Surface treatment agent, method for producing film-forming base material, and film-forming base material

Abstract

The present invention provides a surface treatment agent that sufficiently improves the coatability of a resin composition on both a metal surface and a resin surface, a method for manufacturing a film-formed substrate, and a film-formed substrate. The present invention is a surface treatment agent or the like for treating a substrate surface including a metal surface and a resin surface, and includes at least one amine compound selected from the group consisting of an alkyl amine having a carbon number of 19 to 24 in an alkyl group, an alkenyl amine having a carbon number of 18 to 22 in an alkenyl group, and a salt thereof, in an amount of 0.001 to 1.2 mass%.

Description

Technical Field

[0001] This invention relates to a surface treatment agent, a method for manufacturing a film-forming substrate, and the film-forming substrate itself. Background Technology

[0002] Film-forming substrates, on which a hardenable resin composition such as solder resist and etch resist is formed on the surface of a metal substrate, are used, for example, in printed circuit boards with copper openings for electrical connections due to soldering and coated with solder resist. These film-forming substrates are generally manufactured by applying the resin composition to desired areas on the surface of a metal substrate using methods such as stencil printing or photolithography involving exposure and development. However, in recent years, methods for forming films by inkjet printing the resin composition have attracted attention.

[0003] Inkjet printing eliminates the need for a printing plate or photomask and offers advantages such as fewer steps, simplicity, and the ability to form a film only on the necessary areas. However, inkjet printing requires the use of solder resists with lower viscosity than conventional methods, which can lead to leakage after coating. As a technique to reduce this leakage, examples include surface treatments described in Patent Documents 1 to 4, which involve bringing a surface treatment agent into contact with the metal surface to adjust the wettability of the metal surface on the substrate.

[0004] However, even though these conventional surface treatment techniques can improve the wettability of the metal surface on the substrate, the modification of the resin surface is still insufficient when the substrate is mixed with a resin surface. Generally, the substrate surface may contain resin surfaces such as insulating resins in addition to metal, and it is required to improve the coating properties of solder resist on both the metal and resin surfaces.

[0005] Existing technical documents Patent documents Patent Document 1: Japanese Patent Application Publication No. 2015-192963; Patent Document 2: International Publication No. 2016 / 111035; Patent document 3: International Publication No. 2016 / 111036; Patent document 4: International Publication No. 2019 / 082681. Summary of the Invention

[0006] The problem that the invention aims to solve The present invention addresses the problems of the prior art, and provides a surface treatment agent, a method for manufacturing a film-forming substrate, and a film-forming substrate that can sufficiently improve the coatability of both the metal surface and the resin surface of the resin composition when a film of a resin composition is formed on the surface of a substrate.

[0007] means for solving problems The surface treatment agent of the present invention is a surface treatment agent for treating the surface of a substrate including a metal surface and a resin surface, comprising at least 0.001% by mass and less than 1.2% by mass of an amine compound selected from the group consisting of alkylamines having 19 to 24 carbon atoms of alkyl groups, alkenylamines having 18 to 22 carbon atoms of alkenyl groups and their salts.

[0008] In the surface treatment agent of the present invention, the amine compound may be at least one selected from the group consisting of aminononadecane, arachididine, henicosylamine, dicamine, triamine, tetramine, and oleylamine.

[0009] The surface treatment agent of the present invention may have a pH of 4.0 or higher and a pH of 14 or lower.

[0010] The method for manufacturing a film-forming substrate of the present invention is a method for manufacturing a film-forming substrate on which a film of a resin composition is formed on the surface of a substrate, comprising: a surface treatment step in which a surface treatment agent is brought into contact with the surface of a substrate having a metal surface and a resin surface, and the surface treatment is performed such that the contact angle between the metal surface and the resin surface and the diallyl glycol is 35° or more and 100° or less; and a film-forming step in which a film of the resin composition is formed on the surface-treated substrate surface by inkjet printing.

[0011] In the method for manufacturing the film-forming substrate of the present invention, the surface treatment agent may also include at least 0.001% by mass and less than 1.2% by mass of an amine compound selected from the group consisting of alkylamines with 19 to 24 carbon atoms of alkyl groups, alkenylamines with 18 to 22 carbon atoms of alkenyl groups and their salts.

[0012] The method for manufacturing the film-forming substrate of the present invention may also involve forming a film by inkjet printing using a resin composition that has been hardened by heating, ultraviolet irradiation or light irradiation during the film-forming step.

[0013] The method for manufacturing the film-forming substrate of the present invention may also include, prior to the surface treatment step, an etching step in which the surface of the substrate is etched using a micro-etching agent.

[0014] The method for manufacturing the film-forming substrate of the present invention may also etch the metal surface in the etching step such that the surface roughness (Ra) is 0.1 μm or more and 0.8 μm or less.

[0015] In the manufacturing method of the film-forming substrate of the present invention, the surface treatment agent may also be of pH 4.0 or higher and pH 14 or lower.

[0016] The film-forming substrate of the present invention is a film-forming substrate on which a film of resin composition is formed on the surface of a substrate. It has a substrate surface, which has a metal surface and a resin surface. The contact angle of the metal surface and the resin surface with respect to dipropylene glycol is 35° or more and 100° or less. The surface roughness (Ra) of the metal surface is 0.1 μm or more and 0.8 μm or less.

[0017] The film-forming substrate of the present invention may also include at least one resin selected from the group consisting of polyimide resin, epoxy resin, polyethylene terephthalate resin, polypropylene resin, polyvinyl chloride resin, polyolefin resin, polyurethane resin, and polyacetal resin on the surface of the resin.

[0018] In the film-forming substrate of the present invention, the resin composition can also be hardened by heating, ultraviolet irradiation or light irradiation.

[0019] Invention Effects According to the present invention, when a film of resin composition is formed on the surface of a substrate, the coatability of both the metal surface and the resin surface of the resin composition is sufficiently improved. Detailed Implementation Hereinafter, embodiments of the surface treatment agent, the method for manufacturing the film-forming substrate (hereinafter also referred to as the manufacturing method), and the film-forming substrate of the present invention will be described.

[0020] (First embodiment: surface treatment agent) The surface treatment agent of this embodiment is a surface treatment agent for treating the surface of a substrate including a metal surface and a resin surface, comprising at least 0.001% by mass and less than 1.2% by mass of an amine compound selected from the group consisting of alkylamines with 19 to 24 carbon atoms of alkyl groups, alkenylamines with 18 to 22 carbon atoms of alkyl groups and their salts.

[0021] In the surface treatment agent of this embodiment, by treating the surface of a substrate including a metal surface and a resin surface, the treated surface can be adjusted to the desired contact angle as described later.

[0022] <Substrate> The substrate treated with the surface treatment agent of this embodiment is not particularly limited as long as it includes a metal surface and a resin surface. Examples include: circuit boards used in printed wiring boards, or other parts or all of various electronic and electrical machines, medical machines, vehicle-mounted machines, automobile parts, and marine machinery.

[0023] There are no particular limitations on the metals that make up the metal surface, but examples include: copper, tin, stainless steel, aluminum, nickel, titanium and their alloys.

[0024] There is no particular limitation on the resin constituting the resin surface, but examples may include at least one resin selected from the group consisting of polyimide resin, epoxy resin, polyethylene terephthalate resin, polypropylene resin, polyvinyl chloride resin, polyolefin resin, polyurethane resin, and polyacetal resin.

[0025] Epoxy resin is mostly used as a material for FR-4 substrates, which are circuit boards used in printed wiring boards and the like. When the surface treatment agent of this embodiment is applied to a circuit board made of a substrate (such as an FR-4 substrate) using epoxy resin, the metal portion of the FR-4 substrate and the epoxy resin portion become a metal surface and a resin surface existing on the surface of the substrate, respectively. The surface treatment agent of this embodiment can then contact these two surfaces and perform surface treatment on both surfaces.

[0026] <Amine compounds> The surface treatment agent of this embodiment comprises 0.001% by mass and 1.2% by mass of at least one amine compound selected from the group consisting of alkylamines (hereinafter also referred to as alkylamines) having 19 to 24 carbon atoms of an alkyl group, alkenylamines (hereinafter also referred to as alkenylamines) having 18 to 22 carbon atoms of an alkenyl group, and their salts.

[0027] Furthermore, in this embodiment, the so-called alkylamines and alkenylamines are aliphatic primary amines, and refer to amine compounds selected from the group consisting of alkyl or alkenyl groups whose aliphatic hydrocarbon groups have the aforementioned number of carbons.

[0028] Examples of alkylamines include: nonadecylamine (19 carbon atoms), icosylamine (20 carbon atoms), dodecylamine (21 carbon atoms), dodecylamine (22 carbon atoms), dodecylamine (23 carbon atoms), dodecylamine (24 carbon atoms), etc.

[0029] Examples of alkenylamines include oleylamine (18 carbon atoms) and cis-13-docosenamide (22 carbon atoms).

[0030] Examples of salts of the alkylamines and alkenylamines include, for example, organic and inorganic acid salts of alkylamines; and organic and inorganic acid salts of alkenylamines.

[0031] These amine compounds can also be used alone or in combination of multiple types.

[0032] The content of the amine compound in the surface treatment agent is 0.001% by mass or more and 1.2% by mass or less, or 0.003% by mass or more and 1.2% by mass or less, or 0.005% by mass or more and 1.0% by mass or less, or 0.01% by mass or more and 0.3% by mass or less.

[0033] By controlling the relevant content range, the coatability of both surfaces of the metal and resin relative to the resin composition can be improved.

[0034] The pH value of the surface treatment agent in this embodiment is not particularly limited, but examples include: pH 4.0 or higher and pH 14 or lower, or pH 5.0 or higher and pH 13 or lower, or pH 6.0 or higher and pH 12 or lower. When the surface treatment agent is within the above-mentioned pH range, it becomes easier to adjust to the desired contact angle range, and therefore is preferred.

[0035] The optimal pH value of the surface treatment agent can be appropriately selected according to the type of amine compound or the type of resin composition forming the film. For example, if the amine compound contained in the surface treatment agent is an alkenylamine, a pH of 4.0 or higher and a pH of 14 or lower is preferred. If the amine compound contained in the surface treatment agent is an alkylamine, a pH of 5.0 or higher and a pH of 11.0 or lower, or a pH of 6.0 or higher and a pH of 10 or lower is preferred.

[0036] As a means of adjusting the pH value of surface treatment agents, it can be adjusted by formulating the aforementioned amine compounds or other known pH adjusters. There are no particular limitations on pH adjusters, but examples include hydrochloric acid, sulfuric acid, acetic acid, sodium hydroxide, ammonia, ethanolamine, or salts thereof (e.g., sodium acetate); general buffers such as acetate buffer, phosphate buffer, citrate buffer, citrate-phosphate buffer, borate buffer, Good's buffer, etc.; and chelating agents, amino acids, etc., used for pH adjustment.

[0037] By using the surface treatment agent of this embodiment to treat the metal surface and the resin surface, the contact angle of the two surfaces can be easily set to a desired range. Here, the desired range of contact angles refers to the contact angles of the two surfaces with respect to diallyl glycol being within a specific range.

[0038] The desired range of contact angles can be categorized as follows: for metal surfaces and resin surfaces, the contact angle relative to diallyl glycol is 35° or higher and 100° or lower, or 36° or higher and 95° or lower, or 36° or higher and 90° or lower, etc.

[0039] Since the contact angles of the metal surface and the resin surface relative to dipropylene glycol are within the above range, the coating properties of the resin composition will not be hindered, and leakage will be easily suppressed.

[0040] More specifically, examples include metal surfaces with contact angles of 35° or more and 100° or less with diallyl glycol, or 36° or more and 95° or less, or 37° or more and 90° or less.

[0041] The contact angle of the resin surface relative to diallyl glycol can be 35° or more and 100° or less, or 37° or more and 75° or less, or 40° or more and 70° or less, etc.

[0042] Furthermore, in this embodiment, the reason for evaluating the coatability of the resin composition by setting the contact angle relative to dipropylene glycol within a specific range is as follows.

[0043] In the past, when evaluating the coatability of a specific material surface relative to a specific substance, such as its adhesion and ease of leakage, the contact angle with respect to that substance was measured. However, this required obtaining the specific resin composition for measurement, making it difficult to measure compositions that were not readily available. Furthermore, it required measurement for each individual resin composition, which was time-consuming in evaluating the coatability of a large number of resin compositions.

[0044] In the case of resin compositions, especially etch resist inks and solder resist inks as described later, which are cured by heating, ultraviolet irradiation or light irradiation, since they are coated onto circuit boards and other materials in the uncured state to form a film, it is required to adjust the contact angle of the substrate surface to an appropriate range relative to the uncured state (the actual coated state) of the resin composition. However, it is very complicated to obtain all kinds of products, measure the contact angle, and select a resin composition suitable for a specific substrate.

[0045] On the other hand, JIS R3257 "Test Method for Wetness of Substrate Glass Surface" describes a method for determining the wettability of a substrate glass surface by measuring the contact angle using distilled water. However, distilled water and resin composition have very different physical properties, so using distilled water to measure the contact angle as an evaluation of the adhesion or leakage ease of the resin composition may not be appropriate.

[0046] From this perspective, the results of examining substances that can be used to measure curable resin compositions, particularly solder resists and other surface treatment agents suitable for use in this embodiment, indicate that the free energy of diallyl glycol is closer to that of curable resin compositions. Furthermore, it is correlated with the contact angle when using various curable resin compositions, thus revealing the most suitable contact angle measurement method for this embodiment.

[0047] Therefore, the contact angle referred to in this embodiment refers to the value measured by changing distilled water to diallyl glycol in the static drop method described in JIS R3257 "Test Method for Wetting of Substrate Glass Surface". Specifically, it refers to the value measured by the method shown in the following embodiments.

[0048] In addition to the amine compound, the surface treatment agent of this embodiment may also contain any other components such as defoamers, rust inhibitors, and solvents.

[0049] The surface treatment agent of this embodiment is preferably a solution in which the amine compound and other components are dissolved in water or other known solvents.

[0050] (Second embodiment: Method for manufacturing film-forming substrate) The method for manufacturing a film-forming substrate according to this embodiment is a method for manufacturing a film-forming substrate on which a film of resin composition is formed on the surface of a substrate. The method includes: a surface treatment step in which a surface treatment agent is brought into contact with the surface of a substrate having a metal surface and a resin surface, and the surface treatment is performed such that the contact angle between the metal surface and the resin surface and the diallyl glycol is 35° or more and 100° or less; and a film forming step in which a film of resin composition is formed on the surface-treated substrate surface by inkjet printing.

[0051] <Film-forming substrate> The film-forming substrate manufactured by the manufacturing method of this embodiment is the same substrate as the substrate in the first embodiment. There is no particular limitation as long as it is a substrate on which a film of resin composition is formed on the surface by inkjet printing.

[0052] The metal that forms the metal surface of the film-forming substrate may be the same metal as the metal that forms the metal surface of the substrate in the first embodiment.

[0053] The resin on the surface of the resin constituting the film-forming substrate may be the same resin as the resin on the surface of the substrate constituting the first embodiment.

[0054] Metals and resins are not limited to the examples above.

[0055] The manufacturing method of this embodiment is particularly suitable for, for example, manufacturing a circuit board on a substrate on which a solder resist film is formed, the substrate having: a conductor surface (metal surface) made of a copper metal (hereinafter simply referred to as copper) including copper or copper alloys, and a resin surface as an insulator.

[0056] <Etching Steps> The manufacturing method of this embodiment may also optionally include an etching step, in which the substrate surface is etched by a micro-etching agent, before the surface treatment step.

[0057] The so-called micro-etching agent used in the etching process refers to an etching agent that slightly etches the metal surface by contacting it to form fine bumps and depressions (micro-etching) on ​​the metal surface.

[0058] The micro-etching agent used in this embodiment is not particularly limited as long as it can micro-etch the metal constituting the metal surface. For example, when the metal is copper, conventional copper micro-etching agents can be listed, specifically organic acid-based, sulfuric acid-hydrogen peroxide-based, and persulfate-based etching agents.

[0059] As preferred micro-etching agents, organic acid-based micro-etching agents can be cited as examples. Examples include commercially available micro-etching agents containing aqueous solutions of organic acids, copper ions, halide ions, amine-containing compounds, polymers, etc.

[0060] In the etching step, a micro-etching agent is brought into contact with the metal surface to etch, thereby forming fine irregularities on the surface.

[0061] By creating relevant micro-protrusions and depressions, the adhesion between the metal surface and the resin composition is improved.

[0062] The processing conditions in the etching process, namely the processing time, the temperature during micro-etching agent treatment, and the treatment methods such as spraying or immersion treatment, can be adjusted appropriately.

[0063] Furthermore, in this embodiment, since the substrate surface also has a resin surface, the resin surface can be simultaneously contacted with the etching solution during the etching step, or an inhibitor or the like can be provided on the resin surface to prevent it from contacting the etching solution.

[0064] In the etching step, the metal surface is treated such that the surface roughness (Ra) is, for example, 0.1 μm or more and 0.8 μm or less, preferably 0.3 μm or more and 0.7 μm or less. By treating the surface in a manner that falls within the relevant surface roughness range, the adhesion between the metal surface and the resin composition is improved after subsequent surface treatment steps, the leakage of the resin composition is suppressed, and the coating properties are easily improved.

[0065] Furthermore, the surface roughness (Ra) referred to in this embodiment refers to the arithmetic mean roughness measured in accordance with JIS B 0601 (2013).

[0066] The etching amount resulting from the gravimetric method in the etching step is preferably adjusted appropriately to achieve the aforementioned surface roughness, for example, 0.5 μm or more and 2.0 μm or less, preferably about 0.7 μm or more and 1.5 μm or less.

[0067] By setting the etching amount to a range, it is easy to achieve an appropriate surface roughness, thereby easily improving the adhesion between the metal surface and the resin composition after subsequent surface treatment steps.

[0068] By performing an etching step, the adhesion between the resin composition and the metal surface, as well as the resin surface, can be significantly improved. Simultaneously, a surface treatment step can be performed to prevent the metal surface from becoming roughened after etching, which could lead to leakage. Therefore, leakage of the resin composition can be effectively suppressed, and the adhesion between the resin composition and the metal surface, as well as the resin surface, can be improved simultaneously.

[0069] <Surface Treatment Steps> The manufacturing method of this embodiment includes a surface treatment step, wherein a surface treatment agent is brought into contact with the surface of a substrate having a metal surface and a resin surface, and the surface treatment is performed such that the contact angle between the metal surface and the resin surface and the diallyl glycol is 35° or more and 100° or less.

[0070] In the surface treatment step of this embodiment, as described above, a surface treatment agent that can adjust the contact angle between the micro-etched metal surface and the resin surface is used to perform the etching step.

[0071] In this embodiment, the surface treatment agent that can be used is not particularly limited as long as it can adjust the metal surface and the resin surface within the range of the general contact angle. When the surface treatment agent is the same as that described in the first embodiment, the efficiency of the manufacturing method of this embodiment can be further improved.

[0072] In addition to the surface treatment agent of the first embodiment described above, other surface treatment agents that can be used in this embodiment include, for example, solutions containing anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactant solutions as active ingredients.

[0073] The active ingredients of surface treatment agents can be used alone or in combination of multiple types.

[0074] In addition to the aforementioned active ingredients, the surface treatment agent may also contain any other ingredients such as defoamers, rust inhibitors, and solvents.

[0075] The surface treatment agent is preferably a solution in which the above-mentioned active ingredients and other ingredients are dissolved in water or other known solvents.

[0076] In this embodiment, the surface treatment step can be performed using conventional methods.

[0077] For example, there is no particular limitation on the means of bringing the surface treatment agent into contact with the surface of the metal substrate; conventional surface treatment methods such as impregnation and spraying can be cited.

[0078] Furthermore, the temperature of the surface treatment agent is not particularly limited, but can be 20°C or higher and 40°C or lower, preferably 25°C or higher and 35°C or lower.

[0079] Furthermore, there is no particular limitation on the treatment time with the surface treatment agent (the contact time between the surface treatment agent and the metal substrate), but examples include 10 seconds or more and 2 minutes or less, preferably 30 seconds or more and 1 minute or less.

[0080] The contact angle between the surface-treated metal surface and the resin surface and the diallyl glycol is both 35° or more and 100° or less, or 36° or more and 95° or less, or 36° or more and 90° or less.

[0081] By setting the contact angles of the metal surface and the resin surface relative to dipropylene glycol within the aforementioned range, the coating properties of the resin composition are maintained without hindering its application, and leakage is easily suppressed.

[0082] More specifically, examples include metal surfaces with contact angles of 35° or more and 100° or less with diallyl glycol, or 36° or more and 95° or less, or 37° or more and 70° or less.

[0083] Examples of resin surfaces with a contact angle of 35° or more and 100° or less with diallyl glycol include those with a contact angle of 37° or more and 75° or less, or those with a contact angle of 40° or more and 70° or less.

[0084] Furthermore, when a micro-etching step is performed before the surface treatment step, the contact angle of the micro-etched metal surface with respect to diallyl glycol can be, for example, 35° or more and 100° or less, or 40° or more and 95° or less, or 45° or more and 90° or less.

[0085] When the manufacturing method of this embodiment is used in the manufacturing of circuit boards, by setting the contact angle between the metal surface, which is the conductor surface, and the resin surface, which is the insulator, relative to the dipropylene glycol within the above-mentioned range, leakage and the like can be suppressed when a film of a hardened resin, such as an etch resist or solder resist, is formed as a resin composition in the subsequent film-forming step.

[0086] <Film Formation Steps> The manufacturing method of this embodiment includes: a film-forming step, wherein a film of resin composition is formed on the surface of a surface-treated metal substrate by inkjet printing.

[0087] Examples of resin compositions used in the film-forming step of this embodiment include etch resist inks, solder resist inks, and other curable resin compositions that are cured by heating, ultraviolet light, or light irradiation.

[0088] As an etching resist ink or a solder resist ink, it can be appropriately selected from those known to the public, but it is preferred to use one with a viscosity that has been adjusted to allow for inkjet coating.

[0089] For example, as an etching resist ink, it is best to have a resin composition that is cured by ultraviolet light after coating and can be peeled off by an alkaline aqueous solution. Specifically, examples include monomers containing carboxyl groups, monofunctional monomers, polyfunctional monomers, photopolymerization initiators, and other arbitrary components.

[0090] As a solder resist ink, it is preferred to be a resin composition that can be cured by heat, ultraviolet light or light irradiation, and has heat resistance after curing. Specifically, in addition to the combination of various monomers used in the etching resist ink, examples include curing agents containing epoxy resin compounds or isocyanate compounds and various arbitrary components.

[0091] In the film-forming step, a conventional inkjet device is used to depict the resin composition according to a desired pattern on the metal surface and / or resin surface after etching and surface treatment. For example, the manufacturing method of this embodiment is applicable when solder resist is applied to the outermost layer of a printed circuit board, or when etching resist or plating resist is applied to the inner layer.

[0092] In the manufacturing method of this embodiment, other processing steps may be performed after the film-forming step. For example, after forming the solder resist film in the film-forming step, a plating step may be performed to apply a plating coating to the metal surface exposed from the opening of the solder resist.

[0093] In this case, by performing the etching and surface treatment steps described above, the adhesion of the resin composition of the solder resist and the penetration of the plating solution can be improved.

[0094] In the manufacturing method of this embodiment, conventional processing steps such as cleaning and drying steps can also be performed between the etching step, the surface treatment step, and the film formation step.

[0095] (Third embodiment: film-forming substrate) Next, the film-forming substrate of this embodiment will be described. The film-forming substrate of this embodiment is not limited to being manufactured by the manufacturing method of the film-forming substrate of this embodiment described above, and / or by using the surface treatment agent of this embodiment, but may also be manufactured by the manufacturing method of this embodiment and / or by using the surface treatment agent of this embodiment.

[0096] The film-forming substrate of this embodiment is a film-forming substrate on which a film of resin composition is formed on the surface of a metal substrate, and is a film-forming substrate on which the contact angle of the surface of the metal substrate is 35° or more and 100° or less, and the surface roughness (Ra) is 0.1 μm or more and 0.8 μm or less.

[0097] The film-forming substrate of this embodiment can suppress the leakage of resin composition and has high adhesion between the resin composition and the metal surface and the resin surface.

[0098] The film-forming substrate of this embodiment can be used as a printed circuit board, etc., in which a solder resist film composed of a resin is formed between metal conductors that serve as a metal surface. It can also be used in various electronic and electrical machines, medical devices, vehicle-mounted machines, automobile parts, and marine machinery parts.

[0099] While the surface treatment agent, the method for manufacturing the film-forming substrate, and the film-forming substrate related to this embodiment are as described above, the embodiments disclosed in this invention are illustrative in all respects and not intended to be limiting. The scope of this invention is indicated not by the description but by the scope of claims, and is intended to include all modifications within the meaning and scope equivalent to the scope of claims.

[0100] [Example] Next, embodiments and comparative examples of the present invention will be described together. However, the present invention is not limited to or construed as described in the following embodiments.

[0101] Experiment 1 <Fabrication of the Experimental Substrate> Prepare a copper plating board (manufactured by Aiko Machinery Co., Ltd.: 12cm×12cm) with a copper plating layer of 35μm thickness as the test substrate.

[0102] Furthermore, this test substrate will be prepared to be sprayed with an organic acid-based micro-etching agent (manufactured by MEC, CZ series) at a temperature of 25°C and a spray pressure of 0.1 MPa on one side, and the etching time will be adjusted to achieve an etching amount of 1.0 μm on one side of the test substrate. The micro-etched substrate will be used as the surface to be treated after water washing.

[0103] Furthermore, as a resin substrate, a copper-clad laminate material for printed circuits (trade name MCL-E-67, manufactured by RESONAC) is prepared to be cut into 12cm×12cm pieces, and the resin substrate with the resin surface (epoxy resin) as the treated surface is prepared.

[0104] <Surface Treatment Agent> Prepare aqueous solutions (temperature 25°C, concentration 0.1% by mass) of each of the amine compounds listed in Table 1, and prepare surface treatment agents that have been adjusted with hydrochloric acid (35%) and sodium hydroxide aqueous solution (24%) to achieve the pH values ​​listed in Table 1.

[0105] In addition, the pH value was measured using pH / ION METER F-72 (manufactured by HORIBA).

[0106] The test substrate, the micro-etched substrate, and the resin substrate were grouped together and their surfaces were treated with various surface treatment agents, which were used as Examples 1 to 20.

[0107] After immersing the treated surfaces of each substrate in the time specified in Table 1, the surface treatment involves washing with water and then drying.

[0108] The amine compounds used are shown below.

[0109] Oleylamine (manufactured by Nippon Oil Company, 18 carbons / alkenylamine) Aminononadecane (manufactured by Tokyo Chemical Industry Co., Ltd., carbon number 19 / alkylamine) Doctidecylamine (manufactured by Nippon Oil Company, 22 carbon atoms / alkylamine) <Contact Angle Measurement 1> For the surface-treated substrate described above, the contact angles relative to dipropylene glycol, solder resist, and distilled water were measured.

[0110] The contact angle of each test substrate was determined using the static drop method as described in JIS R3257 "Test method for wettability of glass substrate surfaces". The measuring apparatus used was an automatic contact angle meter DM-501 manufactured by Kyowa Interface Science Co., Ltd.

[0111] The contact angle relative to diallyl glycol was determined using diallyl glycol (manufactured by Kishida Chemical Company) instead of distilled water as described in JIS R3257 above.

[0112] The contact angle of the solder resist was measured by using a solder resist (manufactured by Taiyo Ink Co., Ltd., item IJSR-4000) instead of distilled water as described in JIS R3257 above.

[0113] The results are shown in Table 1.

[0114] [Table 1]

[0115] As shown in Table 1, in all embodiments, compared to the untreated substrate of the comparative examples, the contact angles of the test substrate, etched substrate, and resin substrate relative to dipropylene glycol increased, and could be adjusted to a range of 35° or higher and 100° or lower. Regarding aminononadecane and dodecylamine, although there were instances where the contact angle deviated from this range at pH 12 or higher, by adjusting the pH to below 10, the aforementioned contact angle range was achieved.

[0116] Furthermore, by comparing the measured contact angles of diallyl glycol and solder resist, it was found that when treated with the same amine compound at the same pH value, a correlation occurs.

[0117] On the other hand, no significant increase in the contact angle relative to distilled water was observed compared to the untreated substrate of the comparative example, particularly the resin substrate, with any surface treatment agent. That is, it was found that no correlation was observed between the contact angle relative to solder resist and the contact angle relative to distilled water.

[0118] Experiment 2 Amine compounds of alkylamines and alkenylamines with different carbon numbers were used to prepare the surface treatment agent in the same manner as in Experiment 1 above. The pH value was adjusted to 10.

[0119] The amine compounds used are shown below.

[0120] Oleylamine (manufactured by Nippon Oil Company, 18 carbons / alkenylamine) Aminononadecane (manufactured by Tokyo Chemical Industry Co., Ltd., carbon number 19 / alkylamine) Doctidecylamine (manufactured by Nippon Oil Company, 22 carbon atoms / alkylamine) Hexylamine (manufactured by Tokyo Chemical Industry, 6-carbon / alkylamine) Octylamine (manufactured by Kishida Chemical, 8-carbon / alkylamine) Dodecylamine (manufactured by Kishida Chemical, 12 carbon atoms / alkylamine) Tetradecylamine (manufactured by Tokyo Chemical Industry Co., Ltd., carbon 14 / alkylamine) The test substrate used was the same as the etched substrate and resin substrate used in Test 1 above.

[0121] Each test substrate was surface-treated in the same manner as in Test 1, and the contact angle relative to diallyl glycol was measured in the same manner as in Test 1.

[0122] The results are shown in Table 2.

[0123] [Table 2]

[0124] As shown in Table 2, while the contact angle of the etched substrate can be improved to some extent in alkylamines with fewer carbon atoms, the contact angle of the resin substrate cannot be improved sufficiently.

[0125] Experiment 3 As a resin substrate, instead of using the epoxy resin copper-clad laminate material used in Tests 1 and 2 above, a polyimide resin board (thickness 0.04 mm, size 40 mm × 40 mm, trade name: Kapton, DU PONT-TORAY CO., LTD.) was treated with the same surface treatment agent as in Test 1 above, and the contact angle relative to dipropylene glycol was measured.

[0126] The results are shown in Table 3.

[0127] [Table 3]

[0128] As shown in Table 3, even compared to the untreated case, the contact angle can still be improved relative to the polyimide resin, and a contact angle of more than 35° can be obtained in each embodiment.

[0129] Experiment 4 A surface treatment agent using oleylamine, one of the amine compounds used in Experiment 1, was prepared. The pH was adjusted to 8.6. The concentration of oleylamine was adjusted to six different concentrations ranging from 0.001% to 1.2% by mass. The same substrates as those used in Experiment 1 (etched and resin substrates) were treated in the same manner as in Experiment 1, and the contact angle relative to diallyl glycol was measured.

[0130] The results are shown in Table 4.

[0131] [Table 4]

[0132] As shown in Table 4, the contact angle can be improved compared to the untreated substrate, even at any concentration.

[0133] Experiment 5 <Determination of Leakage Width> The solder resist leakage width was determined using the etched substrate and resin substrate used in Experiment 1 above.

[0134] After treating each test substrate with the solutions of the various amine compounds listed in Table 5 in the same manner as in Test 1, a solder resist (manufactured by Taiyo Ink Co., Ltd., item IJSR-4000), which is a resin component, was applied using an inkjet solder resist coating apparatus (equipment name: CPS6151, manufactured by MicroCraft Co., Ltd.) with a target linewidth of 100 μm. The substrates were then allowed to fully harden after coating. Furthermore, a commercially available co-solvent was added to each amine compound solution after mixing, based on visual observation of undissolved amine compounds. Each hardened test substrate was photographed using an optical microscope (equipment name: Digital Microscope VHS-5000, manufactured by KEYENCE Co., Ltd.), and the linewidth of any five points on the photographs was measured, and the average value of the five points was calculated.

[0135] As a control, the same measurements were also performed on untreated substrates (etched substrates and resin substrates) without surface treatment. The results are shown in Table 6.

[0136] [Table 5]

[0137] [Table 6]

[0138] As shown in Table 6, regarding the etched substrate, all embodiments and comparative examples, compared to the untreated substrate, consistently achieved a linewidth closer to the target of 100 μm, i.e., leakage was suppressed. Regarding the resin substrate, all embodiments suppressed leakage compared to the untreated substrate, but the comparative examples were the same as the untreated substrate.

Claims

1. A surface treatment agent, characterized in that, The surface treatment agent is used to treat the surface of a substrate including a metal surface and a resin surface, and includes at least 0.001% by mass and less than 1.2% by mass of an amine compound comprising at least one alkylamine selected from the group consisting of alkylamines having 19 to 24 carbon atoms, alkenylamines having 18 to 22 carbon atoms, and their salts.

2. The surface treatment agent according to claim 1, characterized in that, The amine compound is selected from at least one of the group consisting of aminononadecane, arachidamine, henicosylamine, diamine, triamine, tetraamine, and oleylamine.

3. The surface treatment agent according to claim 1 or 2, characterized in that, The surface treatment agent has a pH of 4.0 or higher and a pH of 14 or lower.

4. A method for manufacturing a film-forming substrate, characterized in that, The method for manufacturing the film-forming substrate produces a film-forming substrate on which a film of a resin composition is formed on the surface of a substrate, comprising: The surface treatment step involves contacting a surface treatment agent with a substrate surface having a metal surface and a resin surface, and performing surface treatment in such a way that the contact angle between the metal surface and the resin surface and the dipropylene glycol is 35° or more and 100° or less. as well as The film-forming step involves forming a film of the resin composition on the surface of the surface-treated substrate using an inkjet printing method.

5. The method for manufacturing a film-forming substrate according to claim 4, characterized in that, The surface treatment agent is an amine compound comprising at least 0.001% by mass and less than 1.2% by mass of at least one of the following groups: alkylamines selected from alkyl groups having 19 to 24 carbon atoms, alkenylamines selected from alkenyl groups having 18 to 22 carbon atoms, and their salts.

6. The method for manufacturing a film-forming substrate according to claim 4 or 5, characterized in that, In the film-forming step, a film is formed by inkjet printing using a resin composition that has been cured by heating, ultraviolet irradiation, or light irradiation.

7. The method for manufacturing a film-forming substrate according to claim 4 or 5, characterized in that, The surface treatment step is preceded by an etching step, in which the substrate surface is etched using a micro-etching agent.

8. The method for manufacturing a film-forming substrate according to claim 7, characterized in that, In the etching step, the metal surface is etched in such a way that the surface roughness (Ra) is greater than 0.1 μm and less than 0.8 μm.

9. The method for manufacturing a film-forming substrate according to claim 4 or 5, characterized in that, The surface treatment agent has a pH of 4.0 or higher and a pH of 14 or lower.

10. A film-forming substrate, characterized in that, The film-forming substrate is a film on the surface of a substrate having a resin composition formed thereon; The film-forming substrate comprises: a substrate surface having a metal surface and a resin surface; The contact angle between the metal surface and the resin surface and the diallyl glycol is greater than 35° and less than 100°. The surface roughness (Ra) of the metal surface is greater than 0.1 μm and less than 0.8 μm.

11. The film-forming substrate according to claim 10, characterized in that, The resin surface comprises a resin selected from the group consisting of polyimide resin, epoxy resin, polyethylene terephthalate resin, polypropylene resin, polyvinyl chloride resin, polyolefin resin, polyurethane resin, and polyacetal resin.

12. The film-forming substrate according to claim 10 or 11, characterized in that, The resin composition is hardened by heating, ultraviolet irradiation, or light irradiation.

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