KR20230165755A - Laminates, their cured products, and electronic components containing them - Google Patents

Abstract

[Project] To provide a dry film laminate that exhibits a matte textured appearance after curing and also has good mechanical properties and resolution. [Solution] 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 gross value of 50 or more and a second The gloss value is 30 or less, and the resin layer (B) is a laminate whose third gross value is 50 or more, or the resin layer (A) has (A1) a block copolymer resin and (A2) a photopolymerizable compound, and the resin layer ( B), (B1) A laminate characterized by having an alkali-soluble (meth)acrylate resin was obtained.

Description

Laminates, their cured products, and electronic components containing them

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

An insulating film called solder resist is formed on the surface layer of printed wiring boards used in various electronic devices. Since general solder resist has a gross texture, in the manufacturing process of a printed wiring board or the subsequent component mounting process, if a slight scratch occurs in the solder resist, the appearance becomes defective, which is a factor in reducing yield. In order to avoid or reduce the rate of appearance defects caused by such slight scratches, a solder resist with a matte (matte) texture is often required. In addition, there is a demand for solder resist with a matte texture from the viewpoint of increasing the concealment of the circuit and improving the aesthetics of the board.

As a method of obtaining a solder resist with a matte texture, it has been proposed to use a specific resin composition as a composition for solder resist (for example, patent document 1). In Patent Document 1, an attempt is made to generate diffuse reflection of light incident on the surface of the solder resist by using mutually incompatible components as components of the solder resist composition, thereby reducing the gloss. Additionally, in another method, it is taught that by roughening the surface of the solder resist layer, the glossiness can be suppressed and a solder resist with a matte texture can be obtained (for example, patent document 2). Patent Document 2 describes obtaining a solder resist with a matte texture through a physical roughening method of coating a solder resist composition on a blast-treated support.

International Publication No. WO2001/058977 Japanese Patent Publication No. 2012-141605

However, in the matting method using the incompatibility of the resin described in Patent Document 1, the entire coating film is in a non-uniformly separated state, so there is room for consideration regarding securing the mechanical properties of the coating film.

In addition, in a matting method such as that described in Patent Document 2, which physically transfers the irregularities of the surface of the roughened support to the solder resist composition or dry film applied thereon, the irregularities of the solder resist prepared in this way are , it is lost when additional pressure is applied to the solder resist surface during the component mounting process, etc., and as a result, the gloss value rises again, making it impossible to obtain a matte textured appearance. Additionally, since irregularities exist on the surface of the solder resist during exposure, the irradiated light is scattered, resulting in a problem that resolution is lowered.

That is, the object of the present invention is to provide a laminate that exhibits a matte textured appearance after curing, has excellent circuit hiding properties, and has good mechanical properties and resolution, a cured product thereof, and electronic components containing the same. Do it as

As a result of intensive study, the present inventors have found that there is 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 gross value of 50 or more. The above problem is solved by a laminate wherein the second gloss value is 30 or less, and the resin layer (B) has a third gross value of 50 or more.

Additionally, a laminate comprising a resin layer (A) and a resin layer (B) provided on the resin layer (A), wherein the resin layer (A) includes (A1) a block copolymer resin and (A2) a photopolymerizable compound. The above problem is solved by a laminate wherein the resin layer (B) has an alkali-soluble (meth)acrylate resin (B1).

The (A1) block copolymer resin of the present invention is of type X-Y-X, and preferably has a mass average molecular weight Mw of 20,000 to 400,000.

The (A2) photopolymerizable compound of the present invention has the following general formula (I)

(In general formula (I), R1 means a hydrogen atom or a methyl group)

It is preferable that it is a compound represented by .

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

The object of the present invention is achieved by the cured product of the above laminate.

Furthermore, the object of the present invention is achieved by an electronic component having the cured product of the present invention.

The laminate of the present invention, when applied to a substrate such as a printed wiring board, has mechanical properties that provide good protection for electronic devices in both manufacturing and use of electronic devices when the laminate becomes cured through treatment such as heating. , resolution is obtained and a matte textured appearance is obtained.

1 is a schematic cross-sectional view of a laminate according to an embodiment of the present invention.
Figure 2 is a schematic cross-sectional view of a laminate according to another embodiment of the present invention.
Figure 3 is a diagram for explaining an example of a processing process for producing a cured product using the laminate of the present invention.

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

(Laminate)

As shown in the schematic cross-sectional view of Fig. 1, the laminate of the present invention has the form of a laminate having a resin layer (A) and a resin layer (B) provided on the resin layer (A). When used, the resin layer (B) of the laminate is placed in contact with a substrate (not shown) of electronic components such as a printed wiring board, and the resin layer (A) is connected to the substrate through the resin layer (B). are placed spaced apart.

After the laminate is placed on the substrate as described above, it is subjected to exposure treatment and heat curing, and serves as a cured film, solder resist, cover lay, and other circuit protective films to protect the substrate during the manufacturing process, and even after the product is completed. It exists on the substrate and serves to protect it. Curing of the laminate is performed through exposure and heat treatment. In the present invention, the resin layer (A) and the resin layer (B) are composed of a photosensitive resin composition (A) and a photosensitive resin composition (B), respectively.

The laminate of the present invention is generally subjected to an exposure process, a heat curing process, a development process, a component mounting process, and a reheating process, and becomes a cured product after the heat curing process. The gross value of the resin layer constituting the laminate varies during the above series of processes such as exposure treatment and heat treatment. Here, “heat curing” refers to curing the resin layers (A) and (B) by heating them for a predetermined period of time above the temperature at which the thermosetting components contained in the resin layer (A) and resin layer (B) crosslink (for example, 150°C or more). , that is, curing the photosensitive resin composition by heating.

The resin layer (A) used in the laminate of the present invention is disposed on a substrate through the resin layer (B) as described above, and after a predetermined treatment described later, the resin layer (B) of the resin layer (A) is The first and second gross values of the surface on the side that is not in contact with the surface (the side of the resin layer (A) far from the substrate, also referred to as the outer surface) show predetermined values.

[First gross value]

The first gross value in the laminate of the present invention is (i) the resin layer (B) provided on the substrate and composed of the photosensitive resin composition (B), and the resin layer (B) and the substrate. After exposing a laminated body provided on the opposite side and provided with a resin layer (A) composed of the photosensitive resin composition (A) to light from the resin layer (A) side and before heat curing, the number in the laminated body It corresponds to the value obtained as the gross value of the outer surface of the stratum (A). In addition, when the laminate is provided with 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 and the resin layer (B) is in contact with the substrate. After vacuum lamination on the substrate, it is exposed to light from the resin layer (A) side, and then, after peeling off the first film and before heat curing, the gross value of the outer surface of the resin layer (A) in the laminate is determined. It is equivalent to the value lost. The first gross value is 50 or more, preferably 70 to 100.

In the present invention, a resin layer (B) provided on a substrate, a resin layer (A) provided on the resin layer (B) on the opposite side to the substrate, and optionally a first layer (A) on the resin layer (A) are provided. The laminate including the film was irradiated with ultraviolet rays from the resin layer (A) side using a pressure-sensitive adhesive double-sided exposure machine (model number ORC HMW 680GW) manufactured by Oak, under conditions of an integrated exposure dose of 250 mJ/cm2, and then subjected to ultraviolet rays. 1 Measure the gross value. In addition, when the laminate is provided with the first film as described above, the first gross value is measured 10 minutes after peeling the first film after irradiation with ultraviolet rays.

[Second gross value]

In addition, the second gloss value in the laminate of the present invention is (ii) for the laminate after exposure for which the above-mentioned first gloss value is measured, additional hot air circulation drying is used at 150°C for 60 minutes. It corresponds to the value determined by measuring the gross value of the outer surface of the resin layer (A) in this laminate after heat treatment.

In addition, the heat-curing conditions for measuring the above-mentioned second gross value do not limit the heat-curing conditions at all when the laminate of the present invention is used (mounted) in electronic devices, etc. That is, 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.

In addition, the gross value of the resin layer (A) is the same or approximately the same as the entire resin layer (A), but in the present invention, for clarification of the standard, the gloss value of the resin layer (A) is not in contact with the resin layer (B). The measured value on a part of the surface (outer surface) on the side that is not exposed is used.

[Third gross value]

In addition, the third gross value in the laminate of the present invention is (iii) a resin layer (A) provided on the substrate, and a resin layer (B) provided on the resin layer (A) on the side opposite to the substrate. ) is a value obtained as the gross value of the outer surface of the resin layer (B) in the laminate after exposing the laminate provided with it to light and then heat curing. That is, it is measured in the same procedure as the second gross value, except that the lamination order of the resin layer (A) and the resin layer (B) with respect to the substrate is different. In addition, when the laminate is provided with a first film in contact with the resin layer (A) and/or a second film in contact with the resin layer (B), the first film is peeled so that the resin layer (A) is in contact with the substrate. The substrate was laminated in a first chamber at 80°C using a vacuum laminator (CVP-300: manufactured by Nikko Materials) under the conditions of a vacuum pressure of 3 hPa and a vacuum time of 30 seconds, followed by a press pressure of 0.5 MPa and a press time of 30 seconds. After pressing, exposing from the resin layer (B) side, and then peeling off the second film and heat-curing, the value is equivalent to the value obtained as the gross value of the outer surface of the resin layer (B). The conditions for exposure and heat curing for measuring the third gloss value are the same as those used for measuring the second gloss value.

In addition, the “gloss value” in the present invention refers to the value measured by light irradiation at an incident angle of 60° on a horizontally stacked laminate using a gloss meter (micro-TRI-gloss) manufactured by BYK Additives & Instruments. It means value.

(Manufacturing process of laminate)

Hereinafter, the manufacturing process of the laminate will be described with reference to FIGS. 2 and 3.

Figure 2 is a schematic cross-sectional view of one embodiment of the laminate before being applied to electronic devices, etc. In this example, the photosensitive resin composition (A) is applied on the first film (1) (e.g., a carrier film to a support film), dried, and then the photosensitive resin composition (B) is applied on the resin layer (A). is applied and dried, and the second film (2) is laminated on the photosensitive resin composition (B). That is, in Figure 2, a dry film (laminated body) in a laminated state is shown.

That is, first, the photosensitive resin compositions (A) and (B) are each diluted with an organic solvent or the like, the viscosity is adjusted to about 0.1 dPa·s to 200 dPa·s, and the photosensitive resin composition (A) is diluted with a comma according to a conventional method. It is applied to one side of the first film 1 using a known device such as a coater. After that, the dried resin layer (A) is formed on the first film 1 by usually drying at a temperature of 50 to 140°C for 1 to 30 minutes. The photosensitive resin composition (B) whose viscosity was adjusted in the same manner as above is applied to the side of this resin layer (A) opposite to the first film (1) and dried, thereby providing a layer in contact with the first film (1). , a laminate containing a resin layer (A) and a resin layer (B) is manufactured. The laminate of the present invention may have the above-mentioned first film (1) and other films or resin layers as long as it is a laminate containing the resin layer (A) and the resin layer (B). When applying the laminate to an electronic device, the resin layer (B) is provided on the substrate side, and the resin layer (A) is a surface layer that is provided on the opposite side from the substrate through the resin layer (B) and is visible from the electronic device surface. is formed.

On the side of the resin layer (B) of the laminate located on the opposite side from the resin layer (A), a second peelable film (2) is provided for the purpose of preventing dust from adhering to the surface of the resin layer (B). ) (for example, a cover film or a protective film) can be laminated. As the first film 1 and the second film 2, conventionally known plastic films can be appropriately used, and the adhesive force between the second film 2 and the resin layer (B) is similar to that of the first film 1. It is preferable that it is smaller than the adhesive force of the stratum (A). Since the laminate 10 of the present invention is applied to the above-described substrate by first peeling off the second film 2, this operation is facilitated by controlling the adhesive force as described above. There is no particular limitation on the thickness of the first film 1 and the second film 2, but it is generally appropriately selected in the range of 10 to 150 μm.

In this way, a laminate having a four-layer structure in which the first film 1, the resin layer (A), the resin layer (B), and the second film 2 are laminated in this order is manufactured as a dry film ( Figure 2).

In addition, the laminate of the present invention may have only one side supported or protected by a film (either the first film 1 or the second film 2), or may be a laminate containing no film. Additionally, the laminate (dry film) of the present invention may be wound into a roll shape.

From the viewpoint of coating film strength, the interface between each layer may be friendly. That is, the resin layer (A) and the resin layer (B) have high adhesion, and when the first film 1 or the second film 2 is peeled, or when other layers to be peeled exist as a laminate, At the time of peeling of the layer to be peeled, it is preferable that the resin layer (A) and the resin layer (B) adhere to each other to form a highly durable permanent film.

The laminate obtained as described above is applied to a substrate (object of protection) such as a printed wiring board, and functions as a solder resist, cover lay, or other circuit protective film. As already explained, when the laminate has the second film 2, it is peeled off, placed facing each other so that the entire surface of the resin layer (B) covers the protection target surface of the substrate, and pressed using a laminator. , the laminate and the substrate are brought into close contact.

In addition, in the present invention, the layers or surfaces described as the objects of “on” and “opposite” do not necessarily have to be in contact, and in some cases, they may be provided through another layer. On the other hand, “directly” or “directly” means a state in which layers or surfaces are in contact.

In order to produce a laminate in advance on the first film 1 as described above and laminate it to an electronic device, it is preferable to bond it under pressure and heating using a vacuum laminator or the like. By using such a vacuum laminator, even if the surface of the wiring substrate has irregularities, the dry film is in close contact with the wiring substrate, so air bubbles are not mixed, and the hole filling property of the concave portion of the wiring substrate surface is also improved. Pressurizing conditions are preferably 0.1 to 2.0 MPa, and heating conditions are preferably 40 to 120°C.

In addition, as a method of disposing the laminate of the present invention on a circuit board, the resin layer (A) and the resin layer (B) are each individually produced as a dry film, and this dry film is sequentially applied to the protection target surface of the circuit board. It may also depend on the laminating method. That is, first, the resin layer (B) is formed on the circuit board by laminating the dry film of the resin layer (B) to the circuit board. Thereafter, by laminating the dry film of the resin layer (A) on the resin layer (B), the laminate of the present invention formed on a circuit board can be obtained.

In addition, the photosensitive resin composition (B) is applied and dried directly to the electronic device, and then the photosensitive resin composition (A) is applied and dried on the dried film of the photosensitive resin composition (B), thereby laminating. You may form a sieve. On the electronic device side, a resin layer (B) containing the photosensitive resin composition (B) and a resin layer (A) containing the photosensitive resin composition (A) are sequentially laminated, and the resin layers (B) and (A) are, The laminate of the present invention is constructed while in close contact with an electronic device. The photosensitive resin compositions (A) and (B) used in this case are also subject to viscosity adjustment using an organic solvent, application, drying, etc., similar to the laminate provided on the film.

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.

Application of the photosensitive resin compositions (A) and (B) can also be performed using known equipment such as a blade coater, lip coater, or film coater in addition to the above comma coater, and drying can be performed using a hot air circulation dryer or IR. This is preferably carried out by using a device equipped with a heat source of a steam heating type, such as a hot plate or a convection oven, and known methods such as a method of countercurrent contact with hot air in a dryer and a method of spraying from a nozzle to a support can also be used. there is.

The laminate manufactured in this way is cured through a curing treatment described later to form a permanent film on electronic devices (objects of protection) such as printed wiring boards.

[Resin layer (A)]

The resin layer (A) of the laminate according to the present invention has a gloss value of the surface that does not face the resin layer (B), that is, the surface (outer surface) that becomes visible as the outermost layer of a printed wiring board, etc., after the curing treatment. changes in each process, etc. In detail, the first gross value of the resin layer (A) is 50 or more, preferably 70 or more and 100 or less. If the first gross value is 50 or more, good resolution can be obtained.

In addition, the resin layer (A) of the laminate according to the present invention has a second gross value of 30 or less, preferably 1 or more and 20 or less. If the second gloss value is 30 or less, the appearance of a good matte texture can be exhibited.

[Resin layer (B)]

The resin layer (B) used in the laminate of the present invention has a third gross value of 50 or more, preferably 70 or more and 100 or less. If the gross value of the outer surface of the resin layer (B) is 50 or more, good mechanical properties can be obtained.

In the present 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. Preferably, it is 2 to 30 μm, and the total film thickness of both is 5 to 150 μm. Additionally, it is preferable that the film thickness of the resin layer (B) is larger than the film thickness of the resin layer (A).

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 are developable, and from this point of view, the photosensitive resin compositions (A) and (B) are alkali soluble in at least one or both of them. It is preferable that it contains a resin, especially a carboxyl group-containing resin. In addition, since they all undergo thermal curing to become a cured product, they contain thermosetting resin. Hereinafter, the components of the photosensitive resin compositions (A) and (B) are described.

[Components of photosensitive resin composition (A)]

The photosensitive resin composition (A) constituting the resin layer (A) showing the above-described first and second gross values generally contains an alkali-soluble resin such as a carboxyl group-containing resin, and further contains a thermosetting resin. It is preferable, and may also include polyimide resin, aromatic resin, photosensitive resin, and methyl methacrylate-based comb polymer. In order to achieve the desired gloss value, the photosensitive resin composition (A) needs to add a component that is incompatible with the resin in the photosensitive resin composition (A). This is not limited to a specific component, and 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). For example, polyamideimide, which is incompatible with polyimide resins, fatty acids containing heteroatoms, which are incompatible with carboxyl group-containing resins, or aliphatic block copolymer resins, which are incompatible with aromatic resins, and photosensitive resins. Examples include alicyclic photopolymerizable compounds that are incompatible with methyl methacrylate-based comb polymers, and silicone compounds that are incompatible with methyl methacrylate-based comb polymers. The photosensitive resin composition (A) may further contain a photopolymerizable compound and a photopolymerization initiator as the case may be.

In addition, if the amount of thermosetting resin or photopolymerizable compound mixed with high molecular weight components such as alkali-soluble resin, polyimide resin, or polyamidoimide resin is large, incompatibility tends to occur, and such photosensitive resin composition (A) can be used. Stratum (A) represents the gross value desired by the present invention. This mixing amount is not particularly limited, but for example, the total amount of the thermosetting resin and photopolymerizable compound can be 30 to 170 parts by mass per 100 parts by mass of the high molecular weight component.

(Alkali-soluble resin used in photosensitive resin composition (A))

In the photosensitive resin composition (A), it is preferable that it contains an alkali-soluble resin as described above, and all known alkali-soluble resins can be used, and a carboxyl group-containing resin is especially preferable. In the photosensitive resin composition (A), specific examples of the alkali-soluble resin that can be used include the following.

(1) Carboxyl group-containing resin having an imide structure and an amide structure

Carboxyl group-containing resins having an imide structure and an amide structure can be used, especially polyamidoimide group-containing resins having a structure represented by the following general formula (1) and a structure shown by the following general formula (2).

Here, X ₁ is the residue of aliphatic diamine (a) derived from dimer acid and having 24 to 48 carbon atoms. X ₂ is the residue of aromatic diamine (b) having a carboxyl group. Y is each independently a cyclohexane ring or an aromatic ring.

Specifically, polyamidoimide resins having this structure include those represented by the following general formula (3).

In the general formula (3), n is a natural number.

(2) Carboxyl group-containing resin with an imide structure and no amide structure

The carboxyl group-containing resin that has an imide structure and does not have an amide structure is not particularly limited as long as it is a resin that has a carboxyl group and an imide ring. For the synthesis of a carboxyl group-containing resin that has an imide structure and no amide structure, a known and common method of introducing an imide ring into the carboxyl group-containing resin can be used. For example, a resin obtained by reacting a carboxylic acid anhydride component with an amine component and/or an isocyanate component can be mentioned. Imidization may be performed by thermal imidation or chemical imidation, and it can be produced by using these in combination.

Here, examples of the carboxylic acid anhydride component include tetracarboxylic acid anhydride and tricarboxylic acid anhydride. However, it is not limited to these acid anhydrides, and any compound having an acid anhydride group and a carboxyl group that reacts with an amino group or an isocyanate group can be used. , including its derivatives, can be used. In addition, these carboxylic acid anhydride components may be used individually or in combination.

Examples of tetracarboxylic acid anhydride include pyromellitic dianhydride, 3-fluoropyromellitic dianhydride, 3,6-difluoropyromellitic dianhydride, and 3,6-bis(trifluoromethyl). Pyromellitic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 4,4'-oxalate Cydiphthalic dianhydride, 2,2'-difluoro-3,3',4,4'-biphenyltetracarboxylic dianhydride, 5,5'-difluoro-3,3',4,4 '-Biphenyltetracarboxylic dianhydride, 6,6'-difluoro-3,3',4,4'-Biphenyltetracarboxylic dianhydride, 2,2',5,5',6 ,6'-hexafluoro-3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2'-bis(trifluoromethyl)-3,3',4,4'- Biphenyltetracarboxylic dianhydride, 5,5'-bis(trifluoromethyl)-3,3',4,4'-biphenyltetracarboxylic dianhydride, 6,6'-bis(trifluoromethyl) Romethyl)-3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2',5,5'-tetrakis(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 dianhydride and 2,2',5,5',6,6 '-Hexakis(trifluoromethyl)-3,3',4,4'-biphenyltetracarboxylic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 3,3" ,4,4"-terphenyltetracarboxylic dianhydride, 3,3'",4,4'"-quaterphenyltetracarboxylic dianhydride, 3,3"",4,4""-quink Phenyltetracarboxylic dianhydride, methylene-4,4'-diphthalic dianhydride, 1,1-ethylidene-4,4'-diphthalic dianhydride, 2,2-propylidene-4,4'-di Phthalic dianhydride, 1,2-ethylene-4,4'-diphthalic dianhydride, 1,3-trimethylene-4,4'-diphthalic dianhydride, 1,4-tetramethylene-4,4'-di Phthalic dianhydride, 1,5-pentamethylene-4,4'-diphthalic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoro Propropane dianhydride, difluoromethylene-4,4'-diphthalic dianhydride, 1,1,2,2-tetrafluoro-1,2-ethylene-4,4'-diphthalic dianhydride, 1, 1,2,2,3,3-hexafluoro-1,3-trimethylene-4,4'-diphthalic dianhydride, 1,1,2,2,3,3,4,4-octafluoro -1,4-Tetramethylene-4,4'-diphthalic dianhydride, 1,1,2,2,3,3,4,4,5,5-decafluoro-1,5-pentamethylene-4 ,4'-diphthalic dianhydride, thio-4,4'-diphthalic dianhydride, sulfonyl-4,4'-diphthalic 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-dicarboxy) Phenoxy)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]-1, 1,1,3,3,3-hexafluoropropane dianhydride, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, bis(3,4-dicarboxyphenok C) Dimethylsilane dianhydride, 1,3-bis(3,4-dicarboxyphenoxy)-1,1,3,3-tetramethyldisiloxane dianhydride, 2,3,6,7-naphthalenetetracarboxyl Acid dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic acid Dianhydride, 1,2,7,8-phenanthrenetetracarboxylic acid dianhydride, 1,2,3,4-butanetetracarboxylic acid dianhydride, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, cyclopentanetetracarboxylic dianhydride, cyclohexane-1,2,3,4-tetracarboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride, 3, 3',4,4'-bicyclohexyltetracarboxylic acid dianhydride, carbonyl-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, methylene-4,4'- Bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,2-ethylene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,1-ethyl Liden-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 2,2-propylidene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) Dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-propylidene-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'-difluoroxy-4,4'-diphthalic dianhydride, 5,5'-difluoroxy -4,4'-diphthalic dianhydride, 6,6'-difluoroxy-4,4'-diphthalic dianhydride, 3,3',5,5',6,6'-hexafluoroxy -4,4'-diphthalic dianhydride, 3,3'-bis(trifluoromethyl)oxy-4,4'-diphthalic dianhydride, 5,5'-bis(trifluoromethyl)oxy-4 ,4'-diphthalic dianhydride, 6,6'-bis(trifluoromethyl)oxy-4,4'-diphthalic dianhydride, 3,3',5,5'-tetrakis(trifluoromethyl ) Oxy-4,4'-diphthalic dianhydride, 3,3',6,6'-tetrakis(trifluoromethyl)oxy-4,4'-diphthalic dianhydride, 5,5',6, 6'-tetrakis(trifluoromethyl)oxy-4,4'-diphthalic dianhydride, 3,3',5,5',6,6'-hexakis(trifluoromethyl)oxy-4, 4'-diphthalic dianhydride, 3,3'-difluorosulfonyl-4,4'-diphthalic dianhydride, 5,5'-difluorosulfonyl-4,4'-diphthalic dianhydride, 6,6'-difluorosulfonyl-4,4'-diphthalic dianhydride, 3,3',5,5',6,6'-hexafluorosulfonyl-4,4'-diphthalic dianhydride Water, 3,3'-bis(trifluoromethyl)sulfonyl-4,4'-diphthalic dianhydride, 5,5'-bis(trifluoromethyl)sulfonyl-4,4'-diphthalic dianhydride Water, 6,6'-bis(trifluoromethyl)sulfonyl-4,4'-diphthalic dianhydride, 3,3',5,5'-tetrakis(trifluoromethyl)sulfonyl-4, 4'-diphthalic dianhydride, 3,3',6,6'-tetrakis(trifluoromethyl)sulfonyl-4,4'-diphthalic dianhydride, 5,5',6,6'-tetra Kiss(trifluoromethyl)sulfonyl-4,4'-diphthalic dianhydride, 3,3',5,5',6,6'-hexakis(trifluoromethyl)sulfonyl-4,4' -Diphthalic dianhydride, 3,3'-difluoro-2,2-perfluoropropylidene-4,4'-diphthalic dianhydride, 5,5'-difluoro-2,2-perfluor Lopropylidene-4,4'-diphthalic dianhydride, 6,6'-difluoro-2,2-perfluoropropylidene-4,4'-diphthalic dianhydride, 3,3',5, 5',6,6'-hexafluoro-2,2-perfluoropropylidene-4,4'-diphthalic dianhydride, 3,3'-bis(trifluoromethyl)-2,2-purple Fluoropropylidene-4,4'-diphthalic dianhydride, 5,5'-bis(trifluoromethyl)-2,2-perfluoropropylidene-4,4'-diphthalic dianhydride, 6, 6'-difluoro-2,2-perfluoropropylidene-4,4'-diphthalic dianhydride, 3,3',5,5'-tetrakis(trifluoromethyl)-2,2- Perfluoropropylidene-4,4'-diphthalic dianhydride, 3,3',6,6'-tetrakis(trifluoromethyl)-2,2-perfluoropropylidene-4,4'- Diphthalic dianhydride, 5,5',6,6'-tetrakis(trifluoromethyl)-2,2-perfluoropropylidene-4,4'-diphthalic dianhydride, 3,3',5 ,5',6,6'-hexakis(trifluoromethyl)-2,2-perfluoropropylidene-4,4'-diphthalic dianhydride, 9-phenyl-9-(trifluoromethyl) xanthene-2,3,6,7-tetracarboxylic dianhydride, 9,9-bis(trifluoromethyl)xanthene-2,3,6,7-tetracarboxylic dianhydride, bicyclo 2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic 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), 1,4-(tetramethylene)bis(trimellitate anhydride), 1,5-(pentamethylene)bis(trimellitate anhydride), 1,6-( Hexamethylene)bis(trimellitate anhydride), 1,7-(heptamethylene)bis(trimellitate anhydride), 1,8-(octamethylene)bis(trimellitate anhydride), 1,9-(nona methylene )bis(trimellitate anhydride), 1,10-(decamethylene)bis(trimellitate anhydride), 1,12-(dodecamethylene)bis(trimellitate anhydride), 1,16-(hexadecamethylene )bis(trimellitate anhydride), 1,18-(octadecamethylene)bis(trimellitate anhydride), etc. Examples of tricarboxylic acid anhydride include trimellitic acid anhydride and nuclear hydrogenated trimellitic acid anhydride.

As the amine component, diamines such as aliphatic diamine and aromatic diamine, polyhydric amines such as aliphatic polyetheramine, diamines having a carboxylic acid, diamines having a phenolic hydroxyl group, etc. can be used, but are not limited to these amines. In addition, these amine components may be used individually or in combination.

Examples of the diamine include diamines with one benzene nucleus, 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, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, etc. Phenylmethane, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)- 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenyl Methane, bis(4-aminophenyl)sulfide, 4,4'-diaminobenzanilide, 3,3'-dichlorobenzidine, 3,3'-dimethylbenzidine (o-tolidine), 2,2'-dimethyl Benzidine (m-tolidine), 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'- Diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,3'-diaminobenzophenone, 3,3'-diamino-4,4' -Dichlorobenzophenone, 3,3'-diamino-4,4'-dimethoxybenzophenone, 3,3'-diaminodiphenylmethane, 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 Two benzene nuclei such as seed, 3,4'-diaminodiphenyl sulfoxide, 4,4'-diaminodiphenyl sulfoxide, and 3,3'-dicarboxy-4,4'-diaminodiphenylmethane. Diamine, 1,3-bis(3-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 1,4-bis(3-aminophenyl)benzene, 1,4-bis(4-amino) Phenyl)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-trifluoromethyl benzene, 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-aminophenyl sulfide)benzene, 1,4-bis(4-amino) Phenyl sulfide) benzene, 1,3-bis (3-aminophenyl sulfone) benzene, 1,3-bis (4-aminophenyl sulfone) benzene, 1,4-bis (4-aminophenyl sulfone) 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, etc. diamine with three benzene nuclei, 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) Si)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[4-(4-aminophenoxy)phenyl]ketone, bis[3- (3-aminophenoxy)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)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) Si) phenyl] propane, 2,2-bis [3- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [3-( 4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 2,2-bis[4-(3-aminophenoxy)phenyl]-1,1,1, Benzene nucleus 4 such as 3,3,3-hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, etc. Aromatic diamines such as diamine, 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diamino pentane, 1,6-diaminohexane, 1,7 -Diamino heptane, 1,8-diamino octane, 1, 9-diamino nonane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,2 -Aliphatic diamines such as diaminocyclohexane can be used, and examples of aliphatic polyetheramines include ethylene glycol and/or propylene glycol-based polyhydric amines.

As the isocyanate component, diisocyanates such as aromatic diisocyanates and their isomers and multimers, aliphatic diisocyanates, alicyclic diisocyanates and their isomers, and other general-purpose diisocyanates can be used, but are not limited to these isocyanates. no. In addition, these isocyanate components may be used individually or in combination.

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. Diisocyanate and its isomers, polymers, aliphatic diisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, and dicyclohexylmethane diisocyanate, or alicyclic diisocyanates and isomers obtained by hydrogenating the above aromatic diisocyanates, or Other general-purpose diisocyanates can be mentioned.

(3) Carboxyl group-containing resin without 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 of the conventionally known carboxyl group-containing resins that have a carboxyl group. In particular, a carboxyl group-containing resin having an ethylenically unsaturated double bond in the molecule is more preferable in terms of photocurability and development resistance. And, the unsaturated double bond is preferably derived from acrylic acid or methacrylic acid or their derivatives.

As specific examples of the carboxyl group-containing resin, compounds listed below (which may be either oligomers or polymers) can be suitably used.

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

(3-2) Diisocyanates such as aliphatic diisocyanate, branched aliphatic diisocyanate, alicyclic diisocyanate, and aromatic diisocyanate, carboxyl group-containing dialcohol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid, and polycarbonate-based polyol and polyether. Contains carboxyl groups through polyaddition reaction of diol compounds such as polyols, polyester polyols, polyolefin polyols, acrylic polyols, bisphenol A alkylene oxide adduct diols, and compounds having phenolic hydroxyl groups and alcoholic hydroxyl groups. Urethane resin.

(3-3) Di-functional properties such as diisocyanate, 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. A photosensitive urethane resin containing a carboxyl group produced by polyaddition reaction of (meth)acrylate or a partial acid anhydride modification thereof of an epoxy resin, a di-alcohol compound containing a carboxyl group, and a diol compound.

(3-4) During the synthesis of the resin of (3-2) or (3-3) above, a hydroxyalkyl (meth)acrylate, etc. having one hydroxyl group and one or more (meth)acryloyl groups in the molecule. A photosensitive urethane resin containing a carboxyl group in which a compound is added and the ends are (meth)acrylated.

(3-5) During the synthesis of the resin of (3-2) or (3-3) above, an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate, etc., contains one isocyanate group and one or more (meth ) Photosensitive urethane resin containing a carboxyl group whose terminals are (meth)acrylated by adding a compound having an acryloyl group.

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

(3-7) Carboxyl group-containing photosensitivity obtained by reacting (meth)acrylic acid with a polyfunctional epoxy resin in which the hydroxyl group of the difunctional (solid) epoxy resin was further epoxidized with epichlorohydrin, and dibasic acid anhydride was added to the hydroxyl group generated. profit.

(3-8) Difunctional oxetane resin is reacted with a dicarboxylic acid such as adipic acid, phthalic acid, or hexahydrophthalic acid, and the primary hydroxyl group generated is reacted with phthalic anhydride, tetrahydrophthalic anhydride, or hexahydrophthalic anhydride. A polyester resin containing a carboxyl group to which a dibasic acid anhydride has been added.

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

(3-10) The reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate is reacted with a monocarboxylic acid containing an unsaturated group. , A photosensitive resin containing a carboxyl group obtained by reacting the resulting reaction product with a polybasic acid anhydride.

(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 (3-1) to (10) above.

In addition, in this specification, (meth)acrylate is a general term for acrylates, methacrylates, and mixtures thereof, and the same applies to other similar expressions.

The carboxyl group-containing resin suitably used as the alkali-soluble resin of the present invention as described above has an acid value of preferably 20 to 200 mgKOH/g, and more preferably 60 to 150 mgKOH/g, in order to cope with the photolithography process. do. If this acid value is 20 mgKOH/g or more, the solubility in alkali increases, developability becomes good, and furthermore, the degree of crosslinking with the heat-curing component after light irradiation increases, so sufficient development contrast can be obtained. On the other hand, if the acid value is 200 mgKOH/g or less, accurate pattern drawing becomes easy, and in particular, so-called thermal blurring in the PEB (POST EXPOSURE BAKE) process after light irradiation, which will be described later, can be suppressed, thereby increasing the process margin.

In addition, considering developability and cured film properties, the molecular weight of this carboxyl group-containing resin is preferably 100,000 or less, more preferably 1,000 to 100,000, and still more preferably 2,000 to 50,000. If this molecular weight is 100,000 or less, the alkali solubility of the unexposed area increases and developability improves. On the other hand, if the molecular weight is 1,000 or more, sufficient development resistance and cured material properties can be obtained in the exposed area after exposure and PEB.

(Thermosetting resin used in photosensitive resin composition (A))

The photosensitive resin composition (A) preferably contains a thermosetting resin. As the thermosetting resin, conventionally known thermosetting resins can be used, and commonly known resins having functional groups capable of curing reaction by heat such as cyclic (thio)ether groups, such as epoxy resins, can be used.

Examples of the epoxy resin 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, and alicyclic epoxy resin. formula epoxy resin, trihydroxy phenylmethane type epoxy resin, bixylenol type or biphenol type epoxy resin, or mixtures thereof; Bisphenol S-type epoxy resin, bisphenol A novolac-type epoxy resin, tetraphenylolethane-type epoxy resin, heterocyclic epoxy resin, diglycidyl phthalate resin, tetraglycidylxylenoylethane resin, naphthalene group-containing epoxy resin, DC Examples include epoxy resins having a chlorpentadiene skeleton, glycidyl methacrylate copolymer epoxy resins, cyclohexyl maleimide and glycidyl methacrylate copolymer epoxy resins, and CTBN-modified epoxy resins. Among these, the photosensitive resin composition (A) is used as a component, and a particularly preferable epoxy resin is a bisphenol A type epoxy resin, a novolak type epoxy resin, or a combination thereof.

As for the mixing amount of the thermosetting resin, the equivalent ratio with the alkali-soluble resin (alkali-soluble group such as carboxyl group: heat-reactive group such as epoxy group) is preferably 1:0.1 to 1:10. By setting the mixing ratio within this range, development becomes good and a fine pattern can be easily formed. The equivalence ratio is more preferably 1:0.2 to 1:5.

(Photopolymerizable compound)

When the laminate of the present invention and its cured product are applied as a solder resist, etc., the photosensitive resin composition (A) preferably contains a photopolymerizable compound, and is one of the light types used in the production of solder resist, etc. All synthetic compounds can be used.

Photopolymerizable compounds contained 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 containing an α-unsaturated glycidyl group. , compounds obtained by adding β-unsaturated carboxylic acid, etc.

Examples of compounds having one ethylenically unsaturated group in the molecule include monofunctional (meth)acrylates, such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and isobutyl (meth)acrylate. Latex, lauryl (meth)acrylate, stearyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, glycidyl (meth)acrylates such as methacrylate, heterocyclic groups such as acryloylmorpholine or tetrahydrofuranyl group, and especially (meth)acrylates having an oxygen-containing cyclic group can be used.

Examples of monofunctional (meth)acrylates having an oxygen-containing cyclic group include compounds represented by the following general formula (I).

(In general formula (I), R1 means a hydrogen atom or a methyl group)

Examples of compounds having two or more ethylenically unsaturated groups in the molecule include diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol; polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, and tris-hydroxyethyl isocyanurate, or polyacrylates such as ethylene oxide or propylene oxide adducts thereof; polyacrylates such as phenoxy acrylate, bisphenol A diacrylate, and their phenol ethylene oxide adducts or propylene oxide adducts; Polyhydric acrylates of glycidyl ether, such as glycerol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, and triglycidyl isocyanurate; and melamine acrylate and at least one type of methacrylate corresponding to the acrylate.

Compounds obtained by adding α,β-unsaturated carboxylic acid to polyhydric alcohol include, for example, ethylene glycol diacrylate, diethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, and propylene glycol diacrylate. Acrylate, polypropylene glycol diacrylate, butylene glycol diacrylate, pentyl glycol diacrylate, 1,6-hexanediol diacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, tetramethylol Methane triacrylate, tetramethylolmethane tetraacrylate, glycerin diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, etc. and the above. At least one type of each methacrylate corresponding to acrylate can be mentioned.

Examples of compounds obtained by adding α,β-unsaturated carboxylic acid to a glycidyl group-containing compound include ethylene glycol diglycidyl ether diacrylate, diethylene glycol diglycidyl ether diacrylate, and trimethylolpropane. triglycidyl ether triacrylate, bisphenol A glycidyl ether diacrylate, phthalic acid diglycidyl ester diacrylate, glycerin polyglycidyl ether polyacrylate, etc.; Others, 2,2-bis(4-acryloyloxydiethoxyphenyl)propane, 2,2-bis-(4-acryloyloxypolyethoxyphenyl)propane, 2-hydroxy-3-acryloyl Oxypropyl acrylate and at least one type of each methacrylate corresponding to the above acrylates can be mentioned. The photopolymerizable compounds described above can be used alone or in combination of two or more.

When the photosensitive resin composition contains an alkali-soluble resin, the amount of the photopolymerizable compound is preferably 5 to 100 parts by mass, more preferably 10 to 90 parts by mass, in terms of solid content, per 100 parts by mass of the alkali-soluble resin. , more preferably 15 to 85 parts by mass. By setting the compounding amount within the above range, photocurability improves, pattern formation becomes easy, and the mechanical strength of the cured product can also be improved.

In addition, as photopolymerizable compounds in the photosensitive resin composition (A), urethane acrylate, polyester acrylate, and epoxy acrylate can be used for the purpose of imparting toughness, etc. to the cured coating film. In addition, for purposes such as viscosity control, monofunctional (meth)acrylates, such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, Uryl (meth)acrylate, stearyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, glycidyl methacrylate (meth)acrylates, acryloylmorpholine, etc. can also be used.

As urethane acrylate, U-108A, UA-112P, UA-5201, UA-512, UA-412A, UA-4200, UA-4400, UA-340P, UA-2235PE manufactured by Shinnakamura Chemical Industry Co., Ltd. , UA-160TM, UA-122P, UA-512, UA-W2, UA-7000, UA-7100, U-6HA, U-6H, U-15HA, UA-32P, U-324A, UA-7200; CN968, CN9006, CN9010, CN962, CN963, CN964, CN965, CN980, CN981, CN982, CN983, CN996, CN9001, CN9002, CN9788, CN9893, CN978, CN9782, made by Arcmassa. CN9783, CN929, CN944B85, CN989, CN9008 ; M-1100, M-1200, M-1210, M-1310, M-1600 manufactured by Toa Gose Co., Ltd.; UN-9000PEP, UN-9200A, UN-7600, UN-333, UN-1255, UN-6060PTM, UN-6060P, SH-500B manufactured by Negami High School Corporation; AH-600, AT-600 manufactured by Kyoesha Chemical Co., Ltd.; Daicel/Allnex Co., Ltd.'s Evecryl 280, Evecryl 284, Evecryl 402, Evecryl 8402, Evecryl 8807, Evecryl 9270, Evecryl 264, Evecryl 265, Evecryl 1259, Evecryl 8201, KRM8296, Evercryl 294/25HD, Evecryl 4820, Evecryl 1290, Evecryl 1290K, KRM8200, Evecryl 5129, Evecryl 8210, Evecryl 8301, Evecryl 8405; UN-3320HA, UN-3320HB, UN-3320HC, UN-3320HS, UN-904, UN-901T, UN-905, UN-952; 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 manufactured by Double Bond. , Doublemer 528, Doublemer 5405, Doublemer 554, Doublemer 571, Doublemer 588, Doublemer 850, Doublemer 523, Doublemer 530M, Doublemer 5433H, Doublemer 564, Doublemer 576, Doublemer 594, Doublemer 87A, Doublemer 7200, Doublemer 7201M, Doublemer 7210, 88A etc. can be mentioned.

As polyester acrylate, Aronics M-6100, M-6200, M-6250, M-6500, M-7100, M-7300K, M-8030, M-8060, M-8100 manufactured by Toagosei Co., Ltd. , M-8530, M-8560, M-9050; Double Bond's Doublemer 2015, Doublemer 2231-TFDOUBLEMER 2319, Doublemer 257, Doublemer 276, Doublemer 284, DOUBLEMER 2019, Doublemer 2232, Doublemer 236, DoubleMer 270, DOUBLEMER 278, DOUBLEMER 285, DOUBLEMER 220, DoubleMer 2315-100, DoubleMer 245 , Doublemer 272, Doublemer 278X25, Doublemer 286, Doublemer 2230-TF, Doublemer 2315HM35, Doublemer 246, Doublemer 275, Doublemer 281, Doublemer 287, etc.

Epoxy (meth)acrylates include (meth)acrylates having a glycidyl group as well as their modified products. Examples of commercial products include Doublemer 1283C, Doublemer 1700, Doublemer 1710, Doublemer 186, and Doublemer 193- manufactured by Double Bond. 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, Examples include Doublemer 176TF-5, Doublemer 193A-TF, Doublemer 6MX75, and Doublemer 6MX75-E.

[Photopolymerization initiator]

Examples of photopolymerization initiators that can be used in the photosensitive resin composition (A) include well-known and commonly used ones. In particular, when used in the PEB process after light irradiation described later, a photopolymerization initiator that also functions as a photobase generator is suitable. The photopolymerization initiator is preferably added when the photosensitive resin composition (A) contains a photopolymerizable alkali-soluble resin or a photopolymerizable compound. Additionally, in this PEB process, a photopolymerization initiator and a photobase generator may be used together.

A photopolymerization initiator that also functions as a photobase generator is one or more types that can function as a catalyst for the polymerization reaction of a thermosetting resin described later by changing the molecular structure or cleavage of the molecule upon irradiation of light such as ultraviolet rays or visible light. It is a compound that produces basic substances. Examples of basic substances include secondary amines and tertiary amines. Photopolymerization initiators that also function as such photobase generators include, for example, α-aminoacetophenone compounds, oxime ester compounds, acyloxyimino groups, N-formylated aromatic amino groups, N-acylated aromatic amino groups, and nitrobenzylcarboxyl groups. Compounds having substituents such as a bamate group and an arcoxybenzylcarbamate group can be mentioned. Among them, oxime ester compounds and α-aminoacetophenone compounds are preferable, and oxime ester compounds are more preferable. As the α-aminoacetophenone compound, one having two or more nitrogen atoms is particularly preferable.

The α-aminoacetophenone compound may have a benzoin ether bond in the molecule, and when irradiated with light, cleavage occurs within the molecule to generate a basic substance (amine) that acts as a curing catalyst.

As an oxime ester compound, any compound that produces a basic substance by light irradiation can be used.

These photopolymerization initiators may be used individually by 1 type, or may be used in combination of 2 or more types. When the photosensitive resin composition contains an alkali-soluble resin, the amount of the photopolymerization initiator in the photosensitive resin composition is preferably 0.1 to 40 parts by mass, more preferably 0.3 to 15 parts by mass, based on 100 parts by mass of the alkali-soluble resin. It is the mass part. In the case of 0.1 mass part or more, good development resistance contrast of the light irradiated part/unirradiated part can be obtained. Additionally, in the case of 40 parts by mass or less, the properties of the cured product improve.

[Surfactants]

The photosensitive resin composition (A) may contain a surfactant having a long-chain fatty acid group and a reactive group in the molecule. The surfactant is not particularly limited, and anionic, cationic, amphoteric, and nonionic surfactants can be used. The surfactant is preferably a solid surfactant at room temperature, and is more preferably a fatty acid containing a hetero atom.

Known compounds can be appropriately used as fatty acids containing heteroatoms, for example, in the present invention, fatty acid amides dispersed in water are included. The type of fatty acid amide may be one that is generally used. 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, N- Substituted amides such as stearyl stearic acid amide, N-oleyl oleic acid amide, N-stearyl oleic acid amide, N-oleyl stearic acid amide, N-stearyl erucic acid amide, and N-oleyl palmitic acid amide, Methylolamides such as methylolstearic acid amide and methylolbehenic acid amide, methylenebisstearic acid amide, ethylenebiscapric acid amide, ethylenebislauric acid amide, ethylenebisstearic acid amide, ethylenebisisostearic acid amide, ethylene Bishydroxystearic acid amide, ethylenebisbehenic acid amide, hexamethylenebisbehenic acid amide, hexamethylenebisbehenic acid amide, hexamethylenebishydroxystearic acid amide, N,N'-distearyl adipic acid amide, N Saturated fatty acid bis amides such as ,N'-distearyl sebacic acid amide, unsaturated aliphatic bis amides such as ethylenebisoleic acid amide, hexamethylene bisoleic acid amide, and N,N'-dioleyladipic acid amide, m- Aromatic bis amides such as xylylenebisstearic acid amide, etc. can be mentioned. These fatty acid amides may be used individually or may be used in mixture of two or more types.

(Block copolymer resin)

This block copolymer resin generally refers to a copolymer resin with a molecular structure in which two or more types of polymer units with different properties are linked by covalent bonds to form a long chain. In the present invention, known and commonly used block copolymer resins can be used, with X-Y type or 3 or more membered block copolymer resins being preferable, and X-Y-X type block copolymer resins being more preferable. X in the X-Y-X type block copolymer resin may be the same or different.

Furthermore, among the X-Y type or X-Y-X type block copolymer resins, it is preferable that X is a polymer unit with a glass transition point Tg of 0°C or higher. More preferably, X is a polymer unit with a glass transition point Tg of 50°C or higher. Moreover, Y is preferably a polymer unit with a glass transition point Tg of less than 0°C, and more preferably a polymer unit with a glass transition point Tg of -20°C or less. The glass transition point Tg is measured by differential scanning calorimetry (DSC).

Additionally, the block copolymer resin is preferably solid at 25°C. Additionally, it may be solid at temperatures outside this range. Because it is solid at the above temperature, it has excellent tackiness when formed into a dry film or applied to a substrate and temporarily dried.

Moreover, among the X-Y type or X-Y-X type block copolymer resins, it is preferable that X has high compatibility with thermosetting resins, and that 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 block in the center is incompatible with the matrix, it is thought that it is easy to exhibit a specific structure in the matrix.

Specifically, polymethyl methacrylate (PMMA), polystyrene (PS), etc. are preferred as the polymer unit etc. are preferable. In addition, if a hydrophilic unit with excellent compatibility with alkali-soluble resins, such as styrene units, hydroxyl group-containing units, carboxyl group-containing units, epoxy group-containing units, and N-substituted acrylamide units, is introduced into part of the polymer unit It becomes possible to improve performance. It is particularly preferred to introduce epoxy group-containing units into some of the polymer units X. Among the above, it is preferable that the polymer unit Additionally, Y is preferably poly n-butyl (meth)acrylate or polybutadiene. X and Y may each be composed of one type of polymer unit, or may be composed of polymer units made of two or more types of components.

Examples of the method for producing block copolymer resin include methods described in Japanese Patent Publication No. 2005-515281 and Japanese Patent Publication No. 2007-516326.

Commercially available X-Y-X type block copolymer resins include acrylic triblock copolymers manufactured using living polymerization manufactured by Arcmas. SBM type represented by polystyrene-polybutadiene-polymethyl methacrylate, MAM type represented by polymethyl methacrylate-polybutylacrylate-polymethyl methacrylate, and further MAM N treated with carboxylic acid modification or hydrophilic group modification. type or MAM A type. SBM types include E41, E40, E21, E20, etc., MAM types include M51, M52, M53, M22, etc., MAM N types include 52N, 22N, etc., and MAM A types include SM4032XM10. , Nanostrength (registered trademark) series, such as M52N, M65N, etc. Additionally, Clarity from Kuraray Co., Ltd. is also a block copolymer derived from methyl methacrylate and butyl acrylate.

As a block copolymer resin, a block copolymer resin whose molecular structure is precisely controlled and synthesized by a living polymerization method is preferable for obtaining the effects of the present invention. This is believed to be because the block copolymer resin synthesized by the living polymerization method has a narrow molecular weight distribution and the characteristics of each unit become clear. 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) and the number average molecular weight (Mn) measured by the method described later.

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.

If the mass average molecular weight of the block copolymer resin is 20,000 or more, the composition has mechanical properties such as flexibility and elasticity, but the adhesion does not become excessively high, the effect of improving flexibility and crack resistance becomes good, and the adhesion also becomes good. On the other hand, if the mass average molecular weight is 400,000 or less, the viscosity of the composition does not become too high and printability and developability are unlikely to decrease.

In addition, in the present invention, the mass average molecular weight and the number average molecular weight are determined using a GPC (gel permeation chromatography) device "GL7700" manufactured by GL Science Co., Ltd. and α-2500 manufactured by Tosoh Corporation as a column. α-4000 is used, the eluent is a 10mM lithium bromide solution of NMP and a 100mM phosphoric acid solution of NMP, and the molecular weight in terms of polystyrene is indicated using polystyrene as the standard material.

Block copolymer resin may be used individually by 1 type, or may be used in combination of 2 or more types. When the photosensitive resin composition contains an alkali-soluble resin, the mixing amount of the block copolymer resin is preferably 1 to 60 parts by mass, more preferably 2 to 50 parts by mass, particularly preferably, based on 100 parts by mass of the alkali-soluble resin. is 3 to 40 parts by mass. When the compounding amount of the block copolymer resin is 1 part by mass or more, flexibility and heat resistance improve, and when it is 60 parts by mass or less, the balance between flexibility and heat resistance becomes good.

[Photosensitive resin composition (B)]

The resin layer (B) is composed of a photosensitive resin composition (B) having a third gross value of 50 or more. 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 further contain a photopolymerizable compound and a photopolymerization initiator as the case may be. In order to achieve the desired gloss value, the photosensitive resin composition (B) requires that components such as resins and monomers in the composition are compatible with each other. That is, it does not include combinations of components that exhibit incompatibility as described above.

Hereinafter, components that can be used in the photosensitive resin composition (B) will be described.

(Alkali-soluble resin in photosensitive resin composition (B))

In the photosensitive resin composition (B), all known alkali-soluble resins can be used. Specific examples of alkali-soluble resins that can be used include the alkali resins described in detail with respect to the photosensitive resin composition (A), as long as the predetermined gross value is achieved. Soluble resins can be used.

(Thermosetting resin in photosensitive resin composition (B))

The photosensitive resin composition (B) contains a thermosetting resin. In the photosensitive resin composition (B), as long as the predetermined gross value is achieved, a compound similar to the thermosetting resin in the photosensitive resin composition (A) is used, and a curing reaction by heat such as a cyclic (thio)ether group is possible. Known and commonly used compounds having a functional group, such as epoxy compounds, are preferably used.

In addition, the details of the photopolymerizable compound and photopolymerization initiator that can be used as components of the photosensitive resin composition (B) are the same as those described in detail regarding the photosensitive resin composition (A).

When the photosensitive resin composition contains an alkali-soluble resin, the amount of the photopolymerizable compound in the photosensitive resin composition (B) is preferably 1 to 100 parts by mass, and 5 to 80 parts by mass, based on 100 parts by mass of the alkali-soluble resin. It is more preferable to deny it.

In addition to the above, photosensitive resin compositions (A) and (B) may further contain the following components.

(Inorganic filler/extending pigment)

Inorganic fillers and extenders can be added to suppress curing shrinkage of the cured product and improve properties such as adhesion and hardness. Such inorganic fillers and extender pigments include, for example, 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, Examples include Neuburg Silicious Earth.

(thermal curing catalyst)

A thermosetting catalyst can be blended with the photosensitive resin compositions (A) and (B) used in the laminate of the present invention. As a thermosetting catalyst, for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, Imidazole derivatives such as 1-cyanoethyl-2-phenylimidazole and 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole; Amines such as dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, and 4-methyl-N,N-dimethylbenzylamine. compounds, hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; Phosphorus compounds, such as triphenylphosphine, etc. are mentioned. Additionally, commercially available products include, for example, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ manufactured by Shikoku Kasei Kogyo Co., Ltd. (all brand names of imidazole-based compounds), and San-Apro Co., Ltd. U-CAT 3513N (trade name of dimethylamine compound), DBU, DBN, U-CAT SA 102 (all bicyclic amidine compounds and salts thereof), etc. These can be used individually or in mixture of two or more types.

Additionally, guanamine, acetoguanamine, benzoguanamine, melamine, tetrahydrophthalic anhydride addition 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, 2,4-diamino-6-methacryloyloxyethyl-S- S-triazine derivatives such as triazine-isocyanuric acid adducts may be used, and preferably, these compounds that also function as adhesion imparting agents are used in combination with a thermosetting catalyst. The thermosetting catalyst may be used individually by one type, or may be used in combination of two or more types.

The compounding amount of the thermosetting catalyst is preferably 0.1 to 5 parts by mass, more preferably 1 to 3 parts by mass, in terms of solid content per entire amount of the photosensitive resin composition.

(coloring agent)

As the colorant, known and commonly used colorants such as red, blue, green, yellow, white, and black can be blended, and any of pigments, dyes, and pigments may be used.

(organic solvent)

The organic solvent can be blended for preparing the photosensitive resin compositions (A) and (B) or for adjusting the viscosity for application to the base material 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 solvents. These organic solvents may be used individually by one type, or may be used as a mixture of two or more types.

(Other Ingredients)

If necessary, components such as mercapto compounds, adhesion promoters, antioxidants, and ultraviolet absorbers can be added. These can be used as known and commonly used ones. In addition, commonly known thickeners such as fine powdered silica, hydrotalcite, organic bentonite, and montmorillonite, and commonly known additives such as silicone-based, fluorine-based, and polymer-based antifoaming agents and/or leveling agents, silane coupling agents, and rust inhibitors are added. can do.

(Manufacturing process of cured product of laminate)

Below, an example of a processing process for manufacturing the laminate of the present invention will be described using FIG. 3. Here, an example of manufacturing a cured dry film shown in FIG. 2 will be described.

[(a) Lamination process]

As shown in Figure 3 (a) as a lamination process, the laminated body 10 of the invention is formed so that the resin layer (B) faces the substrate 20, such as a printed wiring board having a conductor circuit 21, for example. It is placed and laminated by pressing the substrate and the resin layer (B). On the other hand, in other applications, lamination for such electronic devices may not be performed prior. In this embodiment, each process of the curing treatment in a state in which the laminate is placed directly on the base will be explained. In addition, the following processes are not all essential processes, and are appropriately selected and performed depending on the intended use or the composition of the laminate.

[(b) Exposure process]

In curing the laminate of the present invention, an exposure process is performed. In the exposure step, the photopolymerization initiator and photobase generator contained in the resin layer (A), the resin layer (B), or both are irradiated with active energy rays (indicated by arrows in Figure 3(b)). A functional photopolymerization initiator or photobase generator is activated in a negative pattern. As an exposure machine, a direct drawing device, an exposure machine equipped with a metal halide lamp, etc. can be used. The pattern exposure mask is a negative type mask.

As the active energy ray used for exposure, it is preferable to use laser light or scattered light with a maximum wavelength in the range of 350 to 450 nm. By setting the maximum wavelength within this range, the photopolymerization initiator can be activated efficiently. In addition, the exposure amount varies depending on the film thickness, etc., but is usually 100 to 1500 mJ/cm2.

[(c) PEB process]

After the exposure, the exposed portion is cured by heating the resin layer. When the photosensitive resin compositions (A) and (B) of the present invention contain a photopolymerization initiator having a function as a photobase generator or both a photopolymerization initiator and a photobase generator, the base generated in the exposure process, The resin layer (B) can be hardened to the core. The heating temperature is, for example, 80 to 200°C. The heating time is, for example, 10 to 100 minutes. In addition, after the exposure process, when a heating process is performed in the presence of a photopolymerization initiator having a function as a photobase generator or both a photopolymerization initiator and a photobase generator, this heat curing process is performed using PEB (POST EXPOSURE It is called the BAKE) process, and this suppresses curing shrinkage of the coating film after photolithography, and provides excellent resolution as a result.

[(d) Development process]

When the above exposure process is performed, a development process is performed. In the development process, the unexposed portion is removed by alkaline development to form a negative patterned insulating film, particularly a cover lay and solder resist. The developing method may be a known method such as dipping. Additionally, as a developing solution, sodium carbonate, potassium carbonate, potassium hydroxide, amines, imidazoles such as 2-methylimidazole, alkaline aqueous solutions such as tetramethylammonium hydroxide aqueous solution (TMAH), or mixtures thereof can be used.

[(e) Post-cure process]

In addition, after the development process, the cured product of the laminate may be further irradiated with light or 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. Since the post-curing of the laminate 10 in the present invention is, for example, a ring-opening reaction of the epoxy resin by a thermal reaction, deformation and curing shrinkage can be suppressed compared to the case where curing proceeds by a photo radical reaction. there is.

[Component mounting process]

After being developed as described above, if necessary, the cured laminate of the present invention is subjected to a component mounting process (not shown). Through this process, various components can be mounted on a substrate containing the cured product of the present invention, and the electronic component of the present invention can be obtained.

[Reheating process]

The cured laminate after component mounting may be subjected to a reheating process (not shown). The heating temperature of 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. Additionally, the insulating film may be irradiated with light before or after the reheating process.

The cured laminate of the present invention obtained in this way is gross by heat pressing or applying heat or pressure to the cured product during the manufacturing process of the cured product of the above-described laminate, especially the component mounting process. Even when the value increases and the surface with a matte texture is lost, in this reheating process, the gloss value decreases again, making it possible to create a surface with a matte texture. Specifically, even when the outer surface gross value of the cured product of the present invention becomes 50 or more, the outer surface gross value can be brought back to 30 or less by performing a 10-minute reheating process at 260°C.

That is, the cured product of the present invention has a matte texture in the outermost layer (outer surface) of the resin layer (A), so even when the cured product is manufactured as part of an electronic device, scratches, etc. are difficult to be noticed, making the product It can improve the yield and also meet the preference or demand for a matte textured appearance.

In addition, the cured laminate of the present invention can well conceal circuits of electronic devices such as printed wiring boards due to the presence of both the resin layer (A) and the resin layer (B). By using both the resin layer (A) and the resin layer (B), the concealability of the circuit of the electronic device is improved compared to the case of using either the resin layer (A) or the resin layer (B), but this can be It is presumed that this effect is caused by a difference in refractive index resulting from a difference in composition of the photosensitive resin composition constituting the stratum (A) and the resin layer (B). Since the resin layer (A) is made of a layer showing incompatibility, but the resin layer (B) is made of a layer showing compatibility, a difference occurs in the refractive index of the resin layer (A) and the resin layer (B). . By applying such a cured laminate having a difference in refractive index between the resin layer (A) and the resin layer (B) on the circuit, the circuit is sufficiently concealed.

The laminate of the present invention and the cured product obtained therefrom can be applied to a rigid or flexible substrate, especially a printed wiring board in which a copper circuit is formed on a rigid substrate.

In the present invention, electronic components refer to components used in electronic circuits, and include active components such as printed wiring boards, transistors, light-emitting diodes, and laser diodes, as well as passive components such as resistors, condensers, inductors, and connectors. The cured laminate of the present invention provides mechanical properties as an insulating layer for these electronic components and a matte textured appearance.

Hereinafter, the second embodiment of the present invention will be described in detail.

The laminate of the present invention has a resin layer (A) and a resin layer (B), and is provided so that one side of the resin layer (B) is in contact with one side of the resin layer (A), and the resin layer ( A) has a block copolymer resin (A1) and a photopolymerizable compound (A2), and the resin layer (B) has an alkali-soluble (meth)acrylate resin (B1).

The laminated body resin layer (A) and the resin layer (B) of the present invention are arranged to be in contact with each other, and are cured in this arrangement. In this uncured laminate, the components of the resin layer (A) and the components of the resin layer (B) are mixed at the interface, especially through the heating process. As the components of the resin layer (A) and the resin layer (B) are mixed in this way, diffuse reflection of visible light occurs at the interface, so it is presumed that a cured film excellent in circuit concealment can be obtained. In addition, by using the laminate of the present invention, good circuit hiding properties can be obtained, so there is no need to use a roughened plastic film as in the prior art as the first film, and the decrease in resolution due to the unevenness of the support body is eliminated. It is thought that does not occur. Additionally, unlike the prior art, the laminate of the present invention has excellent mechanical strength because the entire resin layer is not in a non-uniform state. Therefore, by using the laminate of the present invention, it is possible to achieve both circuit concealment, mechanical strength, and resolution.

[Resin layer (A)]

The resin composition constituting the resin layer (A) contains 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 described above.

Both X-Y type block copolymer resin and X-Y-X type block copolymer resin can be used, but X-Y-X type block copolymer resin is preferable.

In addition, 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 a block copolymer resin of type

(A1) The compounding amount of the block copolymer resin is preferably in the range of 1 to 30 parts by mass, more preferably 2 to 20 parts by mass, relative to the solid content of the resin layer (A). The effect can be expected at 1 part by mass or more, and at 30 parts by mass or less, developability and applicability become good as a photocurable resin composition.

((A2) Photopolymerizable compound)

The photopolymerizable compound used in the resin layer (A) can be the same as that described in the first embodiment described above.

In particular, a photopolymerizable compound represented by the following general formula (I) is preferably used.

(In general formula (I), R1 means a hydrogen atom or a methyl group)

(A2) The compounding amount of the photopolymerizable compound is preferably 1% by mass to 40% by mass, more preferably 1% by mass to 30% by mass, and still more preferably 1.5% by mass, relative to the solid content of the resin layer (A). % to 20 mass%. By setting the compounding amount within the above range, photocurability can be improved, pattern formation can be facilitated, and the strength of the cured film can also be improved.

Other optional components that may be included in the resin layer (A) will be explained.

((A3) Epoxy resin)

As the epoxy resin, an epoxy resin similar to that described in the first embodiment described above can be used. In particular, bisphenol A type epoxy resin and/or novolac type epoxy resin can be preferably used.

In the resin layer (A), the epoxy resin may be mixed in any amount, but the range is 10 to 40% by mass, and is preferably 15 to 30% by mass, relative to the solid content of the resin layer (A). . By setting the mixing ratio within this range, development becomes good and fine patterns can be formed easily and with high precision.

((A4) Photopolymerization initiator)

As the photopolymerization initiator, a photopolymerization initiator similar to that described in the first embodiment described above can be used. As a photopolymerization initiator, it is preferable to use at least one type of photopolymerization initiator selected from the group consisting of an oxime ester-based photopolymerization initiator having an oxime ester group, an α-aminoacetophenone-based photopolymerization initiator, and an acylphosphine oxide-based photopolymerization initiator.

The amount of the photopolymerization initiator mixed is preferably 0.1% by mass to 20% by mass, and more preferably 1% by mass to 10% by mass, based on the solid content of the resin layer (A). If it is 0.1% by mass or more, photocurability improves, adhesion of the coating film to the substrate becomes good, and coating film properties such as chemical resistance also improve. On the other hand, by setting it to 20% by mass or less, the effect of reducing outgassing is obtained.

[Resin layer (B)]

The resin composition constituting the resin layer (B) contains the following components.

((B1) Alkali-soluble (meth)acrylate resin)

The (B1) alkali-soluble (meth)acrylate resin used in the present invention is preferably one derived from a carboxyl group and a (meth)acryloyl group in the molecule, and also a derivative thereof. (B1) As specific examples of the alkali-soluble (meth)acrylate resin, compounds listed below (which may be either oligomers or polymers) can be suitably used.

(1) Diisocyanates such as aliphatic diisocyanate, branched aliphatic diisocyanate, alicyclic diisocyanate, and aromatic diisocyanate, and bisphenol A-type epoxy resin, hydrogenated bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, and bisphenol S-type epoxy. Alkali resulting from polyaddition reaction between (meth)acrylates or partial acid anhydride modifications of bifunctional epoxy resins such as resins, bixylenol-type epoxy resins, and biphenol-type epoxy resins, and carboxyl group-containing di-alcohol compounds and diol compounds. Soluble urethane-based (meth)acrylate resin.

(2) During the synthesis of the resin of (1) above, a compound having one hydroxyl group and one or more (meth)acryloyl groups in the molecule, such as hydroxyalkyl (meth)acrylate, is added, and the terminal is (meth)acrylated. Alkali-soluble urethane-based (meth)acrylate resin.

(3) During the synthesis of the resin of (1) above, a compound having one isocyanate group and one or more (meth)acryloyl groups in the molecule, such as an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate, is added. Alkali-soluble urethane-based (meth)acrylate resin with (meth)acrylated terminals.

(4) An alkali-soluble (meth)acrylate resin obtained by reacting (meth)acrylic acid with a difunctional or higher multifunctional epoxy resin and adding a dibasic acid anhydride to the hydroxyl group present in the side chain.

(5) Alkali-soluble (meth)acrylate obtained by reacting (meth)acrylic acid with a polyfunctional epoxy resin obtained by adding the hydroxyl group of the difunctional epoxy resin and epoxidizing it with epichlorohydrin, and adding a dibasic acid anhydride to the resulting hydroxyl group. profit.

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

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

(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 (1) to (7) above.

In addition, in this specification, (meth)acrylate is a general term for acrylates, methacrylates, and mixtures thereof, and the same applies to other similar expressions.

Since the alkali-soluble (meth)acrylate resin (B1) described above has a large number of carboxyl groups in the side chain of the backbone polymer, development using a dilute aqueous alkali solution is possible.

Additionally, the acid value of the (B1) alkali-soluble (meth)acrylate resin is suitably in the range of 40 to 200 mgKOH/g, and more preferably in the range of 45 to 120 mgKOH/g. (B1) If the acid value of the alkali-soluble (meth)acrylate resin is 40 mgKOH/g or more, alkali development is performed satisfactorily. On the other hand, if it is 200 mgKOH/g or less, dissolution of the exposed area by the developing solution does not occur, and the line is stretched more than necessary. This does not become thinner, the distinction between the exposed and unexposed areas is maintained, and no dissolution or peeling occurs with the developing solution, and a normal resist pattern can be drawn.

In addition, the mass average molecular weight of the (B1) alkali-soluble (meth)acrylate resin varies depending on the resin skeleton, but is generally preferably in the range of 1,000 to 150,000, and further preferably 2,000 to 100,000. If the mass average molecular weight is 2,000 or more, tack-free performance becomes good, the moisture resistance of the coating film after exposure becomes sufficient, development is performed as designed, and resolution improves. On the other hand, by setting the mass average molecular weight to 150,000 or less, excellent developability is stably obtained and storage stability also becomes good.

The compounding amount of this (B1) alkali-soluble (meth)acrylate resin is 20 to 80% by mass, preferably 30 to 70% by mass, based on the solid content of the resin composition constituting the resin layer (B). It is appropriate. (B1) When the compounding amount of alkali-soluble (meth)acrylate resin is 20% by mass or more, film strength improves. On the other hand, setting it to 80% by mass or less is preferable because the viscosity of the composition becomes good and applicability improves.

These (B1) alkali-soluble (meth)acrylate resins can be used not limited to those listed above, and can be used alone or in a mixture of multiple types. In particular, among alkali-soluble (meth)acrylate resins, those with aromatic rings are preferable because they have a high refractive index and excellent resolution, and those with an additional novolac structure improve not only resolution but also PCT and crack resistance. It is desirable because it is excellent. Among them, alkali-soluble (meth)acrylate resins using phenolic compounds as starting materials, such as (6) and (7), can be suitably used because they have excellent HAST resistance and PCT resistance.

In the present invention, (B1) alkali-soluble (meth)acrylate resin ((B1) component) includes the (A1) block copolymer resin ((A1) component) and (A2) contained in the resin layer (A). ) It is thought that it shows incompatibility with at least one of the photopolymerizable compounds (component (A2)). That is, a mixture of component (A1), component (A2), and component (B1) or a mixture of resin compositions for forming resin layers (A) and (B) containing these components is used to form the resin layer (A) and (B). At the interface, an incompatible mixed state is formed, and as a result, the interface between both layers loses smoothness and generates irregularities. When visible light is incident on the interface having this unevenness, diffuse reflection of visible light occurs, and the circuit of the electronic component is well concealed. In this way, it is presumed that the laminate of the present invention exhibits good circuit hiding properties.

Other optional components that may be included in the resin layer (B) will be explained.

((B2) Epoxy Resin)

It is preferable that the resin composition constituting the resin layer (B) contains (B2) epoxy resin. As the (B2) epoxy resin, one similar to the (A3) epoxy resin described above as a component of the resin layer (A) can be used. The epoxy resin (A3) and the epoxy resin (B2) used in the resin layer (A) and resin layer (B) of the laminate may be of the same type or may be of separate types. Additionally, in the case where multiple types of epoxy resins are used in either or both of the resin layer (A) and the resin layer (B), some of them may be made of the same type of epoxy resin.

The (B2) epoxy resin in the resin layer (B) may be any compounding amount, but the range of 10 to 40% by mass is the standard, with respect to the total solid content of the resin composition constituting the resin layer (B), and is 15%. It is preferably from 30% by mass.

By setting the mixing ratio within this range, development becomes good and fine patterns can be formed easily and with high precision.

[Arbitrary components of the resin layer (A) and the resin layer (B)]

The resin layer (A) and the resin layer (B) may contain other optional components. As arbitrary components that the resin layer (A) and the resin layer (B) may contain, the same components as those described in the first embodiment described above can be used.

(Manufacturing process of laminate)

As the manufacturing process of the laminate and the manufacturing process of the cured product according to the second embodiment of the present invention, processes similar to the manufacturing process of the laminate and the manufacturing process of the cured product according to the first embodiment described above can be appropriately selected and used.

In the present 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. Preferably, it is 2 to 30 μm, and the total film thickness of both is 5 to 150 μm. Additionally, it is preferable that the film thickness of the resin layer (B) is larger than the film thickness of the resin layer (A).

As described in detail above, the cured laminate of the present invention provides mechanical properties as an insulating layer for electronic components and good circuit hiding properties.

Example

The present invention will be described in detail below by showing examples and comparative examples, but the present invention is not limited to the following examples. In addition, the values of “part” and “%” in this Example and Comparative Example are based on mass, unless otherwise specified.

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

1. Synthesis of resin components

(Synthesis Example 1-1: Polyamideimide resin solution having a carboxyl group (Resin 1-1))

In a four-necked 300 mL flask equipped with a nitrogen gas introduction tube, thermometer, and stirrer, 29.49 g (0.054 mol) of aliphatic diamine derived from dimer acid with 36 carbon atoms as dimer diamine (a) (manufactured by Croda Japan, product name PRIAMINE1075), 4.02 g (0.026 mol) of 3,5-diaminobenzoic acid and 73.5 g of γ-butyrolactone as carboxyl group-containing diamine (b) were added and dissolved at room temperature.

Next, 31.71 g (0.160 mol) of cyclohexane-1,2,4-tricarboxylic anhydride (c) and 1.54 g (0.008 mol) of trimellitic anhydride (d) were added, and kept at room temperature for 30 minutes. Additionally, 30 g of toluene was added, the temperature was raised to 160°C, the water generated along with the toluene was removed, the solution was maintained for 3 hours, and the solution was cooled to room temperature to obtain a solution containing the imidide.

6.90 g (0.033 mol) of trimethylhexamethylene diisocyanate and 8.61 g (0.033 mol) of dicyclohexylmethane diisocyanate as diisocyanate compound (e) were added to the solution containing the obtained imidized product, and the temperature was 160°C. was maintained for 32 hours and diluted with 36.8 g of cyclohexanone to obtain a solution (A-2) containing polyamidoimide resin. The mass average molecular weight Mw of the obtained polyamidoimide resin was 5840, the solid content was 40.4 mass%, the acid value was 62 mgKOH/g, and the content of dimer diamine (a) was 40.1 mass%.

(Synthesis Example 1-2: Synthesis of polyimide resin (resin 1-2) solution having phenolic hydroxyl group and carboxyl group)

In a separable three-necked flask equipped with a stirrer, nitrogen introduction tube, dividing ring, and cooling ring, 22.4 g of 3,3'-diamino-4,4'-dihydroxydiphenylsulfone, 2,2'-bis[ Add 8.2 g of 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; Under a nitrogen atmosphere, the mixture was stirred at room temperature and 100 rpm for 4 hours. Next, 20 g of toluene was added, and the mixture was stirred for 4 hours at a silicone bath temperature of 180°C and 150 rpm while distilling off toluene and water to obtain a polyimide resin solution (resin 1-2) having a phenolic hydroxyl group and a carboxyl group. The acid value of the obtained resin (solid content) was 18 mgKOH/g, Mw was 10,000, and the hydroxyl equivalent was 390.

(Synthesis Example 1-3: Synthesis of carboxyl group-containing resin (Resin 1-3) having a bisphenol F-type skeleton)

In the general formula ( _I ) below, After dissolving in , 60.9 parts of 98.5% NaOH was added over 100 minutes at 70°C while stirring.

After the above addition, the reaction was further performed at 70°C for 3 hours. After completion of the reaction, 250 parts of water were added and washing was performed. After oil-water separation, most of the dimethyl sulfoxide and excess unreacted epichlorohydrin were distilled and recovered from the oil layer under reduced pressure, and the reaction product containing the remaining subsalt and dimethyl sulfoxide was dissolved in 750 parts of methyl isobutyl ketone. , 10 more parts of 30% NaOH were added and reacted at 70°C for 1 hour. After completion of the reaction, it was washed twice with 200 parts of water. After oil-water separation, methyl isobutyl ketone was distilled and recovered from the oil layer to obtain epoxy resin (a1) with an epoxy equivalent weight of 310 g/eq and a softening point of 69°C. As for the obtained epoxy resin (a1), when calculated from the epoxy equivalent weight, about 5 out of 6.2 alcoholic hydroxyl groups in the starting material bisphenol F-type epoxy resin were epoxidized. 310 parts of this epoxy resin (a1) and 282 parts of carbitol acetate were added to a flask, heated and stirred at 90°C, and dissolved. The obtained solution was once cooled to 60°C, 72 parts (1 mole) of acrylic acid, 0.5 parts of methylhydroquinone, and 2 parts of triphenylphosphine were added, heated to 100°C, and reacted for about 60 hours to obtain an acid value of 0.2 mgKOH/g. The reactant was obtained. 140 parts (0.92 mol) of tetrahydrophthalic anhydride were added thereto, heated to 90°C, reaction was performed, and carboxyl group-containing resin (Resin 1-3) was obtained. The solid content concentration of the obtained carboxyl group-containing resin varnish was 62% by mass, and the solid acid value (mgKOH/g) was 100.

(Synthesis Example 1-4: Synthesis of carboxyl group-containing resin (Resin 1-4) having a bisphenol A-type skeleton)

In the general formula ( _I ) described _above , 371 parts of bisphenol A-type epoxy resin (epoxy equivalent weight 650 g/eq, softening point 81.1°C) where After dissolving 462.5 parts of dimethyl sulfoxide, 52.8 parts of 98.5% NaOH was added over 100 minutes at 70°C while stirring. After addition, reaction was further performed at 70°C for 3 hours. After completion of the reaction, 250 parts of water were added and washing was performed. After oil-water separation, most of the dimethyl sulfoxide and excess unreacted epichlorohydrin were distilled and recovered from the oil layer under reduced pressure, and the reaction product containing the remaining subsalt and dimethyl sulfoxide was dissolved in 750 parts of methyl isobutyl ketone. , 10 more parts of 30% NaOH were added and reacted at 70°C for 1 hour. After completion of the reaction, it was washed twice with 200 parts of water. After oil-water separation, methyl isobutyl ketone was distilled and recovered from the oil layer to obtain epoxy resin (a2) with an epoxy equivalent weight of 287 g/eq and a softening point of 64.2°C. When calculating from the epoxy equivalent weight of the obtained epoxy resin (a2), about 3.1 of the 3.3 alcoholic hydroxyl groups in the starting material bisphenol A type epoxy resin were epoxidized. 310 parts of this epoxy resin (a2) and 282 parts of carbitol acetate were added to a flask, heated and stirred at 90°C, and dissolved. The obtained solution was once cooled to 60°C, 72 parts (1 mole) of acrylic acid, 0.5 parts of methylhydroquinone, and 2 parts of triphenylphosphine were added, heated to 100°C, and reacted for about 60 hours to obtain an acid value of 0.2 mgKOH/g. The reactant was obtained. 140 parts (0.92 mol) of tetrahydrophthalic anhydride were added thereto, heated to 90°C, reaction was performed, and carboxyl group-containing resin (Resin 1-4) was obtained. The solid content concentration of the obtained carboxyl group-containing resin varnish was 62% by mass, and the solid acid value (mgKOH/g) was 100.

(Synthesis Example 1-5: Synthesis of photosensitive resin (Resin 1-5) having both an ethylenic double bond and a carboxyl group)

220 parts of cresol novolak-type epoxy resin (DIC Co., Ltd., 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 to dissolve. Next, 0.1 part of hydroquinone as a polymerization inhibitor and 2.0 parts of dimethylbenzylamine as a reaction catalyst were added. This mixture was heated to 95 to 105°C, 72 parts of acrylic acid was gradually added dropwise, and reaction was carried out for 16 hours. This reaction product was cooled to 80 to 90°C, 106 parts of tetrahydrophthalic anhydride was added, it was made to react for 8 hours, and it was taken out after cooling.

The photosensitive resin (Resin 1-5) having both an ethylenic double bond and a carboxyl group obtained in this way had a non-volatile content of 65%, a solid acid value of 100 mgKOH/g, and a mass average molecular weight Mw of about 3,500.

(Synthesis Example 1-6: Synthesis of tetrahydrophthalic anhydride-added melamine)

800 milliliters of ion-exchanged water was placed in a 2-liter beaker, a stirrer was placed in it, and the mixture was boiled while stirring on a stirrer with a hot plate. To this hot water, 12.6 g of melamine was added and completely dissolved. Additionally, 500 milliliters of ion-exchanged water was placed in a 1-liter beaker, a stirrer was placed in it, and the mixture was boiled while stirring on a stirrer with a hot plate. To this hot water, 15.2 g of tetrahydrophthalic anhydride was added, heated and stirred for 1 hour, and an aqueous solution of tetrahydrophthalic acid was obtained. This aqueous solution was added to the melamine aqueous solution and stirred. When this liquid mixture was cooled with ice water, crystals precipitated. This crystal was separated by filtration and then dried with a vacuum dryer to obtain a melamine compound.

2. Preparation of photosensitive resin compositions a to f

Resins 1-1 to 1-5 obtained by the above synthesis examples and other components were mixed in the composition shown in Table 1 below, each component was premixed with a stirrer, and then kneaded with a three-roll mill to obtain a photosensitive resin composition. a to f were prepared. Details of components other than Resins 1-1 to 1-5 are listed below in Table 1.

* The ratio of each component in Table 1 above is based on solid content.

[Alkali-soluble resin]

Resin 1-1: prepared according to Synthesis Example 1 (polyamidoimide resin having a carboxyl group)

Resin 1-2: prepared according to Synthesis Example 1-2 (polyimide resin having phenolic hydroxyl group and carboxyl group)

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 having both an ethylenic double bond and a carboxyl group)

[Fatty acid amide] Nikka amide S: N-stearyl stearic acid amide (Mitsubishi Chemical Co., Ltd.)

Nikkaamide OS: N-oleylstearic acid amide (Mitsubishi Chemical Co., Ltd.)

[Photopolymerization initiator]

・IRGACURE OXE02: Oxime-based photopolymerization initiator (manufactured by BASF Japan Co., Ltd.)

[Photopolymerizable compound]

·KRM8296: Trifunctional urethane acrylate (made by Daicel/Allnex Co., Ltd.)

DPHA: Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.)

[Thermosetting resin]

YDF-2004: Bisphenol F-type epoxy resin (manufactured by Nittetsu Chemical & Materials Co., Ltd.)

・EPICLON 860: Bisphenol A type epoxy resin (manufactured by DIC Corporation)

YDC-1312: 2,5-t-butylhydroquinone type epoxy resin (manufactured by Nittetsu Chemical & Materials Co., Ltd.)

・N-655: Cresol novolac type epoxy resin (manufactured by DIC Corporation)

・TEPIC-S: Triglycidyl isocyanurate (manufactured by Nissan Chemical Co., Ltd.)

[Thermal curing catalyst]

THPA melamine: tetrahydrophthalic anhydride added melamine (prepared by Synthesis Example 1-6)

[Constitutional pigment]

・Variace B-31: Barium sulfate (manufactured by Sakai Chemical High School Co., Ltd.)

3. Fabrication of test board

3-1. Production of dry film

The photosensitive resin compositions a to f were adjusted to the same viscosity using the organic solvent MEK. The resin composition described as the resin layer (A) in Tables 2 and 3 below was applied to the first film (material: polyethylene terephthalate, thickness: 25 μm, surface roughness (Ra): 0.03 μm, or 0.3 µm), and dried at 90°C for 15 minutes using a hot air circulation type drying furnace. Next, on the dried resin layer (A), the resin composition described as the resin layer (B) in Tables 2 and 3 was applied so that the film thickness after drying was the film thickness shown in the same table, and the resin composition was applied at 80°C. It was dried for 30 minutes. As a result, a laminate having the resin layer (A) and the resin layer (B) in that order on the first film was obtained. Next, a stretched polypropylene film was pasted as a second film on the resin layer (B), and it was used as a dry film for each Example and Comparative Example. In addition, in the case of a single layer as in Comparative Examples 1-1 to 1-3, after only the resin layer (A) was applied, a second film was pasted on the resin layer (A) to form a dry film.

In addition, for Comparative Example 1-2, since mat PET (PTHA-25, manufactured by Unitica Corporation, surface roughness Ra: 0.3 μm) was used as the first film, the unevenness of the mat PET was affected by the resin layer ( A), and as a result, the resin layer (A) has a physically roughened surface.

3-2. Production of first and second gross value measurement boards

After peeling off the second film of the dry film produced above, it was laminated in a first chamber at 80°C using a vacuum laminator (CVP-300: manufactured by Nikko Materials) under the conditions of a vacuum pressure of 3 hPa and a vacuum time of 30 seconds. , pressing was performed under the conditions of a press pressure of 0.5 MPa and a press time of 30 seconds, and the resin layer (B) was bonded to the printed wiring board so that it was in contact with the printed wiring board to produce first and second gross value measurement boards.

The first and second gross value measurement substrates obtained as described above were exposed from the resin layer (A) side using a pressure-sensitive adhesive double-sided exposure machine (model number ORC HMW 680GW) manufactured by Oak, under conditions of an integrated exposure dose of 250 mJ/cm2. Ultraviolet rays were irradiated (exposure process). Next, the first film provided on each side of the resin layer (A) was removed, and the value of the gloss value measured for the outer surface of the resin layer (A) thereafter was used as the first gross value.

After removing the first film, it was heat-cured at 150°C for 60 minutes, and the gloss value measured for the outer surface of the resin layer (A) was used as the second gross value.

Additionally, this test board was pressed using a vacuum press machine KVHC-PRESS (manufactured by Kitagawa Seiki) at a pressure of 3 MPa and a temperature of 170°C for 30 minutes (heat press process). The laminate after this heat press process was further reheated at 260°C for 10 minutes (reheating process).

3-3. Production of the third gross value measurement board

After peeling off the first film of the dry film produced above, using a vacuum laminator, it was bonded to a printed wiring board so that the resin layer (A) was in contact with the printed wiring board, and a third gross value measurement board was produced. . In addition, the single-layer dry films of Comparative Examples 1-1 to 1-3 are produced by peeling off the first film and then sticking them so that the surface of the resin layer (A) on the first film side is in contact with the printed wiring board.

The third substrate for gross value measurement obtained as above was irradiated with ultraviolet rays from the resin layer B side under conditions of an integrated exposure dose of 250 mJ/cm2 using a reduced-pressure contact type double-sided exposure machine (model number ORC HMW 680GW) manufactured by Oak Corporation (model number ORC HMW 680GW). exposure process). Next, the second film provided on each side of the resin layer (B) was removed, heat cured at 150°C for 60 minutes, and the gloss value measured for the outer surface of the resin layer (B) was used as the third gross value.

4. Measurement of gross value

The first, second and third gloss values of each measurement substrate and the gloss value of the outer surface of the resin layer (A) after the heat press process and reheating process were measured using a gloss meter "micro-TRI-gloss" (BYK Additives & Measured at an incident angle of 60° using an instrument manufactured by Instruments. The measurement results are shown in Tables 2 and 3.

5. Evaluation of gross value

Based on the above measurement results, the gross value of the surface of the resin layer (A) of the test board completely cured by the above treatment was comprehensively evaluated by evaluating the appearance of the matte texture. The standards for comprehensive evaluation of gross values are as follows.

◎: After heat pressing, the gross value becomes 30 or less again by reheating.

×: The gross value exceeds 30 even after reheating.

The results are combined and reported in Tables 2 and 3.

6. Solder heat resistance evaluation

A rosin-based flux was applied to the heat-cured substrate on which the second gross value was measured, immersed in a soldering tank previously set at 260°C and 280°C for 10 seconds, and the occurrence of lifting, expansion, and peeling of the cured coating film was evaluated. . The evaluation criteria are as follows.

◎: No lifting, swelling, or peeling occurred in either immersion at 260°C or 280°C.

○: When immersed at 260°C, no lifting, swelling, or peeling occurred, but when immersed at 280°C, lifting, swelling, or peeling occurred.

×: Floating and peeling occurred in both immersion at 260°C and 280°C.

7. Breaking strength evaluation

The cured resin layer was peeled off from the heat-cured substrate on which the second gross value was measured, and this was used as a test piece for evaluation of breaking strength. About this test piece, the breaking strength was measured and evaluated based on JIS K7127. The evaluation criteria are as follows.

◎: 40 MPa or more

○: 30 MPa or more, less than 40 MPa

×: Less than 30 MPa

8. Surface hardness (pencil hardness) evaluation

The cured resin layer was peeled off from the heat-cured substrate on which the second gross value was measured, and this was used as a test piece for surface hardness evaluation. The cured coating film of the test piece was tested according to the test method of JIS K 5600-5-4:1999, and the highest hardness at which no scratches occurred in the coating film was measured.

9. Circuit concealment evaluation

Using the same evaluation test piece as the evaluation test piece used in the above solder heat resistance evaluation method, the circuit concealability was evaluated by visual observation from a distance of 30 cm. The evaluation criteria are as follows.

◎: The circuit cannot be recognized.

○: Part of the circuit can be recognized.

×: The circuit can be clearly seen.

10. Resolution evaluation (evaluation of minimum aperture diameter))

The first film of the dry film produced by the above-mentioned method is peeled off, and vacuum laminated so that the resin layer (A) is in contact with the printed wiring board. Then, from the resin layer (A) side, a reduced pressure contact type double-sided exposure machine made by Oak (model) Ultraviolet light was irradiated through a step tablet (Kodak No. 2) by No. ORC HMW 680GW. Additionally, the first film was removed from the resin layer (A) of the test substrate, and development (30°C, 0.2 MPa, 1 wt% Na ₂ CO ₃ aqueous solution) was performed for 60 seconds. For each measurement sample, the light amount corresponding to the density portion of the 5th stage of the step tablet, which is the portion remaining after development, was set as the optimal exposure amount.

Similarly, after peeling off the first film of the dry film and vacuum lamination so that the resin layer (A) is in contact with the printed wiring board, a via opening diameter of 500 is applied to the outer surface of the resin layer (A) as a negative mask for resolution evaluation. A negative pattern having dimensions of ㎛, 300 ㎛, 150 ㎛, 100 ㎛, and 80 ㎛ was arranged, and through this, ultraviolet rays were irradiated at the optimal exposure amount using a pressure-sensitive adhesive double-sided exposure machine (model number ORC HMW 680GW) manufactured by Oak. Additionally, 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 board having a cured dry film (laminated body or monolayer film) was produced by heat curing at 150°C for 60 minutes. In this substrate, the pattern openings were observed with an SEM to determine the minimum opening diameter.

The mechanical property measurement results are listed in Tables 2 and 3.

According to the examples of the present invention, in addition to the matte texture of the outer surface of the cured laminate, the cured product showed excellent values for surface hardness, solder heat resistance, breaking strength, and circuit concealment. On the other hand, in any of Comparative Examples 1-1 to 1-3 of the single-layer structure and Comparative Examples 1-4 to 1-6 of the laminated structure, the mechanical properties and surface (corresponding to the outer surface of the laminate of the present invention) were different. Satisfactory results were never obtained on both sides of the loss value.

[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 polyimide resin solution (resin 2-1) having phenolic hydroxyl group and carboxyl group]

A polyimide resin solution (resin 2-1) having a phenolic hydroxyl group and a carboxyl group was obtained in the same manner as Synthesis Example 1-2 in the example of the first embodiment described above.

[Synthesis Example 2-2: Synthesis of carboxyl group-containing novolak-type acrylate resin (Resin 2-2)]

In an autoclave equipped with a thermometer, a nitrogen introduction device and an alkylene oxide introduction device, and a stirring device, 119.4 g of novolak-type cresol resin (manufactured by Aika Kogyo Co., Ltd., brand name "Shonol CRG951", OH equivalent weight: 119.4), potassium hydroxide 1.19 g and 119.4 g of toluene were added, the inside of the system was replaced with nitrogen while stirring, and the temperature was raised by heating. Next, 63.8 g of propylene oxide was slowly added dropwise, and reaction was performed at 125 to 132°C and 0 to 4.8 kg/cm2 for 16 hours. Afterwards, it was cooled to room temperature, and 1.56 g of 89% phosphoric acid was added to the reaction solution to neutralize the potassium hydroxide, and propylene oxide reaction of novolak-type cresol resin with a non-volatile content of 62.1% and a hydroxyl value of 182.2 g/eq. A solution was obtained. This was an average of 1.08 moles of alkylene oxide added per equivalent of phenolic hydroxyl group. Next, 293.0 g of the alkylene oxide reaction solution of the obtained novolak-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 added to a reactor equipped with a stirrer, thermometer, and air intake tube. Then, air was blown in at a rate of 10 ml/min and the mixture was stirred while reacting at 110°C for 12 hours. The water produced by the reaction was an azeotropic mixture with toluene, and 12.6 g of water flowed out. After that, it was cooled to room temperature, and the obtained reaction solution was neutralized with 35.35 g of 15% aqueous sodium hydroxide solution and then washed with water. Thereafter, toluene was distilled off in an evaporator while being replaced with 118.1 g of diethylene glycol monoethyl ether acetate, and a novolak-type acrylate resin solution was obtained. Next, 332.5 g of the obtained novolak-type acrylate resin solution and 1.22 g of triphenylphosphine were introduced into a reactor equipped with a stirrer, a thermometer, and an air blowing tube, and air was blown in at a rate of 10 ml/min and stirred, 60.8 g of tetrahydrophthalic anhydride was gradually added, and reaction was performed at 95 to 101°C for 6 hours. In this way, a carboxyl group-containing resin (resin 2-2) solution with a solid acid value of 88 mgKOH/g, a solid content of 71%, and a mass average molecular weight of 2,000 was obtained.

2. Preparation of resin compositions for resin layers (A) and (B)

According to the composition of the resin layers (A) and (B) in Table 4 below, each component was premixed with a stirrer and then kneaded with a three-roll mill to prepare each resin composition.

*The ratio of each component in the table above is based on solid content.

The details of each component listed in Table 4 are as follows.

Block copolymer resin 1: M65N:

Block copolymer resin 2: M52N:

Photopolymerizable Compound 1: DOUBLEMER 6MX75: DOUBLE BOND CHEMICAL IND. CO., LTD. Compounds represented by the general formula (I)

Photopolymerizable Compound 2: DOUBLEMER 527, DOUBLE BOND CHEMICAL IND. CO., LTD. Manufactured by our company, 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 N870 manufactured by DIC.

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 group and carboxyl group)

Shonol CRG951: manufactured by Aika Kogyo Co., Ltd., novolak-type cresol resin, OH equivalent weight: 119.4)

Coloring pigment (for resin layers (A) and (B)): Paliogen Black S0084: Perylene black pigment (manufactured by BASF)

KAYARAD ZCR-1569H: Acid-modified epoxy acrylate (manufactured by Nippon Kayaku Co., Ltd.) (adduct of dibasic acid anhydride to polyfunctional epoxy (meth)acrylate)

Resin 2-2: synthesized according to Synthesis Example 2-2 (carboxyl group-containing novolak-type acrylate resin)

Epoxy resin 2: Bisphenol A type novolac epoxy resin (manufactured by DIC)

By using mat PET (PTHA-25, manufactured by Unitica Corporation, surface roughness Ra: 0.3 μm) as the first film, irregularities were formed on the surface of the resin layer (A).

3. Production of dry film

Each resin composition obtained as described above was diluted with the organic solvent MEK and adjusted to an appropriate viscosity (10 mPa·s to 100 dPa·s). On the first film (PET film, thickness: 25 μm, surface roughness (Ra): 0.03 μm), a resin composition corresponding to the resin layer (A) shown in Table 4 was applied, and the film thickness after drying was shown in the same table. After applying to a film thickness, it was dried at 90°C for 15 minutes. Next, the resin composition corresponding to the resin layer (B) in Table 4 is applied onto the dried resin layer (A) so that the film thickness after drying is the film thickness shown in the same table, and then incubated at 80°C for 30 minutes. dried. As a result, a laminate having the resin layer (A) and the resin layer (B) in that order on the first film was obtained. However, Comparative Example 2-3 was used as a single-layer dry film containing only the resin layer (A). In addition, for Comparative Example 2-2, since mat PET (PTHA-25, manufactured by Unitica Corporation, surface roughness Ra: 0.3 μm) was used as the first film, the unevenness of the mat PET was reflected in the resin layer (A). ), and as a result, the resin layer (A) had a physically roughened surface.

4. Fabrication and evaluation of test boards

<Production of test board A>

A single-sided printed wiring board on which a circuit with a copper thickness of 15 μm was formed was prepared, and pretreatment was performed using CZ8100 manufactured by Mack. The dry films of each Example and Comparative Example produced as described above were bonded 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 at the optimal exposure amount below using a pressure-sensitive adhesive double-sided exposure machine (model number ORC HMW 680GW) manufactured by Oak, and baked at 100°C for 30 minutes, and then used as the first film when creating the laminate. The PET film was peeled off. After that, development was performed for 60 seconds in a 1 wt% sodium carbonate aqueous solution at 30°C under conditions of a spray pressure of 0.2 MPa, and a cured product of the laminate was obtained as a solder resist pattern. This substrate was irradiated with ultraviolet rays from the top of the resin layer (A) in a UV conveyor furnace under conditions of an integrated exposure dose of 1000 mJ/cm2, then cured by heating at 150°C for 60 minutes, and a cured product consisting of each laminate was prepared. Substrate A was produced.

<Determination of optimal exposure amount>

The optimal exposure amount used in pattern exposure when producing test board A was calculated as follows.

That is, a single-sided printed wiring board on which a circuit with a copper thickness of 15 μm was formed was prepared, and pretreatment was performed using CZ8100 manufactured by Mack. The dry films of each Example and Comparative Example produced as above were bonded 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 optimal exposure dose measurement sample obtained in this way was exposed through a step tablet (Kodak No. 2) using a pressure-sensitive contact type double-sided exposure machine manufactured by Oak (model number ORC HMW 680GW). After exposure, heating was performed at 100°C for 30 minutes. After that, the PET film used as the first film when creating the laminate was peeled off, and development (30°C, 0.2 MPa, 1 wt% Na ₂ CO ₃ aqueous solution) was performed for 60 seconds. For each measurement sample, the light amount corresponding to the density portion of the 5th stage of the step tablet, which is the portion remaining after development, was set as the optimal exposure amount, and was set as the light amount during pattern exposure of test substrates A and B.

<Concealment evaluation>

Using test board A, visual observation was made from a distance of 30 cm to evaluate the concealability of the circuit. The evaluation criteria are as follows.

◎: Hiding power is high and the circuit cannot be visually recognized.

○: Part of the circuit can be recognized.

×: The circuit can be clearly seen.

<Evaluation of adhesion>

In test board A, checkerboard-shaped cuts at 1 mm intervals were made in the cured material on the test piece with a cutter knife, cellophane tape was attached, the cellophane tape was peeled off, and the state of the remaining cured material on the test piece was evaluated according to the following judgment criteria. evaluated.

○: No peeling

×: There is peeling

<Electroless gold plating resistance evaluation>

For the test board A,

Using a commercially available electroless nickel plating bath and an electroless gold plating bath, plating was performed under conditions such that 0.5 μm of nickel and 0.03 μm of gold adhered, and a plating surface with a nominal width of 12 to 19 mm specified in JIS Z 1522 was applied to the plating surface. A tape peeling test was performed by attaching a tape and momentarily tearing off the tape. The presence or absence of staining of the plating was evaluated. The judgment criteria are as follows.

○: No staining or peeling is visible.

×: Slight staining is confirmed after plating.

<Production of test board B>

A single-sided printed wiring board on which a circuit with a copper thickness of 15 μm was formed was prepared, and pretreatment was performed using CZ8100 manufactured by Mack. The dry films of each Example and Comparative Example produced as described above were bonded using a vacuum laminator so that the resin layer (B) was in contact with the substrate, thereby forming a laminate on the substrate. On the laminate resin layer (A) of this substrate, a negative pattern having via opening diameters of 500 μm, 300 μm, 150 μm, 100 μm, and 80 μm was placed as a negative mask for resolution evaluation, and through this, Using a pressure-sensitive adhesive double-sided exposure machine (model number ORC HMW 680GW), the pattern was exposed at the optimal exposure amount determined by the method described above. Additionally, after baking at 100°C for 30 minutes, the PET film used as the first film when creating the laminate was peeled. After that, development was performed for 60 seconds in a 1 wt% sodium carbonate aqueous solution at 30°C under conditions of a spray pressure of 0.2 MPa, and a solder resist pattern was obtained. This substrate was irradiated with ultraviolet rays in a UV conveyor furnace under conditions of an integrated exposure dose of 1000 mJ/cm 2 and then cured by heating at 150° C. for 60 minutes to produce a test substrate B provided with a cured product made of each laminate.

<Resolution evaluation (evaluation of minimum aperture diameter)>

In test board B, the pattern opening was observed with an SEM, and the minimum opening diameter was determined.

<B-HAST resistance>

Test board B was placed in a high-temperature, high-humidity tank in an atmosphere of 130°C and 85% humidity, and a voltage of 3.5V was applied to the comb-shaped electrode portion (n=6) with line/space = 12 μm/13 μm, and maintained in the tank for 300 hours. B-HAST was performed. After 300 hours, B-HAST resistance was evaluated according to the following criteria. A resistance value of less than 1×10 ⁶ Ω was judged to be a short circuit.

◎: No short circuit between all six comb electrodes.

○: Short circuit occurs between one comb-shaped electrode out of six.

×: Short circuit occurs between two or more comb-shaped electrodes out of six.

<Breaking strength>

The cured product of the laminate was peeled from the test board B, and the breaking strength of the peeled cured product was measured and evaluated based on JIS K7127. The evaluation criteria are as follows.

◎: 40 MPa or more

○: 30 MPa or more, less than 40 MPa

The cured product of the laminate according to the example of the present invention showed good results in all evaluations. On the other hand, according to Comparative Examples 2-1 and 2-3, which had different resin compositions or layer structures, it was found that it was difficult to achieve both circuit concealment and mechanical properties. Additionally, in Comparative Example 2-2, although the concealment of the circuit was improved by a physical method, the resolution of the cured product was lowered.

Above, the invention made by the present inventors has been described in detail based on the embodiments. However, the present invention is not limited to the above embodiments, and it goes without saying that various changes can be made without departing from the gist of the invention.

1 first film
A Resin layer (A)
B resin layer (B)
2 second film

Claims (7)

A laminate comprising a resin layer (A) and a resin layer (B) provided on the resin layer (A),
The resin layer (A) has a first gloss value of 50 or more and a second gloss value of 30 or less,
The resin layer (B) has a third gross value of 50 or more,
(i) The first gross value is obtained after exposing the surface of the resin layer (A) to light in a laminate comprising the resin layer (B) and the resin layer (A) in this order on a substrate. It is a value obtained by measuring the gross value of the outer surface of the resin layer (A) in the laminate before heat curing,
(ii) The second gross value is obtained by further subjecting the laminate after the measurement of the first gross value to heat treatment at 150° C. for 60 minutes, and then measuring the outside of the resin layer (A) in the laminate. It is obtained by measuring the surface gross value,
(iii) The third gross value is further calculated by exposing the surface of the resin layer (B) to 150 in a laminate comprising the resin layer (A) and the resin layer (B) in this order on a substrate. A laminate, characterized in that it is obtained by measuring the gross value of the outer surface of the resin layer (B) in the laminate after heat treatment at ℃ for 60 minutes. A laminate comprising a resin layer (A) and a resin layer (B) provided on the resin layer (A),
The resin layer (A) is,
(A1) block copolymer resin,
(A2) Photopolymerizable compound
With
The resin layer (B) is,
(B1) A laminate characterized by having an alkali-soluble (meth)acrylate resin. According to paragraph 2,
The (A1) block copolymer resin is of type XYX and the mass average molecular weight Mw is 20,000 to 400,000. According to paragraph 2 or 3,
The photopolymerizable compound (A2) has the following general formula (I)

(In general formula (I), R1 means a hydrogen atom or a methyl group)
A laminate that is a compound represented by . The method according to any one of claims 1 to 4, further comprising a first film and a second film, and comprising the first film, the resin layer (A), the resin layer (B), and the second film. , A laminate characterized by being provided in this order. A cured product obtained by curing the resin layer of the laminate according to any one of claims 1 to 5. An electronic component having the cured product of claim 6.

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