TWI822452B - Non-photosensitive surface modifiers, laminates, printed circuit boards and electronic devices - Google Patents

Abstract

The non-photosensitive surface modifying agent of the present invention is a non-photosensitive surface modifying agent that forms a surface modifying layer between a metal layer and a resin layer, which contains at least one or more compounds having general formulas (1), (2), Heterocyclic compounds with the structure represented by (3) or (4); [R ₁ represents a hydrogen atom, an aryl group or a heteroaryl group, and may further have a substituent; R ₂ represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a carboxyl group, an ester group, a amide group, a hetero an aryl group or a halogen atom; n and m are each an integer from 0 to 5, and n+m=an integer from 0 to 5 (however, regarding general formula (1), it is an integer from 0 to 4)].

Description

Non-photosensitive surface modifiers, laminates, printed circuit boards and electronic devices

The present invention relates to a non-photosensitive surface modifying agent, a laminate, a printed circuit board and an electronic device, and in particular to a non-photosensitive surface modifying agent that can further improve the adhesion between a metal layer and a resin layer.

In recent years, due to the progress of data society, high-density and high-definition printed wiring boards (also called "printed circuit boards") are required. In the manufacturing process of printed wiring boards, resin materials such as etched photoresist, plating resist, solder resist, prepreg, etc. are bonded to the surface of the metal layer or metal wiring. In the manufacturing process of printed wiring boards and the manufactured products, high adhesion between the metal layer and the resin layer is required. Therefore, in order to improve the adhesion between the metal layer and the resin layer, a method of forming an adhesion-enhancing film on the surface of the metal layer to improve the adhesion with the resin layer is known (see, for example, Patent Document 1); in terms of photosensitivity A method of improving adhesiveness by containing sulfur-containing compounds and nitrogen-containing compounds in the resin (for example, see Patent Document 2).

However, although the techniques of the above-mentioned Patent Documents 1 and 2 improve the adhesion between the metal layer and the resin layer to some extent, they still cannot obtain sufficient adhesion. Especially in recent years, with the development of 5G mobile communications or high-density mounting technology in semiconductor packaging, the requirements for low roughness of the metal layer of printed wiring boards or narrow lines of metal wiring have increased. With this, more metal layers and resins are required than before. layer tightness. [Prior technical literature] [Patent Document]

[Patent Document 1] Japanese Patent Application Publication No. 2017-203073 [Patent Document 2] Japanese Patent Application Publication No. 2020-34933

[Problem to be solved by the invention]

The present invention was completed in view of the above-mentioned problems and situations, and its problem to be solved is to provide a non-photosensitive surface modifying agent that can further improve the adhesion between the metal layer and the resin layer, and to provide a non-photosensitive surface modifying agent using the non-photosensitive surface modifying agent. Laminated bodies, printed circuit boards and electronic devices. [Means to solve the problem]

In order to solve the above-mentioned problems, the inventors of the present invention conducted research into the causes of the above-mentioned problems and found that as a non-photosensitive surface modifying agent forming the surface modifying layer between the metal layer and the resin layer, it contains The heterocyclic compound with a specific structure can further improve the adhesion between the metal layer and the resin layer, thereby completing the present invention. That is, the above-mentioned problems of the present invention are solved by the following means:

1. A non-photosensitive surface modifying agent, which is a non-photosensitive surface modifying agent that forms a surface modifying layer between a metal layer and a resin layer, wherein it contains at least one type of agent having the following general formula (1) , Heterocyclic compounds with the structure represented by (2), (3) or (4); [In the formula, R ₁ represents a hydrogen atom, an aryl group or a heteroaryl group, and may further have a substituent; R ₂ represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a carboxyl group, an ester group, or an amide group. group, heteroaryl group or halogen atom; n and m are respectively an integer from 0 to 5, and n+m=an integer from 0 to 5 (however, regarding general formula (1), it is an integer from 0 to 4); there are When there are multiple substituents _R2 , each substituent _R2 can be the same or different from each other; also, when there are multiple n, each n can be the same or different from each other, and when there are multiple m, each m can be the same as each other. or different].

2. The non-photosensitive surface modifying agent according to item 1, wherein the heterocyclic compound has a structure represented by the general formula (1).

3. The non-photosensitive surface modifier of item 2, wherein the aforementioned heterocyclic compound is a heterocyclic compound having a structure represented by the following general formula (5): [In the formula, R ₁ represents a hydrogen atom, an aryl group or a heteroaryl group, and may further have a substituent].

4. The non-photosensitive surface modifying agent according to any one of items 1 to 3, which contains at least water or alcohol.

5. A laminated body in which a surface modification layer and a resin layer are sequentially provided on a metal layer, wherein the surface modification layer contains at least one or more materials having the following general formulas (1) and (2) ), (3) or (4) heterocyclic compounds: [In the formula, R ₁ represents a hydrogen atom, an aryl group or a heteroaryl group, and may further have a substituent; R ₂ represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a carboxyl group, an ester group, or an amide group. group, heteroaryl group or halogen atom; n and m are respectively an integer from 0 to 5, and n+m=an integer from 0 to 5 (however, regarding general formula (1), it is an integer from 0 to 4); there are When there are multiple substituents _R2 , each substituent _R2 can be the same or different from each other; also, when there are multiple n, each n can be the same or different from each other, and when there are multiple m, each m can be the same as each other. or different].

6. The laminate according to item 5, wherein the heterocyclic compound is a heterocyclic compound having a structure represented by the general formula (1).

7. The laminate of item 6, wherein the heterocyclic compound is a heterocyclic compound having a structure represented by the following general formula (5): [In the formula, R ₁ represents a hydrogen atom, an aryl group or a heteroaryl group, and may further have a substituent].

8. The laminated body according to any one of items 5 to 7, wherein the resin layer is a photosensitive resin composition containing an alkali-soluble resin.

9. The laminated body according to any one of items 5 to 7, wherein the resin layer is a thermosetting resin composition containing at least a resin having an epoxy structure.

10. A printed circuit board using the laminate according to any one of items 5 to 9.

11. An electronic device using the laminated body according to any one of items 5 to 9. [Effects of the invention]

By the above means of the present invention, it is possible to provide a non-photosensitive surface modifying agent that can further improve the adhesion between the metal layer and the resin layer, a laminate, a printed circuit board and an electronic device using the non-photosensitive surface modifying agent. . The display mechanism or action mechanism of the effect of the present invention is still unclear, but it can be inferred as follows. The non-photosensitive surface modifier of the present invention contains at least one or more heterocyclic compounds having the structure represented by the aforementioned general formula (1), (2), (3) or (4), and exists in the structure of the aforementioned heterocyclic compound. The nitrogen atoms (N atoms) in will interact with metals, and the phenolic hydroxyl groups will interact with resin. Therefore, the surface modification layer formed by this non-photosensitive surface modification agent exists between the metal layer and the resin layer, whereby the metal layer and the resin layer are modified by the surface modification layer having the aforementioned interaction. And improve the closeness. The phenolic hydroxyl group can hydrogen bond with the polar group present in the resin or covalently bond with the polymeric resin represented by the epoxy group, and can be closely connected with a stronger interaction force than π-π interaction or van der Waals force. . Especially because the nitrogen atoms and phenolic hydroxyl groups in the structure of the aforementioned heterocyclic compound exist at opposite corners of the molecular skeleton, as shown in Figure 1, the aforementioned heterocyclic compound (such as the exemplary compound (1-1) in Figure 1) The molecular skeleton is coordinated in the vertical direction (the thickness direction of the surface modification layer 30), nitrogen atoms (N) interact with the metal of the metal layer 10, and the phenolic hydroxyl group (OH) can be close to the resin layer 20. It is inferred that a better Strong interaction. In addition, each atomic system shown in FIG. 1 represents the same as that in FIG. 2 .

[Form of carrying out the invention]

The non-photosensitive surface modifying agent of the present invention is a non-photosensitive surface modifying agent that forms a surface modifying layer between a metal layer and a resin layer, which contains at least one or more compounds having the aforementioned general formulas (1) and (2). , heterocyclic compounds with the structure represented by (3) or (4). This feature is a technical feature common to or corresponding to each of the following embodiments.

As an embodiment of the present invention, the aforementioned heterocyclic compound is preferably a heterocyclic compound having a structure represented by the aforementioned general formula (1); especially in order to improve the adhesion between the metal layer and the resin layer, the aforementioned heterocyclic compound is preferred It is a heterocyclic compound having a structure represented by the aforementioned general formula (5). Moreover, in terms of solubility, it is preferable to contain at least water or alcohols.

The laminated body of the present invention is a laminated body in which a surface modification layer and a resin layer are sequentially provided on a metal layer, wherein: The aforementioned surface modification layer contains at least one or more heterocyclic compounds having a structure represented by the aforementioned general formula (1), (2), (3) or (4). Thereby, a laminated body with improved adhesion between the metal layer and the resin layer can be provided.

In order to improve the adhesion resulting from the interaction with the phenolic hydroxyl group contained in the heterocyclic compound, the resin layer is preferably a photosensitive resin composition containing an alkali-soluble resin, or at least a resin with an epoxy structure. thermosetting resin composition.

Moreover, the laminated body of this invention can be suitably used for a printed circuit board or an electronic device.

The present invention, its constituent elements, and forms and aspects for implementing the present invention will be described below. In addition, in this case, "～" is used in the sense of including the numerical values described before and after it as the lower limit value and the upper limit value.

[Non-photosensitive surface modifier] The non-photosensitive surface modifying agent of the present invention is a non-photosensitive surface modifying agent that forms a surface modifying layer between a metal layer and a resin layer, which contains at least one type of the following general formulas (1) and (2) ), (3) or (4).

In the aforementioned general formula (1), R ₁ represents a hydrogen atom, an aryl group or a heteroaryl group, preferably an aryl group, and may further have a substituent. Examples of the substituent include hydroxyl group, amide group, and the like.

In the aforementioned general formulas (1) to (4), R ₂ represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a carboxyl group, an ester group, an amide group or a halogen atom, or a heteroaryl group, and in particular Alkyl groups are preferred.

In the aforementioned general formulas (1) to (4), the aforementioned n and m are respectively integers from 0 to 5, and n+m=an integer from 0 to 5 (however, regarding the general formula (1), it is an integer from 0 to 4. integer). Furthermore, in each general formula, when there are multiple substituents R ₂ , each substituent R ₂ may be the same or different from each other; and when there are multiple n, each n may be the same or different from each other, and there are multiple n When m, each m can be the same or different from each other.

The heterocyclic compound of the present invention is a heterocyclic compound having a structure represented by the aforementioned general formula (1) among the heterocyclic compounds having a structure represented by the aforementioned general formulas (1) to (4). And the interaction between the surface modification layer and the resin layer, the result is better in terms of improving the adhesion between the metal layer and the resin layer.

In addition, the heterocyclic compound of the present invention is preferably a heterocyclic compound having a structure represented by the following general formula (5) in order to improve the adhesion between the metal layer and the resin layer.

In the aforementioned general formula (5), R ₁ represents a hydrogen atom, an aryl group or a heteroaryl group, preferably an aryl group, and may further have a substituent. Examples of the substituent include hydroxyl group, amide group, and the like.

Examples of heterocyclic compounds having structures represented by the aforementioned general formulas (1) to (5) are listed below, but the heterocyclic compounds of the present invention are not limited to these.

The non-photosensitive surface modifying agent of the present invention may contain only one type or two or more types of the aforementioned heterocyclic compounds.

The non-photosensitive surface modifier of the present invention preferably contains at least water or alcohol as a solvent from the viewpoint of solubility. Examples of the alcohol include methanol, ethanol, and 2-propanol. As a solvent, two or more types of water or alcohol may be used in combination. Specifically, the mass ratio (mass %) of water and alcohol is preferably in the range of 100:0 to 50:50, more preferably in the range of 100:0 to 75:25.

In terms of film-forming properties, the aromatic heterocyclic compound is preferably contained in the range of 0.00001 (0.1 ppm) to 0.1 (1000 ppm) mass % relative to the entire non-photosensitive surface modifier; in particular, 0.00001 ( It is suitable to contain it within the range of 0.1ppm) to 0.01 (100ppm) mass %.

In addition, the non-photosensitive surface modifier of the present invention may also contain other components other than the above, but it is composed only of non-polymerizable materials that do not contain polymers, polymerizable monomers or oligomers, that is, do not contain resin. . Examples of the aforementioned other components include surfactants, preservatives, stabilizers, acids, alkalis, and pH adjusters.

[Laminated body] The laminate system of the present invention is a laminate in which a surface modification layer and a resin layer are sequentially provided on a metal layer, wherein the surface modification layer contains at least one or more compounds having the above general formulas (1), (2), (3) ) or a heterocyclic compound with a structure represented by (4).

The heterocyclic compounds having the structures represented by the general formulas (1) to (4) are as described above, and therefore their description is omitted.

Furthermore, in terms of improving the adhesion between the metal layer and the resin layer through the interaction between the metal layer and the surface modification layer and the surface modification layer and the resin layer, the aforementioned heterocyclic compound preferably has the aforementioned general formula (1 ) to (4) include a heterocyclic compound having a structure represented by the aforementioned general formula (1). Especially from the viewpoint of improving the adhesion between the metal layer and the resin layer, the heterocyclic compound is preferably a heterocyclic compound having a structure represented by the general formula (5).

In the laminate of the present invention, the heterocyclic rings of the heterocyclic compound are aligned in a direction that is approximately perpendicular to the metal layer, and the phenolic hydroxyl groups of the heterocyclic compound are aligned in a direction that is approximately perpendicular to the resin layer, so that the phenolic hydroxyl groups can be aligned Being closer to the resin layer can achieve stronger interaction, which is better for improving adhesion.

For the alignment of the aforementioned heterocyclic compound, for example, the quantum chemical calculation software Gaussian16 (manufactured by Gaussian Corporation) is used, DFT calculation is performed, and B3LYP (density functional theory) is used to optimize the structure. As the basis function, copper system uses SDD (Stuttgart/Dresden ECP) for calculation, and other element systems use 6-31G(d). Then, using the Grid scan module of Material Science Suite, a software produced by Schrodinger, an initial position is placed where copper ions become restabilized in the space around the ligand. Regarding the optimal structure calculated above, for example, taking Exemplary Compound (1-1) as an example to illustrate, as shown in Figure 2, the interaction site of the compound (Exemplary Compound (1-1)) and (Cu) In the axial direction, when the center line A perpendicular to the aforementioned axial direction is drawn from the center of the compound, it is preferable that the interaction site with copper (Cu) and the phenolic hydroxyl group (OH) interact with each other relative to the center line A. Oriented toward the opposite side. Specifically, when the optimized structure calculated above is presented in Winmostar, at least one of the angles represented by copper atoms (Cu)-nitrogen atoms (N)-oxygen atoms (O)- is preferably 140° or above ( Refer to Figure 2). For example, in the illustrated compound (1-1), the angle caused by the copper atom-nitrogen atom-oxygen atom is 169°; in the illustrated compound (2-2), it is 168°; and in the illustrated compound (3-8), it is 71°. Through such coordination, from the perspective that the nitrogen atom (N) and the phenolic hydroxyl group (OH) in the structure of the aforementioned heterocyclic compound exist at diagonal angles of the molecular skeleton, the nitrogen atom (N) exists perpendicularly to the metal layer 10 direction, the phenolic hydroxyl group (OH) can be brought closer to the resin layer 20, and stronger interaction can be obtained (see Figure 1).

The laminated body of this invention can be suitably used for a printed circuit board (printed wiring board) or an electronic device, for example. The aforementioned printed circuit board can be formed by a method of forming a metal wiring pattern by photolithography as will be described later. Examples of the electronic device include smartphones, tablet terminals, personal computers, servers, routers, communication base stations, display devices, home appliances, and the like.

Next, the structure of the laminated body of this invention is demonstrated. The laminated body of the present invention is a laminated body in which a surface modification layer and a resin layer are provided in this order on a metal layer. That is, the metal layer is adjacent to the surface modification layer, and the surface modification layer is adjacent to the resin layer.

＜Metal layer＞ The metal layer is a layer mainly composed of metal. Here, the main component means a component containing 50% by mass or more.

Examples of metals used for the aforementioned metal layer include gold, silver, platinum, zinc, palladium, rhodium, osmium, ruthenium, iridium, copper, nickel, cobalt, iron, tin, chromium, titanium, tantalum, tungsten, indium, aluminum, Lead, molybdenum and other metals or their alloys. Among these, from the viewpoint of workability or electrical conductivity, copper or a copper alloy is preferably used as the main component.

The aforementioned metal layer can be formed by metal foil, plating, or vacuum film forming methods.

The thickness of the metal layer is not particularly limited, and may be a thickness that matches the thickness of the metal wiring pattern to be formed, for example.

In the formation of the aforementioned metal wiring pattern, from the viewpoint of using a metal-clad laminate with a metal layer formed on the insulating layer, the laminate of the present invention preferably has an insulating layer below the metal layer. The insulating layer is not particularly limited, and a resin sheet or prepreg generally used as an insulating layer can be used.

If the above-mentioned laminated body with an insulating layer is shown in the figure, it belongs to the laminated body 6 in FIG. 5 which shows the formation step of the photoresist layer mentioned later.

＜Surface modification layer＞ The surface modification layer can be formed by coating the non-photosensitive surface modification agent of the present invention on the surface of the metal layer and drying it.

The thickness of the surface modification layer is not particularly limited, but from the viewpoint of the effects of the present invention, it is preferably in the range of 0.1 to 20 nm.

＜Resin layer＞ The resin layer used in the present invention is not particularly limited, and examples thereof include acrylonitrile/styrene copolymer resin (AS resin), acrylonitrile/butadiene/styrene copolymer resin (ABS resin), fluororesin, polyamide, and polyamide. Thermoplastic resins such as ethylene, polyethylene terephthalate, polyvinylidene chloride, polyvinyl chloride, polycarbonate, polystyrene, polypropylene, cyclopolyolefin resin, liquid crystal polymer; epoxy resin , phenol resin, polyimide, polyurethane, bismaleimide/triazine resin, modified polyphenylene ether, cyanate ester and other thermosetting resins, or ultraviolet curable epoxy resin, Ultraviolet curable resin such as ultraviolet curable acrylic resin, etc. These resins can be modified with functional groups or reinforced with glass fiber, aramid fiber, other fibers, etc.

When the laminate of the present invention is a printed circuit board laminate (when it is a printed circuit board laminate), a commercially available resin film or prepreg (sheet fiber impregnated with liquid resin) can be used for the resin layer, and fluororesin is preferably used. Or cyclopolyolefin resin, liquid crystal polymer, epoxy resin, phenolic resin, polyimide, bismaleimide/triazine resin, modified polyphenylene ether, and cyanate-containing resin. In addition, when the laminate of the present invention forms the wiring of a printed circuit board (when it is a metal wiring pattern), a commercially available liquid photoresist or a dry film photoresist can be used for the resin layer, and an ultraviolet curable ring containing an alkali-soluble resin is preferably used. Oxygen resin, UV curable acrylic resin, polyimide.

The method of forming a metal wiring pattern of the present invention is a method of forming a metal wiring pattern caused by photolithography. Preferably, the non-photosensitive surface modifier of the present invention is used to form a surface between the metal layer and the photoresist. Steps to modify the layer.

＜Metal wiring pattern formation method＞ Specifically, the metal wiring pattern is formed by having the following steps (A) to (F). Step (A): Pickling the metal-clad laminate with a metal layer formed on the insulating layer Step (B): The step of forming a surface modification layer using the non-photosensitive surface modification agent of the present invention on the aforementioned metal layer of the aforementioned metal-clad laminate. Step (C): The step of forming a photoresist layer containing photosensitive resin on the aforementioned surface modification layer Step (D): Patterning the aforementioned photoresist layer through exposure and development Step (E): The step of etching the aforementioned surface modification layer and the aforementioned metal layer through the aforementioned photoresist layer. Step (F): peeling off the photoresist layer from the metal-clad laminate

Each step will be described using Figures 3 to 8.

In step (A), the metal-clad laminate 5 (see FIG. 3 ) with the metal layer 2 formed on the insulating layer 1 is pickled. This can remove dirt, antioxidants, oxide films, etc. attached to the metal surface that hinder the interaction between the non-photosensitive surface modifier and the metal layer. The acid cleaning solution is not particularly limited, and current products can be used. In addition, water washing can be carried out after acid washing.

The insulating layer 1 is an insulating layer that serves as the base material of the metal wiring pattern. The insulating layer 1 may be made of an insulating material such as resin, and may be a prepreg in which a base material such as paper or glass is impregnated with resin.

The metal layer 2 is the same as the metal layer of the above-mentioned laminated body.

In step (B), the non-photosensitive surface modifying agent of the present invention is used to form a surface modification layer 3 on the metal layer 2 of the metal-clad laminate 5 (see FIG. 4 ). Specifically, a non-photosensitive surface modifying agent is coated on the metal layer 2 to form the surface modifying layer 3 . The thickness of the surface modification layer 3 is not particularly limited, but from the viewpoint of the effects of the present invention, it is preferably in the range of 0.1 to 20 nm.

Between step (B) and the next step (C), there is preferably a step of washing the metal-clad laminate 5 on which the surface modification layer 3 is formed. In this way, excess non-photosensitive surface modifier can be removed, which would lead to insufficient interaction with the metal layer.

In step (C), a photoresist layer 4 containing photosensitive resin is formed on the surface modification layer 3 (see FIG. 5 ). Since the laminated body 6 in this state includes the metal layer 2, the surface modification layer 3 and the photoresist layer 4, it belongs to the laminated body of the present invention.

The photoresist layer 4 is not particularly limited as long as it contains a photosensitive resin that can be patterned by photolithography like the photoresist layer of the above-mentioned laminated body. It can be formed by laminating dry film photoresist or coating. Liquid photoresist material.

In step (D), the photoresist layer 4 is patterned by exposure and development (see FIG. 6 ). Specifically, the photoresist layer 4 is exposed using a photomask that can expose the photoresist layer 4 into any pattern shape, and then a developer is used to dissolve and remove the excess portion of the photoresist layer 4 to perform patterning. It is best to wash with water after development.

Exposure conditions and development conditions are not particularly limited, and current products can be applied.

In step (E), the surface modification layer 3 and the metal layer 2 are etched through the photoresist layer 4 (see FIG. 7 ). Specifically, by wet etching using an etching solution, the portion of the surface modification layer 3 and the metal layer 2 that has been removed from the photoresist layer 4 is dissolved, and the surface modification layer 3 and the metal layer 2 are patterned.

The etching conditions are not particularly limited, and current products can be applied.

In step (F), the photoresist layer 4 is peeled off from the metal-clad laminate 5 (see FIG. 8 ). At this time, through the effect of the present invention, the surface modification layer 3 is more easily peeled off from the photoresist layer 4, so the surface modification layer 3 is more likely to remain on the metal layer 2 of the metal-clad laminate 5, but the surface modification layer 3 It can remain on the metal layer 2 and can also be peeled off at the same time as the photoresist layer 4 .

The method for peeling off the photoresist layer 4 is not particularly limited. It is preferable to use a peeling liquid for peeling off. The stripping liquid is not particularly limited, and current products can be applied.

According to the above steps, the metal wiring pattern 7 can be formed.

Since the above-mentioned method of forming a metal wiring pattern can form a high-density and high-definition metal wiring pattern, by mounting the required electronic components on the metal wiring pattern, it is possible to manufacture a high-density and high-definition metal wiring pattern according to the present invention. Printed circuit board (printed wiring board).

＜Method for forming printed circuit board laminate＞ The method for forming a laminate (printed circuit board laminate) of the present invention is a method of forming a resin layer on a metal layer, which includes using the non-photosensitive surface modifier of the present invention to form a surface between the metal layer and the resin layer. Steps to modify the layer. The metal layer may be original or patterned, and the lamination method may use a well-known method such as hot pressing. For the resin layer, commercially available resin films or prepregs (sheet fibers impregnated with liquid resin) can be used. Preferably, fluororesin or cyclopolyolefin resin, liquid crystal polymer, epoxy resin, phenolic resin, or polyimide are used. , bismaleimide/triazine resin, modified polyphenylene ether, and cyanate-containing resin. Surface treatments such as corona treatment or plasma treatment can also be performed on the bonding surface of the resin layer before lamination. [Example]

The present invention will be described in detail below with reference to examples, but the present invention is not limited thereto. In addition, in the following examples, unless otherwise stated, the operation was performed at room temperature (25°C). In addition, unless otherwise stated, "%" and "part" mean "mass %" and "mass part" respectively. The compounds used in the examples are shown below.

[Example 1] For each compound described in Table I and Table II below, the alignment properties were evaluated. Specifically, the quantum chemical calculation software Gaussian16 (manufactured by Gaussian Corporation) was used, DFT calculation was performed, and B3LYP (density functional theory) was used to optimize the structure. As the basis function, copper system uses SDD (Stuttgart/Dresden ECP) for calculation, and other element systems use 6-31G(d). Using the Grid scan module of the Material Science Suite of Schrodinger's software, the initial configuration is to position copper ions in the space around the ligand where they become re-stabilized. When the optimal structure calculated above is presented in Winmostar, the angle represented by copper atom (Cu)-nitrogen atom (N)-oxygen atom (O)- will be selected, and its alignment will be evaluated according to the following criteria. (baseline) AA: Angle of copper atom-nitrogen atom-oxygen atom: more than 140° A: The angle between copper atom-nitrogen atom-oxygen atom is more than 0° and less than 140° B: There is no phenolic hydroxyl group in the structure of the compound.

[Example 2] ＜Preparation of non-photosensitive surface modifier＞ To a solvent composed of 20 mass% of ethanol and 80 mass% of ion-exchanged water, each compound in the following Table I was added so as to become 20 mass ppm, and non-photosensitive surface modifiers 1 to 8 and 12 to 15 were prepared respectively. . In addition, the ratios of ethanol and ion-exchanged water were changed for the non-photosensitive surface modifying agents 10 and 11 so as to be shown in Table I below, and the non-photosensitive surface modifying agent 9 was changed so as to be shown in Table I below. Except for the concentration of compound (1-1), it was prepared in the same manner.

<Formation of metal wiring pattern (laminated body) 1> The following steps (A) to (F) are performed to form the metal wiring pattern 1. (Step (A)) A copper-clad laminated board (MEGTRON 7 R-5785 manufactured by Panasonic Corporation) with a metal layer formed on the insulating layer is acid-cleaned using an acid cleaning solution (CP-30 manufactured by Sanwa Chemical Industry Co., Ltd.) and a spray-type cleaning device. Then wash with water.

(Step (B)) On the metal layer of the acid-cleaned and water-washed copper-clad laminate, use a spray coating device to apply the non-photosensitive surface modifier 1 prepared above, and then wash it with water. After washing with water, remove water with a PVA roller and dry with an air knife at 80°C to form a surface modification layer with a thickness of 5 nm.

(Step (C)) On the surface modification layer, dry film photoresist (AK-4034 manufactured by Asahi Kasei Co., Ltd.) (photo-curable acrylic resin containing alkali-soluble resin) as the resin layer was heated with a hot-rolling laminator at a roll temperature of 105°C. , air pressure 0.35MPa, and lamination speed 1.5m/min for lamination to form a photoresist layer. In addition, the dry film photoresist used (AK-4034 manufactured by Asahi Kasei Co., Ltd.) has a support composed of a polyethylene terephthalate film on one side and a protection composed of a polyethylene film on the other side. Layers. Lamination is performed by peeling off the protective layer and bonding the surface with the protective layer to the metal layer via the surface modification layer.

(Step (D)) Using a chromium glass mask, the photoresist layer was exposed with a parallel light exposure machine (HMW-801 manufactured by Oak Corporation). The exposure conditions are 60mj/cm ² which is the recommended condition for dry film photoresist. The support is peeled off from the exposed photoresist layer. Thereafter, a developer consisting of an aqueous solution of 1 mass % sodium carbonate (Na ₂ CO ₃ ) and an alkali developer were used to dissolve and remove the unexposed portion of the photoresist layer at 30°C, followed by water washing. , imaging. Through the above operations, the photoresist layer is patterned.

(Step (E)) In the immersion method, use an etching solution composed of an aqueous solution of 2 mass % hydrochloric acid (HCl) and 2 mass % ferric chloride (FeCl ₃ ), with a temperature of 30°C and an immersion time of 1 minute. ) conditions to etch the surface modification layer and metal layer.

(Step (F)) The photoresist layer was peeled off from the copper-clad laminate using a stripping solution composed of a 3 mass% aqueous solution of sodium hydroxide (NaOH) at a temperature of 50°C.

<Formation of metal wiring patterns 2 to 15> The metal wiring pattern was formed in the same manner except that the non-photosensitive surface modifying agent 1 was changed to each of the non-photosensitive surface modifying agents 2 to 15 shown in Table I below in the formation of the metal wiring pattern 1. Type 2~15.

[evaluate] ＜Photoresist Adhesion＞ Each metal wiring pattern formed above was observed with a microscope, and the photoresist adhesiveness (thin line forming ability) was evaluated based on the following criteria. The results of the evaluation are shown in Table I below. There is no practical problem in taking the following standards as "AAA", "AA" and "A". (baseline) AAA: The residual rate of metal wiring is over 99%. AA: The residual rate of metal wiring is 97% or more and less than 99%. A: The residual rate of metal wiring is 95% or more and less than 97%. B: The residual rate of metal wiring is less than 95%.

[Example 3] ＜Preparation of non-photosensitive surface modifier＞ The same non-photosensitive surface modifying agents 1 to 15 as in Example 2 were prepared.

<Formation of printed circuit board laminate (laminated body) 1> The following steps (I) to (III) are performed to form the printed wiring board laminated body 1 . (Step (I)) A copper-clad laminated board (R-1766 manufactured by Panasonic Corporation) with a metal layer formed on the insulating layer is acid-cleaned using an acid cleaning solution (CP-30 manufactured by Sanwa Chemical Industry Corporation) and a spray-type cleaning device, and then Wash.

(Step (II)) On the metal layer of the acid-cleaned and water-washed copper-clad laminate, use a spray coating device to apply the non-photosensitive surface modifier 1 prepared above, and then wash it with water. After washing with water, remove water with a PVA roller and dry with an air knife at 80°C to form a surface modifier layer with a thickness of 5 nm.

(Step (III)) The prepreg (R-1661 manufactured by Panasonic Corporation) (epoxy resin) was laminated on the surface modifier layer, and the temperature was increased from normal temperature (25°C) to 10°C/min at a pressure of 3.0 MPa. Heating to 120° C. and holding for 30 minutes, and heating to 190° C. at a temperature rising rate of 10° C./min and holding for 2 hours were performed to perform lamination adhesion, and a printed circuit board laminate 1 was produced.

<Production of printed circuit board laminates 2 to 15> In the preparation of the printed wiring board laminated body 1, the process was carried out in the same manner except that the non-photosensitive surface modifying agent 1 was changed to the non-photosensitive surface modifying agents 2 to 15 shown in the following Table II. Printed circuit board laminates 2 to 15.

[evaluate] <Evaluation of prepreg adhesion> Each of the printed wiring board laminates produced above was cut into strips with a width of 10 mm, and the peel strength was measured at 90 degrees using Tensilon (manufactured by ORIENTEC Co., Ltd.), and the prepreg adhesion was evaluated according to the following criteria. . The results of the evaluation are shown in Table II below. There is no practical problem in taking "AA" and "A" as the following standards. (baseline) AA: Bonding strength: 0.65kN/m or more A: Bonding strength: 0.5kN/m or more and less than 0.65kN/m B: Bonding strength: less than 0.5kN/m

As shown in the above results, it can be seen that the nitrogen atoms and phenolic hydroxyl groups in the structure of the heterocyclic compound contained in the non-photosensitive surface modifier of the present invention exist at opposite corners of the molecular skeleton, and the molecular skeleton is coordinated in the vertical direction. Furthermore, it can be seen that by using the non-photosensitive surface modifying agent of the present invention containing such an aligned heterocyclic compound, the photoresist adhesiveness and prepreg adhesion are improved compared to when the surface modifying agent of the comparative example is used. Excellent sex.

1: Insulation layer 2:Metal layer 3: Surface modification layer 4: Photoresist layer 5:Metal clad laminate 6: Laminated body 7: Metal wiring pattern 10:Metal layer 20:Resin layer 30: Surface modification layer A: Center line

[Fig. 1] A schematic diagram showing the coordination state of a nitrogen atom and a phenolic hydroxyl group present in the structure of the heterocyclic compound of the present invention. [Fig. 2] A diagram illustrating the alignment of the heterocyclic compound of the present invention. [Fig. 3] A diagram showing the steps of forming a metal wiring pattern (metal-clad laminate) [Fig. 4] A diagram showing the steps of forming a metal wiring pattern (formation of the surface modification layer) [Fig. 5] A diagram showing the steps of forming a metal wiring pattern (formation of photoresist layer) [Fig. 6] A diagram showing the steps of forming a metal wiring pattern (patterning of the photoresist layer) [Fig. 7] A diagram showing the steps of forming a metal wiring pattern (surface modification layer and etching of the metal layer) [Fig. 8] A diagram showing the steps of forming a metal wiring pattern (peeling off the photoresist layer)

10:Metal layer 20:Resin layer 30: Surface modification layer

Claims (11)

A non-photosensitive surface modifying agent, which is a non-photosensitive surface modifying agent that forms a surface modifying layer between a metal layer and a resin layer, wherein it contains at least one type of agent having the following general formula (1), ( Heterocyclic compounds with the structures represented by 2), (3) or (4); [In the formula, R ₁ represents a hydrogen atom, an aryl group or a heteroaryl group, and may further have a substituent; R ₂ represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a carboxyl group, an ester group, or an amide group. group, heteroaryl group or halogen atom; n and m are respectively an integer from 0 to 5, and n+m=an integer from 0 to 5 (however, regarding general formula (1), it is an integer from 0 to 4); there are When there are multiple substituents _R2 , each substituent _R2 can be the same or different from each other; also, when there are multiple n, each n can be the same or different from each other, and when there are multiple m, each m can be the same as each other. or different]. The non-photosensitive surface modifying agent of claim 1, wherein the aforementioned heterocyclic compound has a structure represented by the aforementioned general formula (1). The non-photosensitive surface modification agent of claim 2, wherein the aforementioned heterocyclic compound is a heterocyclic compound having a structure represented by the following general formula (5): [In the formula, R ₁ represents a hydrogen atom, an aryl group or a heteroaryl group, and may further have a substituent]. The non-photosensitive surface modifying agent according to any one of claims 1 to 3, which contains at least water or alcohols. A laminated body in which a surface modification layer and a resin layer are sequentially provided on a metal layer, wherein the surface modification layer contains at least one or more compounds having the following general formulas (1), (2), Heterocyclic compounds with structures represented by (3) or (4): [In the formula, R ₁ represents a hydrogen atom, an aryl group or a heteroaryl group, and may further have a substituent; R ₂ represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a carboxyl group, an ester group, or an amide group. group, heteroaryl group or halogen atom; n and m are respectively an integer from 0 to 5, and n+m=an integer from 0 to 5 (however, regarding general formula (1), it is an integer from 0 to 4); there are When there are multiple substituents _R2 , each substituent _R2 can be the same or different from each other; also, when there are multiple n, each n can be the same or different from each other, and when there are multiple m, each m can be the same as each other. or different]. The laminated body of claim 5, wherein the heterocyclic compound is a heterocyclic compound having a structure represented by the general formula (1). The laminated body of claim 6, wherein the aforementioned heterocyclic compound is a heterocyclic compound having a structure represented by the following general formula (5): [In the formula, R ₁ represents a hydrogen atom, an aryl group or a heteroaryl group, and may further have a substituent]. The laminated body according to any one of claims 5 to 7, wherein the resin layer is a photosensitive resin composition containing an alkali-soluble resin. The laminated body according to any one of claims 5 to 7, wherein the resin layer is a thermosetting resin composition containing at least a resin having an epoxy structure. A printed circuit board using the laminate according to any one of claims 5 to 9. An electronic device using the laminate according to any one of claims 5 to 9.