CN117337234A

CN117337234A - Laminate, cured product thereof, and electronic component comprising same

Info

Publication number: CN117337234A
Application number: CN202280025179.9A
Authority: CN
Inventors: 土桥裕大; 周映旋; 冈本大地; 小田桐悠斗; 宫部英和
Original assignee: Taiyo Holdings Co Ltd
Current assignee: Taiyo Holdings Co Ltd
Priority date: 2021-03-31
Filing date: 2022-03-25
Publication date: 2024-01-02

Abstract

[ problem ] to provide a dry film laminate which exhibits a matt appearance after curing and has good mechanical properties and resolution. [ solution ] A laminate is obtained, which is characterized by comprising: the resin layer (A) has A1 st glossiness of 50 or more and A2 nd glossiness of 30 or less, and the resin layer (B) is provided on the resin layer (A), and the 3 rd glossiness of the resin layer (B) is 50 or more, or the laminate is characterized in that the resin layer (A) has (A1) a block copolymer resin and (A2) a photopolymerizable compound, and the resin layer (B) has (B1) an alkali-soluble (meth) acrylate resin.

Description

Laminate, cured product thereof, and electronic component comprising same

Technical Field

The present invention relates to a laminate, particularly a laminate usable as an insulating layer of an electronic component such as a printed circuit board, a cured product thereof, and an electronic component including the same.

Background

An insulating film called a solder layer is formed on a surface layer of a printed circuit board used in various electronic devices. Since the solder resist layer is generally gloss-like, a defective appearance is formed when a minute scratch is generated in the solder resist layer in a manufacturing process of a printed circuit board or a subsequent component mounting process, and this is one of factors that lower the yield. To avoid the appearance failure caused by such a minute scratch or to reduce the proportion thereof, a matt (matt) like solder resist layer is often required. In addition, from the viewpoints of improving the coverage of a circuit and improving the aesthetic feeling of a substrate, there is also a demand for a matte solder resist layer.

As a method for obtaining a matt-like solder resist, a method of using a specific resin composition as a composition for a solder resist has been proposed (for example, patent document 1). In patent document 1, as components of a composition for a solder resist layer, components that are incompatible with each other are used, whereby diffuse reflection of light incident on the surface of the solder resist layer occurs, and the glossiness is lowered. In addition, another method teaches that a matte-like solder resist layer can be obtained by roughening the surface of the solder resist layer to thereby suppress its glossiness (for example, patent document 2). Patent document 2 describes a method of obtaining a matte solder resist by applying a physical roughening method of a solder resist composition to a support subjected to a spray treatment.

Prior art literature

Patent document 1: international publication No. WO2001/058977

Patent document 2: japanese patent application laid-open No. 2012-141605

Disclosure of Invention

Problems to be solved by the invention

However, in the non-compatible matting technique using the resin described in patent document 1, there is room for research to ensure mechanical properties of the coating film because the entire coating film is unevenly separated.

In addition, in the method of matting the roughened support surface described in patent document 2, the irregularities of the solder mask thus provided are removed by applying pressure to the solder mask surface separately in the component mounting step or the like, and as a result, the glossiness is increased again, and a matt appearance cannot be obtained. Further, since the surface of the solder resist layer is uneven during exposure, the irradiated light is scattered, and as a result, there is a problem that the resolution is lowered.

That is, an object of the present invention is to provide: a laminate exhibiting a matt appearance after curing, excellent in circuit coverage, and having good mechanical properties and resolution, a cured product thereof, and an electronic component comprising the same.

Solution for solving the problem

The present inventors have made intensive studies and as a result, have found that the above-described problems can be solved by a laminate comprising: the resin composition comprises a resin layer (A) and a resin layer (B) arranged on the resin layer (A), wherein the 1 st glossiness of the resin layer (A) is more than or equal to 50, the 2 nd glossiness is less than or equal to 30, and the 3 rd glossiness of the resin layer (B) is more than or equal to 50.

The above object can be achieved by a laminate comprising: a resin layer (A), and a resin layer (B) provided on the resin layer (A), wherein the resin layer (A) has: (A1) A block copolymer resin and (A2) a photopolymerizable compound, wherein the resin layer (B) comprises: (B1) alkali-soluble (meth) acrylate resins.

The block copolymer resin (A1) of the present invention is preferably of the X-Y-X type, and has a mass average molecular weight Mw of 20000 to 400000.

The photopolymerizable compound (A2) of the present invention is preferably a compound represented by the following general formula (I),

(in the general formula (I), R1 represents a hydrogen atom or a methyl group).

The laminate of the present invention further includes a 1 st film and a 2 nd film, and may include the 1 st film, the resin layer (a), the resin layer (B), and the 2 nd film in this order.

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

The object of the present invention is also achieved by an electronic component having the cured product of the present invention.

ADVANTAGEOUS EFFECTS OF INVENTION

When the laminate of the present invention is applied to a substrate such as a printed circuit board, and a cured product is formed by a treatment such as heating, mechanical characteristics and resolution of the electronic device are well protected and the laminate has a matt appearance in both manufacturing and using the electronic device.

Drawings

Fig. 1 is a schematic cross-sectional view of a laminate according to an embodiment of the present invention.

Fig. 2 is a schematic cross-sectional view of a laminate according to another embodiment of the present invention.

Fig. 3 is a diagram for explaining an example of a process for producing a cured product thereof using the laminate of the present invention.

Detailed Description

Hereinafter, a 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 a laminate structure including a resin layer (a) and a resin layer (B) provided on the resin layer (a). In use, the resin layer (B) of the laminate is disposed so as to be in contact with a substrate (not shown) such as an electronic component typified by a printed circuit board, and the resin layer (a) is disposed so as to be separated from the substrate by the resin layer (B).

The laminate is disposed on the substrate as described above, and then subjected to exposure treatment and heat curing to form a cured film, thereby forming a solder resist layer, a cover layer, another circuit protection film, and the like, which protects the substrate during the production process, and also protects the substrate after the completion of the production. Curing of the laminate is performed by exposure to light and heat treatment. In the present invention, the resin layer (a) and the resin layer (B) are composed of the photosensitive resin composition (a) and the photosensitive resin composition (B), respectively.

The laminate of the present invention is usually subjected to an exposure step, a heat curing step, a developing step, a component mounting step, and a reheating step, and is then cured after the heat curing step. The glossiness of the resin layers constituting the laminate varies in the above-described series of steps such as exposure treatment and heat treatment. Here, "heat-curing" means that the resin layers (a) and (B) are heated to a temperature higher than a temperature at which thermosetting components contained therein crosslink (for example, 150 ℃ or higher) for a predetermined time to cure the resin layers, that is, the photosensitive resin composition is cured by heating.

After a predetermined process described below in a state where the resin layer (a) is disposed on the substrate via the resin layer (B), the 1 st and 2 nd glossiness of the surface of the resin layer (a) on the side not in contact with the resin layer (B) (also referred to as the surface of the resin layer (a) on the side away from the substrate, the outer surface) are set to predetermined values.

[ 1 st glossiness ]

The 1 st gloss in the laminate of the present invention corresponds to the value obtained as follows: (i) After exposing the laminate from the resin layer (a) side, the laminate is provided with: a resin layer (B) which is provided on the substrate and is composed of a photosensitive resin composition (B); and a resin layer (A) which is provided on the surface of the resin layer (B) opposite to the substrate and is composed of a photosensitive resin composition (A). When the laminate includes the 1 st film in contact with the resin layer (a) and/or the 2 nd film in contact with the resin layer (B), the laminate corresponds to the value obtained as follows: the 2 nd film was peeled off, vacuum laminated on the substrate so that the resin layer (B) was in contact with the substrate, then exposed from the resin layer (a) side, and then the 1 st film was peeled off, and the gloss of the outer surface of the resin layer (a) in the laminate was obtained before heat curing. The 1 st gloss is 50 or more, preferably 70 to 100.

In the present invention, a laminate comprising 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 1 st film on the resin layer (A) was subjected to a pressure-reducing adhesion type double-sided exposure machine (model ORC HMW 680 GW) manufactured by LTD using ORC MANUFACTURING CO., in which the cumulative exposure amount was 250mJ/cm ² Under the conditions of (a), ultraviolet light was irradiated from the resin layer (a) side, and then the 1 st gloss was measured. In the case where the laminate includes the 1 st film as described above, the 1 st film was peeled off after irradiation with ultraviolet light for 10 minutes, and then the 1 st glossiness was measured.

[ 2 nd glossiness ]

Further, the 2 nd glossiness in the laminate of the present invention corresponds to the value obtained as follows: (ii) The exposed laminate subjected to the measurement of the gloss of the 1 st was further dried by hot air circulation, and after heat treatment at 150℃for 60 minutes, the gloss of the outer surface of the resin layer (A) in the laminate was measured to obtain a value.

The heat curing conditions for measuring the 2 nd gloss are not limited to those for use (mounting) the laminate of the present invention on electronic equipment or the like. That is, the heat curing conditions in the case of using the laminate of the present invention can be appropriately selected from the conditions described in the heat curing step described later.

The glossiness of the resin layer (a) is the same or substantially the same as the whole resin layer (a), but in the present invention, a measured value in a part of the surface (outer surface) of the resin layer (a) on the side not in contact with the resin layer (B) is used for the purpose of defining the reference.

[ 3 rd glossiness ]

Further, the 3 rd glossiness in the laminate of the present invention is a value obtained as follows: (iii) a value obtained as the gloss of the outer surface of the resin layer (B) in the laminate after the laminate comprising the resin layer (A) provided on the substrate and the resin layer (B) provided on the surface opposite to the substrate is exposed to light and then cured by heating. That is, the measurement was performed in the same manner as in the 2 nd glossiness except that the lamination order of the resin layer (a) and the resin layer (B) to the substrate was different. When the laminate includes the 1 st film in contact with the resin layer (a) and/or the 2 nd film in contact with the resin layer (B), the value obtained as follows is equivalent to: the 1 st film was peeled off, and the resin layer (a) was brought into contact with the substrate, and then laminated on the substrate in a first chamber at 80 ℃ under vacuum pressure of 3hPa for 30 seconds, and then subjected to pressure under pressure of 0.5MPa for 30 seconds, and then exposed from the resin layer (B), and then the 2 nd film was peeled off, and heat-cured, and then the resultant was used as a value of the glossiness of the outer surface of the resin layer (B). The conditions for exposure and heat curing used for measuring the 3 rd glossiness are the same as those used for measuring the 2 nd glossiness.

The "gloss" in the present invention is a value measured by irradiating a laminate placed horizontally with light at an incident angle of 60 ° using a gloss meter (micro-TRI-gloss) manufactured by BYK Additives & Instruments.

(step of producing laminate)

Hereinafter, a process for manufacturing a laminate will be described with reference to fig. 2 and 3.

Fig. 2 is a schematic cross-sectional view of an embodiment of a laminate before application to an electronic device or the like. In this example, the 1 st film 1 (for example, a carrier film or a support film) is coated with a photosensitive resin composition (a) and dried, then the resin layer (a) is coated with a photosensitive resin composition (B) and dried, and the 2 nd film 2 is laminated on the photosensitive resin composition (B). That is, fig. 2 shows dry films (laminated body) in a laminated state.

Specifically, first, the photosensitive resin compositions (a) and (B) are diluted with an organic solvent or the like to a viscosity of about 0.1dpa·s to 200dpa·s, and the photosensitive resin composition (a) is applied to one surface of the 1 st film 1 by a known device such as a comma coater according to a conventional method. Thereafter, drying is generally performed at a temperature of 50 to 140 ℃ for 1 to 30 minutes, thereby forming a dried resin layer (a) on the 1 st film 1. A photosensitive resin composition (B) having a viscosity adjusted in the same manner as described above was applied to the surface of the resin layer (a) opposite to the 1 st film 1 and dried, whereby a laminate comprising the resin layer (a) and the resin layer (B) provided in contact with the 1 st film 1 was produced. The laminate of the present invention may be a laminate comprising the resin layer (a) and the resin layer (B), and may have the 1 st film 1, other films, and the resin layer. When the laminate is applied to an electronic device, a resin layer (B) is provided on the substrate side, and a resin layer (A) is provided on the opposite side to the substrate via the resin layer (B), so that a surface layer visible from the surface of the electronic device is formed.

On the surface of the laminate on the opposite side of the resin layer (B) from the resin layer (a), a 2 nd film 2 (for example, a cover film or a protective film) that can be peeled off may be laminated for the purpose of preventing dust from adhering to the surface of the resin layer (B) or the like. As the 1 st film 1 and the 2 nd film 2, conventionally known plastic films can be suitably used, and it is preferable that the adhesion force between the 2 nd film 2 and the resin layer (B) is smaller than the adhesion force between the 1 st film 1 and the resin layer (a). In the laminate 10 of the present invention, the application to the substrate is performed by first peeling the 2 nd film 2, and therefore, the adhesion is controlled as described above, and this operation is easy. The thickness of the 1 st film 1 and the 2 nd film 2 is not particularly limited, and is usually suitably selected in the range of 10 to 150. Mu.m.

Thus, a laminate having a 4-layer structure in which the 1 st film 1, the resin layer (a), the resin layer (B), and the 2 nd film 2 are laminated in this order was produced as a dry film (fig. 2).

The laminate of the present invention may be supported or protected on only one side by a film (either the 1 st film 1 or the 2 nd film 2), or may be a laminate containing no film. Further, the laminate (dry film) of the present invention may be wound into a roll.

From the viewpoint of the strength of the coating film, the interface between the layers can be compatible. That is, when the 1 st film 1 and the 2 nd film 2 are peeled off or when another peeled layer is present as a laminate, the resin layer (a) and the resin layer (B) are preferably bonded to each other at the time of peeling of the peeled layer to form a permanent coating film having high durability.

The laminate obtained as described above is applied to a substrate (protected object) such as a printed circuit board, and functions as a solder resist layer, a coverlay layer, or other circuit protective film. As described above, when the laminate has the 2 nd film 2, the laminate is peeled off, and the entire surface of the resin layer (B) is disposed so as to face the protective surface of the substrate, and the laminate is pressed by the laminator, so that the laminate is brought into close contact with the substrate.

In the present invention, "upper" and "opposite" refer to layers, surfaces, and the like described as the objects thereof, but they are not necessarily in contact with each other, and may be provided via other layers, as the case may be. On the other hand, "directly" or "directly" refers to a state of layer, surface contact.

As described above, the 1 st film 1 is laminated in advance, and it is preferable to laminate it to an electronic device by applying pressure and heat using a vacuum laminator or the like. By using such a vacuum laminator, even if the surface of the wiring board has irregularities, the dry film adheres to the wiring board, and thus, there is no mixing of bubbles, and the hole filling property of the concave portion on the surface of the wiring board is improved. The pressurizing condition is preferably 0.1 to 2.0MPa, and the heating condition is preferably 40 to 120 ℃.

In addition, as a method of disposing the laminate of the present invention on a circuit board, the following method may be used: and a method in which the resin layer (A) and the resin layer (B) are separately formed as dry films, and the dry films are sequentially laminated on the surface to be protected of the circuit board. That is, first, the dry film of the resin layer (B) is laminated on the circuit substrate, thereby forming the resin layer (B) on the circuit substrate. Thereafter, the dry film of the resin layer (a) is laminated on the resin layer (B), whereby the laminate of the present invention formed on the circuit substrate can be obtained.

Further, a laminate may be formed by directly coating the photosensitive resin composition (B) on an electronic device and drying the same, and then coating the photosensitive resin composition (a) on a film in a dried state of the photosensitive resin composition (B) and drying the same. The resin layer (B) formed of the photosensitive resin composition (B) and the resin layer (a) formed of the photosensitive resin composition (a) are laminated in this order from the electronic device side, and the resin layers (B) and (a) constitute the laminate of the present invention in a state of adhering to the electronic device. The photosensitive resin compositions (a) and (B) used in this case are also subjected to viscosity adjustment, coating, drying, and the like using an organic solvent, similarly 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 may be appropriately selected from known organic solvents described later.

The photosensitive resin compositions (a) and (B) may be applied by a known device such as a blade coater, a lip coater, or a film coater, in addition to the comma coater, and drying is preferably performed by using a device having a heat source of a vapor-based heating system such as a hot air circulation type drying furnace, an IR furnace, a hot plate, or a convection oven, or a known method such as a method of bringing hot air in a dryer into convection contact or a method of blowing from a nozzle to a support may be used.

The laminate thus produced is cured by a curing process described later to form a permanent coating on an electronic device (object to be protected) or the like of a printed circuit board.

[ resin layer (A) ]

The surface of the resin layer (a) of the laminate of the present invention, which does not face the resin layer (B), i.e., the surface (outer surface) which is considered to be visible as the outermost layer of a printed circuit board or the like, changes in gloss during each step of curing treatment or the like. Specifically, the 1 st glossiness of the resin layer (a) is 50 or more, preferably 70 or more and 100 or less. When the 1 st glossiness is 50 or more, a good resolution can be obtained.

Further, the 2 nd glossiness of the resin layer (a) of the laminate of the present invention is 30 or less, preferably 1 or more and 20 or less. When the 2 nd glossiness is 30 or less, the appearance of the mat appearance can be favorably exhibited.

[ resin layer (B) ]

The 3 rd gloss of the resin layer (B) used in the laminate of the present invention is 50 or more, preferably 70 or more and 100 or less. When the gloss of the outer surface of the resin layer (B) is 50 or more, good mechanical properties can be obtained.

In the present invention, the resin layer (B) after coating and drying has a film thickness of usually 1 to 150. Mu.m, preferably 3 to 120. Mu.m, and the resin layer (A) has a film thickness of usually 0.5 to 50. Mu.m, preferably 2 to 30. Mu.m, and the total film thickness of both may be 5 to 150. Mu.m. The film thickness of the resin layer (B) is preferably larger than that of the resin layer (a).

In the case where the laminate of the present invention and the cured product thereof are used as a solder resist layer or the like, development is preferably performed, and from this point of view, it is preferable that at least either one of the photosensitive resin compositions (a) and (B) or both contain an alkali-soluble resin, particularly a carboxyl-containing resin. In addition, the thermosetting resin is contained because the cured product is formed by heat curing. The components of the photosensitive resin compositions (a) and (B) are described below.

[ component of photosensitive resin composition (A) ]

The photosensitive resin composition (a) constituting the resin layer (a) showing the 1 st and 2 nd glossiness generally contains an alkali-soluble resin such as a carboxyl group-containing resin, preferably also contains a thermosetting resin, and may further contain a polyimide resin, an aromatic resin, a photosensitive resin, and a methyl methacrylate comb-type polymer. In order to achieve a desired gloss, the photosensitive resin composition (a) needs to contain a component that is incompatible with the resin in the photosensitive resin composition (a). The component is not limited to a specific component, and is not limited to a predetermined structure as long as it is a component showing incompatibility with the resin in the photosensitive resin composition (a). Examples thereof include: polyamide imide which shows incompatibility with polyimide resin, fatty acid containing hetero atom which shows incompatibility with carboxyl-containing resin, aliphatic block copolymer resin which shows incompatibility with aromatic resin, alicyclic type photopolymerisable compound which shows incompatibility with photosensitive resin, organosilicon compound which shows incompatibility with methyl methacrylate comb polymer, and the like. The photosensitive resin composition (a) may further contain a photopolymerizable compound and a photopolymerization initiator, as the case may be.

In addition, if the blending amount of the thermosetting resin or the photopolymerizable compound is large with respect to the high molecular weight components such as the alkali-soluble resin, the polyimide resin, the polyamideimide resin, etc., the resin layer (a) using the photosensitive resin composition (a) tends to show non-compatibility, and the desired glossiness of the present invention is shown. The compounding amount is not particularly limited, and for example, the total amount of the thermosetting resin and the photopolymerizable compound may 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))

As described above, the photosensitive resin composition (a) preferably contains an alkali-soluble resin, and a known alkali-soluble resin can be used, and a carboxyl group-containing resin is particularly preferred. Specific examples of the alkali-soluble resin that can be used in the photosensitive resin composition (a) include the following.

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

A carboxyl group-containing resin having an imide structure and an amide structure, in particular, a polyamideimide group-containing resin having a structure represented by the following general formula (1) and a structure represented by the following general formula (2) can be used.

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

Specifically, the polyamide-imide resin having such a structure may be represented by the following general formula (3).

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

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

The carboxyl group-containing resin having an imide structure and not having an amide structure is not particularly limited as long as it is a resin having a carboxyl group and an imide ring. The method of introducing an imide ring into a carboxyl group-containing resin can be used for the synthesis of a carboxyl group-containing resin having an imide structure and not having an amide structure. Examples of the resin include resins obtained by reacting a carboxylic anhydride component with an amine component and/or an isocyanate component. Imidization may be performed by thermal imidization, chemical imidization, or a combination thereof.

The carboxylic anhydride component includes tetracarboxylic anhydride and tricarboxylic anhydride, but is not limited to these anhydrides, and may be any compound having an acid anhydride group and a carboxyl group capable of reacting with an amino group or an isocyanate group, and may be used in combination with derivatives thereof. These carboxylic anhydride components may be used alone or in combination.

Examples of the tetracarboxylic anhydride include: pyromellitic dianhydride, 3-fluoropyromellitic dianhydride, 3, 6-difluoropyromellitic dianhydride, 3, 6-bis (trifluoromethyl) pyromellitic dianhydride, 3',4,4' -benzophenone tetracarboxylic dianhydride, 3', 4' -biphenyl tetracarboxylic dianhydride, 4 '-oxydiphthalic dianhydride, 2' -difluoro-3, 3',4,4' -benzophenone tetracarboxylic dianhydride, 3',4,4' -biphenyltetracarboxylic dianhydride, 4 '-oxydiphthalic dianhydride, 2' -difluoro-3, 3',4,4' -biphenyltetracarboxylic dianhydride, 6 '-bis (trifluoromethyl) -3,3',4 '-biphenyltetracarboxylic dianhydride, 2',5 '-tetrakis (trifluoromethyl) -3,3',4,4 '-biphenyltetracarboxylic dianhydride, 2',6 '-tetrakis (trifluoromethyl) -3,3',4 '-biphenyltetracarboxylic dianhydride, 5', 4,4 '-biphenyltetracarboxylic dianhydride, 2',6 '-tetrakis (trifluoromethyl) -3,3',4,4 '-biphenyltetracarboxylic dianhydride, 5', 3,3"",4,4 '-biphenyltetracarboxylic dianhydride, methylene-4, 4' -diphthalic dianhydride, 1-ethylidene-4, 4 '-diphthalic dianhydride, 2-propylidene-4, 4' -diphthalic dianhydride, 1, 2-ethylene-4, 4 '-diphthalic dianhydride, 1, 3-trimethylene-4, 4' -diphthalic dianhydride 1, 4-tetramethylene-4, 4 '-biphthalic dianhydride, 1, 5-pentamethylene-4, 4' -biphthalic dianhydride, 2-bis (3, 4-dicarboxyphenyl) -1, 3-hexafluoropropane dianhydride, difluoromethylene-4, 4 '-biphthalic dianhydride, 1, 2-tetrafluoro-1, 2-ethylene-4, 4' -biphthalic dianhydride 1, 4-tetramethylene-4, 4 '-biphthalic dianhydride, 1, 5-pentamethylene-4, 4' -biphthalic dianhydride, 2-bis (3, 4-dicarboxyphenyl) -1, 3-hexafluoropropane dianhydride difluoromethylene-4, 4 '-biphthalic dianhydride, 1, 2-tetrafluoro-1, 2-ethylene-4, 4' -biphthalic dianhydride, 1, 4-bis (3, 4-dicarboxyphenoxy) benzene dianhydride, 1, 3-bis [ 2- (3, 4-dicarboxyphenyl) -2-propyl ] benzene dianhydride, 1, 4-bis [ 2- (3, 4-dicarboxyphenyl) -2-propyl ] benzene dianhydride, bis [ 3- (3, 4-dicarboxyphenoxy) phenyl ] methane dianhydride bis [ 4- (3, 4-dicarboxyphenoxy) phenyl ] methane dianhydride, 2-bis [ 3- (3, 4-dicarboxyphenoxy) phenyl ] propane dianhydride, 2-bis [ 4- (3, 4-dicarboxyphenoxy) phenyl ] propane dianhydride, 2-bis [ 3- (3, 4-dicarboxyphenoxy) phenyl ] 1, 3-hexafluoropropane dianhydride 2, 2-bis [ 4- (3, 4-dicarboxyphenoxy) phenyl ] propane dianhydride, bis (3, 4-dicarboxyphenoxy) dimethylsilane dianhydride, 1, 3-bis (3, 4-dicarboxyphenoxy) -1, 3-tetramethyldisiloxane dianhydride, 2,3,6, 7-naphthalene tetracarboxylic dianhydride, 1,2,5, 6-naphthalene tetracarboxylic dianhydride, 3,4,9, 10-pyrene tetracarboxylic dianhydride, 2,3,6, 7-anthracene tetracarboxylic dianhydride, 1,2,7, 8-phenanthrene tetracarboxylic dianhydride, 1,2,3, 4-butane tetracarboxylic dianhydride, 1,2,3, 4-cyclobutane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, cyclohexane-1, 2,3, 4-tetracarboxylic dianhydride, cyclohexane-1, 2,4, 5-tetracarboxylic dianhydride, 3',4,4' -dicyclohexyltetracarboxylic 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-ethylidene-4, 4' -bis (cyclohexane-1, 2-dicarboxylic acid) dianhydride, 2-propylidene-4, 4' -bis (cyclohexane-1, 2-dicarboxylic acid) dianhydride, 1, 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' -difluoromethoxy-4, 4' -diphthalic dianhydride, 5' -difluoromethoxy-4, 4' -diphthalic dianhydride, 6' -difluoromethoxy-4, 4' -diphthalic dianhydride, 3',5,5', 6' -hexafluorooxy-4, 4' -diphthalic dianhydride, 3' -bis (trifluoromethyl) oxy-4, 4' -diphthalic dianhydride, 5' -bis (trifluoromethyl) oxy-4, 4' -diphthalic dianhydride, 6,6 '-bis (trifluoromethyl) oxy-4, 4' -diphthalic dianhydride, 3', 5' -tetrakis (trifluoromethyl) oxy-4, 4 '-diphthalic dianhydride, 3',6,6 '-tetrakis (trifluoromethyl) oxy-4, 4' -diphthalic dianhydride, 5', 6' -tetrakis (trifluoromethyl) oxy-4, 4 '-diphthalic dianhydride, 3',5,5', 6' -hexa (trifluoromethyl) oxy-4, 4 '-biphthalic dianhydride, 3' -difluorosulfonyl-4, 4 '-biphthalic dianhydride, 5' -difluorosulfonyl-4, 4 '-biphthalic dianhydride, 6' -difluorosulfonyl-4, 4 '-biphthalic dianhydride, 3',5,5', 6' -hexafluorosulfonyl-4, 4 '-diphthalic dianhydride, 3' -bis (trifluoromethyl) sulfonyl-4, 4 '-diphthalic dianhydride, 5' -bis (trifluoromethyl) sulfonyl-4, 4 '-diphthalic dianhydride, 6' -bis (trifluoromethyl) sulfonyl-4, 4 '-diphthalic dianhydride, 3',5,5 '-tetra (trifluoromethyl) sulfonyl-4, 4' -diphthalic dianhydride, 3', 6' -tetra (trifluoromethyl) sulfonyl-4, 4 '-diphthalic dianhydride, 5',6,6' -tetra (trifluoromethyl) sulfonyl-4, 4' -biphthalic dianhydride, 3', 5',6,6' -hexa (trifluoromethyl) sulfonyl-4, 4' -diphthalic dianhydride, 3' -difluoro-2, 2-perfluoropropylidene-4, 4' -diphthalic dianhydride, 5' -difluoro-2, 2-perfluoropropylidene-4, 4' -diphthalic dianhydride, 6' -difluoro-2, 2-perfluoropropylidene-4, 4' -diphthalic dianhydride, 3', 5',6,6' -hexafluoro-2, 2-perfluoropropylidene-4, 4' -diphthalic dianhydride, 3' -bis (trifluoromethyl) -2, 2-perfluoropropylidene-4, 4' -diphthalic dianhydride, 5' -bis (trifluoromethyl) -2, 2-perfluoropropylidene-4, 4' -diphthalic dianhydride, 6' -difluoro-2, 2-perfluoropropylidene-4, 4' -diphthalic dianhydride, 3',5,5' -tetrakis (trifluoromethyl) -2, 2-perfluoropropylidene-4, 4' -biphthalic dianhydride, 3', 6' -tetrakis (trifluoromethyl) -2, 2-perfluoropropylidene-4, 4' -biphthalic dianhydride, 5',6,6' -tetra (trifluoromethyl) -2, 2-perfluoropropylidene-4, 4' -biphthalic dianhydride, 3', 5',6,6 '-hexa (trifluoromethyl) -2, 2-perfluoropropylidene-4, 4' -biphthalic dianhydride, 9-phenyl-9- (trifluoromethyl) xanthene-2, 3,6, 7-tetracarboxylic dianhydride, 9-bis (trifluoromethyl) xanthene-2, 3,6, 7-tetracarboxylic dianhydride, bicyclo [ 2,2 ] oct-7-ene-2, 3,5, 6-tetracarboxylic dianhydride, 9-bis [ 4- (3, 4-dicarboxy) phenyl ] fluorene dianhydride, 9-bis [ 4- (2, 3-dicarboxy) phenyl ] fluorene dianhydride, ethylene glycol bis (trimellitate) dianhydride, 1,2- (ethylene) bis (trimellitate) anhydride, 1,3- (trimethylene) bis (trimellitate) anhydride 1,4- (tetramethylene) bis (trimellitic anhydride), 1,5- (pentamethylene) bis (trimellitic anhydride), 1,6- (hexamethylene) bis (trimellitic anhydride), 1,7- (heptamethylene) bis (trimellitic anhydride), 1,8- (octamethylene) bis (trimellitic anhydride), 1,9- (nonamethylene) bis (trimellitic anhydride), 1,10- (decamethylene) bis (trimellitic anhydride), 1,12- (dodecamethylene) bis (trimellitic anhydride), 1,16- (hexadecamethylene) bis (trimellitic anhydride), 1,18- (octadecyl methylene) bis (trimellitic anhydride), and the like. Examples of the tricarboxylic acid anhydride include trimellitic anhydride and nuclear hydrogenated trimellitic anhydride.

The amine component may be a diamine such as an aliphatic diamine or an aromatic diamine, a polyamine such as an aliphatic polyether amine, a diamine having a carboxylic acid, a diamine having a phenolic hydroxyl group, or the like, but is not limited to these amines. In addition, these amine components may be used alone or in combination.

As the diamine, there is used, examples thereof include diamines having 1 benzene nucleus such as p-phenylenediamine (PPD), 1, 3-diaminobenzene, 2, 4-toluenediamine, 2, 5-toluenediamine, 2, 6-toluenediamine, and the like, diaminodiphenyl ethers such as 4,4' -diaminodiphenyl ether, 3' -diaminodiphenyl ether, 3,4' -diaminodiphenyl ether, and the like 4,4' -diaminodiphenylmethane, 3' -dimethyl-4, 4' -diaminobiphenyl, 2' -bis (trifluoromethyl) -4,4' -diaminobiphenyl, 3' -dimethyl-4, 4' -diaminodiphenylmethane, 3',5,5' -tetramethyl-4, 4' -diaminodiphenylmethane, bis (4-aminophenyl) sulfide, 4' -diaminobenzidine, 3' -dichlorobenzidine 3,3' -dimethylbenzidine (o-tolidine), 2' -dimethylbenzidine (m-tolidine), 3' -dimethoxybenzidine, 2' -dimethoxybenzidine, 3' -diaminodiphenyl ether 3,3' -dimethylbenzidine (o-tolidine), 2' -dimethylbenzidine (m-tolidine), and 3,3' -dimethoxy benzidine, 2' -dimethoxy benzidine, 3' -diaminodiphenyl ether, 2, 2-bis (4-aminophenyl) -1, 3-hexafluoropropane 3,3 '-diaminodiphenyl sulfoxide, 3,4' -diaminodiphenyl sulfoxide 2, 2-bis (4-aminophenyl) -1, 3-hexafluoropropane, 3 '-diaminodiphenyl sulfoxide, 3,4' -diaminodiphenyl sulfoxide diamines having 2 benzene nuclei such as 4,4 '-diaminodiphenyl sulfoxide, 3' -dicarboxy-4, 4 '-diaminodiphenyl methane, etc 1, 3-bis (3-aminophenyl) benzene, 1, 3-bis (4-aminophenyl) benzene, 1, 4-bis (3-aminophenyl) benzene, 1, 4-bis (4-aminophenyl) benzene, 1, 3-bis (4-aminophenoxy) benzene, 1, 4-bis (3-aminophenoxy) benzene, 1, 4-bis (4-aminophenoxy) benzene, 1, 3-bis (3-aminophenoxy) -4-trifluoromethylbenzene, 3' -diamino-4- (4-phenyl) phenoxybenzophenone, 3 '-diamino-4, 4' -bis (4-phenylphenoxy) benzophenone, 1, 3-bis (3-aminophenylsulfide) benzene, 3-core diamines such as 1, 3-bis (4-aminophenylsulfide) benzene, 1, 4-bis (4-aminophenylsulfide) benzene, 1, 3-bis (3-aminophenylsulfide) benzene, 1, 3-bis (4-aminophenylsulfide) benzene, 1, 4-bis (4-aminophenylsulfide) benzene, 1, 3-bis [ 2- (4-aminophenyl) isopropyl ] benzene, 1, 4-bis [ 2- (4-aminophenyl) isopropyl ] benzene, 3 '-bis (3-aminophenoxy) biphenyl, 3' -bis (4-aminophenoxy) biphenyl, 4 '-bis (3-aminophenoxy) biphenyl, 4' -bis (4-aminophenoxy) biphenyl, bis [ 3- (3-aminophenoxy) phenyl ] ether, bis [ 3- (4-aminophenoxy) phenyl ] ether, bis [ 4- (3-aminophenoxy) phenyl ] ether, bis [ 4- (4-aminophenoxy) phenyl ] ether, bis [ 4- (3-aminophenoxy) phenyl ] ketone, bis [ 3- (4-aminophenoxy) phenyl ] ketone, bis [ 4- (3-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-bis [ 3- (3-aminophenoxy) phenyl ] propane, 2-bis [ 3- (4-aminophenoxy) phenyl ] propane, 2-bis [ 4- (3-aminophenoxy) phenyl ] propane 2, 2-bis [ 4- (4-aminophenoxy) phenyl ] propane, 2-bis [ 3- (3-aminophenoxy) phenyl ] 1, 3-hexafluoropropane 2, 2-bis [ 3- (4-aminophenoxy) phenyl ] -1, 3-hexafluoropropane, aromatic diamines such as diamines having 4 benzene nuclei such as 2, 2-bis [ 4- (3-aminophenoxy) phenyl ] -1, 3-hexafluoropropane and 2, 2-bis [ 4- (4-aminophenoxy) phenyl ] -1, 3-hexafluoropropane 1, 2-diaminoethane, 1, 3-diaminopropane, 1, 4-diaminobutane aliphatic diamines such as 1, 5-diaminopentane, 1, 6-diaminohexane, 1, 7-diaminoheptane, 1, 8-diaminooctane, 1, 9-diaminononane, 1, 10-diaminodecane, 1, 11-diaminoundecane, 1, 12-diaminododecane, and 1, 2-diaminocyclohexane, examples of the aliphatic polyether amine include ethylene glycol and/or propylene glycol based polyamines.

As the isocyanate component, there may be used diisocyanates such as aromatic diisocyanates and isomers thereof, polymers, aliphatic diisocyanates, alicyclic diisocyanates and isomers thereof, and other general-purpose diisocyanates, but not limited to these isocyanates. In addition, these isocyanate components may be used alone or in combination.

Examples of the diisocyanate include aromatic diisocyanates such as 4,4' -diphenylmethane diisocyanate, toluene diisocyanate, naphthalene diisocyanate, xylylene diisocyanate, biphenyl diisocyanate, diphenyl sulfone diisocyanate, and diphenyl ether diisocyanate, aliphatic diisocyanates such as isomers, polymers, hexamethylene diisocyanate, isophorone diisocyanate, and dicyclohexylmethane diisocyanate, alicyclic diisocyanates and isomers obtained by hydrogenating the aromatic diisocyanates, and other general-purpose diisocyanates.

(3) Carboxyl group-containing resin having no imide structure

The carboxyl group-containing resin having no imide structure is not particularly limited as long as it is a conventionally known various carboxyl group-containing resins having a carboxyl group. In particular, a carboxyl group-containing resin having an ethylenically unsaturated double bond in the molecule is more preferable from the viewpoints of photocurability and development resistance. Furthermore, the unsaturated double bond is preferably derived from acrylic acid or methacrylic acid or derivatives thereof.

As specific examples of the carboxyl group-containing resin, the compounds listed below (both oligomers and polymers) can be suitably used.

(3-1) A carboxyl group-containing resin obtained by copolymerizing an unsaturated carboxylic acid such as (meth) acrylic acid with an unsaturated group-containing compound such as styrene, alpha-methylstyrene, a lower alkyl (meth) acrylate, isobutylene, etc.

(3-2) a carboxyl group-containing polyurethane resin obtained by the polyaddition reaction of a diisocyanate such as an aliphatic diisocyanate, a branched aliphatic diisocyanate, an alicyclic diisocyanate or an aromatic diisocyanate with a carboxyl group-containing diol compound such as dimethylolpropionic acid or dimethylolbutyric acid, a diol compound such as a polycarbonate polyol, a polyether polyol, a polyester polyol, a polyolefin polyol, an acrylic polyol, a bisphenol A alkylene oxide adduct diol or a compound having a phenolic hydroxyl group or an alcoholic hydroxyl group.

(3-3) a carboxyl group-containing photosensitive polyurethane resin obtained by addition polymerization of a diisocyanate, a (meth) acrylate or a partial anhydride modification thereof, a carboxyl group-containing diol compound, and a diol compound based on a 2-functional epoxy resin such as a bisphenol A-type epoxy resin, a hydrogenated bisphenol A-type epoxy resin, a bisphenol F-type epoxy resin, a bisphenol S-type epoxy resin, a bisxylenol-type epoxy resin, and a bisphenol-type epoxy resin.

(3-4) A carboxyl group-containing photosensitive polyurethane resin obtained by adding a compound having 1 hydroxyl group and 1 or more (meth) acryloyl groups in the molecule, such as hydroxyalkyl (meth) acrylate, to the synthesis of the resin of the above (3-2) or (3-3) to thereby carry out terminal (meth) acrylation.

(3-5) A carboxyl group-containing photosensitive polyurethane resin obtained by terminal (meth) acrylation by adding a compound having 1 isocyanate group and 1 or more (meth) acryloyl groups in the molecule, such as an equimolar reactant of isophorone diisocyanate and pentaerythritol triacrylate, to the synthesis of the resin of the above (3-2) or (3-3).

(3-6) reacting a polyfunctional (solid) epoxy resin having a 2-function or more with (meth) acrylic acid, and adding a dibasic acid anhydride to a hydroxyl group present in a side chain.

(3-7) a carboxyl group-containing photosensitive resin obtained by reacting (meth) acrylic acid with a polyfunctional epoxy resin obtained by epoxidizing the hydroxyl groups of a 2-functional (solid) epoxy resin with epichlorohydrin, and adding a dibasic acid anhydride to the hydroxyl groups thus formed.

(3-8) a carboxyl group-containing polyester resin obtained by reacting a 2-functional oxetane resin with a dicarboxylic acid such as adipic acid, phthalic acid, hexahydrophthalic acid, etc., and adding a dibasic acid anhydride such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, etc., to the generated primary hydroxyl group.

(3-9) reacting a compound having a plurality of phenolic hydroxyl groups in 1 molecule with an alkylene oxide such as ethylene oxide or propylene oxide to obtain a reaction product, reacting the reaction product with an unsaturated group-containing monocarboxylic acid, and reacting the reaction product thus obtained with a polybasic acid anhydride to obtain a carboxyl group-containing photosensitive resin.

(3-10) a carboxyl group-containing photosensitive resin obtained by reacting a compound having a plurality of phenolic hydroxyl groups in 1 molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate to obtain a reaction product, reacting the reaction product with an unsaturated group-containing monocarboxylic acid, and reacting the reaction product thus obtained with a polybasic acid anhydride.

(3-11) A carboxyl group-containing photosensitive resin obtained by further adding a compound having 1 epoxy group and 1 or more (meth) acryloyl groups in 1 molecule to the resins of (3-1) to (10).

In the present specification, (meth) acrylate refers to a term generically referring to acrylate, methacrylate, and a mixture thereof, and the same applies to other similar expressions.

The carboxyl group-containing resin suitable for use as the alkali-soluble resin of the present invention described above has an acid value of preferably 20 to 200mgKOH/g, more preferably 60 to 150mgKOH/g, in order to cope with the photolithography step. When the acid value is 20mgKOH/g or more, the solubility in alkali is increased, the development becomes good, and the degree of crosslinking with the heat-curable component after light irradiation becomes high, so that a sufficient development contrast can be obtained. On the other hand, if the acid value is 200mgKOH/g or less, accurate pattern drawing becomes easy, and particularly so-called hot fogging in a PEB (POST EXPOSURE BAKE) step after light irradiation, which will be described later, can be suppressed, and the process margin becomes large.

In addition, in terms of developability and cured coating film characteristics, the mass average molecular weight Mw of such carboxyl group-containing resin is preferably 100000 or less, more preferably 1000 to 100000, and further preferably 2000 to 50000. If the molecular weight is 100000 or less, alkali solubility of the unexposed portion increases, and developability improves. On the other hand, if the molecular weight is 1000 or more, sufficient development resistance and cured physical properties in the exposed portion can be obtained after exposure to light and PEB.

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

The photosensitive resin composition (a) preferably contains a thermosetting resin. As the thermosetting resin, a conventionally known resin having a functional group capable of undergoing a curing reaction by heat, such as a cyclic (thio) ether group, is used, for example, an epoxy resin.

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, alicyclic epoxy resin, trihydroxyphenyl methane type epoxy resin, xylenol type or biphenol type epoxy resin, and a mixture thereof; bisphenol S-type epoxy resins, bisphenol A novolac-type epoxy resins, tetraphenyl ethane-type epoxy resins, heterocyclic epoxy resins, diglycidyl phthalate resins, tetraglycidyl ditolyl ethane resins, naphthalene-containing epoxy resins, epoxy resins having dicyclopentadiene skeleton, glycidyl methacrylate copolymerized epoxy resins, cyclohexylmaleimide and glycidyl methacrylate copolymerized epoxy resins, CTBN modified epoxy resins, and the like. Among them, particularly preferred epoxy resins as the component of the photosensitive resin composition (a) are bisphenol a type epoxy resins, novolac type epoxy resins, or a combination thereof.

As the compounding amount of the above thermosetting resin, the equivalent ratio to 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 compounding ratio to the range, development becomes good, and a fine pattern can be easily formed. The above equivalent ratio is more preferably 1:0.2 to 1:5.

(photopolymerizable Compound)

In the case where the laminate of the present invention and the cured product thereof are used as a solder resist layer or the like, the photosensitive resin composition (a) preferably contains a photopolymerizable compound, and any photopolymerizable compound conventionally used in the production of a solder resist layer or the like can be used.

Examples of the photopolymerizable compound contained in the photosensitive resin composition (a) include a compound having 2 or more ethylenically unsaturated groups in the molecule, a compound obtained by adding an α, β -unsaturated carboxylic acid to a polyol, a compound obtained by adding an α, β -unsaturated carboxylic acid to a glycidyl group-containing compound, and the like.

Examples of the compound having 1 ethylenically unsaturated group in the molecule include monofunctional (meth) acrylates, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, glycidyl (meth) acrylate and the like, (meth) acrylates having a heterocyclic group such as an acryl morpholine or a tetrahydrofuranyl group, and in particular, (meth) acrylates having a cyclic group containing oxygen.

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

(in the general formula (I), R1 represents a hydrogen atom or a methyl group)

Examples of the compound having 2 or more ethylenically unsaturated groups in the molecule include diacrylates of diols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol; polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol and trihydroxyethyl isocyanurate, and polyhydric acrylic esters such as ethylene oxide adducts and propylene oxide adducts thereof; a phenoxy acrylate, bisphenol a diacrylate, and a polyvalent acrylate such as an ethylene oxide adduct or a propylene oxide adduct of these phenols; polyglycidyl ethers such as diglycidyl ether, triglycidyl ether, trimethylolpropane triglycidyl ether and triglycidyl isocyanurate; and melamine acrylate, and at least 1 of each methacrylate corresponding to the above acrylate, and the like.

Examples of the compound obtained by adding an α, β -unsaturated carboxylic acid to a polyhydric alcohol include ethylene glycol diacrylate, diethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, propylene glycol diacrylate, polypropylene glycol diacrylate, butylene glycol diacrylate, pentylene glycol diacrylate, 1, 6-hexanediol diacrylate, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, glycerol diacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and at least 1 of the respective methacrylates corresponding to the above acrylates.

Examples of the compound obtained by adding an α, β -unsaturated carboxylic acid to a glycidyl group-containing compound include ethylene glycol diglycidyl ether diacrylate, diethylene glycol diglycidyl ether diacrylate, trimethylolpropane triglycidyl ether triacrylate, bisphenol a glycidyl ether diacrylate, phthalic acid diglycidyl ester diacrylate, and glycerol polyglycidyl ether polyacrylate; and at least 1 of 2, 2-bis (4-acryloyloxydiethoxyphenyl) propane, 2-bis- (4-acryloyloxypolyethoxyphenyl) propane, 2-hydroxy-3-acryloyloxypropyl acrylate, and each methacrylate corresponding to the above acrylate, and the like. The photopolymerizable compound may be used in an amount of 1 or 2 or more.

When the photosensitive resin composition contains an alkali-soluble resin in the amount of the photopolymerizable compound, the amount of the photopolymerizable compound to be blended is preferably 5 to 100 parts by mass, more preferably 10 to 90 parts by mass, still more preferably 15 to 85 parts by mass, per 100 parts by mass of the alkali-soluble resin, in terms of solid matter conversion. When the blending amount is in the above range, the photocurability is improved, the patterning becomes easy, and the mechanical strength of the cured product can be improved.

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

Examples of the urethane acrylate include U-108A, UA-112P, UA-5201, UA-512, UA-412A, UA-4200, UA-4400, UA-340P, UA-2235PE, UA-160TM, UA-122P, UA-512, UA-W2, UA-7000, UA-7100, U-6HA, U-6H, U-15HA, and UA-32P, U-324A, UA-7200 manufactured by Xinzhongcun chemical Co., ltd; CN968, CN9006, CN9010, CN962, CN963, CN964, CN965, CN980, CN981, CN982, CN983, CN996, CN9001, CN9002, CN9788, CN9893, CN978, CN9782, CN9783, CN929, CN944B85, CN989, CN9008; m-1100, M-1200, M-1210, M-1310, and M-1600 manufactured by Toyama Synthesis Co., ltd; UN-9000PEP, UN-9200A, UN-7600, UN-333, UN-1255, UN-6060PTM, UN-6060P, SH-500B, manufactured by Utility company; AH-600, AT-600, manufactured by Kabushiki Kaisha Co., ltd; EBECRYL 280, EBECRYL 284, EBECRYL 402, EBECRYL 8402, EBECRYL 8807, EBECRYL 9270, EBECRYL 264, EBECRYL 265, EBECRYL 1259, EBECRYL 8201, KRM8296, EBECRYL 294/25HD, EBECRYL 4820, EBECRYL 1290K, KRM8200, EBECRYL 5129, EBECRYL 8210, EBECRYL 8301, EBECRYL 8405; UN-3320HA, UN-3320HB, UN-3320HC, UN-3320HS, UN-904, UN-901T, UN-905, UN-952; the examples of the "primer" include "primer" and "primer" such as "primer" 5212, primer 5232B, doublemer, primer 5500, primer 570, primer 583-1, primer 5812, primer 5220, primer 527, primer 5400, primer 553, primer 5700, primer 584, primer 5900, primer 5222, primer 528, primer 5405, primer 554, primer 571, primer 588, primer 850, primer 523, primer 530M, doublemer H, doublemer 564, primer 576, primer 594, primer 87 357200, primer 7201M, doublemer 7210, and primer 88A.

Examples of the polyester acrylates include Aronix M-6100, M-6200, M-6250, M-6500, M-7100, M-7300, K, M-8030, M-8060, M-8100, M-8530, M-8560, and M-9050 manufactured by Toyama Synthesis Co., ltd; the Double bond products include Double 2015, double bond 2231-TFdouble bond 2319, double bond 257, double bond 276, double bond 284, double bond 2019, double bond 2232, double bond 236, double bond 270, double bond 278, double bond 285, double bond 220, double bond 2315-100, double bond 245, double bond 272, double bond 278X25, double bond 286, double bond 2230-TF, double bond 2315HM35, double bond 246, double bond 275, double bond 281, double bond 287, and the like.

As epoxy (meth) acrylate, there may be mentioned, in addition to glycidyl group-containing (meth) acrylate, a modified form thereof, and examples of commercial products include, for example, a Double bond 1283 to C, doublemer, a Double bond 1710, a Double bond 186, a Double bond 193 to TP50, a Double bond 127 to 100, a Double bond 129, a Double bond 1701, a Double bond 1720, a Double bond 188, a Double bond 193, a Double bond 127 to TP20, a Double bond 156, a Double bond 1702, a Double bond 176 to TF, a Double bond 191, a Double bond 128, a Double bond 1636, a Double bond 1703, a Double bond 176 to TF 5, a Double bond 193A to TF, a Double bond 6MX75 to E, and the like.

[ photopolymerization initiator ]

The photopolymerization initiator that can be used in the photosensitive resin composition (a) includes known and commonly used photopolymerization initiators. In particular, a photopolymerization initiator having a function as a photobase generator is suitable for use in the PEB step after light irradiation, which will be described later. When the photosensitive resin composition (a) contains a photopolymerizable alkali-soluble resin or a photopolymerizable compound, it is desirable to add a photopolymerization initiator. In the PEB step, a photopolymerization initiator and a photobase generator may be used in combination.

The photopolymerization initiator having a function as a photobase generator is a compound of 1 or more alkaline substances which undergo a change in molecular structure by irradiation with ultraviolet light, visible light or the like, or undergo molecular cleavage to produce a compound that can function as a catalyst for polymerization of a thermosetting resin to be described later. Examples of the alkaline substance include secondary amines and tertiary amines. Examples of such photopolymerization initiators having a function as a photobase generator include α -aminoacetophenone compounds, oxime ester compounds, compounds having substituents such as acyloxyimino groups, N-formylated aromatic amino groups, N-acylated aromatic amino groups, nitrobenzyl carbamate groups, allyloxybenzyl carbamate groups, and the like. Among them, oxime ester compounds and α -aminoacetophenone compounds are preferable, and oxime ester compounds are more preferable. The α -aminoacetophenone compound is particularly preferably one having 2 or more nitrogen atoms.

The α -aminoacetophenone compound may have a benzoin ether bond in the molecule, and may be cleaved in the molecule when irradiated with light to produce an alkaline substance (amine) exhibiting a curing catalyst function.

The oxime ester compound may be any compound that generates an alkaline substance by irradiation with light.

The photopolymerization initiator may be used alone or in combination of 2 or more. When the photosensitive resin composition contains an alkali-soluble resin, the amount of the photopolymerization initiator to be blended 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. When the amount is 0.1 parts by mass or more, the contrast of development resistance of the irradiated portion/non-irradiated portion can be obtained satisfactorily. When the amount is 40 parts by mass or less, the cured product properties are improved.

[ surfactant ]

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, nonionic surfactants and the like can be used. The surfactant is preferably a surfactant that is solid at room temperature, and more preferably a fatty acid containing a heteroatom.

As the fatty acid containing a hetero atom, a known compound can be suitably used, and for example, in the present invention, a fatty acid amide dispersed in water can be given. The type of fatty acid amide may be a general user. Specifically, examples thereof include unsaturated 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, saturated fatty acid bisamides such as N-stearyl stearic acid amide, N-oleyl oleic acid amide, N-stearyl oleic acid amide, N-oleyl palmitic acid amide, hydroxymethyl amides such as hydroxymethyl stearic acid amide and hydroxymethyl behenic acid amide, methylene bisstearic acid amide, ethylene biscapric acid amide, ethylene bislauric acid amide, ethylene bisstearic acid amide, ethylene bisisostearic acid amide, ethylene bishydroxystearic acid amide, ethylene bisbehenic acid amide, hexamethylenebisstearic acid amide, hexamethylenebisbehenic acid amide, hexamethylenebishydroxystearic acid amide, N ' -distearyl adipic acid amide, N ' -distearyl sebacic acid amide and other saturated fatty acid bisamides such as ethylene bisoleic acid amide, hexamethylenebisoleic acid amide, N ' -dialkylenebisoleic acid amide and other unsaturated bisstearylbisstearic acid amides such as m-bisstearic acid amide. These fatty acid amides may be used alone or in combination of 2 or more.

(Block copolymer resin)

The block copolymer resin is generally a copolymer resin in which two or more kinds of polymer units having different properties are linked by covalent bonds to form a long chain molecular structure. In the present invention, as the block copolymer resin, a block copolymer resin of X-Y type or 3-or more members, which is a known general-purpose person, is preferably used, and an X-Y-X type block copolymer resin is more preferably used. X in the X-Y-X block copolymer resin may be the same or different.

In the X-Y type or X-Y-X type block copolymer resin, X is preferably a polymer unit having a glass transition point Tg of 0℃or higher. More preferably, X is a polymer unit having a glass transition point Tg of 50 ℃ or higher. Further, Y is preferably a polymer unit having a glass transition point Tg of less than 0 ℃, more preferably a polymer unit having a glass transition point Tg of-20 ℃ or less. The glass transition point Tg is determined by Differential Scanning Calorimetry (DSC).

The block copolymer resin is further preferably solid at 25 ℃. In addition, it may be solid at a temperature outside this range. The adhesive properties are excellent when the adhesive is solid at the above temperature, and when the adhesive is dried by applying the adhesive to a substrate and temporarily drying the substrate.

In addition, among the X-Y type or X-Y-X type block copolymer resins, X is preferably one having high compatibility with the thermosetting resin, and Y is preferably one having low compatibility with the thermosetting resin. It is considered that the block copolymer resin having the blocks at both ends compatible with the matrix and the block at the center incompatible with the matrix is formed in this manner, whereby a specific structure is easily shown in the matrix.

Specifically, polymethyl methacrylate (PMMA), polystyrene (PS), and the like are preferable as the polymer unit X, and poly (n-butyl (meth) acrylate (PBA), polybutadiene (PB), and the like are preferable as the polymer unit Y. In addition, when a hydrophilic unit having excellent compatibility with an alkali-soluble resin, represented by a styrene unit, a hydroxyl group-containing unit, a carboxyl group-containing unit, an epoxy group-containing unit, an N-substituted acrylamide unit, or the like, is introduced into a part of the polymer unit X, the compatibility can be further improved. It is particularly preferable to introduce an epoxy group-containing unit into a part of the polymer unit X. Among the above, the polymer unit X is preferably polystyrene, polyglycidyl methacrylate, or N-substituted polyacrylamide, polymethyl (meth) acrylate, or a carboxylic acid-modified product or hydrophilic group-modified product thereof. Y is preferably poly (n-butyl (meth) acrylate), polybutadiene or the like. X and Y may be each composed of 1 polymer unit or may be composed of polymer units based on 2 or more components.

Examples of the method for producing the block copolymer resin include those described in Japanese patent application laid-open No. 2005-515281 and Japanese patent application laid-open No. 2007-516326.

As a commercial product of the X-Y-X block copolymer resin, there is mentioned an acrylic triblock copolymer produced by living polymerization manufactured by Arkema Co. Examples thereof include SBM type represented by polystyrene-polybutadiene-polymethyl methacrylate, MAM type represented by polymethyl methacrylate-polybutyl acrylate-polymethyl methacrylate, and MAM N type and MAM A type modified by carboxylic acid and hydrophilic groups. Examples of the SBM type include E41, E40, E21, E20, etc., examples of the MAM type include M51, M52, M53, M22, etc., examples of the MAM N type include 52N, 22N, etc., examples of the MAM a type include SM4032XM10, nanostrength (registered trademark) series, for example, M52N, M N, etc. The Clarity made by Kuraray, inc. is also a block copolymer derived from methyl methacrylate and butyl acrylate.

As the block copolymer resin, a block copolymer resin having a precisely controlled molecular structure synthesized by living polymerization is preferable in order to obtain the effects of the present invention. This is considered 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 are clearly known. The molecular weight distribution of the block copolymer resin used is preferably 2.5 or less, more preferably 2.0 or less.

The molecular weight distribution is calculated based on the ratio (Mw/Mn) of the mass average molecular weight (Mw) to the number average molecular weight (Mn) measured by a method described later.

The mass average molecular weight Mw of the block copolymer resin (A1) of the present invention is preferably 20000 to 400000, particularly preferably 80000 to 350000.

If the mass average molecular weight of the block copolymer resin is 20000 or more, the composition has mechanical properties such as flexibility and elasticity, and the adhesiveness is not excessively high, and the effect of improving the bending property and crack resistance is good, and the tackiness is also good. On the other hand, if the mass average molecular weight is 400000 or less, the viscosity of the composition does not excessively increase, and the printability and developability are not easily reduced.

In the present invention, the mass average molecular weight and the number average molecular weight are molecular weights in terms of polystyrene using a GPC (gel chromatography) apparatus "GL7700" manufactured by GL Sciences Inc., using α -2500 and α -4000 manufactured by Tosoh corporation as columns, using a 10mM lithium bromide solution of NMP and a 100mM phosphoric acid solution of NMP as eluent, and using polystyrene as a standard substance.

The block copolymer resin may be used alone or in combination of 2 or more. When the alkali-soluble resin is contained in the photosensitive resin composition in the amount to be blended with the block copolymer resin, the amount is preferably 1 to 60 parts by mass, more preferably 2 to 50 parts by mass, and particularly preferably 3 to 40 parts by mass, relative to 100 parts by mass of the alkali-soluble resin. If the amount of the block copolymer resin is 1 part by mass or more, the flexibility and heat resistance are improved, and if it is 60 parts by mass or less, the flexibility and heat resistance are well balanced.

[ photosensitive resin composition (B) ]

The resin layer (B) is composed of a photosensitive resin composition (B) having a 3 rd glossiness of 50 or more. The photosensitive resin composition (B) generally contains an alkali-soluble resin such as a carboxyl group-containing resin and also 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 a desired gloss, the photosensitive resin composition (B) needs to have components such as a resin and a monomer in the composition compatible with each other. That is, the above-described combinations of the components showing incompatibility are not contained.

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

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

The photosensitive resin composition (B) may be any known alkali-soluble resin, but specific examples of the alkali-soluble resin that can be used include those having a predetermined gloss, and those described in detail with respect to the photosensitive resin composition (a) may be used.

(thermosetting resin in photosensitive resin composition (B))

The photosensitive resin composition (B) contains a thermosetting resin. The photosensitive resin composition (B) may have a predetermined glossiness, and the same compound as the thermosetting resin in the photosensitive resin composition (a) may be used, and a known and commonly used compound having a functional group capable of a curing reaction by heat, such as a cyclic (thio) ether group, may be preferably used, for example, an epoxy compound.

The details of the photopolymerizable compound and photopolymerization initiator that can be used as the components of the photosensitive resin composition (B) are as described in detail with respect to the photosensitive resin composition (a).

When the photosensitive resin composition (B) contains an alkali-soluble resin, the amount of the photopolymerizable compound to be blended is preferably 1 to 100 parts by mass, more preferably 5 to 80 parts by mass, relative to 100 parts by mass of the alkali-soluble resin.

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

(inorganic filler/extender pigment)

The inorganic filler and extender pigment may be blended to suppress curing shrinkage of the cured product, improve properties such as adhesion and hardness. Examples of such inorganic fillers and extender pigments include barium sulfate, amorphous silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, alumina, titanium oxide, aluminum hydroxide, silicon nitride, aluminum nitride, boron nitride, and noriburg silica.

(Heat curing catalyst)

The photosensitive resin compositions (a) and (B) used in the laminate of the present invention may be blended with a heat curing catalyst. Examples of the heat curing catalyst include imidazole derivatives such as imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, and 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; amine compounds such as dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, and 4-methyl-N, N-dimethylbenzylamine, and hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; phosphorus compounds such as triphenylphosphine. Examples of commercially available products include 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (both trade names of imidazole-based compounds), U-CAT 3513N (trade names of dimethylamine-based compounds) manufactured by San-Apro Ltd, DBU, DBN, U-CAT SA 102 (both bicyclic amidine compounds and salts thereof), and the like, which are manufactured by Kaku Kagaku Co., ltd. These may be used alone or in combination of 2 or more.

Furthermore, S-triazine derivatives such as guanamine, methylguanamine, benzoguanamine, melamine, tetrahydrophthalic anhydride-added melamine, 2, 4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2, 4-diamino-S-triazine, 2-vinyl-4, 6-diamino-S-triazine-isocyanuric acid adducts, and 2, 4-diamino-6-methacryloyloxyethyl-S-triazine-isocyanuric acid adducts may be used, and these compounds also functioning as adhesion-imparting agents are preferably used in combination with a heat curing catalyst. The heat curing catalyst may be used alone or in combination of 2 or more.

The amount of the heat curing catalyst to be blended is preferably 0.1 to 5 parts by mass, more preferably 1 to 3 parts by mass, in terms of solid matter conversion, relative to the total amount of the photosensitive resin composition.

(colorant)

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

(organic solvent)

The organic solvent may be blended for preparing the photosensitive resin compositions (a) and (B) and for adjusting the viscosity of the 1 st film 1 (carrier film) to be applied to a substrate. Examples of such organic solvents include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, and petroleum solvents. The organic solvent may be used alone or as a mixture of 2 or more.

(other Components)

If necessary, a mercapto compound, an adhesion promoter, an antioxidant, an ultraviolet absorber, and the like may be further blended. As these, known and commonly used ones can be used. Further, known and commonly used thickeners such as fine silica powder, hydrotalcite, organobentonite and montmorillonite, antifoaming agents such as silicone system, fluorine system and polymer system, and/or additives such as leveling agents, silane coupling agents and rust inhibitors may be blended.

(step of producing cured product of laminate)

An example of a process for producing the laminate of the present invention will be described below with reference to fig. 3. Here, an example of producing a cured product of the dry film shown in fig. 2 will be described.

[ (a) lamination Process ]

As shown in fig. 3 as a lamination step (a), the laminate 10 of the present invention is laminated, for example, as follows: the substrate 20 such as a printed circuit board having the conductor circuit 21 is arranged so that the resin layers (B) face each other, and the substrate and the resin layers (B) are laminated by pressure bonding. On the other hand, in other applications, lamination to electronic devices may not be performed prior to such lamination. In this embodiment, each step of the curing treatment in a state where the laminate is directly disposed on the substrate will be described. The following steps are not necessarily all steps, and are appropriately selected and performed according to the application and the composition of the laminate.

[ (b) Exposure procedure ]

When the laminate of the present invention is cured, an exposure step is performed. In the exposure step, the photopolymerization initiator having a function as a photobase generator, or the photobase generator contained in the resin layer (a), the resin layer (B), or both are activated into a negative pattern by irradiation with active energy rays (indicated by arrows in fig. 3 (B)). As the exposure machine, a direct drawing apparatus, an exposure machine equipped with a metal halide, or the like can be used. The patterned mask for exposure is a negative type mask.

As the active energy ray used in the exposure, a laser light having a maximum wavelength in the range of 350 to 450nm or scattered light is preferably used. By setting the maximum wavelength to this range, the photopolymerization initiator can be activated efficiently. The exposure amount varies depending on the film thickness, etc., but is usually 100 to 1500mJ/cm ² The following is performed.

[ (c) PEB Process ]

After the exposure, the resin layer is heated to cure the exposed portion. In the case where the photosensitive resin compositions (a) and (B) of the present invention have a photopolymerization initiator functioning as a photobase generator or contain both the photopolymerization initiator and the photobase generator, the resin layer (B) can be cured deep by the alkali generated in the exposure step. The heating temperature is, for example, 80 to 200 ℃. The heating time is, for example, 10 to 100 minutes. In the case where a heating step 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 after the exposure step, this heating and curing step is referred to as a PEB (POST EXPOSURE BAKE) step, and thus curing shrinkage of the coating film after the photolithography is suppressed, and as a result, excellent resolution is provided.

[ (d) development Process ]

When the exposure step is performed, a developing step is performed. In the development step, the unexposed portion is removed by alkali development, and a negative pattern-like insulating film, particularly a cap layer and a solder resist layer, is formed. The developing method may be a known method such as dipping. As the developer, an aqueous alkali solution such as an aqueous solution of an imidazole such as sodium carbonate, potassium hydroxide, amines, or 2-methylimidazole, or an aqueous alkali solution such as an aqueous tetramethylammonium hydroxide solution (TMAH), or a mixture thereof may be used.

[ (e) post-curing procedure ]

After the development step, the cured product of the laminate may be irradiated with light, or may be heated at 150 ℃. The heating temperature is, for example, 80 to 170℃and the heating time is 5 to 100 minutes. Since post-curing of the laminate 10 in the present invention is, for example, a ring-opening reaction of an epoxy resin by a thermal reaction, strain and curing shrinkage can be suppressed as compared with the case where curing is performed in a photo radical reaction.

[ component mounting Process ]

After the development as described above, the cured product of the laminate of the present invention is applied to a component mounting step (not shown) as needed. By this step, various components are mounted on the substrate having the cured product of the present invention, and the electronic component of the present invention can be obtained.

[ reheating step ]

The laminate cured product after component mounting may be subjected to a reheating step (not shown). The reheating step is carried out at a heating temperature of, for example, 120 to 300 ℃, particularly 250 to 300 ℃ for a heating time of, for example, 5 to 120 minutes. The insulating film may be irradiated with light before or after the reheating step.

In the cured product of the laminate of the present invention thus obtained, when heat, pressure, or the like is applied to the cured product in the step of producing the cured product of the laminate, particularly in the step of mounting the component, and the cured product is thermally pressurized or the like, the glossiness increases, and when the matt-like surface is lost, the glossiness decreases again in the reheating step, whereby the matt-like surface can be formed. Specifically, when the glossiness of the outer surface of the cured product of the present invention is 50 or more, the reheating step may be performed at 260 ℃ for 10 minutes, so that the glossiness of the outer surface may be 30 or less again.

That is, since the outermost layer (outer surface) of the resin layer (a) of the cured product of the present invention is matt, even when the cured product is formed as a part of an electronic device and is produced into a product, scratches and the like are less likely to be noticeable, the yield of the product is improved, and the preference or demand for having a matt appearance can be satisfied.

In addition, the laminate cured product of the present invention can satisfactorily cover the circuit of an electronic device such as a printed circuit board by 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 coverage of the circuit of the electronic device is improved as compared with the case of using either the resin layer (a) or the resin layer (B), but it is presumed that this is an effect due to the difference in refractive index caused by the difference in composition of the photosensitive resin composition constituting the resin layer (a) and the resin layer (B). The resin layer (a) is a layer showing incompatibility, but the resin layer (B) is a layer showing compatibility, and thus, a difference occurs in refractive index between the resin layer (a) and the resin layer (B). The laminate cured product having the difference in refractive index between the resin layer (a) and the resin layer (B) is applied to the circuit, whereby the circuit is sufficiently covered.

The laminate and the cured product obtained by the method of the present invention can be applied to a rigid or flexible substrate, particularly a printed wiring board having a copper circuit formed on a rigid substrate.

In the present invention, an electronic component means a component used for an electronic circuit, and includes passive components such as a resistor, a capacitor, an inductor, and a connector in addition to active components such as a printed circuit board, a transistor, a light emitting diode, and a laser diode. The laminate cured product of the present invention provides mechanical properties and a matt-like appearance as an insulating layer of these electronic parts.

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

The laminate of the present invention comprises a resin layer (A) and a resin layer (B), wherein one surface of the resin layer (A) is in contact with one surface of the resin layer (B), and the resin layer (A) comprises: (A1) A block copolymer resin and (A2) a photopolymerizable compound, the resin layer (B) having: (B1) alkali-soluble (meth) acrylate resins.

The resin layer (a) and the resin layer (B) of the laminate of the present invention are disposed in contact with each other, and cured in this disposition. In the uncured laminate, in particular, the constituent components of the resin layer (a) and the constituent components of the resin layer (B) are mixed at the interface by a heating step. It is presumed that the components of the resin layer (a) and the resin layer (B) are mixed in this manner, and diffuse reflection of visible light at the interface is caused, and therefore, a cured film excellent in the coverage of the circuit can be obtained. Further, since a good circuit coverage can be obtained by using the laminate of the present invention, it is considered that the roughened plastic film as in the prior art is not required to be used as the 1 st film, and the reduction in resolution due to the irregularities of the support is not generated. Further, 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, the use of the laminate of the present invention can achieve both the hiding power of the circuit and the 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 for the resin layer (a) may be the same as that described in the first embodiment.

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

The mass average molecular weight Mw of the block copolymer resin is preferably 20000 to 400000, more preferably 80000 to 350000. The mass average molecular weight was determined using the method described above. The X-Y-X type block copolymer resin is more preferable, and the mass average molecular weight is preferably 20000 to 400000, particularly preferably 80000 to 350000.

(A1) The blending 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). When the amount is 1 part by mass or more, the effect can be expected, and when it is 30 parts by mass or less, the developability as a photocurable resin composition becomes good.

((A2) photopolymerizable Compound)

The photopolymerizable compound used in the resin layer (a) may be the same as those described in the first embodiment.

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

(in the general formula (I), R1 represents a hydrogen atom or a methyl group)

(A2) The amount of the photopolymerizable compound to be blended is preferably 1 to 40% by mass, more preferably 1 to 30% by mass, and still more preferably 1.5 to 20% by mass, based on the solid content of the resin layer (a). By setting the blending amount to the above range, the photocurability is improved, the patterning becomes easy, and the strength of the cured film can be improved.

Further, any component that can be contained in the resin layer (a) will be described.

((A3) epoxy resin)

As the epoxy resin, the same epoxy resin as that described in the first embodiment can be used. Bisphenol a type epoxy resins and/or novolak type epoxy resins may be particularly preferably used.

The amount of the epoxy resin to be blended in the resin layer (a) may be any amount, but the amount is preferably 15 to 30% by mass, with respect to the solid content of the resin layer (a), in the range of 10 to 40% by mass. By setting the compounding ratio to the range, development becomes good, and a fine pattern can be formed easily and with high accuracy.

((A4) photopolymerization initiator)

As the photopolymerization initiator, the same photopolymerization initiator as described in the first embodiment can be used. As the photopolymerization initiator, 1 or more photopolymerization initiators selected from the group consisting of oxime ester photopolymerization initiators having an oxime ester group, α -aminoacetophenone photopolymerization initiators, and acylphosphine oxide photopolymerization initiators are preferably used.

The amount of the photopolymerization initiator to be blended is preferably 0.1 to 20% by mass, more preferably 1 to 10% by mass, based on the solid content of the resin layer (a). When the content is 0.1% by mass or more, the photocurability is improved, the adhesion between the coating film and the substrate is good, and the coating film characteristics such as chemical resistance are also improved. On the other hand, the amount of the catalyst is 20 mass% or less, thereby achieving a deaeration reducing effect.

[ resin layer (B) ]

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

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

As the (B1) alkali-soluble (meth) acrylate resin used in the present invention, those having a carboxyl group and a (meth) acryloyl group in the molecule and derived from derivatives thereof are preferable. As specific examples of the alkali-soluble (meth) acrylate resin (B1), the compounds listed below (both oligomers and polymers) may be suitably used.

(1) An alkali-soluble urethane (meth) acrylate resin obtained by the addition polymerization reaction of a diisocyanate such as aliphatic diisocyanate, branched aliphatic diisocyanate, alicyclic diisocyanate or aromatic diisocyanate, a 2-functional epoxy resin such as bisphenol a epoxy resin, hydrogenated bisphenol a epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, xylenol epoxy resin or bisphenol epoxy resin, or a partial anhydride modified product thereof, and a carboxyl group-containing diol compound and a diol compound.

(2) An alkali-soluble urethane (meth) acrylate resin obtained by adding a compound having 1 hydroxyl group and 1 or more (meth) acryloyl groups in the molecule, such as hydroxyalkyl (meth) acrylate, to the synthesis of the resin of (1) above, and performing terminal (meth) acrylation.

(3) An alkali-soluble urethane (meth) acrylate resin obtained by adding a compound having 1 isocyanate group and 1 or more (meth) acryloyl groups in the molecule, such as an equimolar reactant of isophorone diisocyanate and pentaerythritol triacrylate, to the synthesis of the resin of the above (1), and performing terminal (meth) acrylation.

(4) An alkali-soluble (meth) acrylate resin obtained by reacting a polyfunctional epoxy resin having a 2-function or more with (meth) acrylic acid, and adding a dibasic acid anhydride to a hydroxyl group present in a side chain.

(5) An alkali-soluble (meth) acrylate resin obtained by reacting a (meth) acrylic acid with a polyfunctional epoxy resin obtained by epoxidizing a hydroxyl group of a 2-functional epoxy resin with epichlorohydrin and adding a dibasic acid anhydride to the hydroxyl group thus formed.

(6) An alkali-soluble (meth) acrylate resin obtained by reacting a compound having a plurality of phenolic hydroxyl groups in 1 molecule with an alkylene oxide such as ethylene oxide or propylene oxide to obtain a reaction product, reacting the reaction product with (meth) acrylic acid, and reacting the reaction product obtained by the reaction with a polybasic acid anhydride.

(7) An alkali-soluble (meth) acrylate resin obtained by reacting a compound having a plurality of phenolic hydroxyl groups in 1 molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate to obtain a reaction product, reacting the reaction product with (meth) acrylic acid, and reacting the reaction product obtained by the reaction with a polybasic acid anhydride.

(8) An alkali-soluble (meth) acrylate resin obtained by further adding a compound having 1 epoxy group and 1 or more (meth) acryloyl groups in a molecule to the resins of (1) to (7).

In the present specification, (meth) acrylate is a term generically used for acrylate, methacrylate, and a mixture thereof, and the same applies to other similar expressions.

The aforementioned (B1) alkali-soluble (meth) acrylate resin has a large number of carboxyl groups in the main chain/side chain of the polymer, and therefore, development based on a dilute alkali aqueous solution becomes possible.

In addition, the acid value of the alkali-soluble (meth) acrylate resin (B1) is suitably in the range of 40 to 200mgKOH/g, more preferably in the range of 45 to 120 mgKOH/g. (B1) If the acid value of the alkali-soluble (meth) acrylate resin is 40mgKOH/g or more, alkali development proceeds satisfactorily, whereas if it is 200mgKOH/g or less, dissolution of the exposed portion by the developer does not occur, the line is not narrowed to a desired level or more, the distinction between the exposed portion and the unexposed portion is maintained, dissolution peeling or the like does not occur in the developer, and normal drawing of the resist pattern is performed.

The mass average molecular weight of the alkali-soluble (meth) acrylate resin (B1) varies depending on the resin skeleton, but is usually preferably in the range of 1000 to 150000, more preferably 2000 to 100000. When the mass average molecular weight is 2000 or more, the tack-free property becomes good, the moisture resistance of the coating film after exposure becomes sufficient, and the resolution is improved as designed during development. On the other hand, when the mass average molecular weight is 150000 or less, excellent developability is stably obtained, and storage stability is also good.

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

These alkali-soluble (meth) acrylate resins (B1) may be used not only as exemplified above, but also as a mixture of 1 or more. Particularly, among alkali-soluble (meth) acrylate resins, resins having an aromatic ring are preferable because they have a high refractive index and excellent resolution, and further have a novolak structure because they have excellent resolution and PCT and crack resistance. Among them, alkali-soluble (meth) acrylate resins used as the starting materials of phenol compounds are excellent in HAST resistance and PCT resistance as in (6) and (7), and therefore, can be suitably used.

In the present invention, it is considered that the alkali-soluble (meth) acrylate resin (component (B1)) is incompatible with at least one of the block copolymer resin (component (A1)) and the photopolymerizable compound (component (A2)) contained in the resin layer (a). That is, the component (A1), the component (A2), the component (B1), or the mixture of the resin layers (a) and (B) containing the components, or the mixture of the resin compositions for forming the resin layers, is in a non-compatible mixed state at the interface between the resin layers (a) and (B), and as a result, the smoothness of the interface between the two layers is lost, and irregularities are generated. If visible light is incident on the interface having the irregularities, diffuse reflection of the visible light occurs, and the circuit of the electronic component is well covered. The laminate of the present invention thus presumably shows good circuit coverage.

Further, an arbitrary component that can be contained in the resin layer (B) will be described.

((B2) epoxy resin)

The resin composition constituting the resin layer (B) preferably contains (B2) an epoxy resin. As the epoxy resin (B2), the same ones as the epoxy resin (A3) described above as the constituent of the resin layer (a) can be used. The epoxy resin (A3) and the epoxy resin (B2) used in the resin layers (a) and (B) of the laminate may be the same type or different types. Further, when a plurality of epoxy resins are used for either or both of the resin layer (a) and the resin layer (B), a part of them may be the same type of epoxy resin.

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

By setting the compounding ratio to the range, development becomes good, and a fine pattern can be formed easily and with high accuracy.

[ optional Components of resin layer (A) and resin layer (B) ]

The resin layer (a) and the resin layer (B) may contain any component other than these. As any component that can be contained in the resin layer (a) and the resin layer (B), the same component as described in the first embodiment can be used.

(step of producing laminate)

The steps of the second embodiment of the present invention for producing the laminate and the cured product may be selected and used as appropriate in the same manner as the steps of the first embodiment.

In the present invention, the thickness of the resin layer (B) after coating and drying is usually 1 to 150. Mu.m, preferably 3 to 120. Mu.m, and the thickness of the resin layer (A) is usually 0.5 to 50. Mu.m, preferably 2 to 30. Mu.m, and the total thickness of both layers may be 5 to 150. Mu.m. In addition, the film thickness of the resin layer (B) is preferably larger than that of the resin layer (a).

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

Examples

The present invention will be specifically described with reference to examples and comparative examples, but the present invention is not limited to the examples. The values of "parts" and "%" in the present example and comparative example are based on mass unless otherwise specified.

Examples 1-1 to 1-7 (embodiment 1) and comparative examples 1-1 to 1-6

1. Synthesis of resin component

( Synthesis example 1-1: polyamide-imide resin solution with carboxyl group (resin 1-1) )

29.49g (0.054 mol) of an aliphatic diamine (PRIAMINE 1075, product name, manufactured by Croda Japan Plan) derived from a dimer acid having 36 carbon atoms as a dimer diamine (a), 4.02g (0.026 mol) of 3, 5-diaminobenzoic acid as a carboxyl group-containing diamine (b), and 73.5g of gamma-butyrolactone were charged and dissolved in a four-port 300mL flask equipped with a nitrogen inlet pipe, a thermometer, and a stirrer.

Then, 31.71g (0.160 mol) of cyclohexane-1, 2, 4-tricarboxylic acid anhydride (c) and 1.54g (0.008 mol) of trimellitic anhydride (d) were charged, and the mixture was kept at room temperature for 30 minutes. 30g of toluene was further charged, the temperature was raised to 160℃and the water formed with toluene was removed, followed by holding for 3 hours and cooling to room temperature, whereby a solution containing an imide compound was obtained.

To the obtained imide compound-containing solution, 6.90g (0.033 mol) of trimethylhexamethylene diisocyanate and 8.61g (0.033 mol) of dicyclohexylmethane diisocyanate as the diisocyanate compound (e) were charged, and the mixture was kept at 160℃for 32 hours, and diluted with 36.8g of cyclohexanone to obtain a polyamide-imide resin-containing solution (A-2). The obtained polyamideimide resin had a mass average molecular weight Mw of 5840, a solid content of 40.4 mass%, an acid value of 62mgKOH/g, and a dimer diamine (a) content of 40.1 mass%

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

Into a detachable three-necked flask equipped with a stirrer, a nitrogen inlet tube, a fractionating ring and a condensing ring, 22.4g of 3,3 '-diamino-4, 4' -dihydroxydiphenyl sulfone, 8.2g of 2,2 '-bis [4- (4-aminophenoxy) phenyl ] propane, 30g of NMP, 30g of gamma-butyrolactone, 27.9g of 4,4' -oxydiphthalic anhydride and 3.8g of trimellitic anhydride were charged, and stirred under a nitrogen atmosphere at room temperature and 100rpm for 4 hours. Then, 20g of toluene was added thereto, and the mixture was stirred at 180℃and 150rpm in a silicone bath while toluene and water were distilled off for 4 hours, to obtain a polyimide resin solution (resin 1-2) having phenolic hydroxyl groups and carboxyl groups. The acid value of the obtained resin (solid component) was 18mgKOH, mw was 10000, and hydroxyl equivalent was 390.

( Synthesis examples 1 to 3: synthesis of carboxyl group-containing resin (resins 1 to 3) having bisphenol F type skeleton )

X in the following general formula (I) is CH ₂ 380 parts of bisphenol F-type epoxy resin having an average polymerization degree n of 6.2 (epoxy equivalent: 950g/eq, softening point: 85 ℃ C.) and 925 parts of epichlorohydrin were dissolved in 462.5 parts of dimethyl sulfoxide, and then 98.5% of NaOH60.9 parts was added thereto at 70 ℃ C. For 100 minutes with stirring.

The above addition was followed by a further reaction at 70℃for 3 hours. After the completion of the reaction, 250 parts of water was added thereto to wash the reaction mixture with water. After oil-water separation, most of dimethyl sulfoxide and excess unreacted epichlorohydrin were distilled off from the oil layer under reduced pressure, and the reaction product containing residual byproduct salt and dimethyl sulfoxide was dissolved in 750 parts of methyl isobutyl ketone, and 30% of NaOH10 parts was further added to react at 70℃for 1 hour. After the completion of the reaction, water washing was performed 2 times with 200 parts of water. After oil-water separation, methyl isobutyl ketone was recovered from the oil layer by distillation to obtain an epoxy resin (a 1) having an epoxy equivalent of 310g/eq and a softening point of 69 ℃. The epoxy resin (a 1) obtained was epoxidized at about 5 out of 6.2 alcoholic hydroxyl groups in the bisphenol F-type epoxy resin as the starting material, as calculated from the epoxy equivalent. 310 parts of the epoxy resin (a 1) and 282 parts of carbitol acetate were put into a flask, and heated, stirred and dissolved at 90 ℃. The resulting solution was cooled to 60℃briefly, and 72 parts (1 mol) of acrylic acid, 0.5 part of methylhydroquinone and 2 parts of triphenylphosphine were added thereto, and the mixture was heated to 100℃to react for about 60 hours, thereby obtaining a reactant having an acid value of 0.2 mgKOH/g. To this was added 140 parts (0.92 mol) of tetrahydrophthalic anhydride, and the mixture was heated to 90℃to effect a reaction, thereby obtaining carboxyl group-containing resins (resins 1 to 3). The resulting carboxyl group-containing resin varnish had a solid content concentration of 62% by mass and a solid content acid value (mgKOH/g) of 100.

( Synthesis examples 1 to 4: synthesis of carboxyl group-containing resin (resins 1 to 4) having bisphenol A skeleton )

X in the general formula (I) is C (CH) ₃ ) ₂ After 371 parts of bisphenol A type epoxy resin (epoxy equivalent: 650g/eq, softening point: 81.1 ℃ C.) having an average polymerization degree n of 3.3 and 925 parts of epichlorohydrin were dissolved in 462.5 parts of dimethyl sulfoxide, 98.5% of NaOH52.8 parts was added under stirring at 70 ℃ C. For 100 minutes. The reaction was further carried out at 70℃for 3 hours after the addition. After the completion of the reaction, 250 parts of water was added thereto to wash the reaction mixture with water. After oil-water separation, most of dimethyl sulfoxide and excess unreacted epichlorohydrin were distilled off from the oil layer, and the reaction product containing residual byproduct salt and dimethyl sulfoxide was dissolved in 750 parts of methyl isobutyl ketone, and 30% of NaOH10 parts was further added to react at 70℃for 1 hour. After the completion of the reaction, 200 parts of water was used2 water washes were performed. After oil-water separation, methyl isobutyl ketone was recovered from the oil layer by distillation to obtain an epoxy resin (a 2) having an epoxy equivalent of 287g/eq and a softening point of 64.2 ℃. The epoxy resin (a 2) obtained was epoxidized about 3.1 out of 3.3 alcoholic hydroxyl groups in the bisphenol A-type epoxy resin as the starting material, as calculated from the epoxy equivalent. 310 parts of the epoxy resin (a 2) and 282 parts of carbitol acetate were put into a flask, heated at 90 ℃, stirred and dissolved. The resulting solution was cooled to 60℃briefly, and 72 parts (1 mol) of acrylic acid, 0.5 part of methylhydroquinone and 2 parts of triphenylphosphine were added thereto, and the mixture was heated to 100℃to react for about 60 hours, thereby obtaining a reactant having an acid value of 0.2 mgKOH/g. To this was added 140 parts (0.92 mol) of tetrahydrophthalic anhydride, and the mixture was heated to 90℃to effect a reaction, thereby obtaining carboxyl group-containing resins (resins 1 to 4). The resulting carboxyl group-containing resin varnish had a solid content concentration of 62% by mass and a solid content acid value (mgKOH/g) of 100.

( Synthesis examples 1 to 5: synthesis of photosensitive resin (resin 1-5) having both olefinic double bond and carboxyl group )

220 parts of cresol novolak type epoxy resin (EPICLON N-695, epoxy equivalent: 220, manufactured by DIC Co., ltd.) was placed in a four-necked flask equipped with a stirrer and a reflux condenser, 214 parts of carbitol acetate was added thereto, and the mixture was heated and dissolved. Next, 0.1 part of hydroquinone as a polymerization inhibitor and 2.0 parts of dimethylbenzylamine as a reaction catalyst were added. The mixture was heated to 95-105℃and 72 parts of acrylic acid was slowly added dropwise thereto and reacted for 16 hours. The reaction product is cooled to 80-90 ℃, 106 parts of tetrahydrophthalic anhydride is added for reaction for 8 hours, and the reaction product is taken out after cooling.

The photosensitive resin (resins 1 to 5) having both an olefinic double bond and a carboxyl group thus obtained had a nonvolatile content of 65%, an acid value of the solid matter of 100mgKOH/g, and a mass average molecular weight Mw of about 3500.

( Synthesis examples 1 to 6: synthesis of tetrahydrophthalic anhydride addition melamine )

800 ml of ion exchange water was placed in a 2-liter beaker, and a stirrer was placed therein to boil the water while stirring the water on a stirrer with a hot plate. To this hot water, 12.6g of melamine was added to dissolve completely. In addition, 500 ml of ion exchange water was placed in a 1-liter beaker, and a stirrer was placed therein, and the mixture was boiled while being stirred on a stirrer with a hot plate. To this hot water, 15.2g of tetrahydrophthalic anhydride was added, and the mixture was heated and stirred for 1 hour to obtain an aqueous solution of tetrahydrophthalic acid. The aqueous solution was added to the aqueous melamine solution and stirred. When the mixture was cooled in ice water, crystals were precipitated. After the crystals were filtered off, they were dried in a vacuum dryer to obtain melamine compounds.

2. Preparation of photosensitive resin compositions a to f

The resins 1-1 to 1-5 obtained in the above synthesis examples and other components were compounded with the compositions shown in table 1 below, and after premixing the components in a mixer, the components were kneaded in a three-roll mill to prepare photosensitive resin compositions a to f. Details of the components other than the resins 1-1 to 1-5 are shown in Table 1 and the following tables.

TABLE 1

The proportions of the components in table 1 are based on the solid components.

[ alkali-soluble resin ]

Resin 1-1: preparation from Synthesis example 1 (Polyamide imide resin having carboxyl groups)

Resin 1-2: prepared from Synthesis examples 1-2 (polyimide resin having phenolic hydroxyl groups and carboxyl groups)

Resin 1-3: prepared from Synthesis examples 1 to 3 (carboxyl group-containing resin having bisphenol F type skeleton)

Resin 1-4: prepared from Synthesis examples 1 to 4 (carboxyl group-containing resin having bisphenol A type skeleton)

Resin 1-5: prepared in Synthesis examples 1 to 5 (photosensitive resin having both an olefinic double bond and a carboxyl group)

[ fatty acid amide ]. Nikka amide S: n-stearyl stearamide (Mitsubishi chemical Co., ltd.)

Nikka amide OS: n-oleyl stearamide (Mitsubishi chemical Co., ltd.)

[ photopolymerization initiator ]

IRGACURE OXE02: oxime photopolymerization initiator (BASF Japan Co., ltd.)

[ photopolymerizable Compound ]

KRM8296:3 functional urethane acrylate (Daicel-Allnex Ltd.)

DPHA: dipentaerythritol hexaacrylate (manufactured by Japanese chemical Co., ltd.)

[ thermosetting resin ]

YDF-2004: bisphenol F type epoxy resin (NIPPON STEEL Chemical & materialco., ltd.)

EPICLON 860: bisphenol A type epoxy resin (DIC Co., ltd.)

YDC-1312:2, 5-t-butylhydroquinone type epoxy resin (NIPPON STEEL Chemical & Material Co., ltd.)

N-655: cresol novolak type epoxy resin (DIC Co., ltd.)

TEPIC-S: triglycidyl isocyanurate (manufactured by Nissan chemical Co., ltd.)

[ Heat curing catalyst ]

THPA melamine: tetrahydrophthalic anhydride addition of Melamine (prepared from Synthesis examples 1-6)

[ extender pigment ]

BARIACE B-31: barium sulfate (made by Sakai chemical industry Co., ltd.)

3. Manufacture of test substrate

3-1 preparation of Dry film

The photosensitive resin compositions a to f were adjusted to have the same viscosity with the organic solvent MEK. The resin compositions shown in the following resin layers (A) in tables 2 and 3 were applied to the 1 st film (material: polyethylene terephthalate thickness: 25 μm, surface roughness (Ra): 0.03 μm or 0.3 μm) shown in tables 2 and 3 so that the film thickness after drying became the same film thickness shown in the same table, and dried for 15 minutes at 90℃in a heated air circulation drying oven. Next, the resin compositions shown in tables 2 and 3 as the resin layer (B) were applied to the dried resin layer (a) so that the film thickness after drying became the same film thickness shown in the table, and dried at 80 ℃ for 30 minutes. Thus, a laminate having a resin layer (a) and a resin layer (B) in this order on the 1 st film was obtained. Next, a stretched polypropylene film as a 2 nd film was laminated on the resin layer (B) as a dry film of each of examples and comparative examples. In the case of a single layer, as in comparative examples 1-1 to 1-3, only the resin layer (a) was applied, and then the 2 nd film was bonded to the resin layer (a) to form a dry film.

In comparative examples 1 to 2, a mat PET (PTHA-25, manufactured by Unitika Co., ltd., surface roughness Ra:0.3 μm) was used as the 1 st film, and therefore, the irregularities of the mat PET were transferred to the resin layer (A), and as a result, the resin layer (A) had a physically roughened surface.

3-2. Production of substrate for measuring glossiness 1 and 2

The 2 nd film of the dry film thus obtained was peeled off, and then laminated in a first chamber at 80℃under vacuum pressure of 3hPa for 30 seconds and under pressure of 0.5MPa for 30 seconds by a vacuum laminator (CVP-300: manufactured by Nikko-Materials Co., ltd.), followed by lamination of the resin layer (B) on a printed wiring board and contact of the printed wiring board, whereby a 1 st and 2 nd substrate for measuring glossiness was produced.

The 1 st and 2 nd substrates for measuring glossiness obtained as described above were subjected to cumulative exposure of 250mJ/cm by a pressure-reduced adhesion type double-sided exposure machine (model ORC HMW 680 GW) manufactured by LTD. With ORC MANUFACTURING CO., LTD.) ² Under the condition of (a), ultraviolet rays are irradiated from the resin layer (a) side (exposure step). Next, the 1 st film provided on the resin layer (a) side was removed, and the value of the glossiness measured on the outer surface of the resin layer (a) was set as the 1 st glossiness.

After the above 1 st film was removed, heat curing was performed at 150℃for 60 minutes, and the gloss measured on the outer surface of the resin layer (A) was regarded as the 2 nd gloss.

The test substrate was further subjected to pressurization (hot pressurization step) with a vacuum presser KVMC-PRESS (North Sichuan Seisakusho Co., ltd.) at a pressure of 3MPa and a temperature of 170 ℃. The laminate after the hot pressing step was further reheated at 260 ℃ for 10 minutes (reheating step).

3-3. Production of substrate for measuring 3 rd glossiness

The 1 st film of the dry film thus produced was peeled off, and then a resin layer (a) was laminated on a printed wiring board by a vacuum laminator to contact the printed wiring board, thereby producing a 3 rd substrate for measuring glossiness. The single-layer dry films of comparative examples 1-1 to 1-3 were produced by peeling the 1 st film and then bonding the 1 st film-side surface of the resin layer (a) to a printed wiring board.

The substrate for measuring 3 rd glossiness obtained as described above was subjected to cumulative exposure of 250mJ/cm by a pressure-reduced adhesion type double-sided exposure machine (model ORC HMW 680 GW) made of ORC MANUFACTURINGCO., LTD. ² Under the condition of (a) irradiating ultraviolet rays from the resin layer B side (an exposure step). Next, the 2 nd film provided on the resin layer (B) side was removed, and the film was thermally cured at 150 ℃ for 60 minutes, and the glossiness measured on the outer surface of the resin layer (B) was set as the 3 rd glossiness.

4. Determination of gloss

The 1 st, 2 nd, and 3 rd gloss of each measurement substrate and the gloss of the outer surface of the resin layer (A) after the hot pressing step and the reheating step were measured at an incident angle of 60℃by a gloss meter "micro-TRI-gloss" (manufactured by BYK Additives & Instruments). The measurement results are shown in tables 2 and 3.

5. Evaluation of gloss

Based on the measurement results, the gloss of the surface of the resin layer (a) of the test substrate completely cured by the above treatment was comprehensively evaluated as a means for evaluating the appearance of a matt sample. The reference for the comprehensive evaluation of glossiness is as follows.

And (3) the following materials: after the hot pressing, the gloss again becomes 30 or less due to reheating.

X: after reheating, the gloss also becomes more than 30.

The results are shown in tables 2 and 3 together

6. Evaluation of Heat resistance of welding

Rosin flux was applied to the substrate after heat curing, in which the measurement of the 2 nd glossiness was performed, and immersed in a solder bath set at 260 ℃ and 280 ℃ in advance for 10 seconds, and the occurrence of lifting, swelling, and peeling of the cured coating film was evaluated. The evaluation criteria are as follows.

And (3) the following materials: no floating, swelling or peeling was generated in any of the impregnations at 260℃and 280 ℃.

And (2) the following steps: the impregnation at 260℃did not cause floating, swelling and peeling, but the impregnation at 280℃did cause floating, swelling and peeling.

X: both 260℃and 280℃of impregnation gave rise to and peel off.

7. Evaluation of breaking Strength

From the heat-cured substrate subjected to measurement of the 2 nd glossiness, the cured resin layer was peeled off, and used as a test piece for breaking strength evaluation. The test piece was measured for breaking strength according to JIS K7127 and evaluated. The evaluation criteria are as follows.

And (3) the following materials: 40MPa or more

And (2) the following steps: 30MPa or more and less than 40MPa

X: is lower than 30MPa

8. Evaluation of surface hardness (Pencil hardness)

The cured resin layer was peeled from the heat-cured substrate subjected to measurement of the 2 nd glossiness, and was used as a test piece for evaluating the surface hardness. According to JIS K5600-5-4: 1999 test method the cured coating film of the test piece was tested to determine the highest hardness that did not scratch the coating film.

9. Evaluation of Circuit coverage

The circuit hiding power was evaluated by visual observation from a distance of 30cm using the same evaluation test piece as that used in the above-mentioned evaluation method of the heat resistance. The evaluation criteria are as follows.

And (3) the following materials: no circuit can be seen.

O: a portion of the circuit can be visualized.

X: the circuit can be clearly seen.

10. Resolution evaluation (evaluation of minimum opening diameter)

Stripping offAfter vacuum lamination of the 1 st film of the dry film produced by the above method in such a manner that the resin layer (a) is brought into contact with a printed circuit board, ultraviolet rays are irradiated from the resin layer (a) side by ORC MANUFACTURING co., ltd. A pressure-reduced adhesion type double-sided exposure machine (model ORC HMW 680 GW) via a step exposure meter (Kodak No. 2). Further, the 1 st film was removed from the resin layer (A) of the test substrate, and development was performed for 60 seconds (30 ℃ C., 0.2MPa, 1wt% Na) ₂ CO ₃ An aqueous solution). For each measurement sample, the amount of light corresponding to the concentration portion of the 5 th stage of the stepwise exposure table of the portion remaining after development was taken as the optimum exposure amount.

Similarly, the 1 st film of the dry film was peeled off, vacuum lamination was performed so that the resin layer (a) was in contact with the printed wiring board, and then, a negative pattern having a hole opening diameter of 500 μm, 300 μm, 150 μm, 100 μm, and 80 μm was arranged as a negative mask for resolution evaluation on the outer surface of the resin layer (a), and an ultraviolet ray was irradiated with an optimum exposure amount by a pressure-reducing adhesion type double-sided exposure machine (model ORC HMW 680 GW) manufactured by ORC MANUFACTURING co., ltd. Further, the 1 st film was removed from the resin layer (A) of the test substrate, and development was performed for 60 seconds (30 ℃ C., 0.2MPa, 1wt% Na) ₂ CO ₃ An aqueous solution). The test substrate having a cured dry film (laminate or single layer film) was prepared by heat curing at 150 ℃. In this substrate, the pattern opening was observed with SEM to determine the minimum opening diameter.

The results of the mechanical property measurements are shown in tables 2 and 3.

TABLE 2

TABLE 3

As described above, according to the embodiments of the present invention, the outer surface of the laminate cured product is formed into a matt-like shape, and the surface hardness, heat resistance, breaking strength, and circuit hiding property of the cured product all show excellent values. In contrast, in any of comparative examples 1-1 to 1-3 having a single-layer structure and comparative examples 1-4 to 1-6 having a laminated structure, satisfactory results were not obtained in both of mechanical properties and low gloss of the surface (corresponding to the outer surface of the laminate of the present invention).

Examples 2-1 to 2-12 (second embodiment) and comparative examples 2-1 to 2-3

< preparation of resin composition >

1. Synthesis of resin component

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

In the same manner as in Synthesis example 1-2 in the example of the first embodiment, a polyimide resin solution (resin 2-1) having phenolic hydroxyl groups and carboxyl groups was obtained.

Synthesis example 2-2: synthesis of carboxyl group-containing novolak type acrylate resin (resin 2-2)

A novolak-type cresol resin (Aica Kogyo Co.. Ltd., trade name: 119.4; OH equivalent weight) 119.4g, potassium hydroxide 1.19g and toluene 119.4g were charged into an autoclave equipped with a thermometer, a nitrogen introducing device, and a stirring device, and the inside of the autoclave was stirred while being replaced with nitrogen gas, and heated to raise the temperature. Then, 63.8g of propylene oxide was slowly added dropwise thereto at 125 to 132℃and 0 to 4.8kg/cm ² The reaction was carried out for 16 hours. Then, the reaction solution was cooled to room temperature, and 1.56g of 89% phosphoric acid was added to neutralize potassium hydroxide to obtain a propylene oxide reaction solution of a novolak-type cresol resin having a nonvolatile content of 62.1% and a hydroxyl value of 182.2g/eq. Which is obtained by adding 1.08 moles of alkylene oxide to 1 equivalent of phenolic hydroxyl groups on average. Then, 293.0g of the obtained alkylene oxide reaction solution of novolak-type cresol resin, 43.2g of acrylic acid, 11.53g of methanesulfonic acid, 0.18g of methylhydroquinone and 252.9g of toluene were charged into a reactor equipped with a stirrer, a thermometer and an air blowing tube, and air was blown at a rate of 10 ml/min, and reacted at 110℃for 12 hours while stirring. Water produced by the reaction as an azeotropic mixture with toluene 12.6g of water are distilled off. Thereafter, the reaction solution was cooled to room temperature, and then, 35.35g of the obtained reaction solution was neutralized with 15% aqueous sodium hydroxide solution, followed by washing with water. Then, toluene was replaced with 118.1g of diethylene glycol monoethyl ether acetate in an evaporator and distilled off to obtain a novolak-type acrylic resin solution. Then, 332.5g of the obtained novolak type acrylic resin solution and 1.22g of triphenylphosphine were charged into a reactor equipped with a stirrer, a thermometer and an air blowing tube, and air was blown at a rate of 10 ml/min, 60.8g of tetrahydrophthalic anhydride was slowly added while stirring, and the mixture was reacted at 95 to 101℃for 6 hours. Thus, a carboxyl group-containing resin (resin 2-2) solution having an acid value of 88mgKOH/g in the solid content, 71% in the solid content and a mass average molecular weight of 2000 was obtained.

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

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

TABLE 4

* The proportions of the components in the above table are based on the solid components.

Details of the components shown in table 4 are as follows.

Block copolymer resin 1: M65N: X-Y-X block copolymer resin having a mass average molecular weight (Mw) of about 100000 ～ 300000, manufactured by Arkema Co., ltd., NANOSTRENGTH (registered trademark)

Block copolymer resin 2: M52N: X-Y-X block copolymer resin having a mass average molecular weight (Mw) of about 100000, manufactured by Arkema Co., ltd., nano-STRENGTH (registered trademark)

Photopolymerizable compound 1: DOUBLEMER 6MX75: DOUBLE BOND CHEMICAL IND.CO., LTD. Company-manufactured compounds of general formula (I)

Photopolymerizable compound 2: DOUBLEMER 527, DOUBLE BOND CHEMICAL IND.CO., LTD. Co., ltd., 6 functional acrylate aliphatic urethane acrylate oligomer

Photopolymerizable compound 3: DHPA: dipentaerythritol hexaacrylate (manufactured by Japanese chemical Co., ltd.)

Epoxy resin 1: bisphenol A type novolak epoxy resin N870, manufactured by DIC Co., ltd

Photopolymerization initiator: oxime ester photopolymerization initiator IRUGACURE OXE02 (BASF Japan Co., ltd.)

Resin 2-1: synthesis example 2-1 (polyimide resin having phenolic hydroxyl group and carboxyl group)

One of the manchums CRG951: aica Kogyo Co..Ltd. Prepared, novolak type cresol resin, OH equivalent: 119.4)

Coloring pigment (for resin layers (a) and (B): paliogen Black S0084: pyrene black pigment (BASF Co., ltd.)

KAYARAD ZCR-1569H: acid-modified epoxy acrylate (adduct of dibasic acid anhydride of multifunctional epoxy (meth) acrylate) (manufactured by Nippon Kagaku Co., ltd.)

Resin 2-2: synthesis of (carboxyl group-containing novolak type acrylate resin) from Synthesis example 2-2

Epoxy resin 2: bisphenol A type novolak epoxy resin (DIC Co., ltd.)

A matte PET (PTHA-25, manufactured by Unitika Co., ltd., surface roughness Ra:0.3 μm) was used as the 1 st film to form irregularities on the surface of the resin layer (A).

3. Preparation of dry film

The resin compositions obtained as described above were diluted with an organic solvent MEK to have appropriate viscosities (10 mPas to 100 dPa.s). The 1 st film (PET film, thickness: 25 μm, surface roughness (Ra): 0.03 μm) was coated with a resin composition corresponding to the resin layer (A) shown in Table 4 so that the film thickness after drying became the same film thickness shown in the table, and then dried at 90℃for 15 minutes. Next, a resin composition corresponding to the resin layer (B) of table 4 was applied to the dried resin layer (a) so that the film thickness after drying became the film thickness described in the same table, and then dried at 80 ℃ for 30 minutes. Thus, a laminate having a resin layer (a) and a resin layer (B) in this order on the 1 st film was obtained. Among them, comparative examples 2 to 3 formed a single film dry film of only the resin layer (a). Further, for comparative example 2-2, a matte PET (PTHA-25, manufactured by Unitika Co., ltd., surface roughness Ra:0.3 μm) was used as the 1 st film, and therefore, the irregularities of the matte PET were transferred to the resin layer (A), and as a result, the resin layer (A) had a physically roughened surface.

4. Fabrication and evaluation of test substrates

< manufacturing of test substrate A >

A single-sided printed circuit board on which a circuit having a copper thickness of 15 μm was formed was prepared, and pretreatment was performed using MEC co., ltd. The dry films of each example and comparative example produced as described above were laminated with the resin layer (B) in contact with the substrate by a vacuum laminator, to form a laminate on the substrate.

The substrate was subjected to pattern exposure with an optimal exposure amount described below using a vacuum adhesion type two-sided exposure machine (model ORC HMW 680 GW) manufactured by ORC MANUFACTURING co., ltd., and baked at 100 ℃ for 30 minutes, and then the PET film used as the 1 st film when the laminate was formed was peeled off. Thereafter, development was performed for 60 seconds from a 1wt% aqueous sodium carbonate solution at 30℃under a spray pressure of 0.2MPa to obtain a cured product of the laminate as a solder resist pattern. For the substrate, from the upper part of the resin layer (A), the exposure amount was accumulated in a UV transfer furnace at 1000mJ/cm ² After ultraviolet irradiation at 150 ℃ for 60 minutes, a test substrate a having a cured product formed from each laminate was produced.

Determination of optimum Exposure

The optimum exposure amount used for pattern exposure in producing the test substrate a was determined as follows.

That is, a single-sided printed circuit board on which a circuit having a copper thickness of 15 μm is formed is prepared, and pretreatment is performed using MEC co., ltd. The dry films of each example and comparative example produced as described above were laminated with the resin layer (B) in contact with the substrate by a vacuum laminator, to form a laminate (measurement sample) on the substrate. For each of the thus obtained optimal exposure measurement samples, ORC MANUFACTURING co., ltdIs exposed by means of a step exposure meter (Kodak No. 2). After exposure, heating was performed at 100℃for 30 minutes. Thereafter, the PET film used as the 1 st film in the laminate was peeled off and developed for 60 seconds (30 ℃ C., 0.2MPa, 1wt% Na) ₂ CO ₃ An aqueous solution). For each measurement sample, the light amount of the portion remaining after development, which corresponds to the concentration portion of the stage 5 of the stepwise exposure table, was taken as the optimum exposure amount, and the light amount at the time of pattern exposure of the test substrates a and B was taken as the light amount.

< evaluation of hiding Property >

The test substrate A was used, and the coverage of the circuit was evaluated by visual observation from a distance of 30 cm. The evaluation criteria are as follows.

And (3) the following materials: high covering power and no visual circuit.

And (2) the following steps: a portion of the circuit can be visualized.

X: the circuit can be clearly seen.

< evaluation of adhesion >

On the test substrate A, checkered cuts were made at 1mm intervals in the cured product on the test piece by a cutter, and after the cellophane tape was adhered, the cellophane tape was peeled off, and the state of the cured product remaining on the test piece was evaluated on the basis of the following determination.

O: no separation

X: with separation

< evaluation of electroless gold plating resistance >)

With respect to the above-mentioned test substrate a,

the tape was peeled off by applying a tape having a nominal width (nominal width) of 12 to 19mm, which was defined in JIS Z1522, to the surface of the plating film by plating with nickel of 0.5 μm and gold of 0.03 μm using a commercially available electroless nickel plating bath and electroless gold plating bath, and instantaneously peeling the tape. The presence or absence of penetration of plating was evaluated. The decision criteria are as follows.

O: no penetration and peeling are observed

X: after plating, slight penetration was confirmed

< manufacturing of test substrate B >

A single-sided printed circuit board on which a circuit having a copper thickness of 15 μm was formed was prepared, and pretreatment was performed using MEC co., ltd. The dry films of each example and comparative example produced as described above were laminated with the resin layer (B) in contact with the substrate by a vacuum laminator, to form a laminate on the substrate. Negative patterns having hole opening diameters of 500 μm, 300 μm, 150 μm, 100 μm, and 80 μm were arranged on the resin layer (a) of the laminate of the substrates as a negative mask for resolution evaluation, and pattern exposure was performed with a pressure-reducing adhesion type double-sided exposure machine (model ORC HMW 680 GW) manufactured by ltd. With ORC MANUFACTURING co., therebetween, at an optimum exposure amount determined in the above-described manner. Further, after baking at 100℃for 30 minutes, the PET film used as the 1 st film in the laminate was peeled off. Then, a 1wt% sodium carbonate aqueous solution at 30℃was developed under a spray pressure of 0.2MPa for 60 seconds to obtain a solder resist pattern. For the substrate, the cumulative exposure was 1000mJ/cm in a UV transfer furnace ² After ultraviolet irradiation at 150 ℃ for 60 minutes, a test substrate B having a cured product formed from each laminate was produced.

< evaluation of resolution (evaluation of minimum opening diameter)) >

In the test substrate B, the pattern opening was observed with SEM to determine the minimum opening diameter.

< B-HAST resistance >

The test substrate B was placed in a high-temperature and high-humidity tank at 130 ℃ under an atmosphere of 85% humidity, and a voltage of 3.5V was applied to a comb-shaped electrode portion (n=6) having a line width/line distance=12 μm/13 μm, thereby performing B-HAST in the tank for 300 hours. After 300 hours, B-HAST resistance was evaluated according to the following criteria. The resistance value is lower than 1 multiplied by 10 ⁶ Omega is determined as a short circuit.

And (3) the following materials: no short circuit occurs between 6 all comb electrodes

O: short-circuiting between 1 comb-shaped electrode among 6

X: short-circuiting between 2 or more comb electrodes among 6

< breaking Strength >

The cured product of the laminate was peeled off from the test substrate B, and the peeled cured product was evaluated by measuring the breaking strength according to JIS K7127. The evaluation criteria are as follows.

And (3) the following materials: 40MPa or more

And (2) the following steps: 30MPa or more and less than 40MPa

The cured product of the laminate of 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 having different resin compositions or layer compositions, it is difficult to achieve both of the hiding performance and the mechanical properties of the circuit. Further, in comparative example 2-2, the coverage of the circuit was improved by physical means, but the resolution of the cured product was lowered.

The present invention made by the present inventors has been specifically described above based on the embodiments, but the present invention is not limited to the above embodiments, and various modifications are of course possible within the scope not departing from the gist thereof.

Description of the reference numerals

1. 1 st film

A resin layer (A)

B resin layer (B)

2. Film 2

Claims

1. A laminate is characterized by comprising: a resin layer (A), and a resin layer (B) provided on the resin layer (A),

the resin layer (A) has a 1 st glossiness of 50 or more and a 2 nd glossiness of 30 or less,

the 3 rd glossiness of the resin layer (B) is 50 or more,

(i) The 1 st gloss is a value obtained as follows: in a laminate comprising the resin layer (B) and the resin layer (A) on a substrate in this order, after exposing the surface of the resin layer (A) and before heat curing, a value obtained by measuring the glossiness of the outer surface of the resin layer (A) in the laminate,

(ii) the 2 nd gloss is determined as follows: further heating the laminate after measuring the 1 st gloss at 150 ℃ for 60 minutes, and measuring the gloss of the outer surface of the resin layer (A) in the laminate,

(iii) the 3 rd gloss is determined as follows: the gloss of the outer surface of the resin layer (B) in the laminate was measured after exposing the surface of the resin layer (B) to light and further heating at 150 ℃ for 60 minutes.

2. A laminate is characterized by comprising: a resin layer (A), and a resin layer (B) provided on the resin layer (A),

the resin layer (A) has:

(A1) Block copolymer resin

(A2) A photopolymerizable compound which is capable of producing a light-curable resin,

the resin layer (B) has:

(B1) Alkali-soluble (meth) acrylate resins.

3. The laminate according to claim 2, wherein the (A1) block copolymer resin is of the X-Y-X type and has a mass average molecular weight Mw of 20000 to 400000.

4. The laminate according to claim 2 or 3, wherein the photopolymerizable compound (A2) is a compound represented by the following general formula (I),

in the general formula (I), R1 represents a hydrogen atom or a methyl group.

5. The laminate according to any one of claims 1 to 4, further comprising a1 st film and a2 nd film, wherein the 1 st film, the resin layer (a), the resin layer (B), and the 2 nd film are provided in this order.

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

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