KR102572426B1 - Photosensitive element, resin composition for forming barrier layer, method for forming resist pattern, and method for producing printed wiring board - Google Patents

Abstract

A photosensitive element having a support film, a barrier layer, and a photosensitive layer in this order for the purpose of providing a photosensitive element capable of improving the peelability of the barrier layer and the support film without using a release accelerator, wherein the above A photosensitive element is provided in which the barrier layer contains a water-soluble resin and an alcohol having 3 or more carbon atoms.

Description

Photosensitive element, resin composition for barrier layer formation, resist pattern formation method, and printed wiring board manufacturing method

The present disclosure relates to a method for forming a photosensitive element, a resin composition for forming a barrier layer, a resist pattern, and a method for manufacturing a printed wiring board.

Conventionally, in the field of manufacturing printed wiring boards, as a resist material used for etching treatment or plating treatment, a photosensitive resin composition and a layer formed using the photosensitive resin composition on a support film (hereinafter also referred to as "photosensitive layer") A photosensitive element having is widely used.

A printed wiring board is manufactured using the photosensitive element, for example, in the following procedure. That is, first, the photosensitive layer of the photosensitive element is laminated on a substrate for circuit formation such as a copper-clad laminate. At this time, the surface of the photosensitive layer opposite to the surface in contact with the support film is laminated so that it adheres closely to the circuit forming surface of the substrate for circuit formation. In addition, lamination is performed, for example, by heat-pressing the photosensitive layer on the substrate for circuit formation (normal pressure lamination method).

Next, radicals are generated by exposing a desired region of the photosensitive layer through a support film using a mask film or the like. The generated radicals contribute to the crosslinking reaction (photocuring reaction) of the photopolymerizable compound through several reaction pathways. Next, after the support film is peeled off, the uncured portion of the photosensitive layer is dissolved or dispersed and removed with a developing solution to form a resist pattern. Next, using the resist pattern as a resist, an etching process or a plating process is performed to form a conductor pattern, and finally the photocured portion (resist pattern) of the photosensitive layer is peeled off (removed).

By the way, in recent years, a method of forming an excellent resist pattern by exposing the photosensitive layer after exfoliating the support film before exposure has been studied. However, when the photosensitive layer is exposed to light after peeling off the support film, the generated radicals come into contact with oxygen in the air, thereby rapidly stabilizing (activating) the radicals and making it difficult for the photocuring reaction of the photopolymerizable compound to proceed. . Therefore, in this method, a photosensitive element having a barrier layer (intermediate layer) having a gas barrier property between the support film and the photosensitive layer is used for the purpose of reducing the influence of oxygen mixing in the case of exposing the support film for exposure. Its use has been studied (see, for example, Patent Literatures 1 to 3).

Patent Document 1: Japanese Patent No. 5483734 Patent Document 2: Japanese Unexamined Patent Publication No. 2013-24913 Patent Document 3: Japanese Patent No. 5551255

In the photosensitive element provided with the barrier layer containing the water-soluble resin described in Patent Literatures 1 to 3, since the affinity between the water-soluble resin and the support film is high, the adhesion between the barrier layer and the support film is strong. there is. In this case, when peeling the support film from the barrier layer of the photosensitive element, it becomes difficult to peel the support film, and the barrier layer or the photosensitive layer may be damaged.

Until now, by adding a release accelerator such as silicone or fluorine-based surfactant to a resin composition for forming a barrier layer containing a water-soluble resin, the adhesiveness between the barrier layer and the support film is reduced, and the separation between the barrier layer and the support film is reduced. It is proposed to improve sexuality.

However, it has been found that there is a problem that clouding easily occurs in the barrier layer formed by adding a peeling accelerator such as a surfactant. In addition, since a peeling accelerator such as a surfactant is present at the interface between the barrier layer and the supporting film, in the long term, the composition of the interface fluctuates or the adhesiveness between the barrier layer and the supporting film changes, resulting in stable peeling of the supporting film. There is a problem that it is difficult to maintain the properties (peelability between the barrier layer and the supporting film).

The present disclosure has been made in view of the problems of the prior art, and formation of a photosensitive element, a resin composition for forming a barrier layer, and a resist pattern capable of improving the peelability between a barrier layer and a support film without using a peeling accelerator. It aims at providing the manufacturing method of a method and a printed wiring board.

In order to achieve the above object, the present disclosure provides a photosensitive element including a support film, a barrier layer, and a photosensitive layer in this order, wherein the barrier layer contains a water-soluble resin and an alcohol having 3 or more carbon atoms. provides

In the photosensitive element of the present disclosure, by containing an alcohol having 3 or more carbon atoms in the barrier layer, peelability between the barrier layer and the support film can be improved without using a peel accelerator. According to such a photosensitive element, since the supporting film can be smoothly peeled off from the barrier layer, defects in the barrier layer and the photosensitive layer can be suppressed. In addition, since the peelability between the barrier layer and the supporting film can be improved even without using the peeling accelerator, occurrence of blurring of the barrier layer and change over time in the peelability of the supporting film due to the presence of the peeling accelerator can be suppressed. Therefore, it can be said that a resist pattern excellent in resolution and resist pattern shape can be formed by using the photosensitive element of the present disclosure.

In the photosensitive element of the present disclosure, the alcohol having 3 or more carbon atoms is at least one selected from the group consisting of compounds represented by the following formulas (1) to (3) and compounds represented by the following general formula (4). may contain According to such a photosensitive element, the peelability of the barrier layer and the supporting film can be further improved.

[In Formula (4), R ¹¹ represents an alkyl group, R ¹² represents an alkylene group, and the sum of the carbon atoms of the group of R ¹¹ and the group of R ¹² is 3 or more.]

In the photosensitive element of the present disclosure, the solubility of the alcohol having 3 or more carbon atoms in water at 20°C may be 300 mL/100 mL of water or more. According to such a photosensitive element, layer separation of the barrier layer can be further suppressed, and a photosensitive element excellent in practical use can be provided.

In the photosensitive element of the present disclosure, the content of the alcohol having 3 or more carbon atoms in the barrier layer may be more than 0 mass% and 2.0 mass% or less based on the total amount of the barrier layer. According to such a photosensitive element, diffusion of alcohols in a later step can be suppressed.

In the photosensitive element of the present disclosure, the water-soluble resin may contain polyvinyl alcohol. According to such a photosensitive element, the gas barrier property of the barrier layer can be further improved, and deactivation of radicals generated by actinic light used for exposure can be further suppressed.

In the photosensitive element of the present disclosure, the support film may be a polyester film. According to such a photosensitive element, the mechanical strength and heat resistance of the support film can be improved, and at the same time, defects such as wrinkles in the barrier layer that occur when forming the barrier layer on the support film can be suppressed, and workability can be improved. can improve

The present disclosure also provides a resin composition for forming a barrier layer containing a water-soluble resin, an alcohol having 3 or more carbon atoms, and water. According to such a resin composition for forming a barrier layer, it is possible to form a barrier layer with excellent releasability from the support film even without using a release accelerator.

In the resin composition for forming a barrier layer of the present disclosure, the alcohol having 3 or more carbon atoms is selected from the group consisting of compounds represented by the formulas (1) to (3) and compounds represented by the formula (4) You may contain at least 1 type. According to such a resin composition for barrier layer formation, an excellent barrier layer can be formed by peelability with a support film.

In the resin composition for barrier layer formation of the present disclosure, the solubility of the alcohol having 3 or more carbon atoms in water at 20°C may be 300 mL/100 mL of water or more. According to such a resin composition for forming a barrier layer, a barrier layer in which layer separation is suppressed can be formed.

In the resin composition for forming a barrier layer of the present disclosure, the content of the alcohol having 3 or more carbon atoms may be 100 to 500 parts by mass with respect to 500 parts by mass of water. According to such a resin composition for forming a barrier layer, a barrier layer excellent in peelability from a support film can be formed, and since the solubility of the water-soluble resin is improved, the barrier layer can be easily formed.

In the resin composition for forming a barrier layer of the present disclosure, the water-soluble resin may contain polyvinyl alcohol. According to such a resin composition for forming a barrier layer, a barrier layer excellent in gas barrier properties can be formed.

The present disclosure also provides a step of arranging a photosensitive layer, a barrier layer, and a support film in this order from the substrate side on a substrate using the photosensitive element of the present disclosure, and removing the support film to obtain the barrier layer. It provides a method of forming a resist pattern comprising a step of exposing the photosensitive layer to light through actinic light and a step of removing the barrier layer and the uncured portion of the photosensitive layer from the substrate. According to this resist pattern formation method, since the resist pattern is formed using the photosensitive element of the present disclosure, it is possible to form a resist pattern with excellent resolution and resist pattern shape.

The present disclosure also provides a method for manufacturing a printed wiring board comprising a step of forming a conductor pattern by etching or plating a substrate on which a resist pattern is formed by the method of forming a resistor pattern of the present disclosure. According to such a printed wiring board manufacturing method, since a resist pattern is formed by the resist pattern formation method of the present disclosure, a resist pattern excellent in resolution and resist pattern shape can be formed, and a printed wiring board suitable for high density printed wiring boards. A manufacturing method can be provided.

According to the present disclosure, it is possible to provide a photosensitive element, a resin composition for forming a barrier layer, a method for forming a resist pattern, and a method for manufacturing a printed wiring board capable of improving the peelability between a barrier layer and a support film without using a peeling accelerator. there is.

[Fig. 1] A schematic cross-sectional view showing an embodiment of a photosensitive element of the present disclosure.
[Fig. 2] It is a diagram schematically showing an example of a manufacturing process of a printed wiring board by a semi-additive construction method.

EMBODIMENT OF THE INVENTION Hereinafter, preferred embodiment of this disclosure is described in detail, referring drawings as needed. In the following embodiments, it goes without saying that the constituent elements (including element steps and the like) are not necessarily essential, except when specifically specified or when it is clearly considered essential in principle. It should be interpreted that this is the same also regarding numerical values and ranges, and does not unduly limit the present disclosure.

In addition, in this specification, (meth)acrylic acid means at least one of acrylic acid and methacrylic acid corresponding to it. In addition, the same applies to other similar expressions such as (meth)acrylate.

In addition, in this specification, the term "process" is included in this term, not only as an independent process, but also in cases where the desired action of the process is achieved even if it cannot be clearly distinguished from other processes.

In addition, in this specification, the numerical range expressed using "-" represents the range which includes the numerical value described before and after "-" as a minimum value and a maximum value, respectively. In addition, in the numerical range described step by step in this specification, you may replace the upper limit or lower limit of the numerical range of a certain stage with the upper limit or lower limit of the numerical range of another stage. In addition, in the numerical range described in this specification, you may replace the upper limit value or the lower limit value of the numerical range with the value shown in the Example. In addition, in this specification, the term "layer" includes a structure formed on a part of the structure in addition to a structure formed on the entire surface when observed in a plan view.

[Photosensitive element]

As shown in FIG. 1 , the photosensitive element 1 of the present embodiment includes a support film 2, a barrier layer 3, and a photosensitive layer 4 in this order, and a protective layer 5 and the like. You may further provide other layers of. Further, the barrier layer contains a water-soluble resin and an alcohol having 3 or more carbon atoms. By using the photosensitive element of this embodiment, the peelability of a barrier layer and a support film can be improved. Further, since the photosensitive element of the present embodiment can suppress layer separation of the barrier layer, it is excellent in practical use. Hereinafter, each layer in the photosensitive element according to this embodiment will be described in detail.

<support film>

As the support film of this embodiment, it can be used without particular limitation. Examples include polyester films such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT) and polyethylene-2,6-naphthalate (PEN), and polyolefin films such as polypropylene and polyethylene. there is. Among them, you may use a polyester film. By using a polyester film as the support film, there is a tendency that the mechanical strength and resistance to heat of the support film can be improved. In addition, by using a polyester film, defects such as wrinkles in the barrier layer that occur when forming the barrier layer on the support film can be suppressed, and workability tends to be improved. Moreover, you may use the polyester film containing particle|grains (lubricant etc.) from a viewpoint which can suppress generation|occurrence|production of the micro omission of a resist pattern. In the case of using a polyester film containing particles (lubricant, etc.), a barrier layer may be formed on the side having the particles (lubricant, etc.). As such a polyester film, for example, a polyester film in which particles (lubricant, etc.) are kneaded, a polyester film in which a layer containing particles (lubricant, etc.) is formed on both sides, or a single surface ), a polyester film having a layer containing particles (such as a lubricant) may be used. In addition, a single layer or a multilayer may be sufficient as a support film.

As a method of adding particles such as a lubricant to the support film, for example, a method of mixing particles (lubricant, etc.) with the support film, a layer containing particles (lubricant, etc.) on the support film, roll coating, flow coating , a method of forming using a known method such as spray coating, curtain flow coating, dip coating, or slit die coating.

The haze of the supporting film may be 0.01 to 5.0%, 0.01 to 1.5%, 0.01 to 1.0%, or 0.01 to 0.5%. When the haze is 0.01% or more, the support film itself tends to be easily manufactured, and when the haze is 5.0% or less, when forming the photosensitive layer of the photosensitive element, foreign matter in the photosensitive layer tends to be easily detected. there is Here, "haze" means haze. The haze in this disclosure refers to a value measured using a commercially available haze meter (turbidity meter) in accordance with the method specified in JIS K 7105. The haze can be measured with a commercially available turbidity meter such as NDH-5000 (manufactured by Nippon Densoku Kogyo Co., Ltd., trade name).

In addition, as a support film, you may obtain what can be used as a support film of a photosensitive element among commercially available general industrial films, process it suitably, and use it. Specifically, for example, "FB-40" (trade name, manufactured by Toray Industries, Ltd.), "A4100", "A1517" (trade name, manufactured by Toyobo Seki Co., Ltd.), "G2H" (tei), which are PET films, Gene DuPont Film Co., Ltd. product, product name), etc. are mentioned.

The thickness of the support film is 1 to 200 μm, 1 to 100 μm, 1 to 60 μm, 5 to 60 μm, 10 to 60 μm, 10 to 50 μm, 10 to 40 μm, 10 to 30 μm, or 10 to 30 μm. 25 micrometers may be sufficient. When the thickness of the support film is 1 µm or more, tearing of the support film tends to be suppressed when the support film is peeled off. In addition, when the thickness of the support film is 200 μm or less, economic benefits tend to be easily obtained.

<Barrier layer>

The photosensitive element of this embodiment includes a barrier layer between the support film and the photosensitive layer. In addition, the barrier layer contains water-soluble resin and alcohols having 3 or more carbon atoms. According to the photosensitive element of the present embodiment, since the support film can be smoothly peeled from the barrier layer even when the barrier layer does not contain a peeling accelerator, when the photosensitive layer is exposed to light through the barrier layer after peeling the support film, Deterioration of the resolution of the formed resist pattern can be suppressed. The barrier layer may be a layer formed using the resin composition for forming a barrier layer of the present embodiment described later, and the resin composition for forming a barrier layer of the present embodiment contains a water-soluble resin, an alcohol having 3 or more carbon atoms, and water. contain In addition, the barrier layer may have water solubility or may have solubility to a developing solution. Further, from the viewpoint of further improving the gas barrier properties of the barrier layer, the adhesive force between the support film and the barrier layer may be smaller than the adhesive force between the barrier layer and the photosensitive layer. That is, it can also be said that unintentional separation between the barrier layer and the photosensitive layer is suppressed when the supporting film is separated from the photosensitive element.

(water soluble resin)

Here, “water-soluble resin” means a resin having a solubility of 5 g or less in 100 mL of hexane at 25° C. This solubility can be calculated by mixing 25°C hexane and dried water-soluble resin and examining the presence or absence of cloudiness. Specifically, sample 1 obtained by putting a mixture of water-soluble resin A (g) and hexane (100 mL-A) after drying into a colorless and transparent glass container with a polished glass lid, and a sample obtained by adding 100 mL of hexane alone Prepare 2 each. Next, after sufficiently shaking the sample in the glass container to mix, it is confirmed that bubbles have disappeared. Immediately after confirmation, the liquid state of sample 1 and the liquid state of sample 2 are compared with the liquid state of sample 2 by placing both containers side by side under diffused daylight or light equivalent thereto. Sample 1 and Sample 2 were compared, and the addition amount A (g) when sample 1 was observed to be more cloudy or when solid content began to float was added to 100 mL of hexane at 25 ° C. of the water-soluble resin. for solubility.

Examples of the water-soluble resin include polyvinyl alcohol, polyvinylpyrrolidone, and water-soluble polyimides. From the viewpoint of further improving the gas barrier properties of the barrier layer and further suppressing deactivation of radicals generated by actinic light used for exposure, the water-soluble resin may also contain polyvinyl alcohol. Polyvinyl alcohol can be obtained, for example, by saponifying polyvinyl acetate obtained by polymerizing vinyl acetate. The degree of saponification of the polyvinyl alcohol used in the present embodiment may be 50 mol% or more, 70 mol% or more, or 80 mol% or more. In addition, the upper limit of this saponification degree is 100 mol%. By including polyvinyl alcohol having a saponification degree of 50 mol% or more, the gas barrier property of the barrier layer is further improved, and the resolution of the formed resist pattern tends to be further improved. In addition, "degree of saponification" in this specification refers to the value measured based on JIS "K" 6726 (1994) (test method of polyvinyl alcohol) prescribed|regulated by the Japanese Industrial Standards.

The said polyvinyl alcohol may use together 2 or more types of things, such as a degree of saponification, a viscosity, a degree of polymerization, and a modified species. The average polymerization degree of polyvinyl alcohol may be 300 to 5000, 300 to 3500, or 300 to 2000. In addition, the said water-soluble resin can be used individually by 1 type or in combination of 2 or more types. Water-soluble resin may also contain polyvinyl alcohol and polyvinyl pyrrolidone, for example. In this case, the mass ratio (PVA:PVP) of polyvinyl alcohol and polyvinylpyrrolidone may be 40:60 to 90:10, 50:50 to 90:10, or 60:40 to 90:10.

The content of the water-soluble resin in the resin composition for forming a barrier layer of the present embodiment is 50 to 300 parts by mass, 60 to 250 parts by mass, and 70 to 200 parts by mass with respect to 500 parts by mass of water, from the viewpoint of improving gas barrier properties. part, 80 to 150 parts by mass, or 80 to 125 parts by mass may be sufficient.

(Alcohols with 3 or more carbon atoms)

Alcohols having 3 or more carbon atoms may be either monohydric alcohols or polyhydric alcohols (excluding plasticizers for polyhydric alcohol compounds described later). The number of carbon atoms in alcohols having 3 or more carbon atoms means the sum of the number of carbon atoms in the alcohols, and may be 10 or less, 8 or less, 7 or less, 6 or less, or 5 or less. Alcohols having 3 or more carbon atoms may contain at least one selected from the group consisting of compounds represented by the following formulas (1) to (3) and compounds represented by the following general formula (4). By containing these C3 or more alcohols, the peelability of a barrier layer and a support film can be further improved.

In Formula (4), R ¹¹ represents an alkyl group and R ¹² represents an alkylene group. In addition, the sum of carbon atoms of the group of R ¹¹ and the group of R ¹² is 3 or more. In addition, the sum of the carbon atoms of the R ¹¹ group and the R ¹² group may be 10 or less, 8 or less, 7 or less, 6 or less, or 5 or less from the viewpoint of improving affinity with water. The alkyl group represented by R ¹¹ may be an alkyl group having 1 to 4 carbon atoms, and the alkylene group represented by R ¹² may be an alkylene group having 1 to 3 carbon atoms. In addition, the alkyl group represented by R ¹¹ and the alkylene group represented by R ¹² may or may not each have a substituent. In the case of having a substituent, the number of carbon atoms of the group of R ¹¹ and the number of carbon atoms of the group of R ¹² shall each include the number of carbon atoms of the substituent. Moreover, 2-butoxyethanol or 1-methoxy-2-propanol may be sufficient as the C3 or more alcohol represented by General formula (4).

You may use the said C3 or more alcohol individually by 1 type or in combination of 2 or more types. In addition, the solubility of alcohols having 3 or more carbon atoms in water at 20°C is 300 mL/100 mL or more of water, 500 mL/100 mL of water or more, or 1000 mL/100 mL of water or more, from the viewpoint of being able to further suppress the layer separation of the barrier layer. may be continued

The "solubility of alcohols having 3 or more carbon atoms in water at 20°C" in the present specification can be calculated by mixing the alcohols with water at 20°C and examining the presence or absence of cloudiness. Specifically, sample 3 obtained by putting a mixture of AmL of the alcohol and water (100-A)mL into a colorless and transparent glass container with a polished glass lid, and sample 4 obtained by adding only water (100mL), respectively. Prepare. Subsequently, samples 3 and 4 in the glass container were thoroughly shaken and mixed, and it was confirmed that the bubbles had disappeared. Immediately after confirmation, the liquid state in Sample 3 and the liquid state in Sample 4 were compared with the liquid state in Sample 4, with both containers placed side by side under diffused daylight or a light equivalent thereto. Sample 3 and Sample 4 are compared, and the addition amount AmL of the alcohol when Sample 3 is observed more blurry is taken as the solubility of the alcohol in water at 20°C.

The content of alcohols having 3 or more carbon atoms in the resin composition for barrier layer formation of the present embodiment is 100 to 500 parts by mass, 110 to 480 parts by mass, 120 to 460 parts by mass, and 125 to 440 parts by mass with respect to 500 parts by mass of water. Part by mass, 125 to 420 parts by mass, or 125 to 400 parts by mass may be sufficient. When this content is 100 parts by mass or more, the peelability between the formed barrier layer and the supporting film tends to improve, and when it is 500 parts by mass or less, the solubility of the water-soluble resin is improved and the barrier layer tends to be easily formed. there is.

The content of alcohols having 3 or more carbon atoms in the barrier layer of the present embodiment is greater than 0% by mass and 2.0% by mass, based on the total amount of the barrier layer (the total amount of solids in the resin composition for forming a barrier layer forming the barrier layer). It may be 0.001 to 2.0% by mass or 0.005 to 1.0% by mass below. When this content is 2.0% by mass or less, diffusion of alcohols in the subsequent step tends to be suppressed, and when it exceeds 0% by mass, the peelability between the barrier layer and the support film tends to improve, By being 0.001 mass % or more, there exists a tendency for the peelability of a barrier layer and a support film to improve more.

The resin composition for forming a barrier layer of the present embodiment may contain alcohols having less than 3 carbon atoms. When containing alcohols of less than 3 carbon atoms, the content may be 125 to 375 parts by mass or 150 to 325 parts by mass with respect to 500 parts by mass of water. When the content is 125 parts by mass or more, the solubility of the water-soluble resin is improved and the barrier layer tends to be easily formed, and when the content is 375 parts by mass or less, the peelability between the formed barrier layer and the supporting film tends to be improved. there is In addition, the content of alcohols having less than 3 carbon atoms in the barrier layer of the present embodiment is 0.1 based on the total amount of alcohols in the barrier layer from the viewpoint of improving the peelability between the barrier layer and the supporting film. 10 mass % may be sufficient, or 0.1-10 mass parts may be sufficient with respect to 100 mass parts of the total amount of C3 or more alcohols in a barrier layer.

In addition, the resin composition for forming a barrier layer of the present embodiment may contain known additives such as plasticizers and surfactants within a range not interfering with the effects of the present disclosure. Moreover, you may contain a peeling accelerator within the range which does not interfere with the effect of this indication.

As a plasticizer, a polyhydric alcohol compound can be contained, for example from a viewpoint of improving ductility. For example, glycerols such as glycerin, diglycerin, and triglycerin, (poly)alkyls such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, and polypropylene glycol Len glycols, trimethylol propane, etc. are mentioned. These plasticizers can be used individually by 1 type or in combination of 2 or more types.

The barrier layer in the photosensitive element of this embodiment can be formed, for example, by applying the resin composition for barrier layer formation of this embodiment onto a support film and drying it.

The thickness of the barrier layer is not particularly limited. The thickness of the barrier layer may be 12 µm or less, 10 µm or less, 8 µm or less, 7 µm or less, or 6 µm or less from the viewpoint of ease of removing the barrier layer. In addition, the thickness of the barrier layer may be 1.0 μm or more, 1.5 μm or more, 2 μm or more, 3 μm or more, or 4 μm or more from the viewpoints of ease of forming the barrier layer and resolution.

In addition, although the barrier layer in this embodiment may have photosensitivity, the photosensitivity is lower than the photosensitivity of the photosensitive layer. In addition, the barrier layer does not have to have photosensitivity. When the barrier layer does not have photosensitivity, the photosensitivity stability of the photosensitive layer tends to be further improved. In addition, "photosensitivity" means, for example, when the photosensitive layer is exposed to light, heat treatment is performed after exposure as necessary, and then the photosensitive layer is developed using a developing solution for removing uncured portions of the photosensitive layer. It means that a pattern can be formed.

<Photosensitive layer>

The photosensitive layer of this embodiment is a layer formed using the photosensitive resin composition mentioned later. The photosensitive resin composition can be used according to a desired purpose, and may be of a negative type or a positive type, as long as the properties of the photosensitive resin composition are changed by light irradiation (for example, photocuring). The photosensitive resin composition may contain (A) a binder polymer, (B) a photopolymerizable compound, and (C) a photopolymerization initiator. Moreover, you may contain (D) photosensitizer, (E) polymerization inhibitor, or other components as needed. Hereinafter, each component used in the photosensitive resin composition in the present embodiment will be described in more detail.

((A) binder polymer)

(A) The binder polymer (hereinafter also referred to as "component (A)") can be produced by radical polymerization of a polymerizable monomer, for example. Examples of the polymerizable monomer include polymerizable styrene derivatives substituted at the α-position or aromatic ring such as styrene, vinyltoluene and α-methylstyrene, acrylamide such as diacetone acrylamide, acrylonitrile, Vinyl alcohol ethers such as vinyl-n-butyl ether, (meth)acrylic acid alkyl esters, (meth)acrylic acid benzyl esters such as benzyl methacrylate, (meth)acrylic acid tetrahydrofurfuryl ester, (meth)acrylic acid dimethylamino Ethyl ester, (meth)acrylic acid diethylaminoethyl ester, (meth)acrylic acid glycidyl ester, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, (meth)acrylic acid, α-bromoacrylic acid, α-chloroacrylic acid, β-furyl (meth)acrylic acid, β-styryl (meth)acrylic acid, maleic acid, maleic anhydride, monomethyl maleate , maleic acid monoesters such as monoethyl maleate and monoisopropyl maleate, fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid and propiolic acid. These can be used individually by 1 type or in combination of 2 or more types.

In these, you may also include (meth)acrylic-acid alkylester from a viewpoint of plasticity improving. Examples of (meth)acrylic acid alkyl esters include compounds represented by the following general formula (II), and compounds in which the alkyl group of these compounds is substituted with a hydroxyl group, an epoxy group, a halogen group, or the like.

H ₂ C=C(R ⁶ )-COOR ⁷ (II)

In general formula (II), R ⁶ represents a hydrogen atom or a methyl group, and R ⁷ represents an alkyl group having 1 to 12 carbon atoms. Examples of the C1-C12 alkyl group represented by R ⁷ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, and Structural isomers of these groups are exemplified.

Examples of the (meth)acrylic acid alkyl ester represented by the general formula (II) include (meth)acrylic acid methyl ester, (meth)acrylic acid ethyl ester, (meth)acrylic acid propyl ester, (meth)acrylic acid butyl ester, ( (meth)acrylic acid pentyl ester, (meth)acrylic acid hexyl ester, (meth)acrylic acid heptyl ester, (meth)acrylic acid octyl ester, (meth)acrylic acid 2-ethylhexyl ester, (meth)acrylic acid nonyl ester, (meth)acrylic acid decyl ester , (meth)acrylic acid undecyl ester, (meth)acrylic acid dodecyl ester, etc. are mentioned. These can be used individually by 1 type or in combination of 2 or more types.

In addition, component (A) may contain a carboxyl group from the standpoint of alkali developability. (A) component containing a carboxyl group can be manufactured by radically polymerizing the polymerizable monomer and other polymerizable monomers which have a carboxyl group, for example. As the polymerizable monomer having the carboxyl group, (meth)acrylic acid or methacrylic acid may be used. Moreover, the acid value of (A) component containing a carboxyl group may be 50-250 mgKOH/g, 50-200 mgKOH/g, or 100-200 mgKOH/g.

The carboxyl group content of component (A) (the blending ratio of polymerizable monomers having carboxyl groups relative to the total amount of polymerizable monomers used in the binder polymer) is 12 to 50% by mass from the viewpoint of improving alkali developability and alkali resistance in a balanced manner, It may be 12 to 40% by mass, 15 to 35% by mass, 15 to 30% by mass, or 20 to 30% by mass. When the carboxyl group content is 12% by mass or more, the alkali developability tends to be improved, and when the content of the carboxyl group is 50% by mass or less, alkali resistance tends to be excellent.

In addition, since the content of the structural unit derived from the polymerizable monomer having a carboxyl group in the component (A) is correlated with the compounding ratio of the polymerizable monomer having a carboxyl group, it is 12 to 50% by mass and 12 to 40% by mass. %, 15 to 35% by mass, 15 to 30% by mass, or 20 to 30% by mass may be sufficient.

In addition, component (A) may use styrene or a styrene derivative as a polymerizable monomer from the standpoint of adhesiveness and chemical resistance. When the above styrene or styrene derivative is used as a polymerizable monomer, its content (the blending ratio of styrene or styrene derivative relative to the total amount of polymerizable monomers used in component (A)) further improves adhesion and chemical resistance, It may be 10 to 60% by mass, 15 to 50% by mass, 30 to 50% by mass, 35 to 50% by mass, or 40 to 50% by mass. When this content is 10% by mass or more, the adhesion tends to be improved, and when it is 60% by mass or less, it is possible to suppress the enlargement of peeling pieces during development and the increase in the time required for peeling tends to be suppressed.

In addition, since the content of the structural unit derived from styrene or a styrene derivative in component (A) is correlated with the compounding ratio of the styrene or styrene derivative, it is 10 to 60% by mass, 15 to 50% by mass, and 30 to 50% by mass. , 35 to 50% by mass, or 40 to 50% by mass may be sufficient.

In addition, component (A) may use (meth)acrylic acid benzyl ester as a polymerizable monomer from the viewpoint of resolution and aspect ratio. The content of the structural unit derived from (meth)acrylic acid benzyl ester in component (A) is 15 to 50% by mass, 15 to 45% by mass, and 15 to 40% by mass from the viewpoint of further improving resolution and aspect ratio. , 15 to 35% by mass, or 20 to 30% by mass may be sufficient.

These binder polymers can be used individually by 1 type or in combination of 2 or more types. As (A) component in the case of using in combination of 2 or more types, for example, 2 or more types of binder polymers which consist of different polymerizable monomers, 2 or more types of binder polymers of different weight average molecular weights, and 2 or more types of binder polymers of different degrees of dispersion. More than one kind of binder polymer may be mentioned.

(A) component can be manufactured by a conventional method. Specifically, for example, it can be produced by radical polymerization of (meth)acrylic acid alkyl ester, (meth)acrylic acid, and styrene.

The weight average molecular weight of component (A) may be 20,000 to 300,000, 40,000 to 150,000, 40,000 to 120,000, or 50,000 to 80,000 from the viewpoint of improving mechanical strength and alkali developability in a well-balanced manner. When the weight average molecular weight of component (A) is 20,000 or more, the developing solution resistance tends to be excellent, and when it is 300,000 or less, the development time tends to be suppressed. In addition, the weight average molecular weight in this specification is a value measured by gel permeation chromatography (GPC) and converted by a calibration curve prepared using standard polystyrene.

The content of the component (A) is 30 to 80 parts by mass, 40 to 75 parts by mass, 50 to 70 parts by mass, or 50 parts by mass, based on 100 parts by mass of the total solid content of component (A) and component (B) described later. It may be -60 parts by mass. If content of (A) component is in this range, the coating-film property of the photosensitive resin composition and the intensity|strength of a photocured part become more favorable.

((B) photopolymerizable compound)

The photosensitive resin composition according to this embodiment may also contain (B) a photopolymerizable compound (hereinafter, also referred to as "component (B)"). Component (B) can be used without particular limitation as long as it is a compound capable of photopolymerization or a compound capable of photocrosslinking. For example, a compound having at least one ethylenically unsaturated bond in the molecule can be used.

As the component (B), for example, a compound obtained by reacting a polyhydric alcohol with an α,β-unsaturated carboxylic acid, a bisphenol A (meth)acrylate compound such as a bisphenol A (meth)acrylate compound, and having a urethane bond ( Urethane monomers such as meth)acrylate compounds, nonylphenoxyethyleneoxy(meth)acrylate, nonylphenoxyoctaethyleneoxy(meth)acrylate, γ-chloro-β-hydroxypropyl-β'-(meth)acryl Royloxyethyl-o-phthalate, β-hydroxyethyl-β'-(meth)acryloyloxyethyl-o-phthalate, β-hydroxypropyl-β'-(meth)acryloyloxyethyl-o -phthalates, and (meth)acrylic acid alkyl esters. These can be used individually by 1 type or in combination of 2 or more types.

Among the above, the component (B) may contain a bisphenol-type (meth)acrylate compound from the standpoint of improving resolution, adhesiveness, and suppression of the occurrence of register hems in a well-balanced manner. As said bisphenol-type (meth)acrylate compound, the compound represented by the following general formula (III) may be sufficient.

In general formula (III), R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or a methyl group. X and Y each independently represent an ethylene group or a propylene group, and XO and YO each independently represent an oxyethylene group (hereinafter sometimes referred to as "EO group") or an oxypropylene group (hereinafter referred to as "PO group"). It is sometimes referred to as ".). p ₁ , p ₂ , q ₁ and q ₂ each independently represent a numerical value of 0 to 40. However, both of p ₁ + q ₁ and p ₂ + q ₂ are 1 or more. When X is an ethylene group and Y is a propylene group, p ₁ + p ₂ is 1 to 40, and q ₁ + q ₂ is 0 to 20. When X is a propylene group and Y is an ethylene group, p ₁ + p ₂ is 0 to 20, and q ₁ + q ₂ is 1 to 40. Since p ₁ , p ₂ , q ₁ and q ₂ represent the number of structural units of the EO group or PO group, they represent integer values in a single molecule, and represent average rational numbers in an aggregate of a plurality of molecules. In addition, the EO group and the PO group may respectively exist continuously, blockwise, or randomly.

In general formula (III), when both X and Y are ethylene groups, p ₁ + p ₂ + q ₁ + q ₂ may be 1 to 20, 1 to 10, or 1 to 7 from the viewpoint of better resolution and adhesion. .

Examples of the compound represented by formula (III) include 2,2-bis(4-((meth)acryloxypolyethoxy)phenyl)propane and 2,2-bis(4-((meth)acryl Oxypolypropoxy)phenyl)propane, 2,2-bis(4-((meth)acryloxypolyethoxypolypropoxy)phenyl)propane, etc. are mentioned. These can be used individually by 1 type or in combination of 2 or more types.

Examples of commercially available bisphenol type (meth)acrylate compounds include 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (manufactured by Shin-Nakamura Chemical Industry Co., Ltd. "BPE -200"), 2,2-bis(4-(methacryloxypentaethoxy)phenyl)propane ("BPE-500" manufactured by Shin-Nakamura Chemical Industry Co., Ltd. or "FA-" manufactured by Hitachi Chemical Co., Ltd.) 321 M"), 2,2-bis(4-(methacryloxypentadecaethoxy)phenyl)propane ("BPE-1300" manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), 2,2-bis(4- (methacryloxy polyethoxy) phenyl) propane (Kyoeisha Chemical Co., Ltd. "BP-2EM" (EO group: 2.6 (average value))) etc. are mentioned.

The content of the bisphenol type (meth)acrylate compound is 1 to 50% by mass, 3 to 40% by mass, 10 to 10% by mass, based on the total solid content of component (A) and component (B), from the viewpoint of further improving chemical resistance. It may be 40% by mass, 20 to 40% by mass, or 30 to 40% by mass.

In addition, the content of the bisphenol type (meth)acrylate compound is 30 to 99% by mass, 50 to 97% by mass, 60 to 95% by mass relative to the total solid content of component (B) from the viewpoint of further improving chemical resistance. , 70 to 95% by mass, or 80 to 90% by mass may be sufficient.

In addition, the content of the compound represented by the general formula (III) in which the total number of EO groups and PO groups is 1 to 7 is, from the viewpoint of better resolution, relative to the total solid content of component (A) and component (B) , 1 to 50% by mass, 2 to 48% by mass, 3 to 45% by mass, 5 to 40% by mass, 10 to 30% by mass, or 10 to 25% by mass may be sufficient.

In addition, from the standpoint of further improving the conformability to unevenness of the substrate, a compound obtained by reacting an α,β-unsaturated carboxylic acid with a polyhydric alcohol may be contained. As such a compound, polyalkylene glycol di(meth)acrylate having both an EO group and a PO group in the molecule, dipentaerythritol (meth)acrylate having an EO group, and the like can be used. As what is commercially available as dipentaerythritol (meth)acrylate which has EO group, "DPEA-12" by Nippon Kayaku Co., Ltd. etc. are mentioned, for example. The content of dipentaerythritol (meth)acrylate having an EO group is 1 to 10% by mass, 1.5 to 8% by mass, or 2 to 8% by mass, from the viewpoint of improving resolution, with respect to the total solid content of component (B). , 2.5 to 8% by mass, or 3 to 8% by mass may be sufficient.

In addition, in the molecule of polyalkylene glycol di(meth)acrylate having both EO and PO groups, the EO and PO groups may respectively exist continuously, blockwise or randomly. Further, the PO group may be either an oxy-n-propylene group or an oxyisopropylene group. In the (poly)oxyisopropylene group, the secondary carbon of the propylene group may be bonded to the oxygen atom, or the primary carbon may be bonded to the oxygen atom.

Examples of commercially available polyalkylene glycol di(meth)acrylates having both an EO group and a PO group include polyalkyl having EO groups: 6 (average value) and PO groups: 12 (average value) Lenglycol di(meth)acrylate ("FA-023M", "FA-024M" by Hitachi Chemical Co., Ltd.) etc. are mentioned. In addition, the content of the polyalkylene glycol di(meth)acrylate having both EO and PO groups is 1, from the viewpoint of the ability to follow irregularities of the substrate and the improvement in resolution, with respect to the total solid content of component (B). It may be - 15% by mass, 1.5 - 15% by mass, 2 - 13% by mass, or 3 - 13% by mass.

The content of the component (B) may be 20 to 70 parts by mass, 25 to 60 parts by mass, or 30 to 50 parts by mass with respect to 100 parts by mass of the total solid content of the component (A) and the component (B). When the content of the component (B) is within this range, the photosensitivity and coating properties are further improved in addition to the resolution, adhesiveness, and suppression of occurrence of resist hemming of the photosensitive resin composition.

((C) photopolymerization initiator)

The photosensitive resin composition concerning this embodiment may contain at least 1 sort(s) of (C) photoinitiator (henceforth "component (C)"). Component (C) is not particularly limited as long as it can polymerize component (B), and can be appropriately selected from commonly used photopolymerization initiators.

As component (C), for example, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-methyl-1-[4-(methylthio)phenyl] Aromatic ketones such as -2-morpholinopropanone-1, quinones such as alkylanthraquinone, benzoin ether compounds such as benzoin alkyl ether, benzoin compounds such as benzoin and alkylbenzoin, benzyldimethylketal, etc. 2 such as benzyl derivatives of , 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, acridine derivatives such as 4,5-triarylimidazole dimer, 9-phenylacridine, and 1,7-(9,9'-acridinyl) heptane; and the like. These can be used individually by 1 type or in combination of 2 or more types.

In these, you may contain a 2,4,5- triaryl imidazole dimer from a viewpoint of improving resolution. Examples of the 2,4,5-triarylimidazole dimer include 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer and 2-(o-chlorophenyl)- 4,5-bis-(m-methoxyphenyl) imidazole dimer and 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer. Among these, you may contain a 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer from a viewpoint of improving photosensitivity stability.

As a 2,4,5-triarylimidazole dimer, for example, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole is B It is commercially available as -CIM (manufactured by Hodogaya Gagaku Kogyo Co., Ltd., product name).

Component (C) further improves photosensitivity and adhesiveness, and from the viewpoint of further suppressing the light absorption of component (C), even if at least one type of 2,4,5-triarylimidazole dimer is included, and may include a 2-(2-chlorophenyl)-4,5-diphenylimidazole dimer. In addition, the structure of a 2,4,5-triaryl imidazole dimer may be symmetrical or asymmetrical.

The content of component (C) is 0.01 to 30 parts by mass, 0.1 to 10 parts by mass, 1 to 7 parts by mass, 1 to 6 parts by mass, based on 100 parts by mass of the total solid content of component (A) and component (B). It may be 1 to 5 parts by mass or 2 to 5 parts by mass. When the content of component (C) is 0.01 part by mass or more, photosensitivity, resolution and adhesion tend to improve, and when it is 30 parts by mass or less, the resist pattern shape tends to be excellent.

((D) Photosensitizer)

The photosensitive resin composition according to this embodiment may also contain (D) a photosensitizer (hereinafter, also referred to as "component (D)"). By containing component (D), there exists a tendency that the absorption wavelength of the actinic light used for exposure can be used effectively.

As component (D), for example, pyrazolines, dialkylaminobenzophenones, anthracenes, coumarins, xanthones, oxazoles, benzoxazoles, thiazoles, benzothiazoles, triazoles, stilbenes, triazines, thiophenes, naphthalimides, and triarylamines. These can be used individually by 1 type or in combination of 2 or more types. From the standpoint of being able to use the absorption wavelength of actinic light used for exposure more effectively, component (D) may also contain pyrazolines, anthracenes, or dialkylaminobenzophenones, especially dialkyl Amino benzophenones may also be included. As what is commercially available as dialkylamino benzophenones, Hodogaya Chemical Industry Co., Ltd. "EAB" etc. are mentioned, for example.

(D) When containing component, the content is 1.0 mass part or less, 0.5 mass part or less, 0.15 mass part or less, 0.12 mass part or less with respect to 100 mass parts of total solids of (A) component and (B) component. , or 0.10 parts by mass or less may be sufficient. When the content of component (D) is 1.0 parts by mass or less with respect to 100 parts by mass of the total solid content of component (A) and component (B), the deterioration of the shape of the resist pattern and the occurrence of resist hemming can be suppressed, and the resolution is improved more. tend to be able to In addition, the content of component (D) may be 0.01 part by mass or more with respect to 100 parts by mass of the total solid content of component (A) and component (B) from the standpoint of easy to obtain high photosensitivity and good resolution.

((E) polymerization inhibitor)

The photosensitive resin composition according to the present embodiment may also contain (E) a polymerization inhibitor (hereinafter, also referred to as “component (E)”). By containing the component (E), there is a tendency that the exposure amount necessary for photocuring the photosensitive resin composition can be adjusted to an exposure amount optimal for exposure with a projection exposure machine.

(E) component may also contain the compound represented by the following general formula (I) from a viewpoint of further improving resolution.

In formula (I), R ⁵ is a halogen atom, a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an amino group, an aryl group, a mercapto group, an alkylmercapto group having 1 to 10 carbon atoms; The alkyl group represents a carboxylalkyl group having 1 to 10 carbon atoms, an alkoxy group or a heterocyclic group having 1 to 20 carbon atoms, m and n are selected so that m is an integer of 2 or more, n is an integer of 0 or more, and m + n = 6 It is an integer, and when n is an integer greater than or equal to 2, R ^<5> may be the same or different, respectively. In addition, the aryl group may be substituted with an alkyl group having 1 to 20 carbon atoms.

R ⁵ may be a hydrogen atom or an alkyl group having 1 to 20 carbon atoms from the viewpoint of further improving the compatibility with the component (A). The C1-C20 alkyl group represented by R ⁵ may be a C1-C4 alkyl group. m may be 2 or 3, or 2 from the standpoint of further improving the resolution.

Examples of the compound represented by the general formula (I) include catechol, resorcinol (resorcinol), 1,4-hydroquinone, 3-methylcatechol, 4-methylcatechol, and 3-ethylcatechol. , 4-ethylcatechol, 3-propylcatechol, 4-propylcatechol, 3-n-butylcatechol, 4-n-butylcatechol, 3-tert-butylcatechol, 4-tert-butylcatechol Alkylcatechols such as 3,5-di-tert-butylcatechol, 2-methylresorcinol, 4-methylresorcinol, 5-methylresorcinol (orsynol), 2-ethylresorcinol, 4 -Ethylresorcinol, 2-propylresorcinol, 4-propylresorcinol, 2-n-butylresorcinol, 4-n-butylresorcinol, 2-tert-butylresorcinol, 4-tert - Alkylresorcinols such as butylresorcinol, alkylhydroquinones such as methylhydroquinone, ethylhydroquinone, propylhydroquinone, tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone, pyrogalol, phloroglucin, etc. can be heard These can be used individually by 1 type or in combination of 2 or more types.

Among the compounds represented by the general formula (I), from the standpoint of further improving resolution, alkylcatechol may be used.

The content of component (E) is 0.001 to 0.3 part by mass, 0.01 to 0.2 part by mass, 0.02 to 0.15 part by mass, or 0.03 to 0.1 part by mass with respect to 100 parts by mass of the total solid content of component (A) and component (B). may be continued When the content of the component (E) is 0.3 parts by mass or less, the exposure time can be shortened and tends to contribute to the improvement of mass production efficiency. In addition, by setting the content of component (E) to 0.001 parts by mass or more, the photoreaction of the photocured portion can sufficiently proceed, and the resist swelling property is suppressed by the reaction rate improvement, and the resolution tends to be better. .

Moreover, content of (E) component may be 0.03-0.4 mass part, 0.05-0.4 mass part, 0.05-0.2 mass part, or 0.05-0.1 mass part with respect to 100 mass parts of solid content of (A) component. When the content of component (E) is 0.05 parts by mass or more relative to component (A), the thermal stability of the photosensitive resin composition tends to be improved, and when it is 0.4 parts by mass or less, yellowing of the photosensitive resin composition can be suppressed. tend to have

(other ingredients)

In the photosensitive resin composition according to the present embodiment, dyes such as malachite green, Victoria pure blue, brilliant green, and methyl violet, tribromophenylsulfone, leuco crystal violet, diphenylamine, benzylamine, and triphenyl, as necessary. Photochromic agents such as amine, diethylaniline, o-chloroaniline and tertiary butyl catechol, antipyretic colorants, plasticizers such as p-toluenesulfonamide, pigments, fillers, antifoaming agents, flame retardants, adhesion imparting agents, leveling agents, peeling agents 0.01-20 mass parts of additives, such as an accelerator, antioxidant, fragrance|flavor, imaging agent, and a thermal crosslinking agent, respectively can be contained with respect to 100 mass parts of total solids of (A) component and (B) component. These additives can be used individually by 1 type or in combination of 2 or more types.

In addition, the photosensitive resin composition according to the present embodiment may contain at least one organic solvent as necessary in order to improve the handleability of the photosensitive composition or to adjust the viscosity and storage stability. As the organic solvent, a commonly used organic solvent can be used without particular limitation. Specifically, for example, organic solvents such as methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N,N-dimethylformamide, propylene glycol monomethyl ether, or a mixture thereof A solvent can be mentioned. These can be used individually by 1 type or in combination of 2 or more types.

<protective layer>

In the photosensitive element of this embodiment, a protective layer may be laminated on the surface of the photosensitive layer opposite to the surface in contact with the barrier layer. As a protective layer, you may use polymer films, such as polyethylene and a polypropylene, etc., for example. Moreover, the same polymer film as the support film mentioned above may be used, and a different polymer film may be used.

Hereinafter, a method of manufacturing a photosensitive element in which a support film, a barrier layer, a photosensitive layer, and a protective layer are sequentially laminated will be described.

<Method of manufacturing photosensitive element>

First, a mixed solvent of, for example, a water-soluble resin containing polyvinyl alcohol, water heated to 70 to 90 ° C. so that the solid content is 10 to 20% by mass, and alcohols containing alcohols having 3 or more carbon atoms is added gradually, stirred for about 1 hour, and dissolved uniformly to obtain a resin composition for forming a barrier layer containing polyvinyl alcohol and alcohols having 3 or more carbon atoms. In this specification, "solid content" refers to the non-volatile matter except for volatilizing substances, such as water and an organic solvent, of a resin composition. That is, it refers to components other than solvents such as water and organic solvents that remain without volatilizing in the drying step, and include liquid, starch syrup, and waxy components at room temperature around 25°C.

Next, the resin composition for forming a barrier layer is applied onto the support film and dried to form a barrier layer. The coating of the resin composition for forming the barrier layer on the supporting film may be performed by a known method such as roll coating, comma coating, gravure coating, air knife coating, die coating, bar coating, spray coating, etc. there is.

The drying of the applied resin composition for forming a barrier layer is not particularly limited as long as at least a part of the solvent such as water can be removed, but may be dried at 70 to 150°C for 5 to 30 minutes. After drying, the amount of solvent remaining in the barrier layer may be 2% by mass or less from the standpoint of preventing diffusion of the solvent in a later step.

Next, a photosensitive resin composition may be coated on the barrier layer of the support film on which the barrier layer is formed in the same manner as the coating of the resin composition for forming a barrier layer, followed by drying to form a photosensitive layer on the barrier layer. Next, by laminating a protective layer on the photosensitive layer thus formed, a photosensitive element comprising a support film, a barrier layer, a photosensitive layer, and a protective layer in this order can be produced. In addition, a photosensitivity provided with a support film, a barrier layer, a photosensitive layer, and a protective layer in this order by bonding together a barrier layer formed on a support film and a photosensitive layer formed on a protective layer. element can be obtained.

The thickness of the photosensitive layer in the photosensitive element can be appropriately selected depending on the application, but may be 1 to 200 μm, 5 to 100 μm, or 10 to 50 μm as a thickness after drying. When the thickness of the photosensitive layer is 1 μm or more, industrial coating becomes easy and productivity tends to improve. In addition, when the thickness of the photosensitive layer is 200 μm or less, the photosensitivity is high and the photocurability of the resist bottom is excellent, so there is a tendency that a resist pattern with excellent resolution and aspect ratio can be formed.

The melt viscosity at 110°C of the photosensitive layer of the photosensitive element can be appropriately selected according to the type of substrate in contact with the photosensitive layer, but after drying, at 110°C, it is 50 to 10000 Pa·s, 100 to 5000 Pa·s, or may be 200 to 1000 Pa·s. When the melt viscosity at 110°C is 50 Pa·s or more, wrinkles and voids do not occur in the lamination process, and productivity tends to improve. In addition, when the melt viscosity at 110°C is 10000 Pa·s or less, the adhesion to the substrate in the lamination step tends to improve, and adhesion failure tends to be reduced.

The shape of the photosensitive element according to this embodiment is not particularly limited. For example, it may be in the form of a sheet, or it may be in the form of a roll wound around a core. When winding up in roll shape, you may wind up so that a support film may become the outside. As a winding core, plastics, such as a polyethylene resin, a polypropylene resin, a polystyrene resin, a polyvinyl chloride resin, or an ABS resin (acrylonitrile-butadiene-styrene copolymer), etc. are mentioned, for example.

An end surface separator may be provided on the end face of the roll-shaped photosensitive element roll obtained in this manner, or a moisture-proof end face separator may be provided from the standpoint of edge fusion resistance. As a packing method, it may be wrapped in a black sheet having low moisture permeability.

The photosensitive element according to the present embodiment can be suitably used in, for example, a resist pattern formation method and a printed wiring board manufacturing method described later.

[Formation method of register pattern]

The resist pattern formation method according to the present embodiment includes (i) a step of arranging a photosensitive layer, a barrier layer, and a support film in this order from the substrate side on a substrate using the photosensitive element (hereinafter referred to as " (i) also referred to as “photosensitive layer and barrier layer forming step”), and (ii) removing the supporting film and exposing the photosensitive layer to actinic light through the barrier layer (hereinafter referred to as “(ii) exposure and (iii) a step of removing uncured portions of the barrier layer and the photosensitive layer from the substrate (hereinafter also referred to as a "(iii) developing step"). process may be included. In addition, a resist pattern can also be called a photocured pattern of the photosensitive resin composition, and can also be called a relief pattern. Depending on the purpose, the resist pattern in this embodiment may be used as a resist or may be used for other purposes such as a protective film.

((i) photosensitive layer and barrier layer formation process)

In the photosensitive layer and barrier layer forming step, a photosensitive layer and a barrier layer are formed on a substrate using the photosensitive element. The substrate is not particularly limited, but usually a substrate for circuit formation having an insulating layer and a conductor layer formed on the insulating layer, or a die pad (base material for lead frame) such as an alloy base material is used.

As a method of forming the photosensitive layer and the barrier layer on the substrate, for example, in the case of using a photosensitive element having a protective layer, after removing the protective layer, the photosensitive layer of the photosensitive element is pressed to the substrate while heating, A photosensitive layer and a barrier layer may be formed on the substrate. In this way, a laminate comprising the substrate, the photosensitive layer, the barrier layer and the support film in this order can be obtained.

In the case where the photosensitive layer and barrier layer formation step is performed using a photosensitive element, it may be performed under reduced pressure from the standpoint of adhesion and followability. Heating at the time of crimping may be performed at a temperature of 70 to 130°C, and crimping may be performed at a pressure of 0.1 to 1.0 MPa (1 to 10 kgf/cm ² ), but these conditions can be appropriately selected as needed. In addition, if the photosensitive layer of the photosensitive element is heated to 70 to 130 DEG C, it is not necessary to preheat the substrate beforehand, but preheating of the substrate may be performed in order to further improve adhesion and followability.

((ii) exposure process)

In the exposure process, the support film is removed and the photosensitive layer is exposed to actinic light through the barrier layer. As a result, the exposed portion irradiated with actinic light is photocured and a photocured portion (latent image) may be formed, or the unexposed portion to which actinic light is not irradiated is photocured and a photocured portion is formed. There may be. In the case where the photosensitive layer and the barrier layer are formed using the photosensitive element, the support film present on the photosensitive layer is peeled off and then exposed. By exposing the photosensitive layer through the barrier layer, a resist pattern excellent in resolution and resist pattern shape can be formed.

As the exposure method, a known exposure method can be applied, and for example, a method in which actinic light is irradiated onto an image through a negative or positive mask pattern called artwork (mask exposure method) ), a laser-direct-imaging (LDI) exposure method, or a method (projection exposure method) of irradiating an image through a lens using actinic rays obtained by projecting an image on a photomask. Among them, a projection exposure method may be used from the viewpoint of excellent resolution. That is, the photosensitive element or the like according to the present embodiment is applied by a projection exposure method. In addition, the projection exposure method can also be referred to as an exposure method using actinic light having an amount of attenuated energy.

The light source of the actinic light is not particularly limited as long as it is a known light source that is normally used, and examples include carbon arc lamps, mercury vapor arc lamps, ultra-high pressure mercury lamps, high-pressure mercury lamps, xenon lamps, gas lasers such as argon lasers, YAG lasers, etc. A solid-state laser, a semiconductor laser such as a gallium nitride-based blue-violet laser, or the like that effectively emits ultraviolet rays is used. Moreover, you may use what emits visible light effectively, such as a flood light bulb for photography, and a solar lamp. Among these, a light source capable of emitting i-line monochromatic light with an exposure wavelength of 365 nm, a light source capable of emitting h-line monochromatic light with an exposure wavelength of 405 nm, or an ihg crosstalk ( A light source capable of emitting actinic light at an exposure wavelength of a dark line may be used, and among these, a light source capable of emitting i-line monochromatic light having an exposure wavelength of 365 nm may be used. As a light source capable of emitting i-line monochromatic light with an exposure wavelength of 365 nm, an ultra-high pressure mercury lamp or the like is exemplified.

((iii) development process)

In the developing step, uncured portions of the barrier layer and the photosensitive layer are removed from the substrate. By the developing process, a resist pattern composed of a photocured portion in which the photosensitive layer is photocured is formed on the substrate. When the barrier layer is water-soluble, after removing the barrier layer by washing with water, the uncured portion other than the photocured portion may be removed with a developing solution. When the barrier layer is soluble in the developing solution, the photocured portion may be removed. Together with the other uncured portions, the barrier layer may be removed with a developing solution. Wet development is mentioned as a developing method.

In the case of wet development, it can develop by a well-known wet development method using the developing solution corresponding to the photosensitive resin composition. As the wet developing method, for example, a dip method, a paddle method, a high-pressure spray method, brushing, slapping, scrubbing, a method using shaking dipping, etc. are exemplified. , From the viewpoint of improving resolution, the high-pressure spray method is most suitable. You may develop these wet developing methods individually by 1 type or combining 2 or more types of methods.

A developer is appropriately selected depending on the constitution of the photosensitive resin composition. For example, alkaline aqueous solution and organic solvent developing solution are mentioned.

From the standpoint of safety and stability and good operability, an alkaline aqueous solution may be used as the developing solution. As the base of the alkaline aqueous solution, for example, alkali hydroxides such as hydroxides of lithium, sodium or potassium, alkali carbonates such as carbonates or bicarbonates of lithium, sodium, potassium or ammonium, alkali metal phosphates such as potassium phosphate, sodium phosphate, pyrolysis Alkali metal pyrophosphates such as sodium phosphate and potassium pyrophosphate, sodium borate, sodium metasilicate, tetramethylammonium hydroxide, ethanolamine, ethylenediamine, diethylenetriamine, 2-amino-2-hydroxymethyl-1,3- Propanediol, 1,3-diamino-2-propanol and morpholine are used.

As the alkaline aqueous solution used for development, for example, a 0.1 to 5% by mass dilute solution of sodium carbonate, a 0.1 to 5% by mass dilute solution of potassium carbonate, a 0.1 to 5% by mass dilute solution of sodium hydroxide, and a 0.1 to 5% by mass 4 A dilute solution of sodium borate or the like can be used. In addition, the pH of the alkaline aqueous solution used for development may be in the range of 9 to 11, and the temperature of the alkaline aqueous solution can be adjusted according to the developability of the photosensitive layer. Further, in the alkaline aqueous solution, for example, a surface active agent, an antifoaming agent, and a small amount of an organic solvent for accelerating image development may be incorporated. Examples of the organic solvent used for the alkaline aqueous solution include 3-acetone alcohol, acetone, ethyl acetate, alkoxyethanol having an alkoxy group of 1 to 4 carbon atoms, ethyl alcohol, isopropyl alcohol, butyl alcohol, and diethylene glycol mono. methyl ether, diethylene glycol monoethyl ether and diethylene glycol monobutyl ether.

Examples of organic solvents used in the developing solution include 1,1,1-trichloroethane, N-methylpyrrolidone, N,N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, and γ- Butyrolactone can be mentioned. From the viewpoint of preventing ignition, these organic solvents may be used as an organic solvent developer by adding water so as to be in the range of 1 to 20% by mass.

(Other processes)

In the resist pattern formation method according to the present embodiment, after removing the uncured portion in the developing step, heating at 60 to 250°C or exposure at an exposure amount of 0.2 to 10 J/cm ² is performed as necessary to resist the resist pattern. You may also include the process of further hardening.

[Method of Manufacturing Printed Wiring Board]

The method for manufacturing a printed wiring board according to the present embodiment includes a step of forming a conductor pattern by etching or plating a substrate on which a resist pattern is formed by the above resist pattern formation method, and, if necessary, a step of removing the resist pattern. You may also include other processes, such as. The method for manufacturing a printed wiring board according to the present embodiment can be suitably used for formation of a conductor pattern by using the method for forming a resist pattern using the photosensitive element. Application to the method is more suitable. A conductor pattern can also be referred to as a circuit.

In the etching process, a resist pattern formed on a substrate having a conductor layer is used as a mask, and the conductor layer of the substrate not covered with the resist is etched away to form a conductor pattern.

A method of etching treatment is appropriately selected depending on the conductor layer to be removed. Examples of the etchant include cupric chloride solution, ferric chloride solution, alkaline etching solution, and hydrogen peroxide-based etchant. Since the etch factor is good, a ferric chloride solution is used can also

On the other hand, in the plating process, copper, solder, or the like is plated on the conductor layer of the substrate not covered by the resist, using the resist pattern formed on the substrate having the conductor layer as a mask. After the plating process, the resist is removed by removing the resist pattern described later, and further, the conductor layer covered by the resist is etched to form a conductor pattern.

The method of the plating treatment may be an electroplating treatment or an electroless plating treatment, but among them, an electroless plating treatment may be used. Examples of the electroless plating treatment include copper plating such as copper sulfate plating and copper pyrophosphate plating, solder plating such as high-slow solder plating, Watt bath (nickel sulfate-nickel chloride) plating, and nickel sulfuramine plating. Gold plating, such as nickel plating, hard gold plating, and soft gold plating, is mentioned.

After the above etching treatment or plating treatment, the resist pattern on the substrate is removed. The resist pattern can be removed by, for example, an aqueous solution more strongly alkaline than the alkaline aqueous solution used in the developing step. As this strongly alkaline aqueous solution, 1-10 mass % sodium hydroxide aqueous solution, 1-10 mass % potassium hydroxide aqueous solution, etc. are used, for example. Among these, you may use 1-5 mass % sodium hydroxide aqueous solution or potassium hydroxide aqueous solution.

Examples of the resist pattern removal method include an immersion method and a spray method, and these may be used alone or in combination.

When the resist pattern is removed after performing the plating process, a desired printed wiring board can be manufactured by further etching the conductor layer covered with the resist by the etching process and forming the conductor pattern. The method of etching treatment at this time is appropriately selected according to the conductor layer to be removed. For example, the etchant described above can be applied.

The method for manufacturing a printed wiring board according to the present embodiment can be applied not only to single-layer printed wiring boards but also to multi-layer printed wiring boards, and is also applied to the production of printed wiring boards and the like having small-diameter through holes. possible.

The method for manufacturing a printed wiring board according to the present embodiment can be suitably used for manufacturing a high-density package substrate, particularly for manufacturing a wiring board by a semi-additive method. In addition, an example of the manufacturing process of the wiring board by the semi-additive construction method is shown in FIG.

In FIG. 2( a ), a substrate (substrate for circuit formation) on which a conductor layer 40 is formed on an insulating layer 50 is prepared. The conductor layer 40 is, for example, a copper layer. In FIG. 2( b ), the photosensitive layer 30 and the barrier layer 20 are formed on the conductor layer 40 of the substrate by the photosensitive layer and barrier layer forming process. In FIG. 2(c), in the exposure step, actinic light 80 projecting an image of a photomask onto the photosensitive layer 30 through the barrier layer 20 is irradiated, and the photosensitive layer 30 ) to form a photocured part. In FIG. 2(d), a resist pattern 32 as a photocured portion is formed on the substrate by removing a region (including a barrier layer) other than the photocured portion formed by the exposure step from the substrate in the developing step. do. In FIG. 2(e), a plating layer 60 is formed on the conductor layer 40 of the substrate not covered with the resist by a plating process using the resist pattern 32 as a photocured portion as a mask. In Fig. 2(f), after the resist pattern 32 as a photocured portion is peeled off with an aqueous solution of strong alkali, the conductor layer 40 masked by the resist pattern 32 is removed by flash etching treatment, followed by etching. A conductor pattern 70 including the plating layer 62 after treatment and the conductor layer 42 after etching treatment is formed. The materials of the conductor layer 40 and the plating layer 60 may be the same or different. When the conductor layer 40 and the plating layer 60 are made of the same material, the conductor layer 40 and the plating layer 60 may be integrated. In addition, although the projection exposure method was demonstrated in FIG. 2, the resist pattern 32 may be formed by using both the mask exposure method and the LDI exposure method.

As mentioned above, although preferred embodiment of this indication was described, this indication is not limited to the said embodiment in any way.

Example

Hereinafter, the present disclosure will be described in more detail based on examples, but the present disclosure is not limited to the following examples. In addition, "part" and "%" are based on mass unless otherwise specified.

First, the binder polymer (A-1) shown in Tables 1 to 3 was synthesized according to Synthesis Example 1.

<Synthesis Example 1>

A solution a was prepared by mixing 125 g of methacrylic acid, 25 g of methyl methacrylate, 125 g of benzyl methacrylate, and 225 g of styrene as polymerizable monomers, and 1.5 g of azobisisobutyronitrile.

Furthermore, 1.2 g of azobisisobutyronitrile was dissolved in 100 g of a liquid mixture of 60 g of methyl cellosolve and 40 g of toluene (mass ratio 3:2) to prepare a solution b.

On the other hand, to a flask equipped with a stirrer, a reflux condenser, a thermometer, a dropping funnel, and a nitrogen gas inlet tube, 400 g of a mixture of methyl cellosolve and toluene having a mass ratio of 3:2 (hereinafter also referred to as “mixture x”) was added, It was stirred while blowing nitrogen gas and heated to 80 degreeC.

The solution a was added dropwise to the liquid mixture x in the flask at a constant dropping rate over 4 hours, and then stirred at 80°C for 2 hours. Subsequently, the solution b was added dropwise to the solution in the flask over 10 minutes at a constant dropping rate, and then the solution in the flask was stirred at 80°C for 3 hours. Furthermore, the temperature of the solution in the flask was raised to 90°C over 30 minutes, kept warm at 90°C for 2 hours, and then cooled to room temperature to obtain a solution of binder polymer (A-1). The solution of this binder polymer (A-1) was prepared so that the non-volatile component (solid content) would be 50 mass % by adding the liquid mixture x.

The weight average molecular weight of the binder polymer (A-1) was 50,000, and the acid value was 163 mgKOH/g. In addition, the acid value was measured by the neutralization titration method. Specifically, after adding 30 g of acetone to 1 g of the binder polymer solution, dissolving it more uniformly, adding an appropriate amount of phenolphthalein as an indicator to the binder polymer solution, and performing titration using a 0.1 N KOH aqueous solution. Measured. The weight average molecular weight was determined by gel permeation chromatography (GPC) and converted using a standard polystyrene standard curve. The conditions of GPC are shown below.

-GPC conditions-

Pump: Hitachi L-6000 type (manufactured by Hitachi Seisakusho Co., Ltd.)

Column: 3 columns in total as follows (Column specification: 10.7mmφ×300mm, all manufactured by Hitachigasei Co., Ltd.)

Gelpack　GL-R420

Gelpack　GL-R430

Gelpack　GL-R440

Eluent: tetrahydrofuran

Sample concentration: 120 mg of a binder polymer having a solid content of 50% by mass was sampled and dissolved in 5 mL of tetrahydrofuran to prepare a sample.

Measurement temperature: 25 degrees Celsius

Flow rate: 2.05mL/min

Detector: Hitachi L-3300 RI (manufactured by Hitachi Seisakusho Co., Ltd., product name)

<Preparation of resin composition for forming barrier layer>

Next, the resin composition for barrier layer formation was obtained by mixing each component shown to following Table 1 - Table 3 in the quantity (unit: mass part) shown in the table|surface. Specifically, the water-soluble resin was slowly added to room temperature water and alcohols, and after the entire amount was added, it was heated to 90°C. After reaching 90 degreeC, it stirred for 1 hour, cooled to room temperature, and obtained the resin composition for barrier layer formation. In addition, the compounding quantities other than the solvent in Table 1 - Table 3 are all compounding quantities in solid content.

<Preparation of photosensitive resin composition>

Next, the photosensitive resin composition was obtained by mixing each component shown to following Table 1 - Table 3 in the quantity (unit: mass part) shown in the table|surface.

Details of each component in Tables 1 to 3 are as follows.

(water soluble resin)

*1: Polyvinyl alcohol = PVA-205 (Kuraray Co., Ltd., product name, degree of saponification = 87 mol%, average degree of polymerization = 500)

*2: Polyvinyl alcohol = PVA-203 (Kuraray Co., Ltd., product name, degree of saponification = 87 mol%, average degree of polymerization = 300)

*3: Polyvinyl alcohol = PVA-210 (Kuraray Co., Ltd., product name, degree of saponification = 87 mol%, average degree of polymerization = 1000)

*4: Polyvinylpyrrolidone K-30 (manufactured by Nippon Shokubai Co., Ltd., product name)

(A) Component: Binder polymer

*5: (A-1) (binder polymer (A-1) obtained in Synthesis Example 1)

Methacrylic acid / methyl methacrylate / benzyl methacrylate / styrene

= 25/5/25/45 (mass ratio), weight average molecular weight = 50,000, solid content = 50 mass%, methylcellosolve/toluene = 3/2 (mass ratio) solution

(B) component: photopolymerizable compound having an ethylenically unsaturated bond

*6: FA-321M (manufactured by Hitachi Chemical Co., Ltd., product name)

2,2-bis(4-(methacryloxypentaethoxy)phenyl)propane

*7: FA-024M (manufactured by Hitachigasei Co., Ltd., product name)

EOPO modified dimethacrylate

*8: BPE-200 (manufactured by Shin Nakamura Chemical Industry Co., Ltd., product name)

2,2-bis(4-(methacryloxydiethoxy)phenyl)propane

*9: BP-2 EM (manufactured by Kyoeisha Chemical Co., Ltd., product name)

2,2-bis(4-(methacryloxypolyethoxy)phenyl)propane

*10: DPEA-12 (manufactured by Nippon Kayaku Co., Ltd., product name)

Ethylene oxide modified dipentaerythritol hexaacrylate

(C) component: photopolymerization initiator

*11: B-CIM (manufactured by Hodogaya Gagaku Kogyo Co., Ltd., product name)

2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole

(D) component: photosensitizer

*12: EAB (manufactured by Hodogaya Gagaku Kogyo Co., Ltd., product name)

4,4'-bis(diethylamino)benzophenone

(E) Ingredient: Polymerization inhibitor

*13: TBC (manufactured by DIC Co., Ltd.)

4-tert-butylcatechol

[Examples 1 to 15 and Comparative Examples 1 to 7]

<Production of photosensitive element>

As a support film for the photosensitive element, PET films shown in Tables 1 to 3 were prepared.

Details of the PET films shown in Tables 1 to 3 are as follows.

FB40: Biaxially oriented PET film with a three-layer structure having a lubricant layer on the front and back (manufactured by Toray Industries, Ltd., product name, thickness: 16 μm)

A1517: Biaxially oriented PET film with a two-layer structure having a lubricant layer on one side (manufactured by Toyobo Seki Co., Ltd., product name, thickness: 16 μm)

G2H: Biaxially oriented PET film with a single layer structure (lubricant kneading type) containing a lubricant (manufactured by Teijin DuPont Film Co., Ltd., product name, thickness: 15.5 µm)

(Manufacture of barrier layer)

Subsequently, a resin composition for forming a barrier layer was applied on a PET film (support film) to a uniform thickness, and dried in a hot air convection dryer at 95° C. for 10 minutes to form a barrier layer having a thickness of 5 μm after drying. did. In addition, when the density of the lubricant is different on both sides of the PET film, a barrier layer is formed on the side with less lubricant, and when the PET film has a lubricant layer on one side, a barrier layer is formed on the side of the PET film on the side of the lubricant layer. layer was formed.

(Production of photosensitive layer)

Next, the photosensitive resin composition was applied on the barrier layer of the support film so as to have a uniform thickness, and dried for 10 minutes in a hot air convection dryer at 100° C. to form a photosensitive layer having a thickness after drying of 10 μm.

Next, on this photosensitive layer, a polyethylene protective film (protective layer) (manufactured by Tamapoly Co., Ltd., product name "NF-15") was bonded, and a PET film (support film), a barrier layer, and a photosensitive layer were formed. and a protective layer were laminated in this order to obtain a photosensitive element.

<Measurement of residual alcohol content>

The amount of residual alcohols in the formed barrier layer was measured by gas chromatography mass spectrometry. The measurement conditions for gas chromatography mass spectrometry are as follows. In Table 1, Table 2, and Table 3, the item “amount of alcohol remaining in the barrier layer” indicates the amount of alcohol having 3 or more carbon atoms. In addition, "<1.0" means more than 0 and less than 1.0.

(Measurement conditions for gas chromatography mass spectrometry)

Measuring device: GC/MS QP-2010 (manufactured by Shimadzu Corporation, product name)

Column: HP-5MS (manufactured by Agilent Technology Co., Ltd., product name)

Oｖen　Temp: After heating at 40°C for 5 minutes, the temperature is raised to 300°C at a rate of 15°C/min

Carrier gas: Helium, 1.0mL/min

Interface temperature: 280℃

Ion source temperature: 250°C

Sample Injection Amount: 0.1mL

<Manufacture of laminate>

The copper surface of a copper-clad laminate (substrate, manufactured by Hitachi Chemical Co., Ltd., product name “MCL-E-67”), which is a glass epoxy material in which copper foil with a thickness of 12 μm is laminated on both sides, is acid-treated After washing with water, it dried with an air current. The copper clad laminate was heated to 80 DEG C, and the photosensitive elements were pressed against each copper clad laminate so that the photosensitive layer was in contact with the copper surface while peeling off the protective layer. The crimping was performed at a roll speed of 1.0 m/min at a pressure of 0.40 MPa using a heat roll at 110°C. In this way, a laminate was obtained in which the substrate, the photosensitive layer, the barrier layer, and the supporting film were laminated in this order. These laminates were used as test pieces in the tests shown below. As a laminator, HLM-3000 (manufactured by Taisei Laminator Co., Ltd., product name) was used.

<Evaluation of support film peelability>

The test piece was left to stand for 1 hour in an environment of 23°C and 50% humidity. After that, the PET film serving as the supporting film was peeled off from the test piece under conditions of a peeling angle of 135 degrees and a peeling speed of 500 mm/sec, and the peelability of the supporting film was evaluated according to the following evaluation criteria. The evaluation results are shown in Tables 4 to 6 below.

A: Only the PET film serving as the supporting film was easily peeled off.

B: A barrier layer adhered to a part of the peeled support film, or peeling of the support film was impossible.

<Evaluation of resolution>

In order to investigate the resolution, after peeling the supporting film from the test piece, a Hitachi 41-step step tablet was placed on the barrier layer of the test piece, and the line width / space width as a pattern for resolution evaluation was z / z ( Projection exposure machine (manufactured by Ushio Denki Co., Ltd., product name: UX-2240SM) having a glass mask having a wiring pattern of z = 2 to 20 (changes at 1 μm intervals) (unit: μm) and having a high-pressure mercury lamp with a wavelength of 365 nm -XJ01) was used to expose the photosensitive layer through the barrier layer with an amount of irradiation energy such that the number of remaining steps after development of a Hitachi 41-step step tablet was 8. After exposure, the test piece was washed with water at room temperature to remove the barrier layer. Next, the photosensitive layer was spray developed at 30° C. using a 1% by mass aqueous solution of sodium carbonate in twice the shortest developing time to remove the unexposed portion. Here, the shortest development time was determined by measuring the time required for the unexposed portion to be completely removed by the above development treatment. Among the space widths between the line portions (exposed portions) from which the unexposed portion was cleanly removed by the development treatment, the smallest value (unit: µm) was used as an index for resolution evaluation. In addition, it means that resolution is so good that this numerical value is small. The results are shown in Tables 4 to 6 below.

<Evaluation of register pattern shape>

In the board evaluated in the evaluation of the resolution, the cross-sectional shape of the resist pattern having a line width/space width of 10/10 (unit: µm) was observed with a scanning electron microscope (SEM). The cross-sectional shape of the resist pattern is shown in Tables 4 to 6 below as an evaluation of the resist pattern shape.

In the photosensitive elements of Comparative Examples 1 to 7, the support film peelability was deteriorated and no resist pattern was formed, so resolution and resist pattern shape could not be evaluated.

<Evaluation of barrier layer solution transparency>

As a reference sample, the resins for forming a barrier layer of Examples 1 to 15 and Comparative Examples 1 to 7 except that alcohols in the resin compositions for forming a barrier layer of Examples 1 to 15 and Comparative Examples 1 to 7 were not used. A composition was prepared in the same way as the composition. After that, the transparency of the resin composition solutions for forming a barrier layer of Examples 1 to 15 and Comparative Examples 1 to 7 (hereinafter also referred to as "barrier layer solution") and reference samples were visually observed and evaluated as follows. . The evaluation results are shown in Tables 4 to 6 below.

A: Compared with the reference sample, the cloudiness of the barrier layer solution is equivalent or less.

B: Compared to the reference sample, the barrier layer solution has a lot of cloudiness.

<Evaluation of barrier layer transparency>

The resin compositions for forming a barrier layer of Examples 1 to 15 and Comparative Examples 1 to 7 were applied on a support film to have a uniform thickness, and dried in a hot air convection dryer at 95° C. for 10 minutes, and the thickness after drying was 5 A barrier layer of .mu.m was formed. As a reference sample, the resins for forming a barrier layer of Examples 1 to 15 and Comparative Examples 1 to 7 except that alcohols in the resin compositions for forming a barrier layer of Examples 1 to 15 and Comparative Examples 1 to 7 were not used. A barrier layer was formed using the composition prepared similarly to the composition. Thereafter, the appearance of the barrier layer was visually observed and evaluated as follows. The evaluation results are shown in Tables 4 to 6 below.

A: Compared with the reference sample, the degree of occurrence of fogging and voids in the barrier layer is equivalent or less.

B: Compared to the reference sample, most of the cloudiness or voids occurred in part or all of the barrier layer.

In Examples 1 to 15, when exposure was performed under conditions of a small amount of energy in which the number of remaining step stages was 8 using a high-resolution projection exposure machine, whereas the peelability between the support film and the barrier layer was high, Comparative Examples 1 to 15 In 7, it was confirmed that the peelability between the support film and the barrier layer was low.

As described above, according to the present disclosure, the photosensitive element capable of improving the peelability between the barrier layer and the supporting film without using a peeling accelerator, a resin composition for forming a barrier layer, a method for forming a resist pattern, and manufacturing of a printed wiring board method can be provided.

One… photosensitive element, 2 . . . support film, 3, 20... barrier layer, 4, 30... photosensitive layer, 5 . . . protective layer, 32 . . . register pattern, 40... conductor layer, 42 . . . Conductor layer after etching treatment, 50 . . . insulating layer, 60 . . . plating layer, 62 . . . Plated layer after etching treatment, 70 . . . conductor pattern, 80 . . . active light.

Claims (13)

A photosensitive element comprising a support film, a barrier layer, and a photosensitive layer in this order, wherein the barrier layer contains a water-soluble resin and an alcohol having 3 or more carbon atoms;
A photosensitive element in which the alcohol having 3 or more carbon atoms contains at least one selected from the group consisting of compounds represented by the following formulas (1) to (3) and compounds represented by the following general formula (4).




[In Formula (4), R ¹¹ represents an alkyl group, R ¹² represents an alkylene group, and the sum of the carbon atoms of the group R ¹¹ and the group R ¹² is 3 or more.] The method of claim 1,
The photosensitive element in which the solubility of the alcohol having 3 or more carbon atoms in water at 20°C is 300 mL/100 mL or more in water. According to claim 1 or 2,
The photosensitive element in which the content of the alcohol having 3 or more carbon atoms in the barrier layer is more than 0 mass% and 2.0 mass% or less based on the total amount of the barrier layer. According to claim 1 or 2,
The photosensitive element in which the water-soluble resin contains polyvinyl alcohol. According to claim 1 or 2,
The photosensitive element in which the support film is a polyester film. Containing a water-soluble resin, an alcohol having 3 or more carbon atoms, and water,
A resin for forming a barrier layer, wherein the alcohol having 3 or more carbon atoms contains at least one selected from the group consisting of compounds represented by the following formulas (1) to (3) and compounds represented by the following general formula (4) composition.




[In Formula (4), R ¹¹ represents an alkyl group, R ¹² represents an alkylene group, and the sum of the carbon atoms of the group of R ¹¹ and the group of R ¹² is 3 or more.] The method of claim 6,
The resin composition for forming a barrier layer, wherein the alcohol having 3 or more carbon atoms has a solubility in water at 20°C of 300 mL/100 mL or more of water. According to claim 6 or 7,
The resin composition for barrier layer formation whose content of the said C3 or more alcohol is 100-500 mass parts with respect to 500 mass parts of water. According to claim 6 or 7 ,
The resin composition for barrier layer formation in which the said water-soluble resin contains polyvinyl alcohol. A step of arranging a photosensitive layer, a barrier layer, and a support film in this order on a substrate from the substrate side, using the photosensitive element according to claim 1 or 2;
removing the support film and exposing the photosensitive layer with actinic light through the barrier layer;
A method of forming a resist pattern comprising a step of removing uncured portions of the barrier layer and the photosensitive layer from on the substrate. A method for manufacturing a printed wiring board comprising a step of forming a conductor pattern by etching or plating a substrate on which a resist pattern is formed by the method of forming a resist pattern according to claim 10. delete delete

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