Laminates, cured products thereof, and electronic components containing the same

Abstract

The present invention provides a laminate that exhibits a matte appearance after curing and possesses good mechanical properties and resolution. [Solution] A laminate was obtained comprising a resin layer (A) and a resin layer (B) provided on the resin layer (A), wherein the resin layer (A) has (A1) a block copolymer resin and (A2) a photopolymerizable compound, and the resin layer (B) has (B1) an alkali-soluble (meth)acrylate resin.

Description

Technical Field

[0001] The present invention relates to a laminate, particularly a laminate that can be used as an insulating layer of electronic components such as printed wiring boards, a cured product thereof, and an electronic component containing the same.

Background Art

[0002] An insulating film called a solder resist is formed on the surface layer of a printed wiring board used in various electronic devices. Since a general solder resist has a gloss finish, in the manufacturing process of a printed wiring board and the subsequent component mounting process, if there is a slight scratch on the solder resist, it will result in a defective appearance and contribute to a reduction in yield. In order to avoid such defective appearance due to slight scratches or reduce the ratio thereof, a matte (non-glossy) solder resist is often required. Also, from the viewpoint of enhancing the concealment of circuits and improving the aesthetic appearance of the substrate, there is a demand for a matte solder resist.

[0003] As a method for obtaining a matte solder resist, it has been proposed to use a specific resin composition as a composition for the solder resist (for example, Patent Document 1). In Patent Document 1, by using components that are mutually incompatible as components of the composition for the solder resist, diffused reflection of light incident on the surface of the solder resist is caused to reduce the glossiness. Also, in another method, it is taught that by roughening the surface of the solder resist layer, its glossiness can be suppressed and a matte solder resist can be obtained (for example, Patent Document 2). Patent Document 2 describes obtaining a matte solder resist by a physical roughening method of coating a solder resist composition on a blasted support.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

[0005] However, in the matting method that utilizes the incompatibility of resins described in Patent Document 1, the entire coating film becomes unevenly separated, so there is room for further consideration regarding ensuring the mechanical properties of the coating film.

[0006] Furthermore, in matting methods such as those described in Patent Document 2, in which the irregularities of a roughened support surface are physically transferred to a solder resist composition or dry film applied thereon, the irregularities of the solder resist thus created are lost when additional pressure is applied to the solder resist surface during the component mounting process, etc. As a result, the gloss value increases again, and a matte appearance cannot be obtained. In addition, because irregularities exist on the surface of the solder resist during exposure, the irradiated light is scattered, resulting in a problem of reduced resolution.

[0007] In other words, the present invention aims to provide a laminate, a cured product thereof, and an electronic component containing the same, which exhibit a matte appearance after curing, have excellent circuit concealment, and possess good mechanical properties and resolution. [Means for solving the problem]

[0008] As a result of diligent research, the present inventors have found that the above problem can be solved by a laminate comprising a resin layer (A) and a resin layer (B) provided on the resin layer (A), wherein the resin layer (A) has a first gloss value of 50 or more and a second gloss value of 30 or less, and the resin layer (B) has a third gloss value of 50 or more. Furthermore, the above problem is solved by a laminate comprising a resin layer (A) and a resin layer (B) provided on the resin layer (A), wherein the resin layer (A) has (A1) a block copolymer resin and (A2) a photopolymerizable compound, and the resin layer (B) has (B1) an alkali-soluble (meth)acrylate resin. The (A1) block copolymer resin of the present invention is of the XYX type, and preferably has a mass-average molecular weight Mw of 20,000 to 400,000. The photopolymerizable compound (A2) of the present invention is of the following general formula (I) [ka] (In general formula (I), R1 represents a hydrogen atom or a methyl group.) It is preferable that the compound is one shown in [the formula].

[0009] The laminate of the present invention further comprises a first film and a second film, and the first film, resin layer (A), resin layer (B), and second film may be provided in this order.

[0010] The object of the present invention is achieved by the cured product of the above-described laminate.

[0011] Furthermore, the objectives of the present invention are achieved by electronic components having the cured product of the present invention. [Effects of the Invention]

[0012] When the laminate of the present invention is applied to a substrate such as a printed circuit board, and the laminate is cured by a process such as heating, it will have mechanical properties and resolution that provide good protection for electronic devices in both the manufacturing and use of the electronic device, and will also have a matte appearance. [Brief explanation of the drawing]

[0013] [Figure 1] This is a schematic cross-sectional view of a laminate according to one embodiment of the present invention. [Figure 2] This is a schematic cross-sectional view of a laminate according to another embodiment of the present invention. [Figure 3] This is a diagram for explaining an example of a processing step for manufacturing a cured product using the laminate of the present invention.

Embodiments for Carrying Out the Invention

[0014] Hereinafter, the first embodiment of the present invention will be described in detail.

[0015] (Laminate) As shown in the schematic cross-sectional view of FIG. 1, the laminate of the present invention has a form of a laminate having a resin layer (A) and a resin layer (B) provided on the resin layer (A). In its use, the resin layer (B) of the laminate is arranged to contact a substrate (not shown) such as a printed wiring board and other electronic components, and the resin layer (A) is arranged to be separated from the substrate through the resin layer (B).

[0016] After the laminate is arranged on the substrate as described above, it is subjected to an exposure treatment and heat curing, and as a cured film, it protects the substrate during the manufacturing process as a solder resist, coverlay, or other circuit protection film, etc., and also exists on the substrate after the product is completed to play a role in protecting it. The curing of the laminate is carried out by heat treatment after exposure. In the present invention, the resin layer (A) and the resin layer (B) are each composed of a photosensitive resin composition (A) and a photosensitive resin composition (B).

[0017] The laminate of the present invention generally undergoes an exposure step, a heat curing step, a development step, a component mounting step, and a re-heating step, and becomes a cured product after the heat curing step. The gloss value of the resin layer constituting the laminate varies during the above series of steps such as exposure treatment and heat treatment. Here, "heat curing" means heating the resin layer (A) and the resin layer (B) at a temperature not lower than the temperature at which the thermosetting components contained therein crosslink (for example, 150 °C or higher) for a predetermined time to cure these resin layers, that is, curing the photosensitive resin composition by heating.

[0018] In the laminate of the present invention, the resin layer (A) is arranged on the substrate via the resin layer (B) as described above. After the predetermined processing described later, the first and second gloss values ​​of the surface of the resin layer (A) that does not come into contact with the resin layer (B) (the surface of the resin layer (A) that is farther from the substrate, also called the outer surface) will show predetermined values.

[0019] [First Gross Value] The first gloss value in the laminate of the present invention corresponds to the value obtained as the gloss value of the outer surface of the resin layer (A) in the laminate after exposure from the resin layer (A) side and before heat curing, when the laminate comprises (i) a resin layer (B) provided on a substrate and composed of a photosensitive resin composition (B), and a resin layer (A) provided on the side opposite to the substrate on the resin layer (B) and composed of a photosensitive resin composition (A). If the laminate comprises a first film in contact with the resin layer (A) and / or a second film in contact with the resin layer (B), the second film is peeled off and the resin layer (B) is vacuum laminated onto the substrate so that it is in contact with the substrate, then exposed from the resin layer (A) side, then the first film is peeled off, and before heat curing, the value obtained as the gloss value of the outer surface of the resin layer (A) in the laminate corresponds to the value obtained as the gloss value of the outer surface of the resin layer (A) in the laminate after exposure from the resin layer (A) side, then the first film is peeled off, and before heat curing. The first gloss value is 50 or more, preferably 70 to 100.

[0020] In this invention, a laminate comprising a resin layer (B) provided on a substrate and a resin layer (A) provided on the resin layer (B) on the side opposite to the substrate, and optionally a first film provided on the resin layer (A), is subjected to an integrated exposure dose of 250 mJ / cm² using an Oak Corporation vacuum contact double-sided exposure machine (model number ORC HMW 680GW). 2 Under these conditions, the first gloss value is measured after irradiating the resin layer (A) with ultraviolet light. If the laminate includes a first film as described above, the first gloss value is measured 10 minutes after the first film has been peeled off following the ultraviolet irradiation.

[0021] [Second gross value] Furthermore, the second gloss value in the laminate of the present invention corresponds to the value obtained by (ii) further heating the laminate after exposure, for which the first gloss value described above is measured, at 150°C for 60 minutes using hot air circulation drying, and then measuring the gloss value of the outer surface of the resin layer (A) in the laminate. Furthermore, the heat curing conditions for measuring the second gross value described above do not limit the heat curing conditions when using (mounting) the laminate of the present invention in electronic devices or the like. In other words, the heat curing conditions when using the laminate of the present invention can be appropriately selected from the conditions described in the heat curing process described later. Although the gloss value of resin layer (A) is the same or approximately the same for the entire resin layer (A), in this invention, in order to clarify the standard, the measurement value is used for a part of the surface (outer surface) of resin layer (A) that is not in contact with resin layer (B).

[0022] [Third Gross Value] Furthermore, the third gloss value in the laminate of the present invention is (iii) a value obtained as the gloss value of the outer surface of the resin layer (B) in the laminate after exposure and heat curing of the laminate comprising a resin layer (A) provided on a substrate and a resin layer (B) provided on the side opposite to the substrate on the resin layer (A). That is, it is measured in the same procedure as the second gloss value, except that the stacking order of the resin layer (A) and the resin layer (B) on the substrate is different. Furthermore, if the laminate comprises a first film in contact with resin layer (A) and / or a second film in contact with resin layer (B), the first film is peeled off, and the resin layer (A) is laminated onto the substrate using a vacuum laminator (CVP-300: manufactured by Nikko Material Co., Ltd.) in a first chamber at 80°C under conditions of a vacuum pressure of 3 hPa and a vacuum time of 30 seconds. After pressing under conditions of a press pressure of 0.5 MPa and a press time of 30 seconds, the substrate is exposed from the resin layer (B) side, the two films are peeled off, and after heat curing, the value obtained corresponds to the gloss value of the outer surface of resin layer (B). The exposure and heat curing conditions for measuring the third gloss value are the same as the conditions used for measuring the second gloss value.

[0023] In this invention, "gloss value" refers to the value measured by irradiating a horizontally placed laminate with light at an incident angle of 60° using a gloss meter (micro-TRI-gloss) manufactured by BYK Additives & Instruments.

[0024] (Laminate manufacturing process) The manufacturing process of the laminate will be explained below with reference to Figures 2 and 3. Figure 2 is a schematic cross-sectional view of one embodiment of a laminate before it is applied to electronic devices, etc. In this example, a photosensitive resin composition (A) is applied to a first film 1 (for example, a carrier film or support film) and dried, then a photosensitive resin composition (B) is applied to the resin layer (A) and dried, and a second film 2 is laminated on top of the photosensitive resin composition (B). In other words, Figure 2 shows a dry film (laminated body) in a laminated state. Specifically, first, the photosensitive resin compositions (A) and (B) are each diluted with an organic solvent or the like to adjust their viscosity to approximately 0.1 dPa·s to 200 dPa·s. Then, the photosensitive resin composition (A) is applied to one side of the first film 1 using a known device such as a comma coater, in accordance with conventional methods. Subsequently, a dried resin layer (A) is formed on the first film 1 by drying at a temperature of 50 to 140°C for 1 to 30 minutes. The viscosity-adjusted photosensitive resin composition (B) is then applied to the side of the resin layer (A) opposite to the first film 1 in the same manner as described above, and dried to produce a laminate consisting of resin layer (A) and resin layer (B) that is provided in contact with the first film 1. The laminate of the present invention may have the above-described first film 1 and other films or resin layers, as long as it is a laminate containing resin layer (A) and resin layer (B). When applying the laminate to electronic devices, resin layer (B) is provided on the substrate side, and resin layer (A) is provided on the opposite side from the substrate via resin layer (B), forming a surface layer visible from the surface of the electronic device.

[0025] On the side of the resin layer (B) of the laminate that is opposite to the resin layer (A), a peelable second film 2 (e.g., a cover film or protective film) can be laminated for purposes such as preventing dust from adhering to the surface of the resin layer (B). Conventional plastic films can be used as the first film 1 and the second film 2, and it is preferable that the adhesive strength between the second film 2 and the resin layer (B) is less than the adhesive strength between the first film 1 and the resin layer (A). Since the laminate 10 of the present invention is applied to the substrate by first peeling off the second film 2, this operation is made easier by controlling the adhesive strength as described above. There are no particular restrictions on the thickness of the first film 1 and the second film 2, but they are generally appropriately selected in the range of 10 to 150 μm.

[0026] Thus, a four-layer laminate consisting of the first film 1, resin layer (A), resin layer (B), and second film 2, stacked in this order, is manufactured as a dry film (Figure 2). Furthermore, the laminate of the present invention may be supported or protected on only one side by a film (either the first film 1 or the second film 2), or it may be a laminate without a film. Moreover, the laminate (dry film) of the present invention may be wound in a roll. From the viewpoint of coating strength, the interfaces between each layer may be well-integrated. That is, it is preferable that resin layer (A) and resin layer (B) have high adhesion, and that when the first film 1 or the second film 2 is peeled off, or when other peelable layers exist in the laminate, when those peelable layers are peeled off, resin layer (A) and resin layer (B) adhere closely to each other to form a highly durable permanent coating.

[0027] The laminate obtained as described above is applied to a substrate (the object to be protected), such as a printed circuit board, and functions as a solder resist, coverlay, or other circuit protective film. As already mentioned, if the laminate has a second film 2, it is peeled off, and the laminate and the substrate are placed facing each other so that the entire surface of the resin layer (B) covers the surface to be protected on the substrate, and the laminate and the substrate are brought into close contact by applying pressure using a laminator.

[0028] In this invention, "above" and "opposing" do not necessarily mean that the layers or surfaces described as the object are in contact; in some cases, they may be provided via other layers. On the other hand, "directly" or "directly" means that the layers or surfaces are in contact.

[0029] As described above, to create the laminate on the first film 1 in advance and laminate it to an electronic device, it is preferable to bond it under pressure and heat using a vacuum laminator or the like. By using such a vacuum laminator, even if the surface of the wiring substrate is uneven, the dry film adheres closely to the wiring substrate, so there is no inclusion of air bubbles, and the ability to fill in depressions on the surface of the wiring substrate is also improved. The pressurizing conditions are preferably 0.1 to 2.0 MPa, and the heating conditions are preferably 40 to 120°C.

[0030] Furthermore, as a method for arranging the laminate of the present invention on a circuit board, the resin layer (A) and resin layer (B) can also be created individually as dry films, and these dry films can be sequentially laminated onto the protective surface of the circuit board. That is, first, the dry film of resin layer (B) is laminated onto the circuit board to form resin layer (B). Then, the dry film of resin layer (A) is laminated onto resin layer (B) to obtain the laminate of the present invention formed on the circuit board.

[0031] Alternatively, a laminate may be formed by directly applying and drying the photosensitive resin composition (B) to the electronic device, and then applying and drying the photosensitive resin composition (A) on the dried film of the photosensitive resin composition (B). From the electronic device side, a resin layer (B) made of the photosensitive resin composition (B) and a resin layer (A) made of the photosensitive resin composition (A) are sequentially laminated, and the resin layers (B) and (A) constitute the laminate of the present invention in close contact with the electronic device. In this case, the photosensitive resin compositions (A) and (B) used are also subjected to viscosity adjustment using an organic solvent, application, drying, etc., similar to the laminate provided on a film.

[0032] In the production of the photosensitive resin composition used in the laminate of the present invention, the organic solvent used for viscosity adjustment is appropriately selected from known organic solvents as described later.

[0033] The photosensitive resin compositions (A) and (B) can be applied using known equipment such as a blade coater, lip coater, or film coater, in addition to the comma coater described above. Drying is preferably carried out using equipment equipped with a steam heating source, such as a hot air circulating drying oven, an IR oven, a hot plate, or a convection oven. Known methods such as applying hot air in a countercurrent to the support and blowing hot air from a nozzle onto the support can also be used.

[0034] The laminate manufactured in this manner is hardened by a curing process described later to form a permanent coating on the electronic equipment (protected object) of the printed circuit board.

[0035] [Resin layer (A)] In the laminate according to the present invention, the gloss value of the resin layer (A) on the surface not facing the resin layer (B), i.e., the outermost layer of a printed circuit board or the like and the surface that is visible (outer surface), changes during each process such as curing. Specifically, the first gloss value of the resin layer (A) is 50 or more, preferably 70 to 100. When the first gloss value is 50 or more, good resolution can be obtained.

[0036] Furthermore, the resin layer (A) of the laminate according to the present invention has a second gloss value of 30 or less, preferably 1 to 20. When the second gloss value is 30 or less, a good matte appearance can be achieved.

[0037] [Resin layer (B)] The resin layer (B) used in the laminate of the present invention has a third gloss value of 50 or more, preferably 70 to 100. When the gloss value of the outer surface of the resin layer (B) is 50 or more, good mechanical properties can be obtained.

[0038] In this invention, the film thickness of the resin layer (B) after coating and drying is generally 1 to 150 μm, preferably 3 to 120 μm, and the film thickness of the resin layer (A) is generally 0.5 to 50 μm, preferably 2 to 30 μm, with the total film thickness of both being 5 to 150 μm. Furthermore, it is preferable that the film thickness of the resin layer (B) is greater than the film thickness of the resin layer (A).

[0039] When the laminate and its cured product of the present invention are applied as a solder resist or the like, it is preferable that they be developable. From this viewpoint, it is preferable that at least one or both of the photosensitive resin compositions (A) and (B) contain an alkali-soluble resin, particularly a carboxyl group-containing resin. Furthermore, since both are cured by thermal curing, they contain a thermosetting resin. The components of the photosensitive resin compositions (A) and (B) are described below.

[0040] [Components of photosensitive resin composition (A)] The photosensitive resin composition (A) constituting the resin layer (A) exhibiting the first and second gloss values ​​described above generally contains an alkali-soluble resin such as a carboxyl group-containing resin, and more preferably contains a thermosetting resin, and may further contain a polyimide resin, an aromatic resin, a photosensitive resin, or a methyl methacrylate comb-type polymer. In order to achieve the desired gloss value, the photosensitive resin composition (A) needs to contain a component that is incompatible with the resin in the photosensitive resin composition (A). This is not limited to a specific component, but is not limited to a predetermined structure as long as it is a component that is incompatible with the resin in the photosensitive resin composition (A). Examples include polyamide-imide which is incompatible with polyimide resin, fatty acids containing heteroatoms which are incompatible with carboxyl group-containing resins, aliphatic block copolymer resin which is incompatible with aromatic resins, alicyclic photopolymerizable compounds which are incompatible with photosensitive resins, and silicone compounds which are incompatible with methyl methacrylate comb-type polymers. The photosensitive resin composition (A) may further optionally contain a photopolymerizable compound and a photopolymerization initiator. Furthermore, when the amount of thermosetting resin or photopolymerizable compound is high relative to high molecular weight components such as alkali-soluble resins, polyimide resins, and polyamide-imide resins, it tends to exhibit mismatch, and a resin layer (A) using such a photosensitive resin composition (A) exhibits the desired gross value of the present invention. This blending amount is not particularly limited, but for example, the total amount of thermosetting resin and photopolymerizable compound per 100 parts by mass of high molecular weight component can be 30 to 170 parts by mass.

[0041] (Alkali-soluble resin used in photosensitive resin composition (A)) In the photosensitive resin composition (A), it is preferable to include an alkali-soluble resin as described above, and any known alkali-soluble resin can be used, with a carboxyl group-containing resin being particularly preferable. Specific examples of alkali-soluble resins that can be used in the photosensitive resin composition (A) include the following.

[0042] (1) Carboxyl group-containing resin having imide and amide structures Carboxyl group-containing resins having imide and amide structures, particularly polyamide-imide group-containing resins having the structure represented by the following general formula (1) and the structure represented by the following general formula (2), can be used. [ka]

[0043] Here, X1 is a residue of an aliphatic diamine (a) derived from a dimer acid with 24 to 48 carbon atoms. X2 is a residue of an aromatic diamine (b) having a carboxyl group. Y is independently either a cyclohexane ring or an aromatic ring.

[0044] Specifically, examples of polyamide-imide resins having such a structure include those represented by the following general formula (3). [ka]

[0045] In the general formula (3) above, X is independently a diamine residue, Y is independently an aromatic ring or a cyclohexane ring, and Z is a residue of a diisocyanate compound. n is a natural number.

[0046] (2) Carboxyl group-containing resin having an imide structure but not an amide structure A carboxyl group-containing resin having an imide structure but lacking an amide structure is not particularly limited as long as it is a resin having a carboxyl group and an imide ring. For the synthesis of a carboxyl group-containing resin having an imide structure but lacking an amide structure, known and conventional methods for introducing an imide ring into a carboxyl group-containing resin can be used. For example, resins obtained by reacting a carboxylic acid anhydride component with an amine component and / or an isocyanate component can be used. Imidation may be carried out by thermal imidation, chemical imidation, or a combination of both.

[0047] Examples of carboxylic acid anhydride components include tetracarboxylic acid anhydrides and tricarboxylic acid anhydrides, but the formula is not limited to these acid anhydrides. Any compound having an acid anhydride group and a carboxyl group that react with an amino group or an isocyanate group, including its derivatives, can be used. Furthermore, these carboxylic acid anhydride components may be used individually or in combination.

[0048] Examples of tetracarboxylic acid anhydrides include pyromellitic dianhydride, 3-fluoropyromellitic dianhydride, 3,6-difluoropyromellitic dianhydride, 3,6-bis(trifluoromethyl)pyromellitic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic acid dianhydride, 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, 4,4'-oxydiphthalic acid dianhydride, 2,2'-difluoro-3,3',4,4'-biphenyltetracarboxylic acid dianhydride, and 5,5'-difluoro-3,3',4,4'-biphenyltetracarboxylic acid dianhydride. Acid dianhydrides, 6,6'-difluoro-3,3',4,4'-biphenyltetracarboxylic acid dianhydride, 2,2',5,5',6,6'-hexafluoro-3,3',4,4'-biphenyltetracarboxylic acid dianhydride, 2,2'-bis(trifluoromethyl)-3,3',4,4'-biphenyltetracarboxylic acid dianhydride, 5,5'-bis(trifluoromethyl)-3,3',4,4'-biphenyltetracarboxylic acid dianhydride, 6,6'-bis(trifluoromethyl)-3,3',4,4'-biphenyltetracarboxylic acid dianhydride, 2,2',5,5'-tetra Lakis(trifluoromethyl)-3,3',4,4'-biphenyltetracarboxylic acid dianhydride, 2,2',6,6'-tetrakis(trifluoromethyl)-3,3',4,4'-biphenyltetracarboxylic acid dianhydride, 5,5',6,6'-tetrakis(trifluoromethyl)-3,3',4,4'-biphenyltetracarboxylic acid dianhydride, and 2,2',5,5',6,6'-hexakis(trifluoromethyl)-3,3',4,4'-biphenyltetracarboxylic acid dianhydride, 1,2,3,4-benzenetetracarboxylic acid dianhydride, 3,3”,4,4 "-Terphenyltetracarboxylic dianhydride, 3,3'",4,4'"-Quaterphenyltetracarboxylic dianhydride, 3,3'",4,4""-Quinkphenyltetracarboxylic dianhydride, Methylene-4,4'-diphthalic acid dianhydride, 1,1-Ethynylidene-4,4'-diphthalic acid dianhydride, 2,2-Propyridene-4,4'-diphthalic acid dianhydride, 1,2-Ethylene-4,4'-diphthalic acid dianhydride, 1,3-Trimethylene-4,4'-diphthalic acid dianhydride, 1,4-Tetramethylene-4,4'-diphthalic acid dianhydride, 1,5-Pentamethylene-4,4'-Diphthalic acid dianhydride, 2,2-Bis(3,4-Dicarboxyphenyl)-1,1,1,3,3,3-Hexafluoropropane dianhydride, Difluoromethylene-4,4'-Diphthalic acid dianhydride, 1,1,2,2-Tetrafluoro-1,2-Ethylene-4,4'-Diphthalic acid dianhydride, 1,1,2,2,3,3-Hexafluoro-1,3-Trimethylene-4,4'-Diphthalic acid dianhydride, 1,1,2,2,3,3,4,4-Octafluoro-1,4-Tetramethylene-4,4'-Diphthalic acid dianhydride, 1,1,2,2,3,3,4,4,5,5-De Cafluoro-1,5-pentamethylene-4,4'-diphthalic acid dianhydride, thio-4,4'-diphthalic acid dianhydride, sulfonyl-4,4'-diphthalic acid dianhydride, 1,3-bis(3,4-dicarboxyphenyl)-1,1,3,3-tetramethylsiloxane dianhydride, 1,3-bis(3,4-dicarboxyphenyl)benzene dianhydride, 1,4-bis(3,4-dicarboxyphenyl)benzene dianhydride, 1,3-bis(3,4-dicarboxyphenoxy)benzene dianhydride, 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride, 1,3 -Bis[2-(3,4-dicarboxyphenyl)-2-propyl]benzene dianhydride, 1,4-bis[2-(3,4-dicarboxyphenyl)-2-propyl]benzene dianhydride, bis[3-(3,4-dicarboxyphenoxy)phenyl]methane dianhydride, bis[4-(3,4-dicarboxyphenoxy)phenyl]methane dianhydride, 2,2-bis[3-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, 2,2-bis[3-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride [Broboxyphenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane dianhydride, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, bis(3,4-dicarboxyphenoxy)dimethylsilane dianhydride, 1,3-bis(3,4-dicarboxyphenoxy)-1,1,3,3-tetramethyldisiloxane dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 1,2,5,6-naphthalenetetracarboxylic acid dianhydride, 3,4,9,10-perylenetetracarboxylic acid dianhydride, 2,3,6,7-Anthracenetetracarboxylic dianhydride, 1,2,7,8-phenanthrenetetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, cyclohexane-1,2,3,4-tetracarboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride, 3,3',4,4'-bicyclohexyltetracarboxylic dianhydride, carbonyl-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, Thiene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,2-ethylene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,1-ethynylidene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 2,2-propyridene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-propyridene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, oxy-4,4'-bis(cyclohexane-1,2 -Dicarboxylic acid) dianhydride, thio-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, sulfonyl-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 3,3'-difluorooxy-4,4'-diphthalic acid dianhydride, 5,5'-difluorooxy-4,4'-diphthalic acid dianhydride, 6,6'-difluorooxy-4,4'-diphthalic acid dianhydride, 3,3',5,5',6,6'-hexafluorooxy-4,4'-diphthalic acid dianhydride, 3,3'-bis(trifluoromethyl)oxy-4,4'-diphthalic acid dianhydride Water, 5,5'-bis(trifluoromethyl)oxy-4,4'-diphthalic acid dianhydride, 6,6'-bis(trifluoromethyl)oxy-4,4'-diphthalic acid dianhydride, 3,3',5,5'-tetrakis(trifluoromethyl)oxy-4,4'-diphthalic acid dianhydride, 3,3',6,6'-tetrakis(trifluoromethyl)oxy-4,4'-diphthalic acid dianhydride, 5,5',6,6'-tetrakis(trifluoromethyl)oxy-4,4'-diphthalic acid dianhydride, 3,3',5,5',6,6'-hexakis(trifluoromethyl)oxy-4,4'-Diphthalic acid dianhydride, 3,3'-Difluorosulfonyl-4,4'-Diphthalic acid dianhydride, 5,5'-Difluorosulfonyl-4,4'-Diphthalic acid dianhydride, 6,6'-Difluorosulfonyl-4,4'-Diphthalic acid dianhydride, 3,3',5,5',6,6'-Hexafluorosulfonyl-4,4'-Diphthalic acid dianhydride, 3,3'-Bis(trifluoromethyl)sulfonyl-4,4'-Diphthalic acid dianhydride, 5,5'-Bis(trifluoromethyl)sulfonyl-4,4'-Diphthalic acid dianhydride, 6,6'-Bis(trifluoromethyl)sulfonyl 4,4'-diphthalic acid dianhydride, 3,3',5,5'-tetrakis(trifluoromethyl)sulfonyl-4,4'-diphthalic acid dianhydride, 3,3',6,6'-tetrakis(trifluoromethyl)sulfonyl-4,4'-diphthalic acid dianhydride, 5,5',6,6'-tetrakis(trifluoromethyl)sulfonyl-4,4'-diphthalic acid dianhydride, 3,3',5,5',6,6'-hexakis(trifluoromethyl)sulfonyl-4,4'-diphthalic acid dianhydride, 3,3'-difluoro-2,2-perfluoropropyridene-4,4'-diphthalic acid dianhydride Water, 5,5'-difluoro-2,2-perfluoropropyridene-4,4'-diphthalic acid dianhydride, 6,6'-difluoro-2,2-perfluoropropyridene-4,4'-diphthalic acid dianhydride, 3,3',5,5',6,6'-hexafluoro-2,2-perfluoropropyridene-4,4'-diphthalic acid dianhydride, 3,3'-bis(trifluoromethyl)-2,2-perfluoropropyridene-4,4'-diphthalic acid dianhydride, 5,5'-bis(trifluoromethyl)-2,2-perfluoropropyridene-4,4'-diphthalic acid dianhydride, 6,6' -Difluoro-2,2-perfluoropropyridene-4,4'-diphthalic acid dianhydride, 3,3',5,5'-tetrakis(trifluoromethyl)-2,2-perfluoropropyridene-4,4'-diphthalic acid dianhydride, 3,3',6,6'-tetrakis(trifluoromethyl)-2,2-perfluoropropyridene-4,4'-diphthalic acid dianhydride, 5,5',6,6'-tetrakis(trifluoromethyl)-2,2-perfluoropropyridene-4,4'-diphthalic acid dianhydride, 3,3',5,5',6,6'-hexakis(trifluoromethyl)-2,2-Perfluoropropyridene-4,4'-diphthalic acid dianhydride, 9-phenyl-9-(trifluoromethyl)xanthene-2,3,6,7-tetracarboxylic acid dianhydride, 9,9-bis(trifluoromethyl)xanthene-2,3,6,7-tetracarboxylic acid dianhydride, bicyclo[2,2,2]octo-7-ene-2,3,5,6-tetracarboxylic acid dianhydride, 9,9-bis[4-(3,4-dicarboxy)phenyl]fluorene dianhydride, 9,9-bis[4-(2,3-dicarboxy)phenyl]fluorene dianhydride, ethylene glycol bistrimellitate dianhydride, 1,2-(ethylene)bis(trimellitate anhydride), 1,3-(trimethylene)bis(trimellitate anhydride) Examples include tetramethylene (trimellitate anhydrous), 1,4-(tetramethylene)bis(trimellitate anhydrous), 1,5-(pentamethylene)bis(trimellitate anhydrous), 1,6-(hexamethylene)bis(trimellitate anhydrous), 1,7-(heptamethylene)bis(trimellitate anhydrous), 1,8-(octamethylene)bis(trimellitate anhydrous), 1,9-(nonameethylene)bis(trimellitate anhydrous), 1,10-(decamethylene)bis(trimellitate anhydrous), 1,12-(dodecamethylene)bis(trimellitate anhydrous), 1,16-(hexadecamethylene)bis(trimellitate anhydrous), and 1,18-(octadecamethylene)bis(trimellitate anhydrous). Examples of tricarboxylic acid anhydrides include trimellitic anhydride and nuclear hydrogenated trimellitic anhydride.

[0049] As amine components, diamines such as aliphatic diamines and aromatic diamines, polyhydric amines such as aliphatic polyetheramines, diamines having carboxylic acids, and diamines having phenolic hydroxyl groups can be used, but are not limited to these amines. Furthermore, these amine components may be used individually or in combination.

[0050] Examples of diamines include single-benzene ring diamines such as p-phenylenediamine (PPD), 1,3-diaminobenzene, 2,4-toluenediamine, 2,5-toluenediamine, and 2,6-toluenediamine; diaminodiphenyl ethers such as 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, and 3,4'-diaminodiphenyl ether; 4,4'-diaminodiphenylmethane; 3,3'-dimethyl-4,4'-diaminobiphenyl; 2,2'-dimethyl-4,4'-diaminobiphenyl; and 2,2 '-Bis(trifluoromethyl)-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, bis(4-aminophenyl) sulfide, 4,4'-diaminobenzanilide, 3,3'-dichlorobenzidine, 3,3'-dimethylbenzidine (o-tollidine), 2,2'-dimethylbenzidine (m-tollidine), 3,3'-dimethoxybenzidine, 2,2'-dimethoxybenzidine, 3,3'-diaminodiphenyl ether, 3 ,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminobenzophenone, 3,3'-diamino-4,4'-dichlorobenzophenone, 3,3'-diamino-4,4'-dimethoxybenzophenone, 3,3'-diaminodiphenyl meta n, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 2,2-bis(3-aminophenyl)propane, 2,2-bis(4-aminophenyl)propane, 2,2-bis(3-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 2,2-bis(4-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 3,3'-diaminodiphenyl sulfoxide, 3,4'-diaminodiphenyl sulfoxide, 4,4'-diaminodiphenyl sulfoxide, 3,3'-dicarboxy-4,Diamines with two benzene rings, such as 4'-diaminodiphenylmethane, 1,3-bis(3-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 1,4-bis(3-aminophenyl)benzene, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(3-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)-4-trifluoromethylbenzene, 3,3'-diamino-4-(4-phenyl)phenoxybenzophenone, 3,3'-diamino-4,4'-di(4-phenylphenoxy)benzophenone, 1,3-bis(3-aminophenyl sulfide)benzene, 1,3-bis(4-aminophenylsulfide)benzene, 1,4-bis(4-aminophenylsulfide)benzene, 1,3-bis(3-aminophenylsulfone)benzene, 1,3-bis(4-aminophenylsulfone)benzene, 1,4-bis(4-aminophenylsulfone)benzene, 1,3-bis[2-(4-aminophenyl)isopropyl]benzene, 1,4-bis[2-(3-aminophenyl)isopropyl]benzene, 1,4-bis[2-(4-aminophenyl)isopropyl]benzene, and other benzene-nuclear diamines, 3,3'-bis(3-aminophenoxy)biphenyl, 3,3'-bis(4-aminophenoxy)biphenyl, 4,4'-bis(3-aminophenoxy)biphenyl, 4,4'-Bis(4-aminophenoxy)biphenyl, bis[3-(3-aminophenoxy)phenyl] ether, bis[3-(4-aminophenoxy)phenyl] ether, bis[4-(3-aminophenoxy)phenyl] ether, bis[4-(4-aminophenoxy)phenyl] ether, bis[3-(3-aminophenoxy)phenyl] ketone, bis[3-(4-aminophenoxy)phenyl] ketone, bis[4-(3-aminophenoxy)phenyl] ketone, bis[3-(3-aminophenoxy)phenyl] ketone, bis[3-(3-aminophenoxy) [Phenoxy)phenyl] sulfide, bis[3-(4-aminophenoxy)phenyl] sulfide, bis[4-(3-aminophenoxy)phenyl] sulfide, bis[4-(4-aminophenoxy)phenyl] sulfide, bis[3-(3-aminophenoxy)phenyl] sulfone, bis[3-(4-aminophenoxy)phenyl] sulfone, bis[4-(3-aminophenoxy)phenyl] sulfone, bis[4-(4-aminophenoxy)phenyl] sulfone, bis[3-(3-aminophenoxy)phenyl] methane, bis[3-(4-aminophenoxy) [xy)phenyl]methane, bis[4-(3-aminophenoxy)phenyl]methane, bis[4-(4-aminophenoxy)phenyl]methane, 2,2-bis[3-(3-aminophenoxy)phenyl]propane, 2,2-bis[3-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[3-(3-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 2,2-bis[3 Aromatic diamines such as benzene ring diamines including -(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 2,2-bis[4-(3-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,Examples of aliphatic diamines include 8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, and 1,2-diaminocyclohexane. Examples of aliphatic polyetheramines include ethylene glycol and / or propylene glycol-based polyhydric amines.

[0051] As the isocyanate component, diisocyanates such as aromatic diisocyanates and their isomers and polymers, aliphatic diisocyanates, alicyclic diisocyanates and their isomers, and other general-purpose diisocyanates can be used, but are not limited to these isocyanates. Furthermore, these isocyanate components may be used individually or in combination.

[0052] Examples of diisocyanates include aromatic diisocyanates such as 4,4'-diphenylmethane diisocyanate, tolylene diisocyanate, naphthalene diisocyanate, xylylene diisocyanate, biphenyl diisocyanate, diphenyl sulfone diisocyanate, and diphenyl ether diisocyanate, as well as their isomers and polymers; aliphatic diisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, and dicyclohexylmethane diisocyanate; alicyclic diisocyanates and isomers obtained by hydrogenating the aforementioned aromatic diisocyanates; or other general-purpose diisocyanates.

[0053] (3) Carboxyl group-containing resins that do not have an imide structure The carboxyl group-containing resin that does not have an imide structure is not particularly limited as long as it is any conventionally known carboxyl group-containing resin that has a carboxyl group. In particular, carboxyl group-containing resins having an ethylenically unsaturated double bond in the molecule are more preferred in terms of photocurability and developability. Furthermore, the unsaturated double bond is preferably derived from acrylic acid, methacrylic acid, or a derivative thereof. Specific examples of carboxyl group-containing resins include the compounds listed below (either oligomers or polymers), which can be suitably used.

[0054] (3-1) Carboxyl group-containing resin obtained by copolymerization of an unsaturated carboxylic acid such as (meth)acrylic acid with an unsaturated group-containing compound such as styrene, α-methylstyrene, lower alkyl (meth)acrylate, or isobutylene.

[0055] (3-2) Carboxyl group-containing urethane resins obtained by polyaddition reactions of diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates with carboxyl group-containing dialcohol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid, and diol compounds such as polycarbonate polyols, polyether polyols, polyester polyols, polyolefin polyols, acrylic polyols, bisphenol A alkylene oxide adduct diols, and compounds having phenolic hydroxyl groups and alcoholic hydroxyl groups.

[0056] (3-3) A carboxyl group-containing photosensitive urethane resin obtained by polyaddition reactions of diisocyanate with (meth)acrylates or partially acid anhydride modified products thereof of difunctional epoxy resins such as bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenol type epoxy resin, and biphenol type epoxy resin, carboxyl group-containing dialcohol compounds, and diol compounds.

[0057] (3-4) A carboxyl group-containing photosensitive urethane resin obtained by adding a compound having one hydroxyl group and one or more (meth)acryloyl groups in the molecule, such as hydroxyalkyl (meth)acrylate, during the synthesis of the resin of (3-2) or (3-3) above, and then (meth)acrylicating the terminal (meth)acrylic.

[0058] (3-5) A carboxyl group-containing photosensitive urethane resin in which a compound having one isocyanate group and one or more (meth)acryloyl groups in the molecule is added to the synthesis of the resin of (3-2) or (3-3) above, and the terminal (meth)acrylic compound is formed by adding such a compound to the end (meth)acrylic compound, such as an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate.

[0059] (3-6) A carboxyl group-containing photosensitive resin obtained by reacting a bifunctional or polyfunctional (solid) epoxy resin with (meth)acrylic acid and adding a dibasic acid anhydride to the hydroxyl groups present in the side chain.

[0060] (3-7) A carboxyl group-containing photosensitive resin obtained by reacting a polyfunctional epoxy resin, in which the hydroxyl groups of a bifunctional (solid) epoxy resin are further epoxidized with epichlorohydrin, with (meth)acrylic acid, and then adding a dibasic acid anhydride to the resulting hydroxyl groups.

[0061] (3-8) A carboxyl group-containing polyester resin obtained by reacting a bifunctional oxetane resin with dicarboxylic acids such as adipic acid, phthalic acid, and hexahydrophthalic acid, and then adding dibasic acid anhydrides such as phthalic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride to the resulting primary hydroxyl groups.

[0062] (3-9) A carboxyl group-containing photosensitive resin obtained by reacting a compound having multiple phenolic hydroxyl groups in one molecule with an alkylene oxide such as ethylene oxide or propylene oxide, reacting the reaction product with an unsaturated group-containing monocarboxylic acid, and then reacting the resulting reaction product with a polybasic acid anhydride.

[0063] (3-10) A carboxyl group-containing photosensitive resin obtained by reacting a compound having multiple phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate, reacting the reaction product with an unsaturated group-containing monocarboxylic acid, and then reacting the resulting reaction product with a polybasic acid anhydride.

[0064] (3-11) A carboxyl group-containing photosensitive resin obtained by adding a compound having one epoxy group and one or more (meth)acryloyl groups in one molecule to the resins of (3-1) to (10) above. In this specification, (meth)acrylate is a general term referring to acrylates, methacrylates, and mixtures thereof, and the same applies to other similar expressions.

[0065] The carboxyl group-containing resin, which is suitably used as the alkali-soluble resin of the present invention as described above, preferably has an acid value of 20 to 200 mgKOH / g, and more preferably 60 to 150 mgKOH / g, in order to accommodate the photolithography process. When the acid value is 20 mgKOH / g or higher, the solubility to alkali increases, the developability improves, and furthermore, the degree of crosslinking with the thermosetting component after light irradiation increases, so sufficient development contrast can be obtained. On the other hand, when the acid value is 200 mgKOH / g or lower, accurate pattern drawing becomes easier, and in particular, the so-called thermal fogging in the PEB (POST EXPOSURE BAKE) process after light irradiation, which will be described later, can be suppressed, and the process margin becomes larger.

[0066] Furthermore, considering the developability and cured film properties, the molecular weight of such carboxyl group-containing resin is preferably 100,000 or less in mass-average molecular weight (Mw), more preferably 1,000 to 100,000, and even more preferably 2,000 to 50,000. When the molecular weight is 100,000 or less, the alkali solubility of the unexposed areas increases, improving developability. On the other hand, when the molecular weight is 1,000 or more, sufficient developability and cured properties can be obtained in the exposed areas after exposure and PEB.

[0067] (Thermosetting resin used in photosensitive resin composition (A)) The photosensitive resin composition (A) preferably contains a thermosetting resin. Conventional thermosetting resins can be used as the thermosetting resin, and known and commonly used resins having functional groups that can undergo a heat-curing reaction, such as cyclic (thio) ether groups, such as epoxy resins, are used. Examples of the epoxy resins mentioned above include bisphenol A type epoxy resin, brominated epoxy resin, novolac type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, glycidylamine type epoxy resin, hydantoin type epoxy resin, alicyclic epoxy resin, trihydroxyphenylmethane type epoxy resin, bixylenol type or biphenol type epoxy resin or mixtures thereof; bisphenol S type epoxy resin, bisphenol A novolac type epoxy resin, tetraphenyloleethane type epoxy resin, heterocyclic epoxy resin, diglycidyl phthalate resin, tetraglycidyl xylenoylethane resin, naphthalene group-containing epoxy resin, epoxy resin having a dicyclopentadiene skeleton, glycidyl methacrylate copolymer epoxy resin, copolymer epoxy resin of cyclohexylmaleimide and glycidyl methacrylate, and CTBN-modified epoxy resin. Of these, particularly preferred epoxy resins as components of the photosensitive resin composition (A) are bisphenol A type epoxy resin or novolac type epoxy, or combination systems thereof.

[0068] The amount of the thermosetting resin blended is preferably such that the equivalent ratio (alkali-soluble group such as carboxyl group: heat-reactive group such as epoxy group) of the thermosetting resin is 1:0.1 to 1:10. By using this blending ratio range, development is improved and fine patterns can be easily formed. The equivalent ratio is more preferably 1:0.2 to 1:5.

[0069] (Photopolymerizable compound) When the laminate and its cured product of the present invention are applied as a solder resist or the like, the photosensitive resin composition (A) preferably contains a photopolymerizable compound, and any photopolymerizable compound conventionally used in the manufacture of solder resists or the like can be used.

[0070] Examples of photopolymerizable compounds included in the photosensitive resin composition (A) include compounds having two or more ethylenically unsaturated groups in the molecule, compounds obtained by adding an α,β-unsaturated carboxylic acid to a polyhydric alcohol, and compounds obtained by adding an α,β-unsaturated carboxylic acid to a glycidyl group-containing compound. Compounds having one ethylenically unsaturated group in the molecule can be monofunctional (meth)acrylates, such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, glycidyl methacrylate, and other (meth)acrylates; heterocyclic groups such as acryloylmorpholine or tetrahydrofuranyl groups, particularly (meth)acrylates having oxygen-containing cyclic groups, can be used.

[0071] Examples of monofunctional (meth)acrylates having an oxygen-containing cyclic group include compounds represented by the following general formula (I). [ka] (In general formula (I), R1 represents a hydrogen atom or a methyl group.)

[0072] Examples of compounds having two or more ethylenically unsaturated groups in their molecules include: diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol; polyhydric acrylates such as polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, and tris-hydroxyethyl isocyanurate, or their ethyloxide adducts or propylene oxide adducts; polyhydric acrylates such as phenoxyacrylate, bisphenol A diacrylate, and their ethylene oxide adducts or propylene oxide adducts; polyhydric acrylates of glycidyl ethers such as glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, and triglycidyl isocyanurate; and melamine acrylate and at least one of the methacrylates corresponding to the above acrylates.

[0073] Compounds obtained by adding α,β-unsaturated carboxylic acids to polyhydric alcohols include, for example, ethylene glycol diacrylate, diethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, propylene glycol diacrylate, polypropylene glycol diacrylate, butylene glycol diacrylate, pentyl glycol diacrylate, 1,6-hexanediol diacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, tetramethylolmethane triacrylate, tetramethylolmethane tetraacrylate, glycerin diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and at least one of the methacrylates corresponding to the above acrylates.

[0074] Compounds obtained by adding an α,β-unsaturated carboxylic acid to a glycidyl group-containing compound include, for example, ethylene glycol diglycidyl ether diacrylate, diethylene glycol diglycidyl ether diacrylate, trimethylolpropane triglycidyl ether triacrylate, bisphenol A glycidyl ether diacrylate, phthalate diglycidyl ester diacrylate, glycerin polyglycidyl ether polyacrylate, etc.; and at least one of 2,2-bis(4-acryloyloxydiethoxyphenyl)propane, 2,2-bis-(4-acryloyloxypolyethoxyphenyl)propane, 2-hydroxy-3-acryloyloxypropyl acrylate, and each of the methacrylates corresponding to the above acrylates. The above photopolymerizable compounds can be used individually or in combination of two or more.

[0075] When the photosensitive resin composition contains an alkali-soluble resin, the amount of photopolymerizable compound added is preferably 5 to 100 parts by mass, more preferably 10 to 90 parts by mass, and even more preferably 15 to 85 parts by mass, based on solid content, per 100 parts by mass of the alkali-soluble resin. By using the above range of amounts, photocurability is improved, pattern formation becomes easier, and the mechanical strength of the cured product can also be improved.

[0076] Furthermore, urethane acrylate, polyester acrylate, and epoxy acrylate can be used as photopolymerizable compounds in the photosensitive resin composition (A) for the purpose of imparting toughness and other properties to the cured coating film. In addition, monofunctional (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, glycidyl methacrylate, and other (meth)acrylates, as well as acryloylmorpholine, can be used for purposes such as viscosity adjustment.

[0077] Examples of urethane acrylates include U-108A, UA-112P, UA-5201, UA-512, UA-412A, UA-4200, UA-4400, UA-340P, UA-2235PE, UA-160TM, UA-122P, UA-512, UA-W2, UA-7000, UA-7100, U-6HA, U-6H, U-15HA, UA-32P, U-324A, UA-7200 from Shin-Nakamura Chemical Industry Co., Ltd.; and from Arkema. CN968, CN9006, CN9010, CN962, CN963, CN964, CN965, CN980, CN981, CN982, CN983, CN996, CN9001, CN9002, CN9788, CN9893, CN978, CN9782, CN9783, CN929, CN944B85, CN989, CN9008; M-1100, M-1200, M-1210, M-1310, M-1600 manufactured by Toagosei Co., Ltd. UN-9000PEP, UN-9200A, UN-7600, UN-333, UN-1255, UN-6060PTM, UN-6060P, SH-500B manufactured by Negami Kogyo Co., Ltd.; AH-600, AT-600 manufactured by Kyoeisha Chemical Co., Ltd.; Evecryl 280, Evecryl 284, Evecryl 402, Evecryl 8402, Evecryl 8807, Evecryl 9270, Evecryl 264, Evecryl manufactured by Daicel Ornex Co., Ltd. 265, Ebekrill 1259, Ebekrill 8201, KRM8296, Ebekrill 294 / 25HD, Ebekrill 4820, Ebekrill 1290, Ebekrill 1290K, KRM8200, Ebekrill 5129, Ebekrill 8210, Ebekrill 8301, Ebekrill 8405; UN-3320HA, UN-3320HB, UN-3320HC, UN-3320HS, UN-904, UN-901T, UN-905, UN-952;Double bond's Doublemer 5212, Doublemer 5232B, Doublemer 541, Doublemer 5500, Doublemer 570, Doublemer 583-1, Doublemer 5812, Doublemer 5220, Doublemer 527, Doublemer 5400, Doublemer 553, Doublemer 5700, Doublemer 584, Doublemer 5900, Doublemer 5222, Doublemer 528, Doublemer 5405, Doublemer 554, Doublemer 571, Doublemer 588, Doublemer 850, Doublemer 523, Doublemer 530M, Doublemer 5433H, Doublemer Examples include the 564, Doublemer 576, Doublemer 594, Doublemer 87A, Doublemer 7200, Doublemer 7201M, Doublemer 7210, and 88A.

[0078] Polyester acrylates include: Aronics M-6100, M-6200, M-6250, M-6500, M-7100, M-7300K, M-8030, M-8060, M-8100, M-8530, M-8560, M-9050 from Toagosei Co., Ltd.; and Doublemer 2015, Doublemer 2231-TF, Doublemer 2319, Doublemer 257, Doublemer 276, Doublemer 284, Doublemer 2019, Doublemer 2232, Doublemer 236, Doublemer 270, Doublemer 278, Doublemer 285, Doublemer 220, Doublemer Examples include 2315-100, Doublemer 245, Doublemer 272, Doublemer 278X25, Doublemer 286, Doublemer 2230-TF, Doublemer 2315HM35, Doublemer 246, Doublemer 275, Doublemer 281, Doublemer 287, etc.

[0079] Epoxy (meth)acrylates include (meth)acrylates having a glycidyl group, as well as their modified forms. Examples of commercially available products include Double Bond's Doublemer 1283C, Doublemer 1700, Doublemer 1710, Doublemer 186, Doublemer 193-TP50, Doublemer 127-100, Doublemer 129, Doublemer 1701, Doublemer 1720, Doublemer 188, Doublemer 193, Doublemer 127-TP20, Doublemer 156, Doublemer 1702, Doublemer 176-TF, Doublemer 191, Doublemer 128, Doublemer 1636, Doublemer 1703, and Doublemer Examples include the 176TF-5, Doublemer 193A-TF, Doublemer 6MX75, and Doublemer 6MX75-E.

[0080] [Photopolymerization initiator] Examples of photopolymerization initiators that can be used in the photosensitive resin composition (A) include those that are known and commonly used. In particular, when used in the PEB step after light irradiation, described later, a photopolymerization initiator that also functions as a photobase generator is preferred. It is desirable to add a photopolymerization initiator if the photosensitive resin composition (A) contains a photopolymerizable alkali-soluble resin or a photopolymerizable compound. In this PEB step, a photopolymerization initiator and a photobase generator may be used in combination.

[0081] A photopolymerization initiator that also functions as a photobase generator is a compound that, upon irradiation with light such as ultraviolet or visible light, undergoes a change in molecular structure or molecular cleavage, thereby generating one or more basic substances that can function as catalysts for the polymerization reaction of thermosetting resins, as described later. Examples of basic substances include secondary amines and tertiary amines. Examples of such photopolymerization initiators that also function as photobase generators include α-aminoacetophenone compounds, oxime ester compounds, and compounds having substituents such as acyloxyimino groups, N-formylated aromatic amino groups, N-acylated aromatic amino groups, nitrobenzylcarbamate groups, and alkoxybenzylcarbamate groups. Among these, oxime ester compounds and α-aminoacetophenone compounds are preferred, with oxime ester compounds being more preferred. As for α-aminoacetophenone compounds, those having two or more nitrogen atoms are particularly preferred.

[0082] Any α-aminoacetophenone compound that has a benzoin ether bond in its molecule and undergoes intramolecular cleavage upon light irradiation, generating a basic substance (amine) that exhibits curing catalytic activity, is acceptable.

[0083] Any oxime ester compound that generates a basic substance upon light irradiation can be used as the oxime ester compound.

[0084] Such photopolymerization initiators may be used individually or in combination of two or more. The amount of photopolymerization initiator in the photosensitive resin composition is preferably 0.1 to 40 parts by mass, and more preferably 0.3 to 15 parts by mass, per 100 parts by mass of alkali-soluble resin, when the photosensitive resin composition contains alkali-soluble resin. When the amount is 0.1 parts by mass or more, a good contrast in developability between the irradiated and unirradiated areas can be obtained. When the amount is 40 parts by mass or less, the cured product properties are improved.

[0085] [Surfactants] The photosensitive resin composition (A) may contain a surfactant having a long-chain fatty acid group and a reactive group in its molecule. The surfactant is not particularly limited, and anionic, cationic, amphoteric, or nonionic surfactants can be used. It is preferable to use a surfactant that is solid at room temperature, and more preferably a fatty acid containing a heteroatom.

[0086] Any known compound can be used as the fatty acid containing a heteroatom; for example, in the present invention, a fatty acid amide dispersed in water can be used. The type of fatty acid amide can be any commonly used one. Specifically, saturated fatty acid monoamides such as lauric acid amide, palmitic acid amide, stearic acid amide, and behenic acid amide; unsaturated fatty acid monoamides such as oleic acid amide, erucic acid amide, and ricinoleic acid amide; substituted amides such as N-stearyl stearate amide, N-oleyl oleic acid amide, N-stearyl oleic acid amide, N-oleyl stearate amide, N-stearyl erucic acid amide, and N-oleyl palmitic acid amide; methylol stearate amide, methylol behenic acid amide, and methylene bis-stearate amide, ethylene bis-capric acid amide, and ethylene bis-laurate amide. Examples include saturated fatty acid bisamides such as ethylenebisstearate, ethylenebisisostearate, ethylenebishydroxystearate, ethylenebisbehenamide, hexamethylenebisstearate, hexamethylenebisbehenamide, hexamethylenebishydroxystearate, N,N'-distearyladipamide, and N,N'-distearylsebacinamide; unsaturated aliphatic bisamides such as ethylenebisoleamide, hexamethylenebisoleamide, and N,N'-dioleyladipamide; and aromatic bisamides such as m-xylylenebisstearate. These fatty acid amides may be used individually or in combination of two or more types.

[0087] (Block copolymer resin) In general, this block copolymer resin refers to a copolymer resin in which two or more polymer units with different properties are linked by covalent bonds to form a long chain molecular structure. In the present invention, known and conventional block copolymer resins can be used, and XY-type or ternary or more block copolymer resins are preferred, with XYX-type block copolymer resins being more preferred. In the XYX-type block copolymer resin, the Xs may be the same or different.

[0088] Furthermore, in the XY-type or XYX-type block copolymer resin, it is preferable that X is a polymer unit with a glass transition temperature Tg of 0°C or higher. More preferably, X is a polymer unit with a glass transition temperature Tg of 50°C or higher. Also, it is preferable that Y is a polymer unit with a glass transition temperature Tg of less than 0°C, and more preferably, a polymer unit with a glass transition temperature Tg of -20°C or lower. The glass transition temperature Tg is measured by differential scanning calorimetry (DSC).

[0089] The block copolymer resin is preferably solid at 25°C. It may also be solid at temperatures outside this range. Being solid at the above temperature results in excellent tackiness when formed into a dry film or when applied to a substrate and partially dried.

[0090] Furthermore, among XY-type or XYX-type block copolymer resins, it is preferable that X has high compatibility with thermosetting resins, and Y has low compatibility with thermosetting resins. In this way, by using a block copolymer resin in which the blocks at both ends are compatible with the matrix and the central block is incompatible with the matrix, it is thought that a unique structure can be easily observed within the matrix.

[0091] Specifically, the polymer unit X is preferably polymethyl methacrylate (PMMA), polystyrene (PS), etc., and the polymer unit Y is preferably poly-n-butyl (meth)acrylate (PBA), polybutadiene (PB), etc. Furthermore, by introducing hydrophilic units with excellent compatibility with alkali-soluble resins, such as styrene units, hydroxyl group-containing units, carboxyl group-containing units, epoxy group-containing units, N-substituted acrylamide units, etc., into a portion of the polymer unit X, compatibility can be further improved. Introducing epoxy group-containing units into a portion of the polymer unit X is particularly preferred. Among the above, the polymer unit X is preferably polystyrene, polyglycidyl methacrylate, or N-substituted polyacrylamide, polymethyl (meth)acrylate, or a carboxylic acid modified product or a hydrophilic group modified product thereof. Also, Y is preferably poly-n-butyl (meth)acrylate or polybutadiene, etc. X and Y may each be composed of one type of polymer unit, or they may be composed of polymer units of two or more components.

[0092] Examples of methods for producing block copolymer resins include the methods described in Japanese Patent Publication No. 2005-515281 and Japanese Patent Publication No. 2007-516326.

[0093] Commercially available XYX-type block copolymer resins include acrylic triblock copolymers manufactured using living polymerization by Arkema. These include SBM types, represented by polystyrene-polybutadiene-polymethyl methacrylate; MAM types, represented by polymethyl methacrylate-polybutyl acrylate-polymethyl methacrylate; and MAM N and MAM A types, which are carboxylic acid-modified or hydrophilic-modified. Examples of SBM types include E41, E40, E21, and E20; examples of MAM types include M51, M52, M53, and M22; examples of MAM N types include 52N and 22N; and examples of MAM A types include SM4032XM10, the Nanostrength® series, such as M52N and M65N. Clarity, manufactured by Kuraray Co., Ltd., is also a block copolymer derived from methyl methacrylate and butyl acrylate.

[0094] For obtaining the effects of the present invention, a block copolymer resin synthesized by living polymerization, in which the molecular structure is precisely controlled, is preferred. This is because block copolymer resins synthesized by living polymerization have a narrow molecular weight distribution, and the characteristics of each unit are clearly defined. The molecular weight distribution of the block copolymer resin used is preferably 2.5 or less, and more preferably 2.0 or less. The molecular weight distribution is calculated based on the ratio (Mw / Mn) of the mass-average molecular weight (Mw) to the number-average molecular weight (Mn), which is measured using the method described later.

[0095] The mass-average molecular weight Mw of the (A1) block copolymer resin of the present invention is preferably 20,000 to 400,000, and particularly preferably 80,000 to 350,000. When the mass-average molecular weight of the block copolymer resin is 20,000 or higher, the composition possesses mechanical properties such as flexibility and elasticity, while also exhibiting good improvements in flexibility and crack resistance without becoming excessively tacky. On the other hand, when the mass-average molecular weight is 400,000 or lower, the viscosity of the composition does not become excessively high, and the printability and developability are not significantly reduced.

[0096] In this invention, the mass-average molecular weight and number-average molecular weight are calculated using a GPC (gel permeation chromatography) apparatus "GL7700" manufactured by GL Sciences Co., Ltd., with α-2500 and α-4000 columns manufactured by Tosoh Corporation, and the eluents being a 10 mM lithium bromide solution of NMP and a 100 mM phosphoric acid solution of NMP, with polystyrene as the standard substance. The results refer to the polystyrene-equivalent molecular weight.

[0097] The block copolymer resin may be used alone or in combination of two or more types. When the photosensitive resin composition contains an alkali-soluble resin, the amount of block copolymer resin blended is preferably 1 to 60 parts by mass, more preferably 2 to 50 parts by mass, and particularly preferably 3 to 40 parts by mass, per 100 parts by mass of the alkali-soluble resin. When the amount of block copolymer resin blended is 1 part by mass or more, flexibility and heat resistance are improved, and when it is 60 parts by mass or less, a good balance between flexibility and heat resistance is obtained.

[0098] [Photosensitive resin composition (B)] The resin layer (B) is composed of a photosensitive resin composition (B) such that the third gloss value is 50 or higher. The photosensitive resin composition (B) generally contains an alkali-soluble resin such as a carboxyl group-containing resin, and further contains a thermosetting resin. The photosensitive resin composition (B) may also optionally contain a photopolymerizable compound and a photopolymerization initiator. In order to achieve the desired gloss value, the components of the photosensitive resin composition (B), such as resins and monomers, must be mutually compatible. That is, it does not contain combinations of components that exhibit the incompatibility described above.

[0099] The following describes the components that can be used in the photosensitive resin composition (B). (Alkali-soluble resin in photosensitive resin composition (B)) In the photosensitive resin composition (B), any known alkali-soluble resin can be used, but as specific examples of usable alkali-soluble resins, the alkali-soluble resins described in detail with respect to the photosensitive resin composition (A) can be used, provided that they meet the predetermined gross value.

[0100] (Thermosetting resin in photosensitive resin composition (B)) The photosensitive resin composition (B) includes a thermosetting resin. In the photosensitive resin composition (B), as long as a predetermined gross value is achieved, the same compound as the thermosetting resin in the photosensitive resin composition (A) is used, and a known and conventional compound having a functional group capable of curing by heat, such as a cyclic (thio) ether group, such as an epoxy compound, is preferably used. Furthermore, details of the photopolymerizable compounds and photopolymerization initiators that can be used as components of photosensitive resin composition (B) are as described in detail with respect to photosensitive resin composition (A).

[0101] The amount of photopolymerizable compound in the photosensitive resin composition (B) is preferably 1 to 100 parts by mass, and more preferably 5 to 80 parts by mass, per 100 parts by mass of alkali-soluble resin, when the photosensitive resin composition contains an alkali-soluble resin. In addition to the above, the photosensitive resin compositions (A) and (B) may further contain the following components:

[0102] (Inorganic fillers / extender pigments) Inorganic fillers and extender pigments can be added to suppress curing shrinkage of the cured product and improve properties such as adhesion and hardness. Examples of such inorganic fillers and extender pigments include barium sulfate, amorphous silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, titanium oxide, aluminum hydroxide, silicon nitride, aluminum nitride, boron nitride, and Neuburg Silica Earth.

[0103] (Thermosetting catalyst) A thermosetting catalyst may be incorporated into the photosensitive resin compositions (A) and (B) used in the laminate of the present invention. Examples of thermosetting catalysts include imidazole derivatives such as imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, and 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole; amine compounds such as dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, and 4-methyl-N,N-dimethylbenzylamine; hydrazine compounds such as adipic acid dihydrazide and sebacate dihydrazide; and phosphorus compounds such as triphenylphosphine. Examples of commercially available products include 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, and 2P4MHZ (all trade names for imidazole compounds) manufactured by Shikoku Chemicals, Inc., and U-CAT 3513N (trade name for a dimethylamine compound), DBU, DBN, and U-CAT SA 102 (all bicyclic amidine compounds and their salts) manufactured by Sunapro Co., Ltd. These can be used individually or in combination of two or more.

[0104] Furthermore, S-triazine derivatives such as guanamine, acetoguanamine, benzoguanamine, melamine, tetrahydrophthalic anhydride-added melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, and 2,4-diamino-6-methacryloyloxyethyl-S-triazine isocyanuric acid adduct can also be used, and preferably these compounds that also function as adhesion imparters are used in combination with the thermosetting catalyst. The thermosetting catalyst may be used alone or in combination of two or more types.

[0105] The amount of thermosetting catalyst blended is preferably 0.1 to 5 parts by mass, and more preferably 1 to 3 parts by mass, based on the solid content of the total amount of the photosensitive resin composition.

[0106] (Coloring agent) As colorants, commonly known and conventional colorants such as red, blue, green, yellow, white, and black can be used, and they may be pigments, dyes, or colorants.

[0107] (Organic solvents) Organic solvents can be added for the preparation of photosensitive resin compositions (A) and (B), or for viscosity adjustment for coating the substrate or the first film 1 (carrier film). Examples of such organic solvents include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, and petroleum-based solvents. Such organic solvents may be used individually or as a mixture of two or more.

[0108] (Other ingredients) If necessary, other components such as mercapto compounds, adhesion promoters, antioxidants, and UV absorbers may be added. These may be known and commonly used. Furthermore, known and commonly used additives such as fine silica, hydrotalcite, organic bentonite, and montmorillonite, as well as silicone-based, fluorine-based, and polymer-based defoamers and / or leveling agents, silane coupling agents, and rust inhibitors may be added.

[0109] (Manufacturing process for cured laminates) Below, an example of the processing steps for manufacturing the laminate of the present invention will be explained using Figure 3. Here, an example of manufacturing a cured product of the dry film shown in Figure 2 will be explained. [(a) Lamination process] As shown in Figure 3 (a) Lamination process, the laminate 10 of the invention is laminated by arranging the resin layer (B) facing the substrate 20, such as a printed circuit board having a conductive circuit 21, and pressing the substrate and the resin layer (B) together. On the other hand, in other applications, such lamination of electronic equipment may not be performed in advance. In this embodiment, each step of the curing treatment when the laminate is directly placed on the substrate will be described. Note that not all of the following steps are essential, and they should be selected as appropriate depending on the application and the composition of the laminate.

[0110] [(b) Exposure process] In curing the laminate of the present invention, an exposure process is performed. In the exposure process, the photopolymerization initiator or photobase generator, which functions as a photopolymerization initiator or photobase generator contained in the resin layer (A), the resin layer (B), or both, is activated in a negative pattern by irradiation with active energy rays (indicated by arrows in Figure 3(b)). As the exposure machine, a direct writing device or an exposure machine equipped with a metal halide lamp can be used. The patterned exposure mask is a negative type mask.

[0111] For exposure, it is preferable to use laser light or scattered light with a maximum wavelength in the range of 350 to 450 nm as the active energy beam. By setting the maximum wavelength within this range, the photopolymerization initiator can be efficiently activated. The exposure dose varies depending on the film thickness, but is usually 100 to 1500 mJ / cm². 2 It will be done at [location].

[0112] [(c) PEB process] After the exposure described above, the exposed area is cured by heating the resin layer. If the photosensitive resin compositions (A) and (B) of the present invention contain a photopolymerization initiator that functions as a photobase generator, or both a photopolymerization initiator and a photobase generator, the resin layer (B) can be cured to its depths by the base generated in the exposure step. The heating temperature is, for example, 80 to 200°C. The heating time is, for example, 10 to 100 minutes. When a heating step is performed after the exposure step in the presence of a photopolymerization initiator that functions as a photobase generator, or both a photopolymerization initiator and a photobase generator, this heat curing step is called a PEB (POST EXPOSURE BAKE) step, which suppresses curing shrinkage of the coating film after photolithography, resulting in excellent resolution.

[0113] [(d) Development process] If the above exposure step is performed, a development step is carried out. In the development step, unexposed areas are removed by alkaline development to form a negative-type patterned insulating film, particularly a coverlay and solder resist. As a development method, known methods such as dipping can be used. As a developer, sodium carbonate, potassium carbonate, potassium hydroxide, amines, imidazoles such as 2-methylimidazole, alkaline aqueous solutions such as aqueous solution of tetramethylammonium hydroxide (TMAH), or mixtures thereof can be used.

[0114] [(e) Post-cure process] Furthermore, after the development process, the cured laminate may be further irradiated with light, or it may be heated to, for example, 150°C or higher. The heating temperature is, for example, 80 to 170°C, and the heating time is 5 to 100 minutes. In the present invention, the post-curing of the laminate 10 is, for example, a ring-opening reaction of epoxy resin by thermal reaction, and therefore strain and curing shrinkage can be suppressed compared to when curing proceeds by a photoradical reaction.

[0115] [Component mounting process] After being developed as described above as necessary, the cured laminate of the present invention is subjected to a component mounting process (not shown). Through this process, various components are mounted on a substrate having the cured laminate of the present invention, thereby obtaining the electronic component of the present invention.

[0116] [Reheating process] The cured laminate after component mounting can be subjected to a reheating process (not shown). The heating temperature in the reheating process is, for example, 120°C to 300°C, particularly 250°C to 300°C, and the heating time is, for example, 5 minutes to 120 minutes. In addition, the insulating film may be further irradiated with light before or after the reheating process.

[0117] Even if the cured laminate of the present invention obtained in this way has its gloss value increased and the matte surface lost due to heat and pressure being applied to the cured laminate during the manufacturing process of the cured laminate, particularly during the component mounting process, the gloss value can be reduced again during the reheating process, resulting in a matte surface. Specifically, even if the gloss value of the outer surface of the cured laminate of the present invention becomes 50 or more, the gloss value of the outer surface can be reduced again to 30 or less by performing a reheating process at 260°C for 10 minutes.

[0118] In other words, since the cured product of the present invention has a matte finish on the outermost layer (outer surface) of the resin layer (A), scratches and other damage are less noticeable when the cured product is incorporated into electronic equipment and manufactured into a product, improving product yield and meeting the preference or demand for a matte appearance.

[0119] Furthermore, the laminated cured product of the present invention can effectively conceal the circuits of electronic devices such as printed circuit boards due to the presence of both resin layer (A) and resin layer (B). By using both resin layer (A) and resin layer (B), the concealment of the electronic device circuits is improved compared to using only one of resin layer (A) or resin layer (B). This is presumed to be due to the difference in refractive index resulting from the difference in the composition of the photosensitive resin compositions constituting resin layer (A) and resin layer (B). Since resin layer (A) is an incompatible layer, while resin layer (B) is a compatible layer, there is a difference in the refractive index of resin layer (A) and resin layer (B). When a laminated cured product having such a difference in refractive index between resin layer (A) and resin layer (B) is applied to a circuit, the circuit is sufficiently concealed.

[0120] The laminate of the present invention and the cured product obtained therefrom are applicable to rigid or flexible substrates, particularly printed circuit boards on which copper circuits are formed on a rigid substrate.

[0121] In this invention, "electronic components" refers to components used in electronic circuits, and includes not only active components such as printed circuit boards, transistors, light-emitting diodes, and laser diodes, but also passive components such as resistors, capacitors, inductors, and connectors. The laminated cured product of this invention provides these electronic components with mechanical properties as an insulating layer and a matte appearance.

[0122] The second embodiment of the present invention will be described in detail below. The laminate of the present invention comprises a resin layer (A) and a resin layer (B), wherein one surface of resin layer (B) is in contact with one surface of resin layer (A), and resin layer (A) comprises (A1) a block copolymer resin and (A2) a photopolymerizable compound, and resin layer (B) comprises (B1) an alkali-soluble (meth)acrylate resin.

[0123] The resin layers (A) and (B) of the laminate of the present invention are arranged in contact with each other and harden in this arrangement. In this unhardened laminate, the components of resin layer (A) and resin layer (B) mix at the interface, particularly through the heating process. As the components of resin layer (A) and resin layer (B) mix in this way, diffuse reflection of visible light occurs at the interface, which is presumed to result in a hardened film with excellent circuit concealment. Furthermore, since good circuit concealment can be obtained by using the laminate of the present invention, there is no need to use a roughened plastic film as the first film as in the conventional technology, and it is thought that there will be no decrease in resolution due to the unevenness of the support. Moreover, unlike the conventional technology, the laminate of the present invention does not have an uneven state throughout the resin layer, so it also has excellent mechanical strength. Therefore, by using the laminate of the present invention, it is possible to achieve both circuit concealment and mechanical strength and resolution.

[0124] [Resin layer (A)] The resin composition constituting the resin layer (A) includes the following components. ((A1) Block copolymer resin) The block copolymer resin used in the resin layer (A) can be the same as that described in the first embodiment above. Both XY-type and XYX-type block copolymer resins can be used, but XYX-type block copolymer resin is preferred. Furthermore, the block copolymer resin preferably has a mass-average molecular weight Mw of 20,000 to 400,000, and more preferably 80,000 to 350,000. The mass-average molecular weight is measured using the method described above. More preferably, it is an XYX type block copolymer resin, and it is preferable that the mass-average molecular weight is 20,000 to 400,000, and particularly preferably 80,000 to 350,000. (A1) The amount of block copolymer resin blended is preferably in the range of 1 to 30 parts by mass, and more preferably 2 to 20 parts by mass, relative to the solid content of the resin layer (A). The effect can be expected with 1 part by mass or more, and with 30 parts by mass or less, the photocurable resin composition will have good developability and coatability.

[0125] ((A2) Photopolymerizable compound) The photopolymerizable compound used in the resin layer (A) can be the same as that described in the first embodiment above. In particular, a photopolymerizable compound represented by the following general formula (I) is preferably used. [ka] (In general formula (I), R1 represents a hydrogen atom or a methyl group.) (A2) The amount of photopolymerizable compound blended is preferably 1% to 40% by mass, more preferably 1% to 30% by mass, and even more preferably 1.5% to 20% by mass, relative to the solid content of the resin layer (A). By using the above blending range, photocurability is improved, pattern formation becomes easier, and the strength of the cured film can also be improved.

[0126] The following describes any other optional components that can be included in the resin layer (A). ((A3) Epoxy resin) As the epoxy resin, the same epoxy resin as described in the first embodiment above can be used. In particular, bisphenol A type epoxy resin and / or novolac type epoxy resin can be preferably used.

[0127] In the resin layer (A), the epoxy resin can be added in any amount, but a range of 10 to 40% by mass relative to the solid content of the resin layer (A) is a guideline, and 15 to 30% by mass is preferred. By using this range of blending ratio, development is improved, and fine patterns can be formed easily and with high precision.

[0128] ((A4) Photopolymerization initiator) As the photopolymerization initiator, a photopolymerization initiator similar to that described in the first embodiment above can be used. Preferably, one or more photopolymerization initiators selected from the group consisting of oxime ester-based photopolymerization initiators having an oxime ester group, α-aminoacetophenone-based photopolymerization initiators, and acylphosphine oxide-based photopolymerization initiators are used.

[0129] The amount of photopolymerization initiator added is preferably 0.1% to 20% by mass, and more preferably 1% to 10% by mass, relative to the solid content of the resin layer (A). If the amount is 0.1% by mass or more, the photocurability is improved, the adhesion of the coating film to the substrate is good, and the coating film properties such as chemical resistance are also improved. On the other hand, if the amount is 20% by mass or less, the outgassing effect can be obtained.

[0130] [Resin layer (B)] The resin composition constituting the resin layer (B) includes the following components. ((B1) Alkali-soluble (meth)acrylate resin) The (B1) alkali-soluble (meth)acrylate resin used in the present invention is preferably one that contains a carboxyl group and a (meth)acryloyl group in its molecule, or a derivative thereof. Specific examples of the (B1) alkali-soluble (meth)acrylate resin include the compounds listed below (which may be oligomers or polymers).

[0131] (1) An alkali-soluble urethane-based (meth)acrylate resin obtained by polyaddition reaction of a diisocyanate such as aliphatic diisocyanate, branched aliphatic diisocyanate, alicyclic diisocyanate, or aromatic diisocyanate with a (meth)acrylate or a partially acid anhydride modified thereof of a difunctional epoxy resin such as bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenol type epoxy resin, or biphenol type epoxy resin, with a carboxyl group-containing dialcohol compound and a diol compound.

[0132] (2) An alkali-soluble urethane-based (meth)acrylate resin obtained by adding a compound having one hydroxyl group and one or more (meth)acryloyl groups in the molecule, such as hydroxyalkyl (meth)acrylate, during the synthesis of the resin in (1) above, and then (meth)acrylizing the terminals.

[0133] (3) An alkali-soluble urethane-based (meth)acrylate resin obtained by adding a compound having one isocyanate group and one or more (meth)acryloyl groups in its molecule, such as an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate, to the synthesis of the resin in (1) above, and then (meth)acrylizing the terminals.

[0134] (4) An alkali-soluble (meth)acrylate resin obtained by reacting a bifunctional or polyfunctional epoxy resin with (meth)acrylic acid and adding a dibasic acid anhydride to the hydroxyl groups present in the side chain.

[0135] (5) A polyfunctional epoxy resin obtained by reacting a bifunctional epoxy resin with epichlorohydrin to further epoxidize the hydroxyl groups of a bifunctional epoxy resin with (meth)acrylic acid, and then adding a dibasic acid anhydride to the resulting hydroxyl groups, thereby obtaining an alkali-soluble (meth)acrylate resin.

[0136] (6) An alkali-soluble (meth)acrylate resin obtained by reacting a reaction product obtained by reacting a compound having multiple phenolic hydroxyl groups in one molecule with an alkylene oxide such as ethylene oxide or propylene oxide with (meth)acrylic acid, and then reacting the resulting reaction product with a polybasic acid anhydride.

[0137] (7) An alkali-soluble (meth)acrylate resin obtained by reacting a reaction product obtained by reacting a compound having multiple phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate with (meth)acrylic acid, and then reacting the resulting reaction product with a polybasic acid anhydride.

[0138] (8) An alkali-soluble (meth)acrylate resin obtained by adding a compound having one epoxy group and one or more (meth)acryloyl groups in one molecule to the resins of (1) to (7) above. In this specification, (meth)acrylate is a general term referring to acrylates, methacrylates, and mixtures thereof, and the same applies to other similar expressions.

[0139] As described above, (B1) alkali-soluble (meth)acrylate resins have numerous carboxyl groups in the side chains of the backbone polymer, making them developable with dilute alkaline aqueous solutions. Furthermore, the acid value of (B1) alkali-soluble (meth)acrylate resin is suitable in the range of 40 to 200 mg KOH / g, and more preferably in the range of 45 to 120 mg KOH / g. When the acid value of (B1) alkali-soluble (meth)acrylate resin is 40 mg KOH / g or higher, alkali development is performed well, while by setting it to 200 mg KOH / g or lower, dissolution of the exposed areas by the developer does not occur, the lines do not thin more than necessary, the distinction between exposed and unexposed areas is maintained, and a normal resist pattern is drawn without dissolution or peeling by the developer.

[0140] Furthermore, the mass-average molecular weight of (B1) alkali-soluble (meth)acrylate resin varies depending on the resin skeleton, but is generally preferred to be in the range of 1,000 to 150,000, and even more preferably in the range of 2,000 to 100,000. When the mass-average molecular weight is 2,000 or more, tack-free performance is good, the moisture resistance of the coating film after exposure is sufficient, development proceeds as designed, and resolution is improved. On the other hand, when the mass-average molecular weight is 150,000 or less, excellent developability is stably obtained, and storage stability is also good.

[0141] The appropriate amount of such (B1) alkali-soluble (meth)acrylate resin is 20 to 80% by mass, preferably 30 to 70% by mass, relative to the solid content of the resin composition constituting the resin layer (B). When the amount of (B1) alkali-soluble (meth)acrylate resin is 20% by mass or more, the film strength is improved. On the other hand, setting it to 80% by mass or less is preferable because it results in good viscosity of the composition and improved coatability.

[0142] These (B1) alkali-soluble (meth)acrylate resins are not limited to those listed above and can be used individually or as a mixture of multiple types. Among alkali-soluble (meth)acrylate resins, those having an aromatic ring are preferred because they have a high refractive index and excellent resolution, and those having a novolac structure are preferred not only because of their resolution but also because they have excellent PCT and crack resistance. Among these, alkali-soluble (meth)acrylate resins that use phenol compounds such as (6) and (7) as starting materials are suitable because they have excellent HAST and PCT resistance.

[0143] In the present invention, (B1) alkali-soluble (meth)acrylate resin (component (B1)) is considered to be incompatible with at least one of the (A1) block copolymer resin (component (A1)) and the (A2) photopolymerizable compound (component (A2)) contained in the resin layer (A). That is, a mixture of components (A1), (A2), and (B1), or a mixture of resin compositions for forming resin layers (A) and (B) containing these components, forms an incompatible mixture at the interface between resin layer (A) and resin layer (B). As a result, the interface between the two layers loses its smoothness and develops irregularities. When visible light is incident on this irregular interface, diffuse reflection of visible light occurs, effectively concealing the circuits of electronic components. In this way, it is presumed that the laminate of the present invention exhibits good circuit concealment.

[0144] The following describes any other optional components that can be included in the resin layer (B). ((B2) Epoxy resin) The resin composition constituting the resin layer (B) preferably includes (B2) epoxy resin. The (B2) epoxy resin can be the same as the (A3) epoxy resin described above as a component of the resin layer (A). The (A3) epoxy resin and (B2) epoxy resin used in the resin layers (A) and (B) of the laminate may be of the same type or different types. Furthermore, when multiple types of epoxy resin are used in either or both of the resin layers (A) and (B), some of them may be of the same type.

[0145] The amount of epoxy resin (B2) in resin layer (B) may be any amount, but it is generally considered to be in the range of 10 to 40% by mass, and preferably 15 to 30% by mass, relative to the total solid content of the resin composition constituting resin layer (B).

[0146] By using this range of mixing ratios, development becomes smoother, and fine patterns can be easily and accurately formed.

[0147] [Optional components of resin layer (A) and resin layer (B)] The resin layer (A) and resin layer (B) may also contain other optional components. The optional components that the resin layer (A) and resin layer (B) may contain are the same components as those described in the first embodiment described above.

[0148] (Laminate manufacturing process) As the manufacturing process for the laminate and the manufacturing process for the cured product according to the second embodiment of the present invention, the same processes as those described above for the manufacturing process for the laminate and the manufacturing process for the cured product can be appropriately selected and used. In this invention, the film thickness of the resin layer (B) after coating and drying is generally 1 to 150 μm, preferably 3 to 120 μm, and the film thickness of the resin layer (A) is generally 0.5 to 50 μm, preferably 2 to 30 μm, with the total film thickness of both being 5 to 150 μm. Furthermore, it is preferable that the film thickness of the resin layer (B) is greater than the film thickness of the resin layer (A).

[0149] As described in detail above, the laminated cured product of the present invention provides mechanical properties as an insulating layer for electronic components and good circuit concealment. [Examples]

[0150] The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to the following examples. Unless otherwise specified, the values ​​of "parts" and "%" in these examples and comparative examples are based on mass.

[0151] [Examples 1-1 to 1-7 (First Embodiment) and Comparative Examples 1-1 to 1-6]

[0152] 1. Synthesis of resin components (Synthesis Example 1-1: Polyamide-imide resin solution containing carboxyl groups (Resin 1-1)) In a 300 mL four-necked flask equipped with a nitrogen gas inlet tube, thermometer, and stirrer, 29.49 g (0.054 mol) of an aliphatic diamine derived from a C36 dimer acid (Croda Japan, product name PRIAMINE1075) as dimer amine (a), 4.02 g (0.026 mol) of 3,5-diaminobenzoic acid as carboxyl group-containing diamine (b), and 73.5 g of γ-butyrolactone were charged and dissolved at room temperature.

[0153] Next, 31.71 g (0.160 mol) of cyclohexane-1,2,4-tricarboxylic acid anhydride (c) and 1.54 g (0.008 mol) of trimellitic anhydride (d) were charged and held at room temperature for 30 minutes. Then, 30 g of toluene was charged, the temperature was raised to 160°C, and after removing the water produced with the toluene, the mixture was held for 3 hours and cooled to room temperature to obtain a solution containing the imidide.

[0154] To the solution containing the obtained imidide, 6.90 g (0.033 mol) of trimethylhexamethylene diisocyanate and 8.61 g (0.033 mol) of dicyclohexylmethane diisocyanate were charged as diisocyanate compound (e), and the mixture was held at 160°C for 32 hours. Dilution with 36.8 g of cyclohexanone yielded a solution (A-2) containing polyamide-imide resin. The obtained polyamide-imide resin had a mass-average molecular weight Mw of 5840, a solid content of 40.4% by mass, an acid value of 62 mg KOH / g, and a dimer amine (a) content of 40.1% by mass.

[0155] (Synthesis Example 1-2: Synthesis of a polyimide resin solution (Resin 1-2) having phenolic hydroxyl groups and carboxyl groups) In a separable three-necked flask equipped with a stirrer, nitrogen inlet tube, fractional distillation ring, and condenser ring, 22.4 g of 3,3'-diamino-4,4'-dihydroxydiphenylsulfone, 8.2 g of 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, 30 g of NMP, 30 g of γ-butyrolactone, 27.9 g of 4,4'-oxydiphthalic anhydride, and 3.8 g of trimellitic anhydride were added, and the mixture was stirred at 100 rpm at room temperature under a nitrogen atmosphere for 4 hours. Then, 20 g of toluene was added, and the mixture was stirred for 4 hours at 150 rpm in a silicone bath at a temperature of 180°C while distilling off the toluene and water to obtain a polyimide resin solution (resin 1-2) having phenolic hydroxyl groups and carboxyl groups. The acid value of the obtained resin (solid content) was 18 mg KOH, Mw was 10,000, and hydroxyl group equivalent was 390.

[0156] (Synthesis Example 1-3: Synthesis of a carboxyl group-containing resin having a bisphenol F-type skeleton (Resin 1-3)) In the general formula (I) below, X is CH2 and the average degree of polymerization n is 6.2. 380 parts of bisphenol F type epoxy resin (epoxy equivalent 950 g / eq, softening point 85°C) and 925 parts of epichlorohydrin were dissolved in 462.5 parts of dimethyl sulfoxide, and then 60.9 parts of 98.5% NaOH were added over 100 minutes at 70°C under stirring.

[0157] [ka]

[0158] After the above addition, the reaction was carried out at 70°C for 3 hours. After the reaction was complete, 250 parts of water were added and the mixture was washed. After oil-water separation, most of the dimethyl sulfoxide and excess unreacted epichlorohydrin were recovered from the oil layer by distillation under reduced pressure. The reaction product containing the remaining by-product salt and dimethyl sulfoxide was dissolved in 750 parts of methyl isobutyl ketone, and 10 parts of 30% NaOH were added, and the mixture was reacted at 70°C for 1 hour. After the reaction was complete, the mixture was washed twice with 200 parts of water. After oil-water separation, methyl isobutyl ketone was recovered from the oil layer by distillation to obtain epoxy resin (a1) with an epoxy equivalent of 310 g / eq and a softening point of 69°C. Based on the epoxy equivalent, the obtained epoxy resin (a1) had approximately 5 of the 6.2 alcoholic hydroxyl groups in the bisphenol F type epoxy resin of the starting material epoxidized. 310 parts of epoxy resin (a1) and 282 parts of carbitol acetate were placed in a flask, heated and stirred at 90°C, and dissolved. The resulting solution was cooled to 60°C, and 72 parts (1 mole) of acrylic acid, 0.5 parts of methylhydroquinone, and 2 parts of triphenylphosphine were added. The mixture was heated to 100°C and reacted for approximately 60 hours to obtain a reaction product with an acid value of 0.2 mgKOH / g. To this, 140 parts (0.92 moles) of tetrahydrophthalic anhydride were added, and the mixture was heated to 90°C to carry out the reaction, yielding a carboxyl group-containing resin (resin 1-3). The solid content concentration of the obtained carboxyl group-containing resin varnish was 62% by mass, and the solid content acid value (mgKOH / g) was 100.

[0159] (Synthesis Example 1-4: Synthesis of a carboxyl group-containing resin having a bisphenol A type skeleton (Resin 1-4)) In the general formula (I) described above, X is C(CH3)2 and the average degree of polymerization n is 3.3. 371 parts of bisphenol A type epoxy resin (epoxy equivalent 650 g / eq, softening point 81.1°C) and 925 parts of epichlorohydrin were dissolved in 462.5 parts of dimethyl sulfoxide. Then, under stirring at 70°C, 52.8 parts of 98.5% NaOH were added over 100 minutes. After the addition, the reaction was carried out at 70°C for a further 3 hours. After the reaction was complete, 250 parts of water were added and the mixture was washed. After oil-water separation, most of the dimethyl sulfoxide and excess unreacted epichlorohydrin were recovered from the oil layer by distillation under reduced pressure. The remaining by-product salt and reaction product containing dimethyl sulfoxide were dissolved in 750 parts of methyl isobutyl ketone, and 10 parts of 30% NaOH were added. The mixture was then reacted at 70°C for 1 hour. After the reaction was complete, the mixture was washed twice with 200 parts of water. After oil-water separation, methyl isobutyl ketone was recovered by distillation from the oil layer to obtain epoxy resin (a2) with an epoxy equivalent of 287 g / eq and a softening point of 64.2°C. Based on the epoxy equivalent, the obtained epoxy resin (a2) had approximately 3.1 of the 3.3 alcoholic hydroxyl groups in the starting material, bisphenol A type epoxy resin, epoxidized. 310 parts of this epoxy resin (a2) and 282 parts of carbitol acetate were placed in a flask and heated and stirred to 90°C to dissolve. The resulting solution was cooled to 60°C, and 72 parts (1 mole) of acrylic acid, 0.5 parts of methyl hydroquinone, and 2 parts of triphenylphosphine were added. The mixture was heated to 100°C and reacted for approximately 60 hours to obtain a reaction product with an acid value of 0.2 mg KOH / g. To this, 140 parts (0.92 moles) of tetrahydrophthalic anhydride were added and heated to 90°C to carry out the reaction, yielding a carboxyl group-containing resin (resin 1-4). The solid content concentration of the obtained carboxyl group-containing resin varnish was 62% by mass, and the solid content acid value (mgKOH / g) was 100.

[0160] (Synthesis Example 1-5: Synthesis of photosensitive resins (Resin 1-5) possessing both ethylenic double bonds and carboxyl groups) 220 parts of cresol novolac epoxy resin (DIC Corporation, EPICLON N-695, epoxy equivalent: 220) were placed in a four-necked flask equipped with a stirrer and reflux condenser, and 214 parts of carbitol acetate were added and heated until dissolved. Next, 0.1 parts of hydroquinone as a polymerization inhibitor and 2.0 parts of dimethylbenzylamine as a reaction catalyst were added. This mixture was heated to 95-105°C, and 72 parts of acrylic acid were gradually added dropwise, and the mixture was reacted for 16 hours. The reaction product was cooled to 80-90°C, 106 parts of tetrahydrophthalic anhydride were added, and the mixture was reacted for 8 hours. After cooling, the product was removed.

[0161] The photosensitive resins (resins 1-5) obtained in this manner, possessing both ethylenic double bonds and carboxyl groups, had a non-volatile content of 65%, a solid acid value of 100 mgKOH / g, and a mass-average molecular weight Mw of approximately 3,500.

[0162] (Synthesis Examples 1-6: Synthesis of tetrahydrophthalic anhydride-added melamine) 800 ml of deionized water was placed in a 2-liter beaker, a stirring bar was added, and the mixture was brought to a boil while stirring on a hot plate stirrer. 12.6 g of melamine was added to this hot water and completely dissolved. 500 ml of deionized water was placed in a 1-liter beaker, a stirring bar was added, and the mixture was brought to a boil while stirring on a hot plate stirrer. 15.2 g of tetrahydrophthalic anhydride was added to this hot water, and the mixture was heated and stirred for 1 hour to obtain an aqueous solution of tetrahydrophthalic acid. This aqueous solution was added to the melamine aqueous solution and stirred. When this mixture was cooled with ice water, crystals precipitated. After filtering off these crystals, the mixture was dried in a vacuum dryer to obtain the melamine compound.

[0163] 2. Preparation of photosensitive resin compositions a to f The resins 1-1 to 1-5 obtained from the above synthesis example and other components were blended in the compositions shown in Table 1 below. After pre-mixing each component with a stirrer, the mixture was kneaded in a three-roll mill to prepare photosensitive resin compositions a to f. Details of the components other than resins 1-1 to 1-5 are described below Table 1.

[0164] [Table 1]

[0165] *The proportions of each component in Table 1 above are based on solid content. [Alkali-soluble resin] Resin 1-1: Prepared according to Synthesis Example 1 (polyamide-imide resin having carboxyl groups) Resin 1-2: Prepared according to Synthesis Example 1-2 (Polyimide resin having phenolic hydroxyl groups and carboxyl groups) Resin 1-3: Prepared according to Synthesis Example 1-3 (Carboxyl group-containing resin having a bisphenol F type skeleton) Resin 1-4: Prepared according to Synthesis Example 1-4 (Carboxyl group-containing resin having a bisphenol A type skeleton) Resin 1-5: Prepared according to Synthesis Example 1-5 (Photosensitive resin possessing both ethylenic double bonds and carboxyl groups) [Fatty Acid Amide] Nikkaamide S: N-Stearyl Stearic Acid Amide (Mitsubishi Chemical Corporation) • Nikkaamide OS: N-oleyl stearate amide (Mitsubishi Chemical Corporation) [Photopolymerization initiator] • IRGACURE OXE02: Oxime-based photopolymerization initiator (manufactured by BASF Japan Ltd.) [Photopolymerizable compound] • KRM8296: Trifunctional urethane acrylate (manufactured by Daicel Ornex Co., Ltd.) • DPHA: Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) [Thermosetting resin] • YDF-2004: Bisphenol F type epoxy resin (manufactured by Nippon Steel Chemical & Material Co., Ltd.) • EPICLON 860: Bisphenol A type epoxy resin (manufactured by DIC Corporation) • YDC-1312: 2,5-t-butylhydroquinone type epoxy resin (manufactured by Nippon Steel Chemical & Material Co., Ltd.) • N-655: Cresol novolac type epoxy resin (manufactured by DIC Corporation) • TEPIC-S: Triglycidyl isocyanurate (manufactured by Nissan Chemical Corporation) [Thermosetting catalyst] • THPA melamine: Tetrahydrophthalic anhydride-added melamine (prepared according to synthesis examples 1-6) [Body pigments] • Variace B-31: Barium sulfate (manufactured by Sakai Chemical Industry Co., Ltd.)

[0166] 3. Fabrication of test substrates 3-1. Preparation of dry film Photosensitive resin compositions a to f were adjusted to the same viscosity with the organic solvent MEK. The resin compositions described as resin layer (A) in Tables 2 and 3 below were applied to the first film (material: polyethylene terephthalate, thickness: 25 μm, surface roughness (Ra): 0.03 μm or 0.3 μm) described in Tables 2 and 3 so that the film thickness after drying was as described in the same table, and dried at 90°C for 15 minutes using a hot air circulating drying oven. Next, the resin compositions described as resin layer (B) in Tables 2 and 3 were applied to the dried resin layer (A) so that the film thickness after drying was as described in the same table, and dried at 80°C for 30 minutes. As a result, a laminate having resin layer (A) and resin layer (B) in order was obtained on the first film. Next, a stretched polypropylene film was laminated onto resin layer (B) as the second film to obtain the dry films of each example and comparative example. In the case of single-layer films, as shown in Comparative Examples 1-1 to 1-3, only the resin layer (A) was applied, and then the second film was laminated onto the resin layer (A) to form a dry film. In Comparative Example 1-2, since matte PET (PTHA-25, manufactured by Unitika Ltd., surface roughness Ra: 0.3 μm) is used as the first film, the irregularities of the matte PET are transferred to the resin layer (A), and as a result, the resin layer (A) has a physically roughened surface.

[0167] 3-2. Preparation of the first and second substrates for measuring gross values. After peeling off the second film of the dry film prepared as described above, the film was laminated in the first chamber at 80°C under the conditions of a vacuum pressure of 3 hPa and a vacuum time of 30 seconds using a vacuum laminator (CVP-300: manufactured by Nikko Material Co., Ltd.). Then, it was pressed under the conditions of a press pressure of 0.5 MPa and a press time of 30 seconds to bond the resin layer (B) to the printed circuit board so that it was in contact with the printed circuit board, thereby creating the first and second substrates for measuring the gross value.

[0168] The first and second substrates for measuring gross values ​​obtained as described above were subjected to an integrated exposure of 250 mJ / cm² using an ORC HMW 680GW vacuum contact double-sided exposure machine manufactured by Oak Corporation. 2 Under these conditions, ultraviolet light was irradiated from the resin layer (A) side (exposure process). Next, the first film provided on each side of the resin layer (A) was removed, and the gloss value measured on the outer surface of the resin layer (A) thereafter was taken as the first gloss value. After removing the first film mentioned above, the resin layer (A) was heat-cured at 150°C for 60 minutes, and the gloss value measured on the outer surface of the resin layer (A) was taken as the second gloss value. Furthermore, this test substrate was pressed using a KVHC-PRESS vacuum press (manufactured by Kitagawa Seiki) at a pressure of 3 MPa and a temperature of 170°C for 30 minutes (hot pressing process). The laminated material after this hot pressing process was then reheated at 260°C for 10 minutes (reheating process).

[0169] 3-3. Creation of a third substrate for measuring gross values After peeling off the first film of the dry film prepared as described above, the resin layer (A) was laminated onto the printed circuit board using a vacuum laminator so that it was in contact with the printed circuit board, thereby creating a third substrate for measuring the gloss value. For the single-layer dry films of Comparative Examples 1-1 to 1-3, the first film was peeled off, and then the resin layer (A) was laminated so that the surface of the resin layer (A) on the first film side was in contact with the printed circuit board.

[0170] The third substrate for measuring the gross value obtained as described above was subjected to an integrated exposure of 250 mJ / cm² using an Oak Corporation vacuum contact double-sided exposure machine (model number ORC HMW 680GW).2 Under these conditions, ultraviolet light was irradiated from the resin layer B side (exposure process). Next, the second film provided on the resin layer (B) side was removed, and the material was heat-cured at 150°C for 60 minutes. The gloss value measured on the outer surface of the resin layer (B) was taken as the third gloss value.

[0171] 4. Measurement of Gross Value The gloss values ​​of the first, second, and third measurement substrates, as well as the gloss value of the outer surface of the resin layer (A) after the hot pressing and reheating processes, were measured using a "micro-TRI-gloss" gloss meter (manufactured by BYK Additives & Instruments) at an incident angle of 60°. The measurement results are shown in Tables 2 and 3.

[0172] 5. Evaluation of Gross Value Based on the above measurement results, the gloss value of the resin layer (A) surface of the test substrate, which had been completely cured by the above process, was comprehensively evaluated as an indicator of its matte appearance. The criteria for the overall gloss value evaluation are as follows: ◎: After heat pressing, reheating will bring the gross value back down to 30 or below. ×: The gross value exceeds 30 even after reheating. The results are presented in accordance with Tables 2 and 3.

[0173] 6. Solder heat resistance evaluation For the second gross value measurement, a rosin-based flux was applied to the heat-cured substrate and immersed for 10 seconds in a solder bath pre-set to 260°C and 280°C. The occurrence of lifting, blistering, and peeling of the cured coating was evaluated. The evaluation criteria are as follows. ◎: No floating, swelling, or peeling occurred during immersion at either 260℃ or 280℃. ○: No floating, swelling, or peeling occurred when immersed at 260°C, but floating, swelling, and peeling occurred when immersed at 280°C. ×: Lifting and peeling occurred in both immersion at 260℃ and 280℃.

[0174] 7. Evaluation of fracture strength For the second gross value measurement, the cured resin layer was peeled off the thermosetting substrate and used as a test specimen for fracture strength evaluation. The fracture strength of this test specimen was measured and evaluated in accordance with JIS K7127. The evaluation criteria are as follows: ◎: 40 MPa or higher ○: 30 MPa or higher, less than 40 MPa ×: Less than 30 MPa

[0175] 8. Surface hardness (pencil hardness) evaluation For the second measurement of the gross value, the cured resin layer was peeled off the thermosetting substrate and used as a test specimen for surface hardness evaluation. The cured coating on the test specimen was tested according to the test method of JIS K 5600-5-4:1999, and the highest hardness at which the coating could not be scratched was measured.

[0176] 9. Circuit Concealment Evaluation Using the same test specimens as those used in the solder heat resistance evaluation method described above, circuit concealment was evaluated by visual observation from a distance of 30 cm. The evaluation criteria are as follows: ◎: The circuit is not visible. ○: Part of the circuit is visible. ×: The circuit can be clearly seen.

[0177] 10. Resolution evaluation (evaluation of minimum aperture diameter) The first film of the dry film prepared by the method described above was peeled off, and the resin layer (A) was vacuum laminated so that it was in contact with the printed circuit board. Then, ultraviolet light was irradiated from the resin layer (A) side using an ORC HMW 680GW vacuum contact double-sided exposure machine (model number ORC HMW 680GW) via a step tablet (Kodak No. 2). Furthermore, the first film was removed from the resin layer (A) of the test substrate, and development (30°C, 0.2 MPa, 1 wt% Na2CO3 aqueous solution) was performed for 60 seconds. For each measurement sample, the light intensity corresponding to the density of the 5th step of the step tablet in the remaining portion after development was set as the optimal exposure amount. Similarly, the first film of the dry film was peeled off, and the resin layer (A) was vacuum laminated so that it was in contact with the printed circuit board. Then, a negative pattern with via aperture diameters of 500 μm, 300 μm, 150 μm, 100 μm, and 80 μm was placed on the outer surface of the resin layer (A) as a negative mask for resolution evaluation, and ultraviolet light was irradiated through this using an ORC HMW 680GW vacuum contact double-sided exposure machine at the optimal exposure level. Furthermore, the first film was removed from the resin layer (A) of the test substrate, and development (30°C, 0.2 MPa, 1 wt% Na2CO3 aqueous solution) was performed for 60 seconds. A test substrate with a cured dry film (laminated or single-layer film) was fabricated by heat curing at 150°C for 60 minutes. On this substrate, the pattern apertures were observed by SEM and the minimum aperture diameter was determined. The results of the mechanical properties measurement should be recorded in accordance with Tables 2 and 3.

[0178] [Table 2]

[0179] [Table 3]

[0180] As described above, according to the embodiments of the present invention, in addition to the matte finish of the outer surface of the cured laminate, excellent values ​​were shown for surface hardness, solder heat resistance, fracture strength, and circuit concealment of the cured product. In contrast, in none of the comparative examples 1-1 to 1-3 of the single-layer structure or comparative examples 1-4 to 1-6 of the laminate structure were satisfactory results obtained in terms of both mechanical properties and low gloss value of the surface (corresponding to the outer surface of the laminate of the present invention).

[0181] [Examples 2-1 to 2-12 (Second Embodiment) and Comparative Examples 2-1 to 2-3] <Preparation of resin composition> 1. Synthesis of resin components [Synthesis Example 2-1: Synthesis of a polyimide resin solution (Resin 2-1) having phenolic hydroxyl groups and carboxyl groups] A polyimide resin solution (resin 2-1) having phenolic hydroxyl groups and carboxyl groups was obtained by the same method as in Synthesis Example 1-2 in the first embodiment described above.

[0182] [Synthesis Example 2-2: Synthesis of Carboxylate Group-Containing Novolac-Type Acrylate Resin (Resin 2-2)] In an autoclave equipped with a thermometer, a nitrogen introduction device / alkylene oxide introduction device, and a stirring device, 119.4 g of novolac-type cresol resin (manufactured by Aica Kogyo Co., Ltd., product name "Schonoru CRG951", OH equivalent: 119.4), 1.19 g of potassium hydroxide, and 119.4 g of toluene were charged. The system was then heated and the temperature increased while stirring and purging with nitrogen. Next, 63.8 g of propylene oxide was gradually added dropwise, at a temperature of 125-132°C and a rate of 0-4.8 kg / cm³. 2The reaction was carried out for 16 hours. After cooling to room temperature, 1.56 g of 89% phosphoric acid was added to the reaction solution to neutralize the potassium hydroxide, yielding a propylene oxide reaction solution of novolac-type cresol resin with a non-volatile content of 62.1% and a hydroxyl value of 182.2 g / eq. This solution had an average of 1.08 moles of alkylene oxide added per equivalent of phenolic hydroxyl groups. Next, 293.0 g of the obtained alkylene oxide reaction solution of novolac-type cresol resin, 43.2 g of acrylic acid, 11.53 g of methanesulfonic acid, 0.18 g of methylhydroquinone, and 252.9 g of toluene were charged into a reactor equipped with a stirrer, thermometer, and air blowing tube, and the reaction was carried out at 110°C for 12 hours while blowing air at a rate of 10 ml / min and stirring. 12.6 g of water was distilled off as an azeotropic mixture with toluene. The reaction solution was then cooled to room temperature, neutralized with 35.35 g of 15% sodium hydroxide aqueous solution, and then washed with water. Toluene was then removed by distillation using an evaporator while substituting with 118.1 g of diethylene glycol monoethyl ether acetate to obtain a novolac-type acrylate resin solution. Next, 332.5 g of the obtained novolac-type acrylate resin solution and 1.22 g of triphenylphosphine were charged into a reactor equipped with a stirrer, thermometer, and air blowing tube. Air was blown in at a rate of 10 ml / min, and while stirring, 60.8 g of tetrahydrophthalic anhydride was gradually added, and the reaction was carried out at 95-101°C for 6 hours. In this way, a carboxyl group-containing resin (resin 2-2) solution with a solids acid value of 88 mg KOH / g, solids content of 71%, and mass average molecular weight of 2,000 was obtained.

[0183] 2. Preparation of resin compositions for resin layers (A) and (B) Each resin composition was prepared by pre-mixing the components in a stirrer according to the formulations of resin layers (A) and (B) shown in Table 4 below, and then kneading them in a three-roll mill.

[0184] [Table 4] *The proportions of each component in the table above are based on solid content.

[0185] The details of each component listed in Table 4 are as follows: Block copolymer resin 1:M65N:XYX type block copolymer resin, mass-average molecular weight (Mw) approximately 100,000 to 300,000, manufactured by Arkema, NANOSTRENGTH® registered trademark. Block copolymer resin 2:M52N:XYX type block copolymer resin, mass-average molecular weight (Mw) approximately 100,000, manufactured by Arkema, NANOSTRENGTH® registered trademark. Photopolymerizable compound 1: DOUBLEMER 6MX75: Manufactured by DOUBLE BOND CHEMICAL IND. CO., LTD. Compound represented by general formula (I) Photopolymerizable compound 2: DOUBLEMER 527, manufactured by DOUBLE BOND CHEMICAL IND. CO., LTD., a hexafunctional acrylate aliphatic urethane acrylate oligomer. Photopolymerizable compound 3: DHPA: Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) Epoxy resin 1: Bisphenol A type novolac epoxy resin, manufactured by DIC Corporation, N870. Photopolymerization initiator: Oxime ester-based photopolymerization initiator IRUGACURE OXE02 (manufactured by BASF Japan) Resin 2-1: Synthesized according to Synthesis Example 2-1 (polyimide resin having phenolic hydroxyl groups and carboxyl groups) Shownol CRG951: Manufactured by Aica Kogyo Co., Ltd., novolac-type cresol resin, OH equivalent: 119.4) Coloring pigment (for resin layers (A) and (B)): Paliogen Black S008 4: Perylene black pigment (manufactured by BASF) KAYARAD ZCR-1569H: Acid-modified epoxy acrylate (manufactured by Nippon Kayaku Co., Ltd.) (Adduct of polyfunctional epoxy (meth)acrylate with dibasic acid anhydride) Resin 2-2: Synthesized according to Synthesis Example 2-2 (carboxyl group-containing novolac-type acrylate resin) Epoxy resin 2: Bisphenol A type novolac epoxy resin (manufactured by DIC Corporation) By using matte PET (PTHA-25, manufactured by Unitika Ltd., surface roughness Ra: 0.3 μm) as the first film, irregularities were formed on the surface of the resin layer (A).

[0186] 3. Creating a dry film Each resin composition obtained as described above was diluted with the organic solvent MEK to adjust to an appropriate viscosity (10 mPa·s to 100 dPa·s). On a first film (PET film, thickness: 25 μm, surface roughness (Ra): 0.03 μm), the resin composition corresponding to resin layer (A) described in Table 4 was applied so that the film thickness after drying was as described in the same table, and then dried at 90°C for 15 minutes. Next, on the dried resin layer (A), the resin composition corresponding to resin layer (B) in Table 4 was applied so that the film thickness after drying was as described in the same table, and then dried at 80°C for 30 minutes. As a result, a laminate having resin layer (A) and resin layer (B) in order was obtained on the first film. However, Comparative Example 2-3 was a single-layer dry film with only resin layer (A). Furthermore, in Comparative Example 2-2, since matte PET (PTHA-25, manufactured by Unitika Ltd., surface roughness Ra: 0.3 μm) was used as the first film, the irregularities of the matte PET were transferred to the resin layer (A), and as a result, the resin layer (A) had a physically roughened surface.

[0187] 4. Fabrication and evaluation of test substrates

[0188] <Fabrication of test board A> A single-sided printed circuit board with a 15 μm thick copper circuit was prepared and pre-treated using a MEC CZ8100. The dry films of each example and comparative example prepared as described above were bonded together using a vacuum laminator so that the resin layer (B) was in contact with the substrate, thereby forming a laminate on the substrate. This substrate was pattern-exposed using an ORC HMW 680GW vacuum contact double-sided exposure machine manufactured by Oak Corporation at the optimal exposure dose described below. After baking at 100°C for 30 minutes, the PET film used as the first film during lamination was peeled off. Subsequently, development was performed with a 1 wt% sodium carbonate aqueous solution at 30°C under a spray pressure of 0.2 MPa for 60 seconds to obtain a cured laminate as a solder resist pattern. This substrate was then subjected to an integrated exposure dose of 1000 mJ / cm² in a UV conveyor oven from the top of the resin layer (A). 2 After irradiating with ultraviolet light under these conditions, the substrate was heated at 150°C for 60 minutes to cure it, and a test substrate A was prepared, which had a cured product consisting of each laminate.

[0189] <Determining the optimal exposure> The optimal exposure amount used in pattern exposure during the fabrication of test substrate A was determined as follows. Specifically, a single-sided printed circuit board with a 15 μm thick copper circuit was prepared, and pretreatment was performed using a MEC CZ8100. The dry films of each example and comparative example prepared as described above were bonded together using a vacuum laminator so that the resin layer (B) was in contact with the substrate, thereby forming a laminate (measurement sample) on the substrate. Each of the resulting optimal exposure measurement samples was exposed using an OAK vacuum contact double-sided exposure machine (model number ORC HMW 680GW) via a step tablet (Kodak No. 2). After exposure, heating was performed at 100°C for 30 minutes. Then, the PET film used as the first film during laminate creation was peeled off, and development (30°C, 0.2 MPa, 1 wt% Na2CO3 aqueous solution) was performed for 60 seconds. For each measurement sample, the light intensity corresponding to the density portion of the 5th step of the step tablet in the remaining portion after development was set as the optimal exposure intensity, and this was used as the light intensity for pattern exposure of test substrates A and B.

[0190] <Concealment Assessment> Using test board A, the circuit's concealment was evaluated by visual observation from a distance of 30 cm. The evaluation criteria were as follows: ◎: High concealment capability; the circuit is not visible. ○: Part of the circuit is visible. ×: The circuit can be clearly seen.

[0191] <Evaluation of adhesion> On test substrate A, a grid pattern of cuts at 1 mm intervals was made in the cured material on the test specimen using a utility knife, cellophane tape was applied, and then the cellophane tape was removed. The condition of the remaining cured material on the test specimen was then evaluated according to the following criteria. ○: No peeling ×: There is peeling.

[0192] <Electroless gold plating resistance evaluation> With respect to the above test substrate A, Using commercially available electroless nickel and electroless gold plating baths, plating was performed under conditions that resulted in a nickel layer of 0.5 μm and a gold layer of 0.03 μm. Tape with a nominal width of 12-19 mm as specified in JIS Z 1522 was applied to the plated surface, and a tape peeling test was performed by instantaneously peeling off the tape. The presence or absence of plating penetration was evaluated. The judgment criteria are as follows. ○: No staining or peeling observed. ×: Slight seepage was observed after plating.

[0193] <Fabrication of test board B> A single-sided printed wiring board with a copper thickness of 15 μm was prepared and pretreated using CZ8100 manufactured by Meck. The dry films of each of the above-prepared examples and comparative examples were laminated on the substrate using a vacuum laminator such that the resin layer (B) was in contact with the substrate, thereby forming a laminate on the substrate. A negative pattern having via opening diameters of 500 μm, 300 μm, 150 μm, 100 μm, and 80 μm was arranged on the resin layer (A) of the laminate of this substrate as a negative mask for resolution evaluation. Through this, pattern exposure was performed using a vacuum contact type double-sided exposure machine (model number ORC HMW 680GW) manufactured by Orc at the optimum exposure amount determined by the above method. Further, after baking at 100 °C for 30 minutes, the PET film used as the first film during laminate production was peeled off. Thereafter, development was performed for 60 seconds under the condition of a spray pressure of 0.2 MPa using a 1 wt% sodium carbonate aqueous solution at 30 °C to obtain a solder resist pattern. This substrate was irradiated with ultraviolet rays in a UV conveyor furnace under the condition of an integrated exposure amount of 1000 mJ / cm 2 and then heated and cured at 150 °C for 60 minutes to produce a test substrate B provided with a cured product composed of each laminate.

[0194] <Resolution evaluation (evaluation of minimum opening diameter)> In test substrate B, the pattern opening was observed with a SEM to determine the minimum opening diameter.

[0195] <B-HAST resistance> Test substrate B was placed in a high-temperature and high-humidity tank under an atmosphere of 130 °C and 85% humidity, and a voltage of 3.5 V was applied to a comb-shaped electrode portion (n = 6) with a line / space = 12 μm / 13 μm to perform in-tank B-HAST for 300 hours. After 300 hours had elapsed, B-HAST resistance was evaluated according to the following criteria. A resistance value of less than 1 × 10 6 Ω was determined as a short circuit. ◎: No short circuit occurred between all six comb-shaped electrodes ○: A short circuit occurred between one of the six comb-shaped electrodes ×: A short circuit occurred between two or more of the six comb-shaped electrodes

[0196] <Breaking strength> The cured laminate was peeled off from test substrate B, and the fracture strength of the peeled cured material was measured and evaluated in accordance with JIS K7127. The evaluation criteria are as follows: ◎: 40 MPa or higher ○: 30 MPa or higher, less than 40 MPa

[0197] The cured laminates according to the embodiments of the present invention showed good results in all evaluations. On the other hand, Comparative Examples 2-1 and 2-3, which have different resin compositions or layer configurations, show that it is difficult to achieve both circuit concealment and mechanical properties. Furthermore, in Comparative Example 2-2, although the circuit concealment was improved by physical methods, the resolution of the cured product decreased.

[0198] Although the present invention has been specifically described above based on embodiments, it goes without saying that the present invention is not limited to the above embodiments and can be modified in various ways without departing from its essence. [Explanation of symbols]

[0199] 1. Film 1 A Resin layer (A) B Resin layer (B) 2. Second film

Claims

1. A laminate comprising a resin layer (A) and a resin layer (B) provided on the resin layer (A), The aforementioned resin layer (A) (A1) Block copolymer resin and (A2) Photopolymerizable compounds, It has, The aforementioned resin layer (B) (B1) A laminate characterized by having an alkali-soluble (meth)acrylate resin.

2. The laminate according to claim 1, wherein the (A1) block copolymer resin is of the X-Y-X type and has a mass-average molecular weight Mw of 20,000 to 400,000.

3. The above (A2) photopolymerizable compound is the following general formula (I) 【Chemistry 1】 (In general formula (I), R1 represents a hydrogen atom or a methyl group.) The laminate according to claim 1 or 2, wherein the compound is represented by [the compound shown].

4. The laminate according to any one of claims 1 to 3, further comprising a first film and a second film, wherein the first film, the resin layer (A), the resin layer (B), and the second film are provided in this order.

5. A cured product obtained by curing the resin layer of the laminate according to claims 1 to 4.

6. An electronic component having the cured product of claim 4.

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