carboxylic acid (a2) is 0.5 mol or more and 1.2 mol relative to 1 mol (mole) of the epoxy group of the epoxy compound (a1) The following is better. In this case, a photosensitive adhesive composition having excellent photosensitivity and stability can be obtained. From the same point of view, relative to 1 mol of epoxy group of epoxy compound (a1), the amount of unsaturated group-containing carboxylic acid (a2-1) is preferably 0.5 mol or more and 1.2 mol or less, with 0.8 mol The above and 1.2 mol or less are preferable. Or, when the carboxylic acid (a2) contains a carboxylic acid other than the unsaturated group-containing carboxylic acid (a2-1), relative to 1 mol of the epoxy group of the epoxy compound (a1), the unsaturated group-containing carboxylic acid ( The amount of a2-1) may be 0.5 mol or more and 0.95 mol or less. In addition, when the carboxylic acid (a2) contains the polybasic acid (a2-2), the amount of the polybasic acid (a2-2) is 0.025 mol or more and 0.25 mol or less relative to 1 mol of the epoxy group of the epoxy compound (a1) Better. In this case, a photosensitive adhesive composition having excellent photosensitivity and stability can be obtained.

The intermediate obtained in the above-mentioned manner will have a specific hydroxyl group produced by the reaction of the epoxy group of the epoxy compound (a1) and the carboxyl group of the carboxylic acid (a2).

Acid monoanhydride (a3-1) is a compound having one acid anhydride group. The acid monoanhydride (a3-1) can contain an anhydride of a dicarboxylic acid. The acid monoanhydride (a3-1) can contain, for example, at least one compound selected from the group consisting of: phthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, methane Tetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride, succinic anhydride, methyl succinic anhydride, maleic anhydride, citraconic anhydride, pentane Diacid anhydride, cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride, and itaconic anhydride. In particular, the acid monoanhydride (a3-1) preferably contains 1,2,3,6-tetrahydrophthalic anhydride. In other words, the acid anhydride (a3) preferably contains 1,2,3,6-tetrahydrophthalic anhydride. In other words, it is preferable that the carboxyl group-containing resin (A1) has the structure (S4), and B in the formula (4) contains 1,2,3,6-tetrahydrophthalic anhydride residues. In this case, while ensuring good developability of the photosensitive adhesive composition, the adhesion of the film formed by the photosensitive adhesive composition is further suppressed, and the insulation reliability and plating resistance of the cured product are further improved. . Relative to the whole acid monoanhydride (a3-1), the amount of 1,2,3,6-tetrahydrophthalic anhydride is preferably 20 mol% or more and 100 mol% or less, and 40 mol% or more and 100 mol % Or less is preferable, but it is not limited to these ranges.

Acid dianhydride (a3-2) is a compound having two acid anhydride groups. The acid dianhydride (a3-2) can contain an anhydride of tetracarboxylic acid. The acid dianhydride (a3-2) can contain, for example, at least one compound selected from the group consisting of: 1,2,4,5-pyromellitic dianhydride, benzophenonetetracarboxylic dianhydride, Methylcyclohexenetetracarboxylic dianhydride, tetracarboxylic dianhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride, ethylenetetracarboxylic dianhydride, 9,9'-bis(3,4-di Carboxyphenyl) dianhydride, glycerol bis(trimellitic acid anhydride) monoacetate, ethylene glycol bis(trimellitic acid anhydride), 3,3',4,4'-diphenyl sulfide Tetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-diketo-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, the acid dianhydride (a3-2) preferably contains 3,3',4,4'-biphenyltetracarboxylic dianhydride. In other words, it is preferable that D in formula (5) and formula (6) contains 3,3',4,4'-biphenyltetracarboxylic dianhydride residue. In this case, while ensuring good developability of the photosensitive adhesive composition, the adhesion of the film formed by the photosensitive adhesive composition is further suppressed, and the insulation reliability and plating resistance of the cured product are further improved. . Relative to the whole acid dianhydride (a3-2), the amount of 3,3',4,4'-biphenyltetracarboxylic dianhydride is preferably 20 mol% or more and 100 mol% or less, and 40 mol% or more and 100 The mol% or less is preferable, but it is not limited to these ranges.

When reacting the intermediate and acid anhydride (a3), an appropriate method can be adopted. For example: adding acid anhydride (a3) to the solvent solution of the intermediate, and further adding thermal polymerization inhibitors and catalysts as needed and stirring and mixing to obtain a reactive solution. The reactive solution is reacted at a temperature of preferably 60°C or higher and 150°C or lower, particularly preferably 80°C or higher and 120°C or lower by a conventional method, to obtain a carboxyl group-containing resin (A1). Suitable solvents, catalysts, and polymerization inhibitors can be used, and the solvents, catalysts, and polymerization inhibitors used in the synthesis of intermediates can also be used directly.

It is preferable that the catalyst particularly contains triphenylphosphine. In other words, it is preferable to react the intermediate and acid anhydride (a3) in the presence of triphenylphosphine. At this time, the reaction between the secondary hydroxyl group in the intermediate and the acid anhydride (a3) is particularly promoted, and a reaction rate (conversion rate) of 90% or more, 95% or more, 97% or more, or almost 100% can be achieved. Therefore, a carboxyl group-containing resin (A1) having at least one of the structure (S4) and the structure (S5) can be obtained with high yield. In addition, ion migration is suppressed in the layer containing the cured product of the photosensitive adhesive composition, and the insulation reliability of the layer is further improved.

When acid anhydride (a3) contains acid dianhydride (a3-2) and acid monoanhydride (a3-1), the amount of acid dianhydride (a3-2) is relative to 1 mol of epoxy group of epoxy compound (a1) It is preferably 0.05 mol or more and 0.24 mol or less. In addition, the amount of the acid monoanhydride (a3-1) is preferably 0.3 mol or more and 0.7 mol or less with respect to 1 mol of the epoxy group of the epoxy compound (a1). In this case, the carboxyl group-containing resin (A1) whose acid value and molecular weight have been appropriately adjusted can be easily obtained.

It is also preferable to react the intermediate and acid anhydride (a3) under air bubbling. At this time, the molecular weight of the generated carboxyl group-containing resin (A1) is suppressed from increasing excessively, and the developability of the photosensitive adhesive composition by the alkaline aqueous solution is particularly improved.

The carboxyl-containing resin (A) may contain only the carboxyl-containing resin (A1), or only the carboxyl-containing resin (A1) other than the carboxyl-containing resin, and may also contain carboxyl-containing resin (A1) and carboxyl-containing resin Carboxyl group-containing resins other than (A1). The carboxyl group-containing resin other than the carboxyl group-containing resin (A1) includes a carboxyl group-containing resin that does not have a bisphenol skeleton (hereinafter also referred to as carboxyl group-containing resin (A2)).

The carboxyl group-containing resin (A2) can contain, for example, a compound having a carboxyl group and not having photopolymerization properties (hereinafter referred to as (A2-1) component). The component (A2-1) contains, for example, a polymer of 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 can contain compounds such as acrylic acid, methacrylic acid, and ω-carboxy polycaprolactone (n≒2) monoacrylate. The ethylenically unsaturated compound having a carboxyl group can also contain reactants of pentaerythritol triacrylate, pentaerythritol trimethacrylate, etc. and dibasic acid anhydride. The ethylenically unsaturated monomer may further contain: 2-(meth)acryloyloxyethyl phthalate, 2-(meth)acryloyloxyethyl-2-hydroxyethyl phthalate, Linear or branched aliphatic or alicyclic (but part of the ring may have an unsaturated bond) (meth)acrylate and other ethylenically unsaturated compounds that do not have a carboxyl group.

The carboxyl group-containing resin (A2) may contain a compound having a carboxyl group and an ethylenically unsaturated group (hereinafter referred to as (A2-2) component). In addition, the carboxyl group-containing resin (A2) may contain only the component (A2-2). The component (A2-2) contains, for example, a resin (referred to as the first resin (x)), which is a reactant of a specific intermediate and at least one compound (x3) selected from the group of polycarboxylic acids and anhydrides thereof, This specific intermediate is a reaction product of an epoxy compound (x1) having two or more epoxy groups in one molecule and an ethylenically unsaturated compound (x2). The first resin (x) can be obtained, for example, by reacting the epoxy group in the epoxy compound (x1) with the carboxyl group in the ethylenically unsaturated compound (x2) to obtain an intermediate, and then the compound (x3) ) Addition to the intermediate. The epoxy compound (x1) can contain an appropriate epoxy compound such as a cresol novolak type epoxy compound, a phenol novolak type epoxy compound, and a biphenol novolak type epoxy compound. In particular, the epoxy compound (x1) preferably contains at least one compound selected from the group of a biphenol novolak type epoxy compound and a cresol novolak type epoxy compound. The epoxy compound (x1) may contain only the biphenol novolak type epoxy compound, or may contain only the cresol novolak type epoxy compound. The epoxy compound (x1) may contain a polymer of the ethylenically unsaturated compound (z). The ethylenically unsaturated compound (z) contains, for example, a compound (z1) having an epoxy group such as glycidyl (meth)acrylate, or further contains 2-(meth)acryloyloxyethyl phthalate, etc. Compounds with epoxy groups (z2). The ethylenically unsaturated compound (x2) preferably contains at least one of acrylic acid and methacrylic acid. The compound (x3) contains, for example, one selected from the group consisting of polycarboxylic acids such as phthalic acid, tetrahydrophthalic acid, and methyltetrahydrophthalic acid, and anhydrides of these polycarboxylic acids The above compound. In particular, the compound (x3) preferably contains at least one polycarboxylic acid selected from the group of phthalic acid, tetrahydrophthalic acid, and methyltetrahydrophthalic acid.

The component (A2-2) may contain a resin (referred to as the second resin (y)), which is a reaction product of a polymer of an ethylenically unsaturated monomer and an ethylenically unsaturated compound having an epoxy group. The unsaturated monomer includes an ethylenically unsaturated compound having a carboxyl group. The ethylenically unsaturated monomer may further include an ethylenically unsaturated compound that does not have a carboxyl group. The second resin (y) is obtained by reacting a part of the carboxyl groups in the polymer with an ethylenically unsaturated compound having an epoxy group. The ethylenically unsaturated monomer may further include an ethylenically unsaturated compound that does not have a carboxyl group. The ethylenically unsaturated compound having a carboxyl group includes, for example, compounds such as acrylic acid, methacrylic acid, ω-carboxy-polycaprolactone (n≒2) monoacrylate, pentaerythritol triacrylate, and pentaerythritol trimethacrylate. The ethylenically unsaturated compound that does not have a carboxyl group contains, for example, 2-(meth)acryloyloxyethyl phthalate, 2-(meth)acryloyloxyethyl-2-hydroxyethyl phthalate Compounds such as esters, linear or branched aliphatic or cycloaliphatic (but part of the ring may have unsaturated bonds) (meth)acrylates and other compounds. The ethylenically unsaturated compound having an epoxy group preferably contains glycidyl (meth)acrylate.

The carboxyl-containing resin (A) may contain only the carboxyl-containing resin (A1), only the carboxyl-containing resin (A2), or the carboxyl-containing resin (A1) and the carboxyl-containing resin (A2). The carboxyl group-containing resin (A) preferably contains a carboxyl group-containing resin (A1) of 30% by mass or more, more preferably contains a carboxyl group-containing resin (A1) of 50% by mass or more,) still more preferably contains a carboxyl group-containing resin ( A1) 60% by mass or more, particularly preferably 100% by mass of the carboxyl group-containing resin (A1). In this case, the heat resistance and insulation reliability of the cured product of the photosensitive adhesive composition can be particularly improved. In addition, it is possible to sufficiently reduce the adhesion of the film formed of the photosensitive adhesive composition. In addition, it is possible to ensure the developability of the photosensitive adhesive composition by an alkaline aqueous solution. Therefore, the photosensitive adhesive composition can also be suitably used for forming an insulating layer.

The photopolymerization initiator (B) is a component capable of improving the photosensitivity of the photosensitive adhesive composition. The photopolymerization initiator (B) preferably contains, for example, an acylphosphine oxide-based photopolymerization initiator (B1). At this time, when the photosensitive adhesive composition is exposed to light such as ultraviolet rays, it is possible to impart high photosensitivity to the photosensitive adhesive composition. In addition, ion migration is suppressed in the layer containing the cured product of the photosensitive adhesive composition, and the insulation reliability of the layer is further improved. In addition, the phosphine oxide-based photopolymerization initiator (B1) does not easily hinder the electrical insulation of the cured product. Therefore, when the photosensitive adhesive composition is exposed and cured, a cured product having excellent electrical insulation properties can also be obtained, and this cured product is suitable as, for example, an interlayer insulating layer.

The phosphine oxide-based photopolymerization initiator (B1) can contain, for example, at least one component selected from the group consisting of: 2,4,6-trimethylbenzyldiphenylphosphine oxide , 2,4,6-trimethylbenzylethylphenylphosphinate and other monophosphine oxide-based photopolymerization initiators; and, bis(2,6-dichlorobenzyl) Phenylphosphine oxide, bis(2,6-dichlorobenzyl)-2,5-dimethylphenylphosphine oxide, bis(2,6-dichlorobenzyl)-4-propylbenzene Phosphine oxide, bis(2,6-dichlorobenzyl)-1-naphthylphosphine oxide, bis(2,6-dimethoxybenzyl)phenyl phosphine oxide, bis(2,6 -Dimethoxybenzyl)-2,4,4-trimethylpentylphosphine oxide, bis(2,6-dimethoxybenzyl)-2,5-dimethylphenyl Phosphine oxide, bis(2,4,6-trimethylbenzyl)phenyl phosphine oxide, (2,5,6-trimethylbenzyl)-2,4,4-trimethylpentyl Diaminophosphine oxide-based photopolymerization initiators such as phosphine oxide. In particular, it is preferable that the acylphosphine oxide-based photopolymerization initiator (B1) contains 2,4,6-trimethylbenzyldiphenylphosphine oxide, and it is also preferable that the acylphosphine oxide-based photopolymerization initiator (B1) contains The starter (B1) contains only 2,4,6-trimethylbenzyl diphenyl phosphine oxide.

The photopolymerization initiator (B) preferably contains a hydroxyketone-based photopolymerization initiator (B2) in addition to the acetoxyphosphine oxide-based photopolymerization initiator (B1). In other words, the photosensitive adhesive composition preferably contains a hydroxyketone-based photopolymerization initiator (B2). In this case, compared with the case where the hydroxyketone-based photopolymerization initiator (B2) is not contained, higher photosensitivity can be imparted to the photosensitive adhesive composition. With this, when the coating film formed of the photosensitive adhesive composition is irradiated with light such as ultraviolet rays to be cured, the coating film can be sufficiently cured from the surface to the deep part. Examples of the hydroxyketone-based photopolymerization initiator (B2) include: 1-hydroxycyclohexyl phenyl ketone, methyl phenylglyoxylate, 1-[4-(2-hydroxyethoxy)phenyl]-2- Hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropanyl)benzyl]phenyl}-2- Methylpropan-1-one, and 2-hydroxy-2-methyl-1-phenylpropan-1-one.

The mass ratio of the phosphine oxide-based photopolymerization initiator (B1) to the hydroxyketone-based photopolymerization initiator (B2) is preferably in the range of 1:0.01 to 1:10. In this case, it is possible to improve the curability near the surface of the coating film formed of the photosensitive adhesive composition and the curability in the deep part in a well-balanced manner.

The photopolymerization initiator (B) also preferably contains a photopolymerization initiator (B3) having a benzophenone skeleton. In other words, it is also preferable that the photosensitive adhesive composition contains an oxyphosphine oxide-based photopolymerization initiator (B1) and a benzophenone skeleton-based photopolymerization initiator (B3), or it contains an oxyphosphine oxide-based photopolymerization initiator (B3). Phosphine-based photopolymerization initiator (B1), hydroxyketone-based photopolymerization initiator (B2), and photopolymerization initiator (B3) having a benzophenone skeleton. At this time, when a part of the coating film formed of the photosensitive adhesive composition is exposed and then developed, hardening of the unexposed part is suppressed, and the resolution is particularly improved. Therefore, it is possible to form a cured product of the photosensitive adhesive composition having a very fine pattern. In particular, when the interlayer insulating layer of a multilayer printed wiring board is made of a photosensitive adhesive composition and a small diameter hole for a through hole is provided in the interlayer insulating layer by photolithography (refer to Fig. 3 ), a hole with a small diameter can be formed accurately and easily. The photopolymerization initiator (B3) having a benzophenone skeleton includes, for example, bis(diethylamino)benzophenone.

The amount of the photopolymerization initiator (B3) having a benzophenone skeleton relative to the phosphine oxide-based photopolymerization initiator (B1) is preferably 0.5% by mass or more and 20% by mass or less. If the amount of the photopolymerization initiator (B3) having a benzophenone skeleton is 0.5% by mass or more relative to the phosphine oxide-based photopolymerization initiator (B1), the resolution is particularly improved. In addition, if the amount of the photopolymerization initiator (B3) having a benzophenone skeleton is 20% by mass or less with respect to the phosphine oxide-based photopolymerization initiator (B1), it has a benzophenone skeleton. The photopolymerization initiator (B3) does not easily hinder the electrical insulation of the cured product of the photosensitive adhesive composition. From the same viewpoint, the amount of bis(diethylamino)benzophenone is preferably 0.5% by mass or more and 20% by mass or less relative to the phosphine oxide-based photopolymerization initiator (B1).

The photosensitive adhesive composition may further contain an appropriate photopolymerization accelerator, sensitizer, and the like. For example, the photosensitive adhesive composition can contain at least one component selected from the group consisting of: 1,2-octanedione, 1-[4-(phenylthio)-,2-(O -Benzyl oxime)], ethyl ketone, 1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-,1-(O-ethyl Oxime esters such as oxime); benzoin and its alkyl ethers; acetophenones such as acetophenone and benzyl dimethyl ketal; anthraquinones such as 2-methylanthraquinone; 2 ,4-Dimethylthioxanthone, 2,4-Diethylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-Diisopropylthioxanthone Thioxanthones (thioxanthone); benzophenones, 4-benzyl-4'-methyldiphenyl sulfide and other benzophenones; 2,4-diisopropyl xanthones, etc. Xanthones (xanthones); and, α-hydroxy ketones such as 2-hydroxy-2-methyl-1-phenylpropan-1-one; 2-methyl-1-[4-(methylthio)benzene Group]-2-(N-morpholinyl)-1-acetone and other compounds containing a nitrogen atom. The photosensitive adhesive composition may contain the following together with the photopolymerization initiator (B): ethyl p-dimethyl benzoate, isoamyl p-dimethyl benzoate, 2-dimethylamino ethyl benzoate Suitable photopolymerization initiators and sensitizers such as tertiary amines. The photosensitive adhesive composition may contain the following together with the photopolymerization initiator (B): a sensitizer for laser exposure, that is, a coumarin derivative such as 7-diethylamino-4-methylcoumarin , Carbocyanine (carbocyanine) pigment series, xanthene pigment series, etc.

The photopolymerizable compound (C) can impart photocuring properties to the photosensitive adhesive composition. The photopolymerizable compound (C) preferably contains at least one selected from the group consisting of a photopolymerizable monomer and a photopolymerizable prepolymer. The photopolymerizable monomer can contain, for example, at least one compound selected from the group consisting of: monofunctional (meth)acrylates such as 2-hydroxyethyl (meth)acrylate; and, diethylene glycol Di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate Ester, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ε-caprolactone modified pentaerythritol hexa(meth)acrylate, tricyclodecane dimethanol di(meth)acrylic acid Polyfunctional (meth)acrylates such as esters.

In particular, the photopolymerizable compound (C) is preferably a trifunctional compound, that is, a compound having 3 unsaturated bonds in one molecule. In this case, the resolution at the time of exposure/development of the film formed of the photosensitive adhesive composition is improved, and the developability of the photosensitive adhesive composition by the alkaline aqueous solution is particularly improved. The trifunctional compound can contain, for example, at least one compound selected from the group consisting of: trimethylolpropane tri(meth)acrylate, ethylene oxide (EO) modified trimethylol Propane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, ethoxylated isocyanurate tri(meth)acrylate, and ε-caprolactone modified ginseng (2-propenyloxy) Ethyl) isocyanurate, and ethoxylated glycerol tri(meth)acrylate.

The photopolymerizable compound (C) also preferably contains a phosphorus-containing compound (a phosphorus-containing unsaturated compound). In this case, the flame retardancy of the cured product of the photosensitive adhesive composition is improved. The phosphorus-containing unsaturated compound can contain, for example, at least one compound selected from the group consisting of: 2-methacryloxyethyl phosphate (a specific example is the model LIGHT manufactured by Kyoeisha Chemical Co., Ltd.) ESTER P-1M, and LIGHT ESTER P-2M), 2-propenoxyethyl phosphate (a specific example is the model LIGHT ACRYLATE P-1A manufactured by Kyoeisha Chemical Co., Ltd.), diphenyl phosphate 2-methyl Propylene oxyethyl ester (specific examples are model MR-260 manufactured by Dahachi Industry Co., Ltd.), and HFA series manufactured by Showa Polymer Co., Ltd. (specific examples are: dipentaerythritol hexaacrylate and 9,10 -Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (HCA) addition reactants, namely models HFA-6003 and HFA-6007; caprolactone modified dipentaerythritol hexaacrylate and 9 , 10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (HCA) addition reactants (namely models HFA-3003 and HFA-6127, etc.).

The photopolymerizable prepolymer can contain, for example, at least one compound selected from the group consisting of: a prepolymer obtained by polymerizing a monomer having an ethylenically unsaturated bond and then adding an ethylenically unsaturated group.物; And, oligomeric (meth)acrylate prepolymers. The oligo(meth)acrylate prepolymers can contain, for example, at least one compound selected from the group consisting of epoxy (meth)acrylate, polyester (meth)acrylate, Urethane (meth)acrylate, alkyd resin (meth)acrylate, silicone resin (meth)acrylate, and spiroalkane resin (meth)acrylate.

The photosensitive adhesive composition preferably contains an organic filler (D). If the photosensitive adhesive composition contains the organic filler (D), the effect of improving the following is more significant: the photosensitive adhesive composition is formed on the first member 1 and the first adhesive layer on the second member 2 The bonding strength when 11 and the second adhesive layer 12 are adhered to each other to join the first member 1 and the second member 2. In addition, the organic filler (D) has high compatibility in the photosensitive adhesive composition, and can impart strong thixotropy to the photosensitive adhesive composition. Therefore, the moldability when forming an adhesive layer from the photosensitive adhesive composition can be improved.

The organic filler (D) preferably has at least one functional group selected from the group consisting of a carboxyl group, an epoxy group, and an amino group. At this time, the following can be particularly improved: the first adhesive layer 11 and the second adhesive layer 12 formed on the first member 1 and the second member 2 from the photosensitive adhesive composition are adhered to each other to bond the first member 1 The bonding strength at the time of bonding with the second member 2.

In particular, when the photosensitive adhesive composition contains an organic filler having a carboxyl group (hereinafter also referred to as an organic filler (D1)), the developability of the photosensitive adhesive composition can be improved. In addition, the photosensitive adhesive composition contains an organic filler (D1), that is, it is possible to reduce the unevenness of the cured product layer due to the fluidity of the photosensitive adhesive composition. Thereby, the thickness of the hardened material layer can be easily made uniform. In this case, the photosensitive adhesive composition may not contain a rheology control agent. The carboxyl group of the organic filler (D1) is, for example, formed as a side chain in its product in the following manner: polymerizing or polymerizing carboxylic acid monomers such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, and itaconic acid. Cross-linked. The carboxylic acid monomer has a carboxyl group and a polymerizable unsaturated double bond. Since the organic filler (D1) improves the thixotropy of the photosensitive adhesive composition, it improves the stability (especially storage stability) of the photosensitive adhesive composition. In addition, since the organic filler (D1) has a carboxyl group, it can improve the developability of the cured product containing the photosensitive adhesive composition, and improve the compatibility of the crystalline epoxy resin (E1) described below, thereby preventing the formation of the photosensitive adhesive composition. In crystallization. The carboxyl group content of the organic filler (D1) is preferably, for example, the acid value of the organic filler (D1), which is 1 mgKOH/g or more and 60 mgKOH/g or less in terms of the acid value obtained by acid-base titration. If the acid value is less than 1 mgKOH/g, the stability of the photosensitive adhesive composition and the developability of the cured product may decrease. If the acid value is greater than 60 mgKOH/g, the moisture resistance reliability of the cured product may be reduced. The acid value of the organic filler (D1) is preferably 3 mgKOH/g or more and 40 mgKOH/g or less.

When the organic filler (D) has an amine group, the organic filler (D) contains, for example, melamine. When the organic filler (D) having an amine group contains melamine, when the content of the carboxyl group-containing resin (A) is 100 parts by mass, the content of melamine is preferably 0.1% by mass or more and 6% by mass or less.

The organic filler (D) also preferably has a hydroxyl group. At this time, it is also possible to further improve the bonding strength when the first adhesive layer 11 and the second adhesive layer 12 formed of the photosensitive adhesive composition are adhered to join the first member 1 and the second member 2.

The average primary particle size of the organic filler (D) is preferably 1 μm or less. The average primary particle size of the organic filler (D) is 1 μm or less, that is, the thixotropy of the photosensitive adhesive composition can be efficiently improved. Therefore, the stability of the photosensitive adhesive composition is further improved. In addition, the average primary particle size of the organic filler (D) is 1 μm or less, that is, the organic filler can be uniformly dispersed, and the following will be improved: the first adhesive layer 11 and the second adhesive layer 12 are adhered to the first member 1 The bonding strength at the time of bonding with the second member 2. The lower limit of the average primary particle diameter of the organic filler (D) is not particularly limited, but it is preferably 0.001 μm or more, for example. In addition, the average primary particle size of the organic filler (D) was measured as D50 using a laser diffraction particle size distribution measuring device. Preferably, the average primary particle size of the organic filler (D) is 0.4 μm or less, and more preferably, the average primary particle size of the organic filler (D) is 0.1 μm or less. In this case, the roughness of the rough surface formed on the hardened product can be made particularly small. In addition, it is possible to suppress scattering during exposure in the photosensitive adhesive composition, and thereby it is possible to further improve the resolution of the photosensitive adhesive composition.

The organic filler (D) is preferably dispersed in the photosensitive adhesive composition so that the maximum particle size is less than 1.0 μm, and more preferably is dispersed so that the maximum particle size is less than 0.5 μm. The maximum particle size is measured using a laser diffraction particle size distribution measuring device. Alternatively, the maximum particle size is measured by observing the cured product using a transmission electron microscope (TEM). The organic filler (D) may aggregate in the photosensitive adhesive composition (for example, secondary particles may be formed). In this case, the maximum particle size means the size of the aggregated particles. If the maximum particle size of the organic filler (D) in the dispersed state is within the aforementioned range, the roughness of the rough surface formed on the cured product can be made smaller. In addition, in the photosensitive adhesive composition, scattering during exposure can be suppressed, thereby further improving the resolution of the photosensitive adhesive composition. In addition, the stability of the photosensitive adhesive composition can be improved. It is particularly preferable that the average primary particle diameter of the organic filler (D) is 0.1 μm or less, and the organic filler (D) is dispersed with a particle diameter of 0.5 μm or less. Furthermore, when particle agglomeration occurs, the maximum particle size is usually larger than the average primary particle size.

The organic filler (D) preferably contains a rubber component. The rubber component can impart flexibility to the cured product of the photosensitive adhesive composition. The rubber component can be composed of resin. The rubber component is preferably composed of cross-linked acrylic rubber, cross-linked nitrile rubber (NBR), cross-linked methyl methacrylate-butadiene-styrene (MBS) and cross-linked styrene butadiene rubber (SBR). At least one polymer selected from the composition group. In this case, the rubber component can impart excellent flexibility to the cured product of the photosensitive adhesive composition. In addition, at this time, it is also possible to provide a more moderately rough surface to the surface of the hardened layer. The rubber component includes a cross-linked structure formed when the monomer constituting the above-mentioned polymer is used for copolymerization. NBR is generally a copolymer of butadiene and acrylonitrile, and is classified as a nitrile rubber. MBS is generally a copolymer composed of three components: methyl methacrylate, butadiene, and styrene, and is classified as a butadiene rubber. SBR is generally a copolymer of styrene and butadiene and is classified as styrene rubber. Specific examples of the organic filler (D) include model XER-91-MEK manufactured by JSR Co., Ltd., model XER-32-MEK manufactured by JSR Co., Ltd., model XSK-500 manufactured by JSR Co., Ltd., and the like. Among these organic fillers (D), XER-91-MEK is a cross-linked rubber (NBR) with a carboxyl group with an average primary particle size of 0.07 μm, and the cross-linked rubber contains 15% by weight of methyl ethyl It is provided as a ketone dispersion with an acid value of 10.0 mgKOH/g. XER-32-MEK is a dispersion obtained by dispersing a polymer (linear particles) of a carboxyl modified hydrogenated nitrile rubber in methyl ethyl ketone at a content of 17% by weight based on the total amount of the dispersion. In addition, XSK-500 is a cross-linked rubber (SBR) having carboxyl and hydroxyl groups with an average primary particle size of 0.07 μm, and is provided as a methyl ethyl ketone dispersion containing 15% by weight of the cross-linked rubber. In this way, the organic filler (D) can be blended in the photosensitive adhesive composition in the dispersion liquid. In other words, the rubber component can be blended in the photosensitive adhesive composition in the dispersion liquid. In addition, specific examples of the organic filler (D) include model XER-92 manufactured by JSR Co., Ltd. in addition to the above.

The organic filler (D) may contain particle components other than the rubber component. In this case, the organic filler (D) can contain, for example, at least one particle component selected from the group consisting of acrylic resin microparticles having a carboxyl group and cellulose microparticles having a carboxyl group. The acrylic resin microparticles having a carboxyl group can contain at least one particle component selected from the group consisting of non-crosslinked styrene-acrylic resin microparticles and crosslinked styrene-acrylic resin microparticles. Specific examples of the non-crosslinked styrene-acrylic resin fine particles include, for example, model FS-201 (average primary particle size 0.5 μm) manufactured by NIPPON PAINT INDUSTRIAL COATINGS Co., Ltd. Specific examples of cross-linked styrene-acrylic resin particles include: model MG-351 (average primary particle size 1.0 μm) manufactured by NIPPON PAINT INDUSTRIAL COATINGS Co., Ltd. and model BGK-001 (average primary particle size 1.0 μm) . In addition, the organic filler (D) may contain particle components other than those selected from the rubber components, acrylic resin fine particles, and cellulose fine particles. At this time, the organic filler (D) can contain a particle component having a carboxyl group. In other words, the component of the particle having a carboxyl group may be different from the component of the particle selected from the rubber component, acrylic resin fine particles, and cellulose fine particles.

Here, when the photosensitive adhesive composition contains an organic filler (D), the organic filler (D) may cause light scattering in the photosensitive adhesive composition during exposure. In this case, the photosensitive adhesive composition preferably contains the aforementioned phosphine oxide-based photopolymerization initiator (B1) and the hydroxyketone-based photopolymerization initiator (B2). Thereby, when the photosensitive adhesive composition is exposed and cured, good developability can be obtained. The mass ratio of the phosphine oxide-based photopolymerization initiator (B1) and the hydroxyketone-based photopolymerization initiator (B2) is preferably in the range of 1:0.01 to 1:1. In addition, from the same point of view, the photosensitive adhesive composition preferably also contains a photopolymerization initiator (B3) having a benzophenone skeleton. As for the agent (B1), the amount of the photopolymerization initiator (B3) having a benzophenone skeleton is particularly preferably 1% by mass or more and 18% by mass or less. In addition, from the same viewpoint, it is particularly preferable that the amount of bis(diethylamino)benzophenone is 1% by mass or more and 18% by mass or less relative to the phosphine oxide-based photopolymerization initiator (B1). .

The photosensitive adhesive composition preferably further contains an epoxy compound (E). In this case, it is possible to further improve the bonding strength when the first adhesive layer 11 and the second adhesive layer 12 formed of the photosensitive adhesive composition are adhered to each other to join the first member 1 and the second member 2. In addition, the insulation of the multilayer substrate 10 formed by joining the first member 1 and the second member 2 can be improved.

The epoxy compound (E) can impart thermosetting properties to the photosensitive adhesive composition. The epoxy compound (E) preferably contains a crystalline epoxy resin (E1). In this case, the developability of the layer formed of the photosensitive adhesive composition can be improved. In addition, at this time, if the photosensitive adhesive composition further contains the above-mentioned organic filler (D1), the carboxyl group in the organic filler (D1) can improve the compatibility of the crystalline epoxy resin (E1). This can prevent recrystallization of the crystalline epoxy resin (E1) in the photosensitive adhesive composition. In addition, the epoxy compound (E) may further contain an amorphous epoxy resin (E2). Here, "crystalline epoxy resin" is an epoxy resin having a melting point, and "amorphous epoxy resin" is an epoxy resin having no melting point.

The crystalline epoxy resin (E1) preferably contains, for example, one or more components selected from the group consisting of: 1,3,5-gin(2,3-epoxypropyl)-1 ,3,5-Triazine-2,4,6(1H,3H,5H)-trione, hydroquinone type crystalline epoxy resin (a specific example is the trade name YDC- manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) 1312), biphenyl type crystalline epoxy resin (a specific example is the trade name YX-4000 manufactured by Mitsubishi Chemical Co., Ltd.), diphenyl ether type crystalline epoxy resin (a specific example is NIPPON STEEL Chemical & Material Co., Ltd. The company’s model YSLV-80DE), bisphenol-type crystalline epoxy resin (a specific example is the product name YSLV-80XY manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), and a phenol ethane type crystalline epoxy resin (specifically Examples are model number GTR-1800 manufactured by Nippon Kayaku Co., Ltd., and bisphenol pyridine type crystalline epoxy resin (a specific example is an epoxy resin having structure (S7)).

The crystalline epoxy resin (E1) preferably has two epoxy groups in one molecule. At this time, the hardened product can be made less likely to crack due to repeated temperature changes.

The crystalline epoxy resin (E1) preferably has an epoxy equivalent of 150 g/eq or more and 300 g/eq or less. This epoxy equivalent is the g weight of the crystalline epoxy resin (E1) containing 1 g equivalent of epoxy groups. The crystalline epoxy resin (E1) has a melting point. The melting point of the crystalline epoxy resin (E1) can be, for example, 70°C or more and 180°C or less.

In particular, the crystalline epoxy resin (E) preferably contains a crystalline epoxy resin (E1-1) having a melting point of 110°C or less. In this case, the developability of the photosensitive adhesive composition with an alkaline aqueous solution is particularly improved. In this case, the resolution (opening property) of the adhesive layer formed of the photosensitive adhesive composition can also be improved. The crystalline epoxy resin (E1-1) having a melting point of 110°C or less contains, for example, at least one component selected from the group consisting of: biphenyl type epoxy resin (a specific example is made by Mitsubishi Chemical Co., Ltd. Model YX-4000), diphenyl ether type epoxy resin (specific example is model YSLV-80DE manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), and bisphenol type epoxy resin (specific example is Nippon Steel & Sumikin Chemical Co., Ltd. Model YSLV-80XY manufactured by Co., Ltd., bisphenol pyridine type crystalline epoxy resin (a specific example is an epoxy resin having a structure (S7)).

The amorphous epoxy resin (E2) preferably contains, for example, at least one component selected from the group consisting of: phenol novolac type epoxy resin (a specific example is the model EPICLON N manufactured by DIC Co., Ltd.) -775), cresol novolac type epoxy resin (specific example is model EPICLON N-695 manufactured by DIC Co., Ltd.), bisphenol A novolac type epoxy resin (specific example is model EPICLON manufactured by DIC Co., Ltd. N-865), bisphenol A type epoxy resin (specifically, model jER1001 manufactured by Mitsubishi Chemical Co., Ltd.), bisphenol F type epoxy resin (specifically model jER4004P manufactured by Mitsubishi Chemical Co., Ltd.), double Phenolic S type epoxy resin (specific examples are the model EPICLON EXA-1514 manufactured by DIC Co., Ltd.), bisphenol AD type epoxy resins, and biphenol novolac type epoxy resins (specific examples are Nippon Kayaku Co., Ltd. Model NC-3000), hydrogenated bisphenol A epoxy resin (specifically, model ST-4000D manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), naphthalene-based epoxy resin (specifically manufactured by DIC Co., Ltd. Model EPICLON HP-4032, EPICLON HP-4700, EPICLON HP-4770), tertiary butyl catechol type epoxy resin (specific example is model EPICLON HP-820 manufactured by DIC Co., Ltd.), dicyclopentadiene type Epoxy resin (specifically, EPICLON HP-7200 manufactured by DIC), adamantane-type epoxy resin (specifically ADAMANTATE XE-201 manufactured by Idemitsu Kosan Co., Ltd.), special bifunctional epoxy resin (Specific examples are models YL7175-500 and YL7175-1000 manufactured by Mitsubishi Chemical Co., Ltd.; models EPICLON TSR-960, EPICLON TER-601, EPICLON TSR-250-80BX, EPICLON 1650-75MPX, EPICLON manufactured by DIC Co., Ltd. EXA-4850, EPICLON EXA-4816, EPICLON EXA-4822, and EPICLON EXA-9726; Model YSLV-120TE manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), rubber-like core-shell polymer modified bisphenol A epoxy Resin (specific example is model MX-156 manufactured by KANEKA Co., Ltd.), rubber-like core-shell polymer modified bisphenol F type epoxy resin (specific example is model MX-136 manufactured by KANEKA Co., Ltd.), and containing Bisphenol F type epoxy resin of rubber particles (a specific example is model Kane Ace MX-130 manufactured by KANEKA Co., Ltd.).

When the photosensitive adhesive composition contains an epoxy compound (E), the photosensitive adhesive composition preferably contains both a crystalline epoxy resin (E1) and an amorphous epoxy resin (E2). In this case, the bonding strength when the adhesive layers made of the photosensitive adhesive composition are adhered to each other can be further improved, and the resolution (opening properties) of the adhesive layer can be further improved.

The epoxy compound (E) may contain a phosphorus-containing epoxy resin. At this time, the flame retardancy of the cured product of the photosensitive adhesive composition is improved. The phosphorus-containing epoxy resin may be contained in the crystalline epoxy resin (E1) or may be contained in the amorphous epoxy resin (E2). Phosphorus-containing epoxy resins include, for example, phosphoric acid modified bisphenol F type epoxy resin (specific examples are EPICLON EXA-9726 and EPICLON EXA-9710 manufactured by DIC Co., Ltd.), Nippon Steel & Sumikin Chemical Co., Ltd. The model Epotohto FX-305 and so on.

The amount of the components in the photosensitive adhesive composition is appropriately adjusted so that the photosensitive adhesive composition has photocuring properties and can be developed with an alkaline solution.

Relative to the solid content of the photosensitive adhesive composition, the amount of the carboxyl group-containing resin (A) is preferably 5% by mass or more and 85% by mass or less, and more preferably 10% by mass or more and 75% by mass or less Preferably, if it is 20% by mass or more and 50% by mass or less), it is still more preferable. In addition, the amount of the carboxyl group-containing resin (A1) relative to the solid content of the photosensitive adhesive composition is preferably 5% by mass or more and 85% by mass or less, and if it is 10% by mass or more and 75% by mass or less It is more preferable, and if it is 20% by mass or more and 50% by mass or less, it is still more preferable. With respect to the carboxyl group-containing resin (A), the amount of the photopolymerization initiator (B) is preferably 0.1% by mass or more and 30% by mass or less, and more preferably 1% by mass or more and 25% by mass or less.

The amount of the photopolymerizable compound (C) relative to the carboxyl group-containing resin (A) is preferably 1% by mass or more and 50% by mass or less, and more preferably 10% by mass or more and 45% by mass or less. It is more preferable if it is within the range of 21% by mass or more and 40% by mass or less.

When the photosensitive adhesive composition contains an organic filler (D), the organic filler (D) is preferably 0.1% by mass or more and 60% by mass or less with respect to the carboxyl group-containing resin (A). Relative to the carboxyl group-containing resin (A), the organic filler (D) is preferably 0.5% by mass or more and 30% by mass or less, more preferably 1% by mass or more and 17% by mass or less, and 3% by mass or more and 15% by mass The following are particularly good.

When the organic filler (D) contains a rubber component, relative to the carboxyl group-containing resin (A), the content of the rubber component is preferably 1% by mass or more and 60% by mass or less, preferably 2% by mass or more and 20% by mass or less , More preferably 3% by mass or more and 17% by mass or less.

When the photosensitive adhesive composition contains the epoxy compound (E), the amount of the epoxy compound (E) is relative to 1 equivalent of the carboxyl group contained in the carboxyl group-containing resin (A), and the epoxy compound (E) The total equivalent of epoxy groups contained is preferably 0.7 or more and 2.5 or less, preferably 0.7 or more and 2.3 or less, and more preferably 0.7 or more and 2.0 or less. In addition, the sum of the equivalents of epoxy groups contained in the crystalline epoxy resin (E1) is preferably 0.1 or more and 2.0 or less with respect to 1 equivalent of the carboxyl groups contained in the carboxyl group-containing resin (A), if it is 0.2 More than 1.9 is preferable, and 0.3 or more and 1.5 or less are more preferable. Alternatively, the sum of the equivalents of epoxy groups contained in the crystalline epoxy resin (E1) may be 0.7 or more and 2.5 or less with respect to 1 equivalent of the carboxyl groups contained in the carboxyl group-containing resin (A).

The photosensitive adhesive composition may further contain components other than the above-mentioned components as long as the effects of the present embodiment are not hindered.

The photosensitive adhesive composition may contain at least one resin selected from the group consisting of: toluene diisocyanate, morpholine diisocyanate blocked with caprolactam, oxime, malonate, etc. Blocked isocyanates such as isophorone, isophorone diisocyanate, and hexamethylene diisocyanate; butylated urea resin; various thermosetting resins other than the foregoing; ultraviolet curable epoxy (meth)acrylate; A resin obtained by adding (meth)acrylic acid to epoxy resins such as bisphenol A type, phenol novolak type, cresol novolak type, alicyclic type, etc.; and, diallyl phthalate resin, High-molecular compounds such as phenoxy resin, urethane resin, and fluororesin.

The photosensitive adhesive composition may contain a curing agent for curing the epoxy compound (E). The hardener can contain, for example, at least one ingredient selected from the group consisting of imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl Imidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole and other imidazole derivatives; dicyandiamide, benzene Methyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl -N,N-Dimethylbenzylamine and other amine compounds; hydrazine compounds such as hexadihydrazine and sebacadiazine; phosphorus compounds such as triphenylphosphine; acid anhydrides; phenols; mercaptans; Lewis acids Amine complexes; and, onium salts. Commercial products of these components are, for example: 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ manufactured by Shikoku Chemical Co., Ltd. (any of them are the trade names of imidazole compounds); San-Apro Co., Ltd. U-CAT3503N, U-CAT3502T (any of them are the trade names of blocked isocyanate compounds of dimethylamine); DBU, DBN, U-CATSA102, U-CAT5002 (any of them are bicyclic amidine) Compounds and their salts).

The photosensitive adhesive composition may further contain an inorganic filler. Examples of inorganic fillers include silica fillers, barium sulfate, carbon nanotubes, talc, bentonite, aluminum hydroxide, magnesium hydroxide, and titanium oxide. For example, when the photosensitive adhesive composition contains white materials such as titanium oxide and zinc oxide, the photosensitive adhesive composition and its hardened material can be whitened.

The photosensitive adhesive composition may contain an adhesiveness imparting agent. If the photosensitive adhesive composition contains an adhesiveness imparting agent, the adhesiveness of the layer in contact with the photosensitive adhesive composition can be more optimized. Examples of the adhesion imparting agent include: acetoguanamine (2,4-diamino-6-methyl-1,3,5-triazine), and benzoguanamine (2,4 -Diamino-6-phenyl-1,3,5-triazine) and other guanamine derivatives; and, 2,4-diamino-6-methacryloxyethyl-s-triazine , 2-vinyl-4,6-diamino-s-triazine, 2-vinyl-4,6-diamino-s-triazine/isocyanuric acid adduct, 2,4-di S-triazine derivatives such as amino-6-methacryloxyethyl-s-triazine and isocyanuric acid adducts.

The photosensitive adhesive composition may contain a rheology control agent. With the rheology control agent, it is easy to make the viscosity of the photosensitive adhesive composition more suitable. Examples of rheology control agents include polar polyamides (models BYK-430 and BYK-431 manufactured by BYK Japan Co., Ltd.) and polyhydroxycarboxamides (models BYK-431 manufactured by BYK Japan Co., Ltd.) in urea modification. 405), modified urea (model BYK-410, BYK-411, BYK-420 manufactured by BYK Japan Co., Ltd.), polymer urea derivative (model BYK-415 manufactured by BYK Japan Co., Ltd.), modified urea Urethane (model BYK-425 manufactured by BYK Japan Co., Ltd.), polyurethane (model BYK-428 manufactured by BYK Japan Co., Ltd.), castor oil wax, polyethylene wax, polyamide wax, bentonite, Kaolin, clay.

The photosensitive adhesive composition may contain at least one component selected from the group consisting of: hardening accelerator; coloring agent; copolymers such as silicone and acrylate; leveling agent; thixotropic agent ; Polymerization inhibitors; anti-halation agents; flame retardants; defoamers; antioxidants; surfactants; and, polymer dispersants.

When preparing the photosensitive adhesive composition of this embodiment, the photosensitive adhesive composition can be prepared, for example, by mixing the raw materials of the photosensitive adhesive composition, and using, for example, a three-roll mill or a ball mill. , Sand mill and other appropriate kneading method to knead. When the raw material contains liquid components, low-viscosity components, etc., the photosensitive adhesive composition can be prepared in the following manner: First, the raw materials are kneaded except for the liquid components, low-viscosity components, etc. After combining and preparing the mixture, a liquid component, a low-viscosity component, etc. are added to the obtained mixture and mixed. When the photosensitive adhesive composition contains a solvent, first, part or all of the raw materials except for the solvent are mixed, and then mixed with the remaining raw materials. In addition, when the photosensitive adhesive composition contains an organic filler (D), when a dispersion liquid of the organic filler (D) or the like is used, the photosensitive adhesive composition can be prepared in the following manner: the organic filler ( The above-mentioned raw material components other than D) are mixed.

In consideration of storage stability, etc., a part of the components of the photosensitive adhesive composition may be mixed to prepare the first agent, and then the rest of the components may be mixed to prepare the second agent. In other words, the photosensitive adhesive composition may include a first agent and a second agent. In this case, for example, the photopolymerizable compound (C), a part of the solvent, and the thermosetting component among the components of the photosensitive adhesive composition can be pre-mixed and dispersed to prepare the first agent. The remainder among the components of the photosensitive adhesive composition is mixed and dispersed to prepare a second agent. At this time, the required amount of the first agent and the second agent can be mixed in a timely manner to prepare a mixed liquid, and the first adhesive layer 11 and the second adhesive layer 12 can be produced from the mixed liquid.

The photosensitive adhesive composition preferably has properties such that a film with a thickness of 25 μm obtained from the photosensitive adhesive composition can be developed with an aqueous sodium carbonate solution. At this time, the first adhesive layer 11 and the second adhesive layer 12 can be made sufficiently thick from the photosensitive adhesive composition by photolithography. Of course, it is also possible to make the first adhesive layer 11 and the second adhesive layer 12 thinner than the thickness of 25 μm from the photosensitive adhesive composition.

Whether or not a film with a thickness of 25 μm can be developed with a sodium carbonate aqueous solution can be confirmed by the following method. The photosensitive adhesive composition is coated on an appropriate substrate to form a wet coating film, and the wet coating film is heated at 80° C. for 40 minutes to form a film with a thickness of 25 μm. In the state where the negative mask is directly attached to the film ^{, the film is exposed to ultraviolet rays under the condition of 500 mJ/cm 2} , and the negative mask has: an exposure part that allows ultraviolet rays to penetrate; and , The non-exposed part that will shield the ultraviolet rays. After the exposure, the film was subjected to the following treatment: after spraying a 1% Na ₂ CO ₃ aqueous solution at 30° C. for 90 seconds at a spray pressure of 0.2 MPa, and spraying pure water for 90 seconds at a spray pressure of 0.2 MPa. After observing the film after this treatment, when the portion corresponding to the non-exposed part of the film was removed and no residue was confirmed, it could be judged that a film with a thickness of 25 μm could be developed with an aqueous sodium carbonate solution. In addition, it can also be confirmed whether or not it can be developed with a sodium carbonate aqueous solution for films of other thicknesses (for example, 30 μm).

With reference to FIGS. 2A to 2E, a method of joining the first member 1 and the second member 2 using the photosensitive adhesive composition of this embodiment and a method of manufacturing the multilayer substrate 10 will be described.

The photosensitive adhesive composition, as described above, is used to adhere the first adhesive layer 11 and the second adhesive layer 12 overlapped on the first member 1 and the second member 2 respectively, and pass through the first adhesive layer 11 and the second adhesive layer 12 are used to join the first member 1 and the second member 2 to form the first adhesive layer 11 and the second adhesive layer 12. Therefore, the photosensitive adhesive composition can be used to produce the multilayer substrate 10 from the first member 1 and the second member 2.

The method of forming the first adhesive layer 11 and the second adhesive layer 12 on the first member 1 and the second member 2, respectively, may be as long as an appropriate method is adopted. Specifically, for example, the method is as follows.

First, the first member 1 and the second member 2 are prepared (refer to FIG. 2A). The first member 1 and the second member 2 are not particularly limited, and may be formed of appropriate materials. The first member 1 and the second member 2 may be formed of the same material. More specifically, the first member 1 and the second member 2 include, for example, polyethylene terephthalate (PET) film, glass, polycarbonate, cycloolefin polymer, liquid crystal polymer, glass epoxy resin Circuit boards with conductor lines, such as base materials, metal-clad laminates, silicon wafers, and printed circuit boards. The first member 1 and the second member 2 may be, for example, a printed circuit board, which, as shown in Figure 1, is provided with: an insulating layer 5; conductor lines 3, 3, which are respectively provided on one surface of the insulating layer 5 and The other surface on the opposite side; and, the through hole 40, which is used to conduct conduction between the conductor lines 3 and 3.

Hereinafter, with reference to FIGS. 2A to 2E, a first example of the manufacturing process of the multilayer substrate 10 when the first member 1 and the second member 2 are printed wiring boards provided with conductor lines 3 will be specifically described.

The photosensitive adhesive composition is coated on the first member 1, and the photosensitive adhesive composition is further heated to make it dry or semi-cured according to needs, that is, the first adhesive layer can be formed on the first member 1 11. In addition, the photosensitive adhesive composition is coated on the second member 2, and the photosensitive adhesive composition is further heated to make it dry or semi-cured as needed, that is, the second member 2 can be fabricated on the second member 2. Adhesive layer 12 (refer to Figure 2B). The method of coating the photosensitive adhesive composition may be any suitable method, for example, dipping method, spray method, spin coating method, roll coating method, curtain coating method, screen printing method, etc. . When the photosensitive adhesive composition is heated, for example, when the photosensitive adhesive composition contains a solvent, in order to volatilize the solvent, the photosensitive adhesive composition is heated, for example, at a temperature in the range of 60 to 120°C.

The first adhesive layer 11 and the second adhesive layer 12 can be respectively produced from a dry film containing a photosensitive adhesive composition or a semi-cured product. At this time, for example, first, the photosensitive adhesive composition is coated on an appropriate support made of polyester, etc., and then heated to form a dry or semi-sensitive adhesive composition on the support. The hardened product is also the dry film. Thereby, a laminate (dry film with support) is obtained, which includes a dry film and a support for supporting the dry film. After overlaying the dry film in the laminate on the first member 1, pressure is applied to the dry film and the first member 1, and then the support is peeled from the dry film, and the dry film is transferred from the support to the first member 1 on. Thereby, a first adhesive layer 11 made of a dry film is provided on the first member 1. In the same way, a second adhesive layer 12 made of a dry film is provided on the second member 2.

The first adhesive layer 11 and the second adhesive layer 12 can be cured by exposure respectively. Since the photosensitive adhesive composition has photosensitivity, it can be exposed and hardened. For example, the first adhesive layer 11 and the second adhesive layer 12 can be exposed to the entire surface by irradiating light such as ultraviolet rays. The light source used for exposure is selected from the group consisting of, for example, chemical lamps, low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, metal halide lamps, light-emitting diodes (LED ), yttrium aluminum garnet (YAG), g-line (436 nm), h-line (405 nm), i-line (365 nm), and a combination of two or more of g-line, h-line and i-line. The light source is not limited to these, as long as it can irradiate light capable of curing the photosensitive adhesive composition. Furthermore, when the first adhesive layer 11 and the second adhesive layer 12 are produced by the above-mentioned dry film method, the dry film in the laminate can be overlapped on the first member 1 and the second member 2, without supporting In the case of body peeling, the dry film is irradiated with light such as ultraviolet rays through the support to expose the dry film, and then the support is peeled from the dry film.

The thickness of each of the first adhesive layer 11 and the second adhesive layer 12 is not particularly limited, and may be, for example, 1 μm or more and 100 μm or less.

Then, the first adhesive layer 11 and the second adhesive layer 12 are overlapped (refer to FIG. 2C). Thereby, a laminate is obtained, which is formed by laminating the first member 1, the first adhesive layer 11, the second adhesive layer 12, and the second member 2 in this order. Use a vacuum laminator (vacuum laminator) or the like to heat-press the laminate (refer to Fig. 2 D). Thereby, the first adhesive layer 11 and the second adhesive layer 12 are adhered, and the first member 1 and the second member 2 are joined through the first adhesive layer 11 and the second adhesive layer 12. Thereby, a multilayer substrate 10 is obtained (refer to FIG. 2E). The conditions of hot pressing only need to be adjusted appropriately in the way that the first adhesive layer 11 and the second adhesive layer 12 are adhered. For example, the pressing pressure is 0.01 MPa or more and 30 MPa or less, and the heating temperature is 50°C or more and 300°C or less. , The hot pressing time is 1 second or more and 60 minutes or less. In this embodiment, it is also preferable that after the laminate is hot-pressed as described above, it is further heated to obtain the multilayer substrate 10. In this way, a multilayer substrate 10 with more excellent bonding strength between the first member 1 and the second member 2 is obtained. The heating conditions may be appropriately set, and the heating temperature is preferably 50°C or more and 300°C or less, and the heating time is preferably 5 minutes or more and 300 minutes or less. The heating temperature is preferably 80°C to 280°C, more preferably 100°C to 250°C, and particularly preferably 130°C to 200°C. The heating time is preferably 10 minutes to 250 minutes, more preferably 20 minutes to 200 minutes, and particularly preferably 30 minutes to 180 minutes. In addition, when the photosensitive adhesive composition contains a crystalline epoxy resin, the heating temperature is more preferably heated above the melting point of the crystalline epoxy resin. At this time, the bonding strength will be further improved.

As described above, according to the present embodiment, the first adhesive layer 11 on the first member 1 and the second adhesive layer 12 on the second member 2 are overlapped to make them adhere, that is, the first adhesive layer 11 and the second adhesive layer 12 can be adhered. The adhesive layer 12 is used to join the first member 1 and the second member 2 to produce a multilayer substrate 10.

Furthermore, in the foregoing, referring to FIGS. 2A to 2E, it has been described that the first member 1 and the second member 2 are joined through the first adhesive layer 11 and the second adhesive layer 12 to produce the multilayer substrate 10 The method of manufacturing the multilayer substrate 10 formed by joining two members (the first member 1 and the second member 2) is not limited to this. As long as the adhesive layers formed of the photosensitive adhesive composition described above are adhered to each other and the members are joined, the multilayer substrate 10 can be produced by joining three or more members.

When the first member 1 and the second member 2 are printed wiring boards, respectively, the printed wiring board may be provided with only one insulating layer as described above, or it may be a multilayer printed wiring board provided with a plurality of insulating layers. In other words, each of the first member 1 and the second member 2 may be a printed wiring board formed by laminating dozens of layers, for example, 10 or more layers.

Furthermore, electrical insulating layers, such as a solder resist layer and an interlayer insulating layer, can be formed from the coating film or dry film of the photosensitive adhesive composition of this embodiment.

The second example of the method of manufacturing the multilayer substrate 10 will be described with reference to FIGS. 3A to 3F. Using the photosensitive adhesive composition of this embodiment, after forming the first adhesive layer 11 and the second adhesive layer 12 with appropriate patterns by photolithography or the like, the first member 1 and the second member 2 are joined . In addition, the description overlapping with the method described in the first example is appropriately omitted. When the first adhesive layer 11 and the second adhesive layer 12 have appropriate patterns, bonding the first adhesive layer 11 and the second adhesive layer 12 to each other can also achieve high bonding between the first member 1 and the second member 2 strength.

First, the first member 1 and the second member 2 are prepared. The first member 1 and the second member 2 are each provided with an insulating layer 5 and a conductor line 3 overlapped on the insulating layer 5 (refer to FIG. 3A). The first member 1 and the second member 2 are, for example, printed wiring boards. The thickness of the first member 1 and the second member 2 is not particularly limited, and is, for example, 1 μm or more and 10 mm or less.

The photosensitive adhesive composition is coated on the first member 1 so as to cover the conductor line 3 to form a film. The film can be heated and dried.

Furthermore, a dry film made of the photosensitive adhesive composition may be overlapped on the first member 1 so as to cover the conductor line 3 to form a film composed of a dry film. At this time, as in the case of the above-mentioned first example, for example, after the dry film in the laminate with the dry film and the support is superimposed on the first member 1, pressure is applied to the dry film and the first member 1, and then the The support is peeled from the dry film, and the dry film is transferred from the support to the first member 1. Thereby, a coating film composed of a dry film is provided on the first member 1. In the same way, a film composed of a dry film is provided on the second member 2.

The first adhesive layer 11 is produced from the film by photolithography (refer to Fig. 3B). Specifically, the film is irradiated with ultraviolet rays while the negative mask is in close contact with the film to partially expose the film, and the exposed part is cured.

The negative mask includes, for example, an exposed portion that allows ultraviolet rays to pass through, and a non-exposed portion that shields ultraviolet rays. The non-exposure part is provided in the position corresponding to the position of the opening 4 mentioned later, for example. The negative mask is a photo tool such as a mask film and a dry plate. The light source of ultraviolet rays may be the same as the light source described above. Furthermore, the exposure method may be a method other than the method using a negative mask. The adhesive layer can be exposed by, for example, a direct drawing method in which ultraviolet rays emitted from a light source are irradiated only on the part of the adhesive layer to be exposed.

The second adhesive layer 12 is formed on the second member 2 in the same method as in the case of the first adhesive layer 11 (refer to FIG. 3B).

Furthermore, when the first adhesive layer 11 is made from a dry film, the dry film in the laminate can be superimposed on the first member 1, and then the support can be irradiated with light such as ultraviolet rays without peeling the support. After exposing the dry film to the film composed of the dry film, the support is peeled off from the film.

Then, the film is developed using a developer such as an alkaline solution, and the unexposed part of the film is removed. In this way, the first adhesive layer 11 with a pattern can be produced. In the example shown in FIG. 3C, the first adhesive layer 11 has an opening 4, and a part of the conductive line 3 is exposed at the bottom of the opening 4.

In the development process, an appropriate developer can be used in accordance with the composition of the photosensitive adhesive composition. The developer is, for example, an alkaline aqueous solution or an organic amine, and the alkaline aqueous solution contains at least one of an alkali metal salt and an alkali metal hydroxide. More specifically, the alkaline aqueous solution contains, for example, at least one component selected from the group consisting of sodium carbonate, potassium carbonate, ammonium carbonate, sodium bicarbonate, potassium bicarbonate, 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 lower alcohols. The organic amine contains, for example, at least one component selected from the group consisting of ethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, and triisopropanolamine.

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

In addition, the second adhesive layer 12 having a pattern is formed on the second member 2 in the same method as the case of forming the first adhesive layer 11 (refer to FIG. 3C).

Then, the first adhesive layer 11 and the second adhesive layer 12 are overlapped as in the case described above with reference to FIGS. 2 C to D. Thereby, a laminate in which the first member 1, the first adhesive layer 11, the second adhesive layer 12, and the second member 2 are sequentially laminated is obtained. Use a vacuum laminator (vacuum laminator) or the like to heat-press the laminate (see Fig. 3 D and Fig. 3 E). Thereby, the first adhesive layer 11 and the second adhesive layer 12 are adhered, and the first member 1 and the second member 2 are joined through the first adhesive layer 11 and the second adhesive layer 12. Thereby, a multilayer substrate 10 is obtained (refer to FIG. 3F).

When the first adhesive layer 11 and the second adhesive layer 12 are overlapped, for example, as shown in FIG. 3D, the opening 4 in the first adhesive layer 11 is overlapped with the opening 4 in the second adhesive layer 12. Thereby, a hole 41 for penetrating the bonding layer 13 is formed in the bonding layer 13 (for example, refer to FIG. 3E). By disposing the conductive material 30 in this hole 41, the conductive line 3 of the first member 1 and the conductive line 3 of the second member 2 can be electrically connected via the conductive material 30. Specifically, for example, the conductive material 30 is arranged on the portion of the conductor line 3 of the first member 1 exposed at the bottom of the opening 4. In this state, the first adhesive layer 11 and the second adhesive layer 12 are overlapped and adhered by hot pressing. At this time, the conductive material 30 will melt, for example, so that the first member 1 and the second member 2 are electrically connected, respectively. Thereby, the conductive material 30 electrically connects the conductive lines 3 to each other. The conductive material 30 is not particularly limited as long as it is a material having conductivity. Examples of the conductive material 30 include solder balls, conductive pastes, and the like.

The conductive material 30 is interposed on the conductive circuit 3 and removed by exposing the first adhesive layer 11 and the second adhesive layer 12 (for example, the opening 4 shown in FIG. 3C). At this time, the conductor lines 3 of the first member 1 and the second member 2 can be electrically connected to each other via the conductive material 30.

Furthermore, electronic components such as semiconductor chips, resistors, inductors, etc. can be arranged in the opening 4 or the hole 41. At this time, it is possible to obtain a multilayer substrate 10 with built-in electronic components.

In this embodiment, it is also preferable that, as described above, after the laminate is hot-pressed, it is further heated to obtain the multilayer substrate 10. Thereby, it is possible to obtain a multilayer substrate 10 in which the bonding strength of the first member 1 and the second member 2 is more excellent.

As described above, in this embodiment, even if the first adhesive layer 11 and the second adhesive layer 12 with patterns are made from the photosensitive adhesive composition and the photolithography method, the first adhesive layer 11 and the second adhesive layer 12 can still be used. Two adhesive layers 12 are used to join the first member 1 and the second member 2. In other words, in the photosensitive adhesive composition of this embodiment, the first adhesive layer 11 and the second adhesive layer 12 have high-definition patterns, and can achieve high bonding strength between the first member 1 and the second member 2. [Example]

Hereinafter, specific embodiments of the present invention are presented. However, the present invention is not limited only by the embodiments.

(1) Synthesis of carboxyl group-containing resin (1-1) Synthesis example 1 (carboxyl group-containing resin A) In a four-necked flask equipped with a reflux cooler, a thermometer, an air blowing tube, and a stirrer, add a bisphenol phenolic ring Oxygen compound (as shown in formula (7) and R ₁ to R ₈ in formula (7) are all hydrogen epoxy equivalent 250 g/eq epoxy compound) 250 parts by mass, 72 parts by mass of acrylic acid, triphenyl 1.5 parts by mass of phosphine, 0.2 parts by mass of methylhydroquinone, 140 parts by mass of propylene glycol monomethyl ether acetate, and 140 parts by mass of diethylene glycol monoethyl ether acetate. Under air bubbling, these are stirred to prepare a mixture. While stirring the mixture in the flask under air bubbling, it was heated at a heating temperature of 115°C and a heating time of 12 hours. In this way, a solution of the intermediate is prepared.

Then, in the solution of the intermediate in the flask, put 60.8 parts by mass of 1,2,3,6-tetrahydrophthalic anhydride and 58.8 parts by mass of 3,3',4,4'-biphenyltetracarboxylic dianhydride Parts and 38.7 parts by mass of propylene glycol monomethyl ether acetate. While stirring these under air bubbling, they were heated under the conditions of a heating temperature of 115°C and a heating time of 6 hours. Then, while stirring under air bubbling, it was heated under the conditions of a heating temperature of 80°C and a heating time of 1 hour. Thereby, a 65% by mass solution of carboxyl group-containing resin A was obtained. The polydispersity of carboxyl-containing resin A is 2.15, the weight average molecular weight is 3096, and the acid value is 105 mgKOH.

(1-2) Synthesis Example 2 (Carboxyl Group-Containing Resin B) In a four-necked flask equipped with a reflux cooler, thermometer, air blowing tube and agitator, add cresol novolac type epoxy resin (manufactured by NIPPON STEEL Chemical & Material Co., Ltd., model YDCN-700-5, epoxy equivalent 203) 203 parts by mass, 106 parts by mass of diethylene glycol monoethyl ether acetate, 0.2 parts by mass of methylhydroquinone, 72 parts by mass of acrylic acid, and 1.5 parts by mass of triphenylphosphine, to prepare a mixture. The mixture was heated under the conditions of a heating temperature of 100°C and a heating time of 4 hours.

Then, 68 parts by mass of tetrahydrophthalic acid, 0.3 parts by mass of methylhydroquinone, 0.5 parts by mass of triphenylphosphine, and 29 parts by mass of diethylene glycol monoethyl ether acetate were added to the mixture and heated The temperature is 90°C and the heating time is 18 hours. Then, 34 parts by mass of naphtha (Swasol 1500) were further added, and heated under the conditions of a heating temperature of 90°C and a heating time of 5 hours. Thereby, a 65% by mass solution of carboxyl group-containing resin B was obtained. The epoxy equivalent of carboxyl-containing resin B is 9871 g/eq.

(2) Preparation of photosensitive adhesive composition [Examples 1 to 18, Comparative Examples 1 to 3] Among the components shown in Tables 1 and 2 described below, the powdery components were dispersed in the carboxyl group-containing resin solution prepared in (1) above using a three-roll mill in advance, and then shown in Tables 1 and 2 described below. All the components of, and if necessary, methyl ethyl ketone (solvent) as a diluent were added to the flask, and stirred and mixed at a temperature of 35°C to prepare a composition to obtain a photosensitive adhesive composition. In addition, the details of the components shown in Table 1 and Table 2 are as follows. In addition, in Table 1 and Table 2, the numerical value which shows the quantity of a component is a solid content quantity, but about organic fillers AC, F, the numerical value shown in a parenthesis is a solid content quantity. ・Photopolymerization initiator A: 2,4,6-trimethylbenzyl diphenyl phosphine oxide (manufactured by BASF Corporation, model Irgacure TPO). ・Photopolymerization initiator B: 1-hydroxycyclohexyl phenyl ketone (manufactured by BASF, model Irgacure 184). ・Photopolymerization initiator C: 4,4'-bis(diethylamino)benzophenone. ・Photopolymerizable compound A: Trimethylolpropane triacrylate. ・Photopolymerizable compound B: A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., model KAYARAD DPHA). ・Dispersion liquid of organic filler A: A dispersion liquid (JSR) obtained by dispersing crosslinked rubber (NBR) with an average primary particle diameter of 0.07 μm in methyl ethyl ketone at a content of 15% by weight relative to the total amount of the dispersion liquid. Co., Ltd., model XER-91-MEK; acid value 10.0 mgKOH/g). ・Dispersion liquid of organic filler B: A dispersion liquid (JSR) obtained by dispersing crosslinked rubber (SBR) with an average primary particle diameter of 0.07 μm in methyl ethyl ketone at a content of 15% by weight relative to the total amount of the dispersion liquid. Co., Ltd., model XSK-500). ・Dispersion liquid of organic filler C: Dispersed in methyl ethyl ketone a polymer of carboxyl modified hydrogenated nitrile rubber (linear particles or rubber) at a content of 17% by weight relative to the total amount of the dispersion. Dispersion (manufactured by JSR Co., Ltd., model XER-32-MEK). ・Organic filler D: epoxy-containing organic filler powder (glycidyl-modified acrylonitrile butadiene rubber with an average primary particle size of 0.3 μm) ・Organic filler E: Micronized melamine (manufactured by Nissan Chemical Co., Ltd.) ・Organic filler F: Kane Ace MX-125 manufactured by KANEKA Co., Ltd. The bisphenol A epoxy resin contains 33% by mass of core-shell type SBR particles. Epoxy equivalent 270 g/eq.). ・Epoxy resin A: Biphenyl type crystalline epoxy resin (manufactured by Mitsubishi Chemical Corporation, trade name YX-4000, melting point 105°C, epoxy equivalent 187 g/eq.). ・Epoxy resin B: Bisphenol-type crystalline epoxy resin (manufactured by NIPPON STEEL Chemical & Material Co., Ltd., trade name YSLV-80XY, melting point 75-85°C, epoxy equivalent 192 g/eq.). ・Solution of epoxy resin C: A long-chain carbon chain-containing bisphenol A epoxy resin (manufactured by DIC Co., Ltd., trade name EPICLON EXA-4816, liquid resin, epoxy equivalent of 410 g/eq) The epoxy equivalent of the solution (solid content 90%) dissolved in diethylene glycol monoethyl ether acetate is 455.56 g/eq.). ・Epoxy resin D: Bisphenol A epoxy resin, manufactured by NIPPON STEEL Chemical & Material Co., Ltd., model YD-128, epoxy equivalent 187 g/eq. ・Solvent: methyl ethyl ketone.

(3) Preparation of test piece In the following manner, test pieces were prepared from the photosensitive adhesive compositions of the respective examples and comparative examples.

After applying the photosensitive adhesive composition on a polyethylene terephthalate (PET) film using an applicator, it was heated at 80°C for 20 minutes, and then the temperature was further increased to 110°C and heated at 110°C 5 It was dried in minutes, thereby forming a dry film with a thickness of 20 μm on the film.

Then, the biaxially stretched polypropylene film was thermocompressed on the formed dry film at a heating temperature of 70°C, and a cover film was formed on the dry film. After peeling the formed cover film from the dry film, overlay the dry film so that one side of a 0.2 mm thick glass epoxy substrate (manufactured by Lee Chang Industrial Co., Ltd., model CS-3357) is covered over the entire surface, and vacuum is used Laminator to heat the lamination. The conditions for heating and lamination were pressure 0.5 MPa, heating temperature 70°C, heating and pressing time 45 seconds. Thereby, a film with a thickness of 20 μm composed of a dry film was formed on the glass epoxy substrate. Let this be a test piece.

(4) Evaluation test The test pieces of Examples 1 to 18 and Comparative Examples 1 to 3 prepared in (3) above were evaluated in the following order. The results are shown in Tables 1 to 2 below.

(4-1) Low stickiness In each of the Examples and Comparative Examples, when the cover film was peeled from the dry film, the evaluation of low adhesion was performed based on the following evaluation criteria. A: When peeling the cover film, the cover film can be peeled off smoothly without a loud peeling sound. B: When the cover film is peeled off, a peeling sound is generated. C: When the cover film is peeled off, a peeling sound is generated, and the photosensitive adhesive composition is transferred to the cover film.

(4-2) Adhesion In each of Examples and Comparative Example 3, the entire surface of the film in the test piece was exposed to harden the film, and the following substrates were prepared: 2 sheets of hardened layer (adhesive layer) with photosensitive adhesive composition on the member Substrate. The adhesive layers of the two substrates were bonded to each other, and a vacuum laminator was used to heat and laminate them. The conditions for heating and lamination were pressure 0.5 MPa, pressing temperature 100°C, and heating time 45 seconds. After heating and lamination, the two substrates were heated under the conditions of a heating temperature of 180°C and a pressing time of 120 minutes. After heating for 120 minutes, in a multilayer substrate in which the adhesive layers of the two members are joined to each other, the adhesive strength is measured in accordance with the method of measuring the adhesive strength of the copper foil of the copper clad laminate in JIS-C6481, and the adhesive strength is measured as follows Benchmarks to evaluate adhesion. Furthermore, in Comparative Example 3, a multilayer substrate was produced and evaluated without reheating after heating and lamination.

In each of Comparative Examples 1 to 2, the entire surface of the film in the test piece was exposed to harden the film, and the following substrate was prepared: a substrate with a cured layer (adhesive layer) of a photosensitive adhesive composition on the member ; And, a substrate without an adhesive layer. After bonding the adhesive layer of the substrate with the adhesive layer on the member to the substrate without the adhesive layer, and fabricating a multilayer substrate under the same conditions as the above, the evaluation was carried out in the same manner as the above. A: The adhesion strength is higher than 1.5 kN/m. B: The adhesion strength is higher than 1.3 kN/m and 1.5 kN/m or less. C: The adhesion strength is higher than 1.1 kN/m and 1.3 kN/m or less. D: The adhesion strength is higher than 0.9 kN/m and 1.1 kN/m or less. E: The adhesion strength is higher than 0.7 kN/m and 0.9 kN/m or less. F: The adhesion strength is 0.7 kN/m or less.

(4-3) Aperture. For the film in the test piece prepared in the above (3) Preparation of the test piece, a negative mask on a non-exposed part with a predetermined mask pattern on a film made of PET (Negative mask with a non-exposed part of a circular pattern with a diameter of 80 μm, 60 μm, 40 μm, and 20 μm) In the state of direct contact, the negative mask is used to reach 250 mJ/cm ^The film is irradiated with light having wavelengths of 365 nm and 405 nm under the condition of 2. Thereby, through holes were formed in the cured product of the film in the test piece. During the development process, a 30°C 1% Na ₂ CO ₃ aqueous solution was sprayed onto the film for 90 seconds at a spray pressure of 0.2 MPa. Then, pure water was sprayed to the film at a spray pressure of 0.2 MPa for 90 seconds. Thereby, the unexposed part of the film is removed. In addition, after exposure, before development, the film made of polyethylene terephthalate was peeled off from the dry film (film). The aperture of the obtained test piece after exposure and development was evaluated by the following criteria. A: The circular pattern with a diameter of 20 μm is open. B: The circular pattern with a diameter of 40 μm is open, but the circular pattern with a diameter of 20 μm is not open. C: The circular pattern with a diameter of 60 μm is open, but the circular pattern with a diameter of 40 μm is not open. D: The circular pattern with a diameter of 80 μm is open, but the circular pattern with a diameter of 60 μm is not open. E: There is no opening in the circular pattern with a diameter of 80 μm.

(4-4) Humidity resistance In each of the Examples and Comparative Examples, an adhesive sample (multilayer substrate) was produced in the same way as the evaluation substrate of "(4-2) Adhesiveness", and then placed in a pressure cooker (PCT) measuring device at a temperature of 121°C. , After leaving for 50 hours under the condition of 100% humidity, observe the adhesion state of the two test pieces, and evaluate the moisture resistance according to the following criteria. A: No peeling occurred. B: Peeling occurred.

[Table 1]

[Table 2]

In addition, the heating and lamination conditions described in "(4-2) Adhesiveness" of the test piece prepared with the same composition as in Example 2 or the heating conditions after the heating and lamination were changed in the following manner. After the samples were produced, the same evaluations as above (Examples 19 to 23) were performed on the samples, and the results are shown in Table 3.

(Example 19) ・The conditions for heating and lamination are pressure 0.4 MPa, heating temperature 100°C, and heating time 45 seconds.

(Example 20) ・The conditions for heating and lamination are pressure 1.0 MPa, heating temperature 70°C, and heating time 45 seconds.

(Example 21) ・The heating conditions after heating and lamination are set to a heating temperature of 150°C and a heating time of 30 minutes.

(Example 22) ・The heating conditions after heating and lamination are set to a heating temperature of 95°C and a heating time of 60 minutes.

(Example 23) ・The heating conditions after heating and lamination are set to a heating temperature of 110°C and a heating time of 60 minutes.

[table 3]

1: The first component 2: The second component 3: Conductor line 4: opening 5: Insulation layer 10: Multilayer substrate 11: The first adhesive layer 12: The second adhesive layer 13: Bonding layer 30: conductive material 40: Through hole

Fig. 1 is a schematic cross-sectional view showing a multilayer substrate according to an embodiment of the present invention. 2A to 2E are cross-sectional views showing an example (first example) of steps of manufacturing a multilayer substrate according to an embodiment of the present invention. 3A to 3F are cross-sectional views showing another example (second example) of the steps of manufacturing a multilayer substrate.

Domestic deposit information (please note in the order of deposit institution, date and number) no Foreign hosting information (please note in the order of hosting country, institution, date, and number) no

1: The first component

2: The second component

3: Conductor line

5: Insulation layer

10: Multilayer substrate

11: The first adhesive layer

12: The second adhesive layer

13: Bonding layer

40: Through hole

Claims (9)

A photosensitive adhesive composition, which contains: Carboxyl-containing resin (A), Photopolymerization initiator (B), and Photopolymerizable compound (C); In addition, the photosensitive adhesive composition is used to form a first adhesive layer and a second adhesive layer on the first member and the second member, respectively, and overlap the first adhesive layer and the second adhesive layer to make It is adhered, and the first member and the second member are joined through the first adhesive layer and the second adhesive layer. The photosensitive adhesive composition according to claim 1, which further contains an organic filler (D). The photosensitive adhesive composition according to claim 2, wherein the organic filler (D) has at least one functional group selected from the group consisting of a carboxyl group, an epoxy group, and an amino group. The photosensitive adhesive composition according to any one of claims 1 to 3, which further contains an epoxy compound (E). The photosensitive adhesive composition according to claim 4, wherein the epoxy compound (E) contains a crystalline epoxy resin (E1). The photosensitive adhesive composition according to any one of claims 1 to 3, wherein the carboxyl group-containing resin (A) has an ethylenically unsaturated group. The photosensitive adhesive composition according to any one of claims 1 to 3, wherein the carboxyl group-containing resin (A) has a bisphenol skeleton. A dry film comprising the dried product of the photosensitive adhesive composition according to any one of claims 1 to 7. A method for manufacturing a multilayer substrate, comprising: the photosensitive adhesive composition according to any one of claims 1 to 7, or the dry film according to claim 8, on a first member and a second member, respectively Make the first adhesive layer and the second adhesive layer, The first adhesive layer and the second adhesive layer are overlapped to make them adhere, and the first member and the second member are joined through the first adhesive layer and the second adhesive layer.

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