TW201710796A - Photosensitive element, resin composition for forming barrier layer, method for forming resist pattern, and method for producing printed wiring board - Google Patents

Abstract

The purpose of the present invention is to provide a photosensitive element which is able to have improved releasability of a barrier layer from a supporting film without using a release accelerator. The present invention provides a photosensitive element which is sequentially provided with a supporting film, a barrier layer and a photosensitive layer in this order, and wherein the barrier layer contains a water-soluble resin and an alcohol having 3 or more carbon atoms.

Description

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

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

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

The printed wiring board is manufactured using the photosensitive element, for example, by the following procedure. That is, first, the photosensitive layer of the photosensitive element is laminated on a circuit formation substrate such as a copper clad laminate. At this time, lamination is performed so that the surface of the photosensitive layer opposite to the surface contacting the support film is in close contact with the surface of the circuit formation substrate on which the circuit is formed. Further, lamination is performed, for example, by heating and pressing a photosensitive layer on a circuit-forming substrate (atmospheric pressure lamination method).

Next, a mask film or the like is used to expose a desired region of the photosensitive layer via a support film, thereby generating radicals. The generated radicals pass through several reaction paths to contribute to the crosslinking reaction (photohardening reaction) of the photopolymerizable compound. Then, after the support film is peeled off, the uncured portion of the photosensitive layer is dissolved or dispersed by the developer to form a resist pattern. Next, a resist pattern is used as a resist, an etching process or a plating process is performed to form a conductor pattern, and finally, a photocured portion (resist pattern) of the photosensitive layer is peeled off (removed).

In addition, in recent years, a method of forming an excellent resist pattern by exposing a support film after peeling off the support film before exposure is being studied. However, when the photosensitive layer is exposed after peeling off the support film, the radical generated is rapidly stabilized (deactivated) by contact with oxygen generated in the air, thereby causing photohardening of the photopolymerizable compound. The reaction is difficult to carry out. Therefore, in this method, in order to reduce the influence of oxygen incorporation during exposure after peeling off the support film, it is being studied to use a barrier layer having a gas barrier property between the support film and the photosensitive layer (middle) Photosensitive element of the layer (for example, refer to Patent Document 1 to Patent Document 3). [Prior Art Document] [Patent Literature]

[Patent Document 1] Japanese Patent No. 5,451, 734 [Patent Document 2] Japanese Patent Laid-Open Publication No. Hei. No. Hei.

[Problems to be Solved by the Invention] In the photosensitive element including the barrier layer containing a water-soluble resin described in Patent Documents 1 to 3, since the affinity between the water-soluble resin and the support film is high, the affinity between the water-soluble resin and the support film is high. There is a case where the adhesion between the barrier layer and the support film is strong. In this case, when the support film is peeled off from the barrier layer of the photosensitive element, it is difficult to peel off the support film, and the barrier layer or the photosensitive layer may be defective.

In the past, it has been proposed to add a release accelerator such as an anthrone or a fluorine-based surfactant to a resin composition for forming a barrier layer containing a water-soluble resin, thereby lowering the adhesion between the barrier layer and the support film. Thereby, the peeling property of the barrier layer and the support film is improved.

However, it is known that there is a problem in that turbidity is likely to occur in the formed barrier layer by adding a peeling accelerator such as these surfactants. Further, since a peeling accelerator such as a surfactant exists at the interface between the barrier layer and the support film, there is a problem in that the interface composition changes or the adhesion between the barrier layer and the support film occurs in a long-term viewpoint. The change is difficult to maintain a stable support film peelability (peelability of the barrier layer and the support film).

The present invention has been made in view of the problems of the prior art, and an object of the invention is to provide a photosensitive element and a resin for forming a barrier layer which can improve the peeling property of a barrier layer and a support film without using a release accelerator. A composition, a method of forming a resist pattern, and a method of producing a printed wiring board. [Means for solving the problem]

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

The photosensitive element of the present invention contains an alcohol having 3 or more carbon atoms in the barrier layer, so that the peeling property of the barrier layer and the support film can be improved without using a release accelerator. According to the photosensitive element, since the support film can be smoothly peeled off from the barrier layer, defects of the barrier layer and the photosensitive layer can be suppressed. Further, since the peeling property of the barrier layer and the support film can be improved without using the release accelerator, generation of turbidity of the barrier layer due to the presence of the release accelerator and temporal change of the peeling property of the support film 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 disclosed in the present invention.

In the photosensitive element of the present invention, the alcohol having 3 or more carbon atoms may contain a compound selected from the following chemical formulas (1) to (3) and represented by the following formula (4). At least one of the group consisting of compounds. According to the photosensitive element, the peeling property of the barrier layer and the support film can be further improved. [Chemical 1] [Chemical 2] [Chemical 3] [Chemical 4] [In the formula (4), R ¹¹ represents an alkyl group, R ¹² represents an alkylene group, and the sum of the carbon numbers 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 alcohol having 3 or more carbon atoms may have a solubility in water of 20 ° C of 300 mL/water of 100 mL or more. According to the photosensitive element, layer separation of the barrier layer can be further suppressed, so that a photosensitive element excellent in practical use can be provided.

In the photosensitive element of the present disclosure, the content of the carbon number of 3 or more carbon atoms in the barrier layer may be more than 0% by mass and 2.0 mass based on the total amount of the barrier layer. %the following. According to the photosensitive element, the diffusion of the alcohol in the subsequent step can be suppressed.

In the photosensitive element of the present disclosure, the water-soluble resin may contain polyvinyl alcohol. According to the photosensitive element, the gas barrier property of the barrier layer can be further increased, and the deactivation of the radical generated by the actinic ray used in the exposure can be further suppressed.

In the photosensitive element of the present disclosure, the support film may be a polyester film. According to the photosensitive element, the mechanical strength and heat resistance of the support film can be improved, and defects such as wrinkles of the barrier layer which are formed when the barrier layer is formed on the support film can be suppressed, and workability can be improved.

Further, the present invention provides a resin composition for forming a barrier layer comprising a water-soluble resin, an alcohol having 3 or more carbon atoms, and water. According to the resin composition for forming a barrier layer, a barrier layer excellent in peelability from the support film can be formed without using a release accelerator.

In the resin composition for forming a barrier layer of the present invention, the alcohol having 3 or more carbon atoms may contain a compound selected from the chemical formula (1) to the chemical formula (3) and the above formula (4). At least one of the groups consisting of the compounds represented. According to the resin composition for forming a barrier layer, a barrier layer which is more excellent in peelability from the support film can be formed.

In the resin composition for forming a barrier layer of the present invention, the alcohol having 3 or more carbon atoms may have a solubility in water of 20 ° C of 300 mL/water of 100 mL or more. According to the 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 invention, the content of the alcohol having 3 or more carbon atoms may be 100 parts by mass to 500 parts by mass based on 500 parts by mass of water. According to the resin composition for forming a barrier layer, a barrier layer which is more excellent in peelability from the 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 invention, the water-soluble resin may contain polyvinyl alcohol. According to the resin composition for forming a barrier layer, a barrier layer having more excellent gas barrier properties can be formed.

In addition, the present disclosure provides a method for forming a resist pattern, comprising: a step of arranging a photosensitive layer, a barrier layer, and a support film in this order from the substrate side using the photosensitive element of the present disclosure; Removing the support film, exposing the photosensitive layer to the exposed layer by using the actinic ray; and removing the uncured portion of the barrier layer and the photosensitive layer from the substrate step. According to the method for forming a resist pattern, the resist pattern is formed using the photosensitive element of the present invention, and thus a resist pattern having excellent resolution and resist pattern shape can be formed.

Further, the present disclosure provides a method of manufacturing a printed wiring board, comprising: performing an etching treatment or a plating treatment on a substrate on which a resist pattern is formed by the method for forming a resist pattern according to the present disclosure, thereby forming The step of the conductor pattern. According to the method of manufacturing a printed wiring board, the resist pattern is formed by the method for forming a resist pattern of the present invention, so that a resist excellent in resolution and resist pattern shape can be provided. A method of manufacturing a printed wiring board having a pattern and a high density of a printed wiring board. [Effects of the Invention]

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 printed wiring board, which can improve the peeling property of the barrier layer and the support film without using a release accelerator. Manufacturing method.

Hereinafter, a preferred embodiment of the present disclosure will be described in detail with reference to the drawings as needed. In the following embodiments, of course, the constituent elements (including the element steps and the like) are not necessarily required except for the case where it is specifically indicated and the case where it is considered to be clearly required in principle. The same is true for numerical values and ranges thereof, and should be construed as not unduly limiting the present disclosure.

In the present specification, the term "(meth)acrylic acid" means at least one of acrylic acid and methacrylic acid corresponding thereto. In addition, other similar expressions such as (meth) acrylate are also the same.

In addition, in the present specification, the term "step" means not only an independent step, but even if it cannot be clearly distinguished from other steps, it is included in the term as long as the intended effect of the step is achieved. .

Further, in the present specification, the numerical range indicated by "~" indicates a range including the numerical values described before and after "~" as the minimum value and the maximum value, respectively. Further, in the numerical range recited in the specification, the upper limit or the lower limit of the numerical range of one stage may be replaced with the upper limit or the lower limit of the numerical range of the other stage. In addition, within the numerical ranges described in the specification, the upper or lower limit of the numerical range may be replaced with the value shown in the embodiment. In addition, in the present specification, the term "layer" includes a partially formed shape structure in addition to the shape structure formed over the entire surface when viewed as a plan view.

[Photosensitive Element] As shown in FIG. 1 , the photosensitive element 1 of the present embodiment includes the support film 2 , the barrier layer 3 , and the photosensitive layer 4 in this order, and may further include another layer such as the protective layer 5 . Further, the barrier layer contains a water-soluble resin and an alcohol having 3 or more carbon atoms. By using the photosensitive element of the present embodiment, the peeling property of the barrier layer and the support film can be improved. Further, since the photosensitive element of the present embodiment can suppress the layer separation of the barrier layer, it is excellent in practical use. Hereinafter, each layer in the photosensitive element of the present embodiment will be described in detail.

<Support film> The support film of the present embodiment can be used without particular limitation. For example, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene-2,6-naphthalate (polyethylene-2) may be mentioned. A polyester film such as 6-naphthalate or PEN), and a polyolefin film such as polypropylene or polyethylene. Among them, a polyester film can be used. By using a polyester film as a support film, there is a tendency to improve the mechanical strength and resistance to heat of the support film. In addition, by using a polyester film, it is possible to suppress defects such as wrinkles of the barrier layer which are formed when the barrier layer is formed on the support film, and the workability tends to be improved. Further, from the viewpoint of suppressing occurrence of minute detachment of the resist pattern, a polyester film containing particles (such as a lubricant) can be used. When a polyester film containing particles (a lubricant or the like) is used, a barrier layer can be formed on a surface having particles (lubricants, etc.). As such a polyester film, for example, a polyester film in which particles (a lubricant or the like) are impregnated, a polyester film in which a layer containing particles (a lubricant or the like) is formed on both surfaces, or a particle-containing particle formed on one surface can be used. A polyester film of a layer (lubricant, etc.). Furthermore, the support film may be a single layer or a plurality of layers.

As a method of adding a particle such as a lubricant to the support film, for example, a method of injecting particles (lubricant or the like) into the support film may be mentioned; and roll coating, flow coating, spray coating, curtain flow coating, dip coating, slitting molding may be used. A method of forming a layer containing particles (a lubricant or the like) on a support film by a known method such as coating.

The haze value of the support 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 value is 0.01% or more, the support film itself tends to be easily produced. When it is 5.0% or less, when a photosensitive layer of a photosensitive element is formed, there is a tendency that foreign matter in the photosensitive layer is easily detected. Here, the "haze value" means haze. The haze value in the present disclosure refers to a value measured using a commercially available haze meter (turbidity meter) according to the method specified in Japanese Industrial Standard (JIS) K 7105. The haze value can be measured, for example, by a commercially available turbidity meter such as NDH-5000 (manufactured by Nippon Denshoku Industries Co., Ltd., trade name).

Further, the support film can be obtained by a user who can obtain a support film as a photosensitive element from a commercially available general industrial film, and can be suitably processed and used. Specifically, for example, "FB-40" (made by Toray Co., Ltd., product name), "A4100", "A1517" (made by Toyobo Co., Ltd.), which is a PET film, Product name), "G2H" (manufactured by Teijin DuPont Films Co., Ltd., product name).

The thickness of the support film may be 1 μm to 200 μm, 1 μm to 100 μm, 1 μm to 60 μm, 5 μm to 60 μm, 10 μm to 60 μm, 10 μm to 50 μm, 10 μm to 40 μm, 10 μm. ~30 μm, or 10 μm to 25 μm. When the film thickness of the support film is 1 μm or more, the support film can be prevented from being damaged when the support film is peeled off. Further, since the thickness of the support film is 200 μm or less, there is a tendency that economic benefits are easily obtained.

<Barrier Layer> The photosensitive element of the present embodiment includes a barrier layer between the support film and the photosensitive layer. Further, the barrier layer contains a water-soluble resin and an alcohol having 3 or more carbon atoms. According to the photosensitive element of the present embodiment, even when the barrier layer is not contained in the barrier layer, the support film can be smoothly peeled off from the barrier layer. Therefore, when the support film is peeled off, the barrier layer pair is interposed. When the photosensitive layer is exposed, 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, 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. Further, the barrier layer may have water solubility or may have solubility in a developer. Furthermore, from the viewpoint of further improving the gas barrier properties of the barrier layer, the adhesion of the support film to the barrier layer may be less than the adhesion of the barrier layer to the photosensitive layer. That is, it can also be said that when the support film is peeled off from the photosensitive element, unintentional peeling of the barrier layer and the photosensitive layer is suppressed.

(Water-Soluble Resin) Here, the "water-soluble resin" means a resin having a solubility of 5 g or less with respect to 100 mL of hexane at 25 ° C. The solubility can be calculated by mixing hexane at 25 ° C with the dried water-soluble resin and investigating the presence or absence of white turbidity. Specifically, Sample 1 and Sample 2 were separately prepared, and the sample 1 was placed in a glass container having a frosted glass stopper and being colorless and transparent, and the dried water-soluble resin A (g) and hexane (100 mL- As a result of the mixture of A), the sample 2 was obtained by placing only 100 mL of hexane in a glass container having a frosted glass stopper and being colorless and transparent. Then, the sample in the glass container was sufficiently shaken and mixed, and it was confirmed that the bubble disappeared. Immediately after the confirmation, the two containers were placed side by side under the conditions of diffused calendering or the same level of light, and the state of the liquid of the sample 1 was compared with the state of the liquid of the sample 2. When the sample 1 was compared with the sample 2, the addition amount A (g) when the sample 1 was more turbid or the suspension of the solid component was observed was observed as the solubility of the water-soluble resin to 100 mL of hexane at 25 °C.

Examples of the water-soluble resin include polyvinyl alcohol, polyvinylpyrrolidone, and water-soluble polyimide. The water-soluble resin may contain polyvinyl alcohol from the viewpoint of further improving the gas barrier properties of the barrier layer and further suppressing the deactivation of radicals generated by the actinic rays used in the exposure. The polyvinyl alcohol can be obtained, for example, by saponifying a 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. Further, the upper limit of the degree of saponification is 100 mol%. By containing a polyvinyl alcohol having a saponification degree of 50 mol% or more, the gas barrier properties of the barrier layer can be further improved, and the resolution of the formed resist pattern tends to be further improved. In addition, the "saponification degree" in this specification is a value measured by JIS K 6726 (1994) (test method of polyvinyl alcohol) prescribed by the Japanese Industrial Standard.

The polyvinyl alcohol may be a mixture of two or more kinds of polyvinyl alcohols having different degrees of saponification, viscosity, degree of polymerization, and modified substances. The average degree of polymerization of the polyvinyl alcohol may be 300 to 5,000, 300 to 3,500, or 300 to 2,000. In addition, the water-soluble resin may be used singly or in combination of two or more. The water-soluble resin may contain, for example, polyvinyl alcohol and polyvinylpyrrolidone. In this case, the mass ratio of polyvinyl alcohol to polyvinylpyrrolidone (PVA (polyvinyl alcohol: PVP (polyvinyl pyrrolidone)) 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 may be 50 parts by mass to 300 parts by mass, and 60 parts by mass to 500 parts by mass of the water. 250 parts by mass, 70 parts by mass to 200 parts by mass, 80 parts by mass to 150 parts by mass, or 80 parts by mass to 125 parts by mass.

(Alcohols having 3 or more carbon atoms) The alcohol having 3 or more carbon atoms may be a monohydric alcohol or a polyhydric alcohol (except for a plasticizer of a polyol compound to be described later). The carbon number of the alcohol having 3 or more carbon atoms is the sum of the carbon numbers in the alcohol, and may be 10 or less, 8 or less, 7 or less, 6 or less, or 5 or less. The alcohol having 3 or more carbon atoms may contain at least one selected from the group consisting of a compound represented by the following chemical formulas (1) to (3) and a compound represented by the following formula (4). By containing these alcohols having 3 or more carbon atoms, the peeling property of the barrier layer and the support film can be further improved. [Chemical 5] [Chemical 6] [Chemistry 7] [化8]

In the formula (4), R ¹¹ represents an alkyl group, and R ¹² represents an alkylene group. Further, the sum of the carbon numbers of the group of R ^{11 and} the group of R ¹² is 3 or more. Further, from the viewpoint of further enhancing the affinity with water, the sum of the carbon numbers of the group of R ^{11 and} the group of R ¹² may be 10 or less, 8 or less, 7 or less, 6 or less, or 5 or less. 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. Further, the alkyl group represented by R ¹¹ and the alkylene group represented by R ¹² may each have a substituent or may have no substituent. In the case of having a substituent, the carbon number of the group of R ¹¹ and the carbon number of the group of R ¹² each include the carbon number of each substituent. Further, the alcohol having 3 or more carbon atoms represented by the formula (4) may be 2-butoxy-ethanol or 1-methoxy-2-propanol.

The alcohol having 3 or more carbon atoms may be used alone or in combination of two or more. Further, from the viewpoint of further suppressing layer separation of the barrier layer, the solubility of the alcohol having 3 or more carbon atoms in water at 20° C. may be 300 mL/water 100 mL or more, 500 mL/water 100 mL or more, or 1000 mL / water 100 mL or more.

In the present specification, the "solubility of alcohol having a carbon number of 3 or more with respect to water at 20 ° C" can be calculated by mixing the alcohol with water at 20 ° C and investigating the presence or absence of white turbidity. Specifically, sample 3 and sample 4 were separately prepared, and the sample 3 was obtained by mixing a mixture of the alcohol A mL and water (100-A) mL in a glass container having a frosted glass stopper and being colorless and transparent. The sample 4 was obtained by placing only water (100 mL) in a glass container having a frosted glass stopper and being colorless and transparent. Then, the sample 3 and the sample 4 in the glass container were sufficiently shaken and mixed, and it was confirmed that the bubble disappeared. Immediately after the confirmation, the two containers were placed side by side under the conditions of diffused calendering or the same level of light, and the state of the liquid in the sample 3 was compared with the state of the liquid in the sample 4. When the sample 3 was compared with the sample 4, the addition amount A mL of the alcohol when the sample 3 was more turbid was observed as the solubility of the alcohol in water at 20 °C.

The content of the alcohol having 3 or more carbon atoms in the resin composition for forming a barrier layer of the present embodiment may be 100 parts by mass to 500 parts by mass, 110 parts by mass to 480 parts by mass, or 120 parts by mass with respect to 500 parts by mass of water. The amount is from 460 parts by mass, from 125 parts by mass to 440 parts by mass, from 125 parts by mass to 420 parts by mass, or from 125 parts by mass to 400 parts by mass. When the content is 100 parts by mass or more, the peeling property of the barrier layer formed and the support film tends to be improved. When the content is 500 parts by mass or less, the solubility of the water-soluble resin is improved, and the barrier layer is easily formed. Propensity.

The content of the alcohol having 3 or more carbon atoms in the barrier layer of the present embodiment may be based on the total amount of the barrier layer (the total amount of the solid content of the resin composition for forming the barrier layer of the barrier layer). More than 0% by mass and 2.0% by mass or less, 0.001% by mass to 2.0% by mass, or 0.005% by mass to 1.0% by mass. When the content is 2.0% by mass or less, the diffusion of the alcohol in the subsequent step tends to be suppressed, and when it exceeds 0% by mass, the peeling property of the barrier layer and the support film tends to increase, and 0.001% by mass or more, and the peeling property of the barrier layer and the support film tends to be further improved.

The resin composition for forming a barrier layer of the present embodiment may contain an alcohol having a carbon number of less than 3. When the alcohol having a carbon number of less than 3 is contained, the content thereof may be from 125 parts by mass to 375 parts by mass, or from 150 parts by mass to 325 parts by mass, based on 500 parts by mass of the water. When the content is 125 parts by mass or more, the solubility of the water-soluble resin is improved, and the barrier layer is likely to be formed, and the barrier layer and the support film are peeled off by being 375 parts by mass or less. The tendency to increase sexuality. Further, from the viewpoint of improving the peeling property of the barrier layer and the support film, the content of the alcohol having a carbon number of less than 3 in the barrier layer of the present embodiment can be based on the total amount of the alcohol in the barrier layer. The amount is 0.1% by mass to 10% by mass, or 0.1 parts by mass to 10 parts by mass based on 100 parts by mass of the total amount of the alcohol having 3 or more carbon atoms in the barrier layer.

In addition, the resin composition for forming a barrier layer of the present embodiment may contain a known additive such as a plasticizer or a surfactant, within a range that does not impair the effects of the present disclosure. Further, a release accelerator may be contained within a range that does not impair the effects of the present disclosure.

As the plasticizer, for example, a polyol compound may be contained from the viewpoint of improving the elongation. Examples thereof include glycerol such as glycerin, diglycerin, and triglycerin, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, and polypropylene glycol (poly). Alkyl glycols, trimethylolpropane, etc. These plasticizers may be used alone or in combination of two or more.

The barrier layer in the photosensitive element of the present embodiment can be formed, for example, by applying the resin composition for forming a barrier layer of the present embodiment to 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 easiness of removal of the barrier layer. Further, the barrier layer may have a thickness of 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 viewpoint of easiness of formation of the barrier layer and analytical properties.

Further, the barrier layer of the present embodiment may have photosensitivity, and its photosensitivity is lower than that of the photosensitive layer. In addition, the barrier layer may not have photosensitivity. In the case where the barrier layer does not have photosensitivity, the photosensitivity stability of the photosensitive layer tends to be further improved. In addition, the term "photosensitivity" refers to, for example, the exposure of the photosensitive layer and, if necessary, the heat treatment after exposure, and then the development of the photosensitive layer by the developer for removing the uncured portion of the photosensitive layer. A resist pattern can be formed.

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

(A) Adhesive Polymer (A) The binder polymer (hereinafter also referred to as "(A) component)" can be produced, for example, by radical polymerization of a polymerizable monomer. Examples of the polymerizable unitary substance include a styrene derivative capable of being polymerized in the α-position or an aromatic ring such as styrene, vinyltoluene or α-methylstyrene, and diacetone. An acrylamide such as acrylamide, an ether of a vinyl alcohol such as acrylonitrile or vinyl-n-butyl ether, an alkyl (meth)acrylate or a benzyl (meth)acrylate such as benzyl methacrylate, Tetrahydrofurfuryl methacrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylate 2 , 2,2-trifluoroethyl ester, 2,2,3,3-tetrafluoropropyl (meth)acrylate, (meth)acrylic acid, α-bromoacrylic acid, α-chloroacrylic acid, β-furanyl (A Acrylic acid, β-styryl (meth)acrylic acid, maleic acid, maleic anhydride, maleic acid monomethyl ester, maleic acid monoethyl ester, maleic acid Maleic acid monoester such as monoisopropyl ester, fumaric acid, cinnamic acid, α-cyano cinnamic acid, itaconic acid, crotonic acid and propiolic acid. These may be used alone or in combination of two or more.

Among these, an alkyl (meth)acrylate may be contained from the viewpoint of plasticity improvement. The (meth)acrylic acid alkyl ester may, for example, be a compound represented by the following formula (II), and a compound in which an 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 the 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 alkyl group having 1 to 12 carbon atoms 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 decyl group, a decyl group, and a decyl group. A base, a dodecyl group, and structural isomers of such groups.

Examples of the (meth)acrylic acid alkyl ester represented by the above formula (II) include methyl (meth)acrylate, ethyl (meth)acrylate, and propyl (meth)acrylate. Methyl)butyl acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate And (meth) methacrylate, decyl (meth) acrylate, eleven (meth) acrylate, dodecyl (meth) acrylate, and the like. These may be used alone or in combination of two or more.

Further, the component (A) may contain a carboxyl group from the viewpoint of alkali developability. The component (A) having a carboxyl group can be produced, for example, by radically polymerizing a polymerizable monomer having a carboxyl group with another polymerizable monomer. The polymerizable monomer having a carboxyl group may be (meth)acrylic acid or methacrylic acid. Further, the carboxyl group-containing (A) component may have an acid value of 50 mgKOH/g to 250 mgKOH/g, 50 mgKOH/g to 200 mgKOH/g, or 100 mgKOH/g to 200 mgKOH/g.

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

In addition, the content of the structural unit derived from the polymerizable ruthenium having a carboxyl group in the component (A) is related to the compounding ratio of the polymerizable oxime having a carboxyl group, and therefore may be 12% by mass to 50% by mass. 12% by mass to 40% by mass, 15% by mass to 35% by mass, 15% by mass to 30% by mass, or 20% by mass to 30% by mass.

Further, from the viewpoint of adhesion and chemical resistance, the component (A) can be used as a polymerizable unitary amount of styrene or a styrene derivative. When the styrene or styrene derivative is used as a polymerizable unitary substance, the content (relative to the polymerization for the component (A)) is obtained from the viewpoint of improving adhesion and chemical resistance. The blending ratio of the styrene or the styrene derivative in the total amount of the monolithic body may be 10% by mass to 60% by mass, 15% by mass to 50% by mass, 30% by mass to 50% by mass, and 35% by mass to 50% by mass. %, or 40% by mass to 50% by mass. When the content is 10% by mass or more, the adhesion tends to be improved. When the content is 60% by mass or less, the release sheet can be prevented from becoming large during development, and the time required for peeling can be suppressed from becoming prolonged. .

Further, the content of the structural unit derived from the styrene or the styrene derivative in the component (A) is related to the blending ratio of the styrene or the styrene derivative, so it may be 10% by mass to 60% by mass, 15 Mass% to 50% by mass, 30% by mass to 50% by mass, 35% by mass to 50% by mass, or 40% by mass to 50% by mass.

Further, from the viewpoint of the resolution and the aspect ratio, the (A) component may also use benzyl (meth)acrylate as a polymerizable unitary body. From the viewpoint of further improving the resolution and the aspect ratio, the content of the structural unit derived from benzyl (meth)acrylate in the component (A) may be 15% by mass to 50% by mass, and 15% by mass to 45% by mass. 15% by mass to 40% by mass, 15% by mass to 35% by mass, or 20% by mass to 30% by mass.

These binder polymers may be used alone or in combination of two or more. When the component (A) used in combination of two or more types is used, for example, two or more kinds of binder polymers containing different polymerizable single-components, and two or more kinds of binder polymers having different weight average molecular weights, And two or more kinds of binder polymers with different degrees of dispersion.

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

The weight average molecular weight of the 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 the mechanical strength and alkali developability in a well-balanced manner. When the weight average molecular weight of the component (A) is 20,000 or more, the development liquid resistance tends to be excellent, and when it is 300,000 or less, the development time tends to be suppressed. Incidentally, the weight average molecular weight in the present specification is a value obtained by conversion using a gel permeation chromatography (GPC) and converted by a calibration curve prepared using standard polystyrene.

The content of the component (A) may be 30 parts by mass to 80 parts by mass, 40 parts by mass to 75 parts by mass, or 50% by mass based on 100 parts by mass of the total solid content of the component (A) and the component (B) to be described later. Parts to 70 parts by mass, or 50 parts by mass to 60 parts by mass. When the content of the component (A) is within this range, the coating property of the photosensitive resin composition and the strength of the photocured portion are further improved.

(B) Photopolymerizable Compound The photosensitive resin composition of the present embodiment may contain (B) a photopolymerizable compound (hereinafter also referred to as "(B) component"). The component (B) is not particularly limited as long as it is a compound capable of photopolymerization and a compound capable of photocrosslinking. For example, a compound having at least one ethylenically unsaturated bond in the molecule can be used.

Examples of the component (B) include a compound obtained by reacting an α,β-unsaturated carboxylic acid with a polyhydric alcohol, a bisphenol-type (meth) acrylate compound such as a bisphenol A-type (meth) acrylate compound, and the like. A urethane monomer such as a (meth) acrylate compound having a urethane bond, a nonylphenoxyvinyloxy (meth) acrylate, or a nonyl phenoxy octaethyleneoxy group (A) Acrylate, γ-chloro-β-hydroxypropyl-β'-(meth)acryloyloxyethyl-phthalate, β-hydroxyethyl-β'-(methyl) Propylene decyloxyethyl-phthalate, β-hydroxypropyl-β'-(meth)acryloyloxyethyl-phthalate, and (meth)acrylic acid Base ester. These may be used alone or in combination of two or more.

Among these, the component (B) may contain a bisphenol-type (meth) acrylate compound from the viewpoint of improving the resolution, the adhesion, and the inhibition of the end portion of the resist in a well-balanced manner. The bisphenol type (meth) acrylate compound may be a compound represented by the following formula (III). [Chemistry 9]

In the 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 ethylidene group or a propyl group, and XO and YO each independently represent an oxyethyl group (hereinafter, sometimes referred to as "EO group") or an oxypropyl group (hereinafter, sometimes referred to as "PO base"). p ₁ , p ₂ , q ₁ and q ₂ each independently represent a numerical value of 0 to 40. However, both p ₁ + q ₁ and p ₂ + q ₂ are 1 or more. When X is an ethyl group and Y is a propyl group, p ₁ + p ₂ is from 1 to 40, and q ₁ + q ₂ is from 0 to 20. When X is a propyl group and Y is an ethyl 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 the PO group, an integer value is represented in a single molecule, and a rational number as an average value is represented in an aggregate of a plurality of molecules. Further, the EO group and the PO group may be continuously present in a block form, or may be randomly present.

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

Examples of the compound represented by the formula (III) include 2,2-bis(4-(methyl)acryloxypolyethoxy)phenyl)propane and 2,2-bis(4-( (Meth)propylene oxypolypropoxy)phenyl)propane, 2,2-bis(4-((meth)propenyloxypolyethoxypolypropoxy)phenyl)propane, and the like. These may be used alone or in combination of two or more.

As a bisphenol type (meth) acrylate compound which can be obtained commercially, for example, 2,2-bis(4-(methacryloxy diethoxy)phenyl)propane (Xin Nakamura Chemical) "BPE-200" manufactured by Industrial Co., Ltd., 2,2-bis(4-(methacryloxypentapentaethoxy)phenyl)propane ("BPE-" manufactured by Shin-Nakamura Chemical Co., Ltd. 500" or "FA-321M" manufactured by Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloxypentadecane)ethoxypropane) (Xinzhongcun Chemical Industry Co., Ltd.) Manufactured "BPE-1300"), 2,2-bis(4-(methacryloxypolyethoxy)phenyl)propane ("BP-2EM" (EO, manufactured by Kyoeisha Chemical Co., Ltd.) Base: 2.6 (average))) and so on.

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

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

In addition, from the viewpoint of improving the resolution, the total amount of solid components of the component (A) and the component (B) is such that the total number of EO groups and PO groups is 1 to 7 (III). The content of the compound to be expressed may be 1% by mass to 50% by mass, 2% by mass to 48% by mass, 3% by mass to 45% by mass, 5% by mass to 40% by mass, 10% by mass to 30% by mass, or 10% by mass. % to 25% by mass.

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

Further, in the molecule of the polyalkylene glycol di(meth)acrylate having both the EO group and the PO group, the EO group and the PO group may be continuously present in a block manner, or may be randomly presence. Further, the PO group may be any of an oxy-n-propyl group or an oxy-iso-propyl group. Further, in the (poly)oxyisopropanyl group, the secondary carbon of the propyl group may be bonded to the oxygen atom, and the primary carbon may be bonded to the oxygen atom.

As a compound which can be obtained commercially as a polyalkylene glycol di(meth)acrylate having both an EO group and a PO group, for example, an EO group: 6 (average value) and a PO group: 12 are exemplified. (Average) polyalkylene glycol di(meth)acrylate ("FA-023M", "FA-024M" manufactured by Hitachi Chemical Co., Ltd.). In addition, from the viewpoint of the followability and the improvement of the unevenness of the substrate, the polyalkylene glycol di(methyl group) having both the EO group and the PO group is added to the total solid content of the component (B). The content of the acrylate may be 1% by mass to 15% by mass, 1.5% by mass to 15% by mass, 2% by mass to 13% by mass, or 3% by mass to 13% by mass.

The content of the component (B) may be 20 parts by mass to 70 parts by mass, 25 parts by mass to 60 parts by mass, or 30 parts by mass to 100 parts by mass based on the total of the solid content of the component (A) and the component (B). 50 parts by mass. When the content of the component (B) is within this range, the sensitivity and the adhesion between the photosensitive resin composition and the inhibition at the end of the resist are further improved, and the light sensitivity and the coating property are also improved. Better.

(C) Photopolymerization Initiator The photosensitive resin composition of the present embodiment may contain at least one (C) photopolymerization initiator (hereinafter also referred to as "(C) component"). The component (C) is not particularly limited as long as it can polymerize the component (B), and can be appropriately selected from the usual photopolymerization initiators.

As the component (C), for example, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1, 2-methyl-1-[4- An aromatic ketone such as (methylthio)phenyl]-2-morpholinyl-acetone-1, an anthracene such as an alkyl hydrazine, a benzoin ether compound such as benzoin alkyl ether, a benzoin compound such as benzoin or alkylbenzoin, benzyl a benzyl derivative such as dimethyl ketal, 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole 2,4,5-triarylimidazole dimer such as dimer, acridine derivative such as 9-phenyl acridine or 1,7-(9,9'-acridinyl)heptane, and the like. These may be used alone or in combination of two or more.

Among these, a 2,4,5-triarylimidazole dimer may be contained from the viewpoint of analytical improvement. As the 2,4,5-triarylimidazole dimer, for example, 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)- 4,5-bis-(m-methoxyphenyl)imidazole dimer, and 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer. Among these, 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer may be contained from the viewpoint of improvement in photostability stability.

As a 2,4,5-triaryl imidazole dimer, for example 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole can be used as B-CIM ( It is commercially available from Hodogaya Chemical Industry Co., Ltd., manufactured under the name of the product.

The component (C) may contain at least one of 2,4,5-triarylimidazole dimers, and may further contain a 2,4,5-triarylimidazole dimer, from the viewpoint of further improving light absorption and adhesion and further suppressing light absorption of the component (C). 2-(2-Chlorophenyl)-4,5-diphenylimidazole dimer. Furthermore, the structure of the 2,4,5-triarylimidazole dimer may be symmetrical or asymmetric.

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

(D) Photosensitizer The photosensitive resin composition of the present embodiment may contain (D) a photosensitizer (hereinafter also referred to as "(D) component"). By containing the component (D), there is a tendency that the absorption wavelength of the actinic rays used in the exposure can be effectively utilized.

Examples of the component (D) include pyrazolines, dialkylaminobenzophenones, anthraquinones, coumarins, xanthones, oxazoles, and benzoxazoles. Thiazoles, benzothiazoles, triazoles, stilbenes, triazines, thiophenes, naphthyl imines and triarylamines. These may be used alone or in combination of two or more. The component (D) may contain a pyrazoline, an anthracene, or a dialkylaminobenzophenone, from the viewpoint of more effectively utilizing the absorption wavelength of actinic rays used in the exposure, wherein It may also contain dialkylaminobenzophenones. Examples of the dialkylamino benzophenone-based compound which can be obtained commercially are, for example, "EAB" manufactured by Hodogaya Chemical Industry Co., Ltd., and the like.

When the component (D) is contained, the content thereof may be 1.0 part by mass or less, 0.5 part by mass or less, 0.15 part by mass or less, or 0.12 part by mass based on 100 parts by mass of the total solid content of the component (A) and the component (B). The following, or 0.10 parts by mass or less. When the content of the component (D) is 1.0 part by mass or less based on 100 parts by mass of the total solid content of the component (A) and the component (B), the resist pattern shape and the resist end portion can be suppressed. The deterioration and the tendency to make the resolution better. In addition, the content of the component (D) may be 0.01 parts by mass or more based on 100 parts by mass of the total solid content of the component (A) and the component (B), from the viewpoint of the high light sensitivity and the good resolution.

(E) Polymerization Inhibitor The photosensitive resin composition of the present embodiment may contain (E) a polymerization inhibitor (hereinafter also referred to as "(E) component"). By containing the component (E), there is a tendency that the exposure amount required for photocuring the photosensitive resin composition can be adjusted to an exposure amount most suitable for exposure by a projection exposure machine.

The component (E) may contain a compound represented by the following formula (I) from the viewpoint of further improving the analytical property. [化10]

In the formula (I), R ⁵ represents 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 amine group, an aryl group, a decyl group or an alkyl group having 1 to 10 carbon atoms. a carboxyalkyl group having a carbon number of 1 to 10, an alkoxy group having 1 to 20 carbon atoms or a heterocyclic group, wherein m and n are integers of 2 or more, and n is an integer of 0 or more, And an integer selected by the mode of m+n=6, when n is an integer of 2 or more, R ⁵ may be the same or different. Further, the aryl group may be substituted with an alkyl group having 1 to 20 carbon atoms.

From the viewpoint of further improving the compatibility with the component (A), R ⁵ may be a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. The alkyl group having 1 to 20 carbon atoms represented by R ⁵ may be an alkyl group having 1 to 4 carbon atoms. For the purpose of further improving the clarification, m may be 2 or 3 or 2.

Examples of the compound represented by the above formula (I) include catechol, resorcinol (resorcin), 1,4-hydroquinone, and 3- Methyl catechol, 4-methyl catechol, 3-ethyl catechol, 4-ethyl catechol, 3-propyl catechol, 4-propyl phthalate Phenol, 3-n-butyl catechol, 4-n-butyl catechol, 3-tert-butyl catechol, 4-tert-butyl catechol, 3,5-di- Alkyl catechol such as tert-butyl catechol, 2-methyl resorcinol, 4-methyl resorcinol, 5-methyl resorcinol (orcin) , 2-ethyl resorcinol, 4-ethyl resorcinol, 2-propyl resorcinol, 4-propyl resorcinol, 2-n-butyl resorcinol, 4-正Alkyl resorcinol such as butyl resorcinol, 2-tert-butyl resorcinol, 4-tert-butyl resorcinol, methyl hydroquinone, ethyl hydroquinone, Alkyl hydroquinone such as propyl hydroquinone, tert-butyl hydroquinone, 2,5-di-tert-butyl hydroquinone, pyrogallol, phloroglucin Wait. These may be used alone or in combination of two or more.

Among the compounds represented by the above formula (I), from the viewpoint of further improving the resolution, the alkyl catechol may be used.

The content of the component (E) may be 0.001 part by mass to 0.3 part by mass, 0.01 part by mass to 0.2 part by mass, and 0.02 part by mass to 0.15 part by mass based on 100 parts by mass of the total solid content of the component (A) and the component (B). Parts, or 0.03 parts by mass to 0.1 parts by mass. When the content of the component (E) is 0.3 parts by mass or less, the exposure time can be shortened, and the productivity of the mass production tends to be improved. In addition, when the content of the component (E) is 0.001 parts by mass or more, the photoreaction of the photocured portion can be sufficiently performed, and the reaction rate can be improved, whereby the resist swelling property can be suppressed and the resist swelling property can be suppressed. The resolution is getting better.

In addition, the content of the component (E) may be 0.03 parts by mass to 0.4 parts by mass, 0.05 parts by mass to 0.4 parts by mass, 0.05 parts by mass to 0.2 parts by mass, or 0.05% by mass based on 100 parts by mass of the solid component of the component (A). Parts to 0.1 parts by mass. When the content of the component (E) is 0.05 parts by mass or more with respect to the component (A), there is a tendency to improve the thermal stability of the photosensitive resin composition; when it is relative to the component (A), the content of the component (E) When it is 0.4 parts by mass or less, the yellowing of the photosensitive resin composition tends to be suppressed.

(Other components) In the photosensitive resin composition of the present embodiment, the peacock may be contained in an amount of 0.01 parts by mass to 20 parts by mass per 100 parts by mass of the total solid content of the component (A) and the component (B). Green (malachite green), Victoria Pure Blue, brilliant green and methyl violet dyes, tribromophenyl fluorene, leuco crystal violet, diphenyl Photochromic agents such as amides, benzylamines, triphenylamines, diethylaniline, o-chloroaniline and tert-butyl catechol; thermal coloring inhibitors, plasticizers such as p-toluenesulfonamide, pigments Additives such as a filler, a defoaming agent, a flame retardant, an adhesion imparting agent, a leveling agent, a peeling accelerator, an antioxidant, a fragrance, an imaging agent, and a thermal crosslinking agent. These additives may be used alone or in combination of two or more.

In addition, the photosensitive resin composition of the present embodiment may contain at least one of organic solvents as needed, in order to improve the handleability of the photosensitive composition or to adjust the viscosity and the storage stability. As the organic solvent, an organic solvent which is usually used can be used without particular limitation. Specific examples thereof include methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N,N-dimethylformamide, propylene glycol monomethyl ether, and the like. An organic solvent or a mixed solvent of these. These may be used alone or in combination of two or more.

<Protective Layer> The photosensitive element of the present embodiment can laminate a protective layer on the surface of the photosensitive layer opposite to the surface contacting the barrier layer. As the protective layer, for example, a polymer film of polyethylene or polypropylene or the like can be used. Further, the same polymer film as the support film may be used, or 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 laminated in this order will be described.

<Method for Producing Photosensitive Element> First, for example, water having a temperature of from 10 ° C to 90 ° C and an alcohol containing an alcohol having a carbon number of 3 or more are added so that the solid content is 10% by mass to 20% by mass. A water-soluble resin containing polyvinyl alcohol is gradually added to the solvent, and the mixture is stirred for about 1 hour to be uniformly dissolved to obtain a resin composition for forming a barrier layer containing polyvinyl alcohol and an alcohol having 3 or more carbon atoms. . In the present specification, the term "solid content" means a non-volatile component other than a substance which volatilizes water, an organic solvent, etc. of a resin composition. In other words, it means a component other than a solvent such as water removal or an organic solvent which remains without being volatilized in the drying step, and also includes a component which is liquid, saccharide or waxy at room temperature of about 25 °C.

Next, the resin composition for forming a barrier layer is applied onto a support film and dried to form a barrier layer. The coating of the barrier layer-forming resin composition onto the support film can be carried out, for example, by a roll coating, a slant wheel coating, a gravure coating, an air knife coating, a die coating, a bar coating, a spray coating, or the like. Come on.

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

Then, the photosensitive resin composition may be applied to the barrier layer on which the barrier film is formed, and the photosensitive resin composition may be applied to the barrier layer in the same manner as the coating of the resin composition for forming the barrier layer. A photosensitive layer is formed. Next, by laminating the protective layer on the photosensitive layer formed as described above, a photosensitive element having a support film, a barrier layer, a photosensitive layer, and a protective layer in this order can be produced. Further, by bonding a barrier layer formed on the support film to a photosensitive layer formed on the protective layer, a photosensitive member having a support film, a barrier layer, a photosensitive layer, and a protective layer in this order can also be obtained. .

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

The melt viscosity of the photosensitive layer in the photosensitive element at 110 ° C can be appropriately selected depending on the kind of the substrate in contact with the photosensitive layer, but after drying, it can be 50 Pa·s to 10000 Pa·s at 100 ° C, 100. Pa·s to 5000 Pa·s or 200 Pa·s 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 step, and productivity tends to be improved. Further, when the melt viscosity at 110 ° C is 10,000 Pa·s or less, the adhesion to the substrate in the lamination step is increased, and the adhesion failure tends to be reduced.

The form of the photosensitive element of the present embodiment is not particularly limited. For example, it may be in the form of a sheet, or may be wound into a roll shape around the core. In the case of winding up into a roll shape, it is possible to wind up the support film so as to be outside. Examples of the winding core include plastics such as a polyethylene resin, a polypropylene resin, a polystyrene resin, a polyvinyl chloride resin, or an ABS resin (Acrylonitrile Butadiene Styrene).

From the viewpoint of the end face protection, the end face separator may be provided on the end surface of the roll-shaped photosensitive element roll obtained as described above, and the moisture-proof end face separator may be provided from the viewpoint of edge fusion resistance. As a method of packing, it can be packaged by enclosing a black sheet having a small moisture permeability.

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

[Method of Forming Resist Pattern] The method of forming a resist pattern according to the present embodiment includes: (i) using the photosensitive element, and sequentially disposing the photosensitive layer, the barrier layer, and the support film from the substrate side a step on the substrate (hereinafter also referred to as "(i) photosensitive layer and barrier layer forming step"); (ii) removing the support film, and blocking the photosensitive layer with the actinic layer by actinic rays a step of exposing the layer (hereinafter also referred to as "(ii) exposure step"); and (iii) removing the barrier layer and the uncured portion of the photosensitive layer from the substrate (hereinafter, also It is called "(iii) development step"); other steps may be included as needed. Further, the resist pattern may be referred to as a photocured material pattern of a photosensitive resin composition, and may also be referred to as a concavo-convex pattern. Further, the resist pattern in the present embodiment can be used as a resist in accordance with the purpose, and can be used for other uses such as a protective film.

((i) Photosensitive layer and barrier layer forming step) In the photosensitive layer and barrier layer forming step, a photosensitive layer and a barrier layer are formed on the substrate using the photosensitive element. The substrate is not particularly limited, and a substrate for circuit formation including a conductive layer and a conductor layer formed on the insulating layer, or a pad (such as a substrate for a lead frame) such as an alloy substrate can be used.

As a method of forming a photosensitive layer and a barrier layer on a substrate, for example, when a photosensitive element having a protective layer is used, after the protective layer is removed, the photosensitive layer of the photosensitive element is bonded to the substrate while being heated. Thereby, a photosensitive layer and a barrier layer are formed on the substrate. Thereby, a laminated body including a substrate, a photosensitive layer, a barrier layer, and a support film in this order can be obtained.

When the photosensitive layer and the barrier layer forming step are carried out using a photosensitive element, it can be carried out under reduced pressure from the viewpoint of adhesion and followability. The heating at the time of crimping can be carried out at a temperature of 70 ° C to 130 ° C, and the crimping can be carried out at a pressure of 0.1 MPa to 1.0 MPa (1 kgf / cm ² to 10 kgf / cm ² ), but these conditions may be required And suitable for selection. Further, when the photosensitive layer of the photosensitive element is heated to 70 to 130 ° C, it is not necessary to preheat the substrate in advance, but in order to further improve adhesion and followability, preheating of the substrate may be performed.

((ii) Exposure Step) In the exposure step, the support film is removed, and the photosensitive layer is exposed by an actinic ray barrier layer. Thereby, the exposed portion irradiated with the actinic ray can be photocured to form a photocured portion (latent image), and the unexposed portion to which the actinic ray is not irradiated can be photocured to form a photocured portion. When the photosensitive layer and the barrier layer are formed using the photosensitive element, the support film existing on the photosensitive layer is peeled off and exposed. By exposing the photosensitive layer to the barrier layer, a resist pattern having excellent resolution and resist pattern shape can be formed.

As the exposure method, a known exposure method can be applied, and for example, a method of irradiating an actinic ray in an image form by interposing a negative mask pattern or a positive mask pattern called an artwork ( Mask exposure method); Laser Direct Imaging (LDI) exposure method; or method of using an actinic ray of an image projected with a reticle and illuminating the lens in an image-like manner (projection exposure mode) Wait. Among them, a projection exposure method can be used from the viewpoint of excellent resolution. That is, the photosensitive element or the like of the present embodiment is applied to a projection exposure method. Further, the projection exposure method may also be referred to as an exposure method using actinic rays of energy attenuation.

The light source of the actinic ray is not particularly limited as long as it is a commonly used light source, and for example, a carbon arc lamp, a mercury vapor arc lamp, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, an argon laser, or the like can be used. A gas source such as a gas laser, a solid-state laser such as a Yttrium Aluminum Garnet (YAG) laser, or a semiconductor laser such as a gallium nitride-based blue-violet laser. Further, a light source such as a photographic floodlight bulb or a sun light that efficiently emits visible light or the like can be used. Among these, in terms of improving the analyticity and alignment well in a well-balanced manner, a light source capable of radiating an i-ray monochromatic light having a wavelength of 365 nm and a h-ray single color capable of radiating an exposure wavelength of 405 nm can be used. A light source of light or a light source that emits an actinic ray of an exposure wavelength of an ihg mixed ray, and a light source that emits i-ray monochromatic light having a wavelength of 365 nm may also be used. Examples of the light source that can emit the i-ray monochromatic light having a wavelength of 365 nm can be, for example, an ultrahigh pressure mercury lamp.

((iii) Developing Step) In the developing step, the barrier layer and the uncured portion of the photosensitive layer are removed from the substrate. A resist pattern including a photocured portion obtained by photohardening the photosensitive layer is formed on a substrate by a developing step. When the barrier layer is water-soluble, after the barrier layer is removed by water washing, the uncured portion other than the photo-cured portion is removed by a developing solution, and when the barrier layer is soluble in the developer, the developer can be used. The uncured portion other than the photocured portion is removed together with the barrier layer. The development method can be exemplified by wet development.

In the case of wet development, development can be carried out by a known wet development method using a developer corresponding to the photosensitive resin composition. Examples of the wet development method include a immersion method, a liquid coating method, a high pressure spray method, a method using brushing, slap, scraping, shaking, etc., and the most suitable one is high pressure from the viewpoint of improving the analytical property. Spray method. These wet development methods may be developed by using one type alone or by combining two or more methods.

The developer is appropriately selected in accordance with the configuration of the photosensitive resin composition. For example, an alkaline aqueous solution and an organic solvent developing solution are mentioned.

From the viewpoint of safety, stability, and workability, an alkaline aqueous solution can be used as the developer. As the base of the alkaline aqueous solution, for example, an alkali hydroxide such as a hydroxide of lithium, sodium or potassium, a carbonate such as lithium, sodium, potassium or ammonium carbonate or a hydrogencarbonate, or a base such as potassium phosphate or sodium phosphate can be used. Metal phosphate, alkali metal pyrophosphate such as sodium pyrophosphate or 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.

As the alkaline aqueous solution for development, for example, a thin solution of 0.1% by mass to 5% by mass of sodium carbonate, a thin solution of 0.1% by mass to 5% by mass of potassium carbonate, and 0.1% by mass to 5% by mass of sodium hydroxide can be used. A thin solution, a thin solution of 0.1% by mass to 5% by mass of sodium tetraborate, or the like. Further, 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 may be adjusted in accordance with the developability of the photosensitive layer. Further, in the alkaline aqueous solution, for example, a surfactant, an antifoaming agent, a small amount of an organic solvent for promoting development, or the like may be mixed. In addition, examples of the organic solvent used in the alkaline aqueous solution include 3-acetone alcohol, acetone, ethyl acetate, alkoxyethanol having an alkoxy group having 1 to 4 carbon atoms, ethanol, and isopropanol. Butanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether and diethylene glycol monobutyl ether.

Examples of the organic solvent used in the organic solvent developing solution include 1,1,1-trichloroethane, N-methylpyrrolidone, N,N-dimethylformamide, and cyclohexanone. Methyl isobutyl ketone and γ-butyrolactone. In view of the prevention of the ignition, the organic solvent can be added as an organic solvent developer so as to be in the range of 1% by mass to 20% by mass.

(Other Steps) In the method for forming a resist pattern according to the present embodiment, after the uncured portion is removed in the developing step, heating at 60 ° C to 250 ° C or 0.2 J/cm ² may be included as needed. Exposure at an exposure amount of 10 J/cm ² , whereby the resist pattern is further hardened.

[Manufacturing Method of Printed Wiring Board] The method of manufacturing a printed wiring board according to the present embodiment includes forming an etching treatment or a plating treatment on a substrate on which a resist pattern is formed by the method of forming the resist pattern. The step of the conductor pattern may include other steps such as a resist pattern removing step as needed. The method for producing a printed wiring board according to the present embodiment can be suitably used for forming a conductor pattern by using a method of forming a resist pattern using the photosensitive element, and is more suitably applied to plating treatment. A method of forming a conductor pattern. Furthermore, the 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 a conductor layer of a substrate not covered with a resist is etched away to form a conductor pattern.

The etching treatment method is appropriately selected corresponding to the conductor layer to be removed. Examples of the etching liquid include a copper chloride solution, a ferric chloride solution, an alkali etching solution, and a hydrogen peroxide-based etching liquid. From the viewpoint of a good etching factor, a ferric chloride solution can be used.

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

The plating treatment may be an electrolytic plating treatment or an electroless plating treatment, and may be an electroless plating treatment. Examples of the electroless plating treatment include copper plating such as copper sulfate plating and copper pyrophosphate plating, solder plating such as high throw solder plating, and watts bath (nickel sulfate). - Nickel plating such as nickel chloride plating, nickel sulfonate plating, gold plating such as hard gold plating or soft gold plating.

After the etching treatment or the plating treatment, the resist pattern on the substrate is removed. The removal of the resist pattern can be performed, for example, by an aqueous solution which is more alkaline than the aqueous alkaline solution used in the development step. As the strongly alkaline aqueous solution, for example, a 1% by mass to 10% by mass aqueous sodium hydroxide solution, a 1% by mass to 10% by mass aqueous potassium hydroxide solution, or the like can be used. Among these, a 1% by mass to 5% by mass aqueous sodium hydroxide solution or an aqueous potassium hydroxide solution can also be used.

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

When the resist pattern is removed after the plating treatment is performed, the conductor layer covered with the resist is etched by an etching process to form a conductor pattern, whereby a desired printed wiring board can be manufactured. The method of the etching treatment at this time is appropriately selected in accordance with the conductor layer to be removed. For example, the etching solution can be applied.

The method for producing a printed wiring board of the present embodiment can be applied not only to the production of a single-layer printed wiring board but also to the production of a multilayer printed wiring board, and can also be applied to a printed wiring board having a small-diameter through hole or the like. Manufacturing.

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

In FIG. 2(a), a substrate (circuit formation substrate) on which the conductor layer 40 is formed on the 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 steps. In FIG. 2(c), by the exposure step, the barrier layer 20 is irradiated onto the photosensitive layer 30 to irradiate the actinic ray 80 of the image on which the photomask is projected, and the photocured portion is formed on the photosensitive layer 30. In FIG. 2(d), a region (including a barrier layer) other than the photo-cured portion formed by the exposure step is removed from the substrate by a developing step, whereby an anti-reflection portion is formed on the substrate. Etchant pattern 32. In FIG. 2(e), the 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), the resist pattern 32 as the photocured portion is peeled off by an aqueous solution of a strong alkali, and then the conductor layer 40 covered by the resist pattern 32 is removed by flash etching. The conductor pattern 70 including the plating layer 62 after the etching treatment and the conductor layer 42 after the etching treatment is formed. The material 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 can be integrated. Although the projection exposure method has been described with reference to FIG. 2, the resist pattern 32 may be formed by a mask exposure method or an LDI exposure method.

The preferred embodiments of the present disclosure have been described above, but the present disclosure is not limited to the above embodiments. [Examples]

Hereinafter, the present disclosure will be more specifically described based on examples, but the present disclosure is not limited to the following examples. In addition, "parts" and "%" are quality standards unless otherwise specified.

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

<Synthesis Example 1> 125 g of methacrylic acid as a polymerizable monomer, 25 g of methyl methacrylate, 125 g of benzyl methacrylate, and 225 g of styrene and 1.5 g of azobisisobutyronitrile were mixed. Prepare solution a.

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

On the other hand, a mixture of methyl cellosolve and toluene having a mass ratio of 3:2 is added to a flask equipped with a stirrer, a reflux condenser, a thermometer, a dropping funnel, and a nitrogen introduction tube (hereinafter, also referred to as "mixing" Liquid x") 400 g, stirred while blowing nitrogen gas, and heated to 80 °C.

The solution a was added dropwise to the mixed solution x in the flask over 4 hours and the dropping rate was fixed, and then stirred at 80 ° C for 2 hours. Then, the solution b was added dropwise to the solution in the flask over 10 minutes and the dropping rate was fixed, and the solution in the flask was stirred at 80 ° C for 3 hours. Further, the solution in the flask was heated to 90 ° C for 30 minutes, and the mixture was kept at 90 ° C for 2 hours, and then cooled to room temperature to obtain a solution of the binder polymer (A-1). The solution of the binder polymer (A-1) was prepared in such a manner that the non-volatile component (solid content) became 50% by mass after the addition of the mixed solution x.

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

-GPC condition - Pump: Hitachi L-6000 (manufactured by Hitachi, Ltd.) Pipe column: The following three total (column specifications: 10.7 mmf × 300 mm, all manufactured by Hitachi Chemical Co., Ltd.) Gelpack GL-R420 Gelpack GL-R430 Gelpack GL-R440 Dissolution: tetrahydrofuran sample concentration: 120 mg of a binder polymer having a solid content of 50% by mass was prepared and dissolved in 5 mL of tetrahydrofuran to prepare a sample. Measurement temperature: 25 ° C Flow rate: 2.05 mL / min Detector: Hitachi L-3300 type RI (manufactured by Hitachi, Ltd., product name)

<Preparation of Resin Composition for Barrier Layer Formation> Next, each component shown in the following Tables 1 to 3 is mixed in the amounts (unit: parts by mass) shown in the table, thereby obtaining a barrier layer. A resin composition for formation. Specifically, the water-soluble resin was slowly added to room temperature water and alcohol, and heated to 90 ° C after adding the entire amount. After reaching 90 ° C, the mixture was stirred for 1 hour and cooled to room temperature to obtain a resin composition for forming a barrier layer. In addition, the compounding amount other than the solvent in Tables 1 - 3 is a compounding quantity based on solid content.

<Preparation of Photosensitive Resin Composition> Next, each component shown in the following Tables 1 to 3 was mixed in the amounts (unit: parts by mass) shown in the table to obtain a photosensitive resin composition.

[Table 1]

[Table 2]

[table 3]

The details of each component in Tables 1 to 3 are as follows. (Water-soluble resin) *1: Polyvinyl alcohol PVA-205 (manufactured by Kuraray Co., Ltd., product name, degree of saponification = 87 mol%, average degree of polymerization = 500) *2: polyvinyl alcohol PVA- 203 (manufactured by Kuraray Co., Ltd., product name, degree of saponification = 87 mol%, average degree of polymerization = 300) *3: polyvinyl alcohol PVA-210 (manufactured by Kuraray Co., Ltd., product name, degree of saponification = 87 Molar %, average polymerization degree = 1000) *4: polyvinylpyrrolidone K-30 (manufactured by Nippon Shokubai Co., Ltd., product name)

(A) component: binder polymer *5: (A-1) (adhesive 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% by mass, methyl cellosolve / 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-(methacryloxy pentoxide) Oxy)phenyl)propane*7:FA-024M (manufactured by Hitachi Chemical Co., Ltd., product name) EOPO modified dimethacrylate*8:BPE-200 (manufactured by Shin-Nakamura Chemical Co., Ltd., product name) 2,2-bis(4-(methylpropenyloxydiethoxy)phenyl)propane*9:BP-2EM (manufactured by Kyoeisha Chemical Co., Ltd., product name) 2,2-double ( 4-(Methethyloxypolyethoxy)phenyl)propane*10:DPEA-12 (manufactured by Nippon Kayaku Co., Ltd.) Ethylene oxide modified dipentaerythritol hexaacrylate

(C) Component: Photopolymerization initiator *11: B-CIM (manufactured by Hodogaya Chemical Industry Co., Ltd., product name) 2,2'-bis(2-chlorophenyl)-4,4',5, 5'-tetraphenylbiimidazole

(D) Ingredients: Photosensitizer *12: EAB (manufactured by Hodogaya Chemical Industry Co., Ltd., product name) 4,4'-bis(diethylamino)benzophenone

(E) component: polymerization inhibitor *13: TBC (manufactured by Di Ai Sheng (DIC) Co., Ltd.) 4-Terbutyl catechol

[Examples 1 to 15 and Comparative Examples 1 to 7] <Preparation of photosensitive element> As the support film of the photosensitive element, PET films shown in Tables 1 to 3 were prepared.

The details of the PET film shown in Tables 1 to 3 are as follows. FB40: Biaxially oriented PET film with a three-layer structure with a lubricant layer on the surface (manufactured by Toray Industries, Inc., product name, thickness: 16 μm) A1517: Double-layer structure with a lubricant layer on one side Axial alignment PET film (manufactured by Toyobo Co., Ltd., product name, thickness: 16 μm) G2H: Biaxially oriented PET film with a single layer structure of lubricant (type of lubricant) (Diane DuPont Film Co., Ltd.) Company manufacturing, product name, thickness: 15.5 μm)

(Production of barrier layer) Then, the resin composition for forming a barrier layer was applied onto a PET film (support film) so as to have a uniform thickness, and dried by a hot air convection dryer at 95 ° C for 10 minutes. A barrier layer having a thickness of 5 μm after drying was formed. Further, when the density of the lubricant on both surfaces of the PET film is different, a barrier layer is formed on the side of the PET film having less lubricant, and in the case where the lubricant film is provided on one side of the PET film, the PET film is lubricated. A barrier layer is formed on the surface of the agent layer side.

(Preparation of photosensitive layer) Next, the photosensitive resin composition was applied to the barrier layer of the support film so that the thickness became uniform, and dried by a hot air convection dryer at 100 ° C for 10 minutes to form a dried A photosensitive layer having a thickness of 10 μm.

Next, a polyethylene protective film (protective layer) (manufactured by Tamapoly Co., Ltd., product name "NF-15") was attached to the photosensitive layer to obtain a PET film (supported in this order). Photosensitive elements of the film), the barrier layer, the photosensitive layer, and the protective layer.

<Measurement of Residual Alcohol Amount> The amount of residual alcohol in the barrier layer formed was measured by gas chromatography mass spectrometry. The measurement conditions of the gas chromatography mass spectrometry are as follows. In addition, the item "the amount of residual alcohol in the barrier layer" in Table 1, Table 2, and Table 3 indicates the amount of the alcohol having 3 or more carbon atoms. Furthermore, "<1.0" means more than 0 and less than 1.0. (Measurement conditions for gas chromatography mass spectrometry) Measurement apparatus: GC/MS QP-2010 (manufactured by Shimadzu Corporation, product name) Column: HP-5MS (manufactured by Agilent Technologies, Inc., product name) Oven Temperature (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: 氦, 1.0 mL / min Interface temperature: 280 ° C Ion source temperature: 250 ° C Sample injection amount: 0.1 mL

<Preparation of a laminated body> A copper-clad laminate (a substrate, manufactured by Hitachi Chemical Co., Ltd., product name "MCL-E-67"), which is an epoxy glass material having a copper foil having a thickness of 12 μm laminated on both sides. The copper surface is subjected to an acid treatment and washed with water, and then dried by a stream of air. The copper clad laminate was heated to 80 ° C, and the protective layer was peeled off, and the photosensitive members were respectively pressure-bonded to the copper clad laminate so that the photosensitive layer contacted the copper surface. The crimping was carried out using a hot roll at 110 ° C at a roll speed of 1.0 m/min under a pressure of 0.40 MPa. In this manner, a laminate in which a substrate, a photosensitive layer, a barrier layer, and a support film are laminated in this order is obtained. These laminates were used as test pieces in the test shown below. As a laminating machine, HLM-3000 (manufactured by Taisei-laminator Co., Ltd.) was used.

<Evaluation of Support Film Peelability> The test piece was allowed to stand in an environment of 23 ° C and a humidity of 50% for 1 hour. Thereafter, the PET film as a support film was peeled off from the test piece under the conditions of a peeling angle of 135 degrees and a peeling speed of 500 mm/sec, and the peeling property of the support film was evaluated by the following evaluation criteria. The results of the evaluation are shown in Tables 4 to 6 below. A: Only the PET film as a support film was easily peeled off. B: A barrier layer is attached to a part of the peeled support film, or the support film cannot be peeled off.

<Evaluation of the resolution degree> In order to investigate the resolution, the support film was peeled off from the test piece, and a Hitachi 41-stage trapezoidal plate was placed on the barrier layer of the test piece, and the line width as a pattern for the evaluation of the resolution was placed. / Glass mask with a width of z/z (z = 2 to 20 (changed at intervals of 1 μm)) (unit: μm), using a projection exposure machine with a high-pressure mercury lamp with a wavelength of 365 nm (oxtail ( Manufactured by Ushio Electric Co., Ltd., product name UX-2240SM-XJ01), the number of remaining stages after development of the Hitachi 41-stage trapezoidal plate is changed to eight-stage irradiation energy, and the photosensitive layer is exposed through the barrier layer. After the exposure, the test piece was washed with water at room temperature, and the barrier layer was removed. Next, the photosensitive layer was spray-developed using a 1% by mass aqueous sodium carbonate solution at 30 ° C for twice the shortest development time, and the unexposed portion was removed. Here, the shortest development time is obtained by measuring the time during which the unexposed portion is completely removed by the development processing. The minimum value (unit: μm) of the spatial width between the line portions (exposure portions) in which the unexposed portions are completely removed by the development process is used as an index for the evaluation of the resolution. Furthermore, the smaller the value, the better the resolution. The results are shown in Tables 4 to 6 below.

<Evaluation of Resist Pattern Shape> The substrate evaluated in the evaluation of the resolution was observed by a scanning electron microscope (SEM) to have a line width/space width of 10/10 (unit: μm). The cross-sectional shape of the resist pattern. The cross-sectional shape of the resist pattern is shown in Tables 4 to 6 below as evaluation of the shape of the resist pattern.

In the photosensitive elements of Comparative Examples 1 to 7, the peeling property of the support film was deteriorated, and the resist pattern could not be formed. Therefore, the resolution and the shape of the resist pattern could not be evaluated.

<Evaluation of Transparency of Barrier Layer Solution> As the reference sample, the alcohols in the resin composition for forming a barrier layer of Examples 1 to 15 and Comparative Examples 1 to 7 were not used. The composition was prepared in the same manner as the resin composition for forming a barrier layer of Examples 1 to 15 and Comparative Examples 1 to 7. Then, the resin composition for forming a barrier layer (hereinafter also referred to as "barrier layer solution") of Examples 1 to 15 and Comparative Examples 1 to 7 was observed by visual observation and a reference sample. Transparency was evaluated as follows. The evaluation results are shown in Tables 4 to 6 below. A: The turbidity of the barrier layer solution was equal to or less than the reference sample. B: A large amount of turbidity was generated in the barrier layer solution as compared with the reference sample.

<Evaluation of the transparency of the barrier layer> The resin composition for forming a barrier layer of Examples 1 to 15 and Comparative Examples 1 to 7 was applied onto a support film so that the thickness became uniform. The hot air convection dryer at 95 ° C was dried for 10 minutes to form a barrier layer having a thickness of 5 μm after drying. As the reference sample, the alcohols in the resin composition for forming a barrier layer of Examples 1 to 15 and Comparative Examples 1 to 7 were not used, and Examples 1 to 1 were used. 15 and the composition prepared in the same manner as the resin composition for forming a barrier layer of Comparative Example 1 to Comparative Example 7 to form a barrier layer. Thereafter, the appearance of the barrier layer was observed by visual observation and evaluated as follows. The evaluation results are shown in Tables 4 to 6 below. A: The degree of turbidity and pore formation in the barrier layer was equal to or less than that of the reference sample. B: A large amount of turbidity or pores were generated in a part or the whole of the barrier layer as compared with the reference sample.

[Table 4]

[table 5]

[Table 6]

In the case of using the high-resolution projection exposure machine, when the exposure was performed under the condition that the number of remaining stages became eight, the peeling property of the support film and the barrier layer was high in the first to the fifteenth embodiments. Here, in Comparative Example 1 to Comparative Example 7, the peeling property of the support film and the barrier layer was low. [Industrial availability]

As described above, according to the present disclosure, it is possible to provide a photosensitive element, a resin composition for forming a barrier layer, and a resist pattern which can improve the peeling property of the barrier layer and the support film without using a release accelerator. A forming method and a method of manufacturing a printed wiring board.

1‧‧‧Photosensitive components
2‧‧‧Support film
3, 20‧‧‧ barrier layer
4, 30‧‧‧Photosensitive layer
5‧‧‧Protective layer
32‧‧‧resist pattern
40‧‧‧Conductor layer
42‧‧‧The etched conductor layer
50‧‧‧Insulation
60‧‧‧ plating layer
62‧‧‧etched plating layer
70‧‧‧ conductor pattern
80‧‧‧Acradiation rays

Fig. 1 is a schematic cross-sectional view showing an embodiment of a photosensitive element of the present disclosure. 2(a) to 2(f) are diagrams schematically showing an example of a manufacturing procedure of a printed wiring board by a semi-additive method.

1‧‧‧Photosensitive components

2‧‧‧Support film

3‧‧‧Barrier layer

4‧‧‧Photosensitive layer

5‧‧‧Protective layer

Claims (13)

A photosensitive element comprising, in order, a support film, a barrier layer, and a photosensitive layer, wherein the barrier layer contains a water-soluble resin and an alcohol having 3 or more carbon atoms. The photosensitive element according to claim 1, wherein the alcohol having 3 or more carbon atoms contains a compound selected from the following chemical formulas (1) to (3) and the following general formula (4) At least one of the groups consisting of the compounds represented, In the formula (4), R ¹¹ represents an alkyl group, R ¹² represents an alkylene group, and the sum of carbon atoms of the group of R ^{11 and} the group of R ¹² is 3 or more. The photosensitive element according to claim 1 or 2, wherein the alcohol having 3 or more carbon atoms has a solubility in water of 20 ° C of 300 mL/water of 100 mL or more. The photosensitive element according to any one of claims 1 to 3, wherein the carbon number of 3 or more in the barrier layer is based on the total amount of the barrier layer The content of the class is more than 0% by mass and is 2.0% by mass or less. The photosensitive element according to any one of claims 1 to 4, wherein the water-soluble resin contains polyvinyl alcohol. The photosensitive element according to any one of claims 1 to 5, wherein the support film is a polyester film. A resin composition for forming a barrier layer comprising a water-soluble resin, an alcohol having 3 or more carbon atoms, and water. The resin composition for forming a barrier layer according to claim 7, wherein the alcohol having 3 or more carbon atoms contains a compound selected from the following chemical formulas (1) to (3) and At least one of the group consisting of the compounds represented by the formula (4), In the formula (4), R ¹¹ represents an alkyl group, R ¹² represents an alkylene group, and the sum of carbon atoms of the group of R ^{11 and} the group of R ¹² is 3 or more. The resin composition for forming a barrier layer according to the above-mentioned item, wherein the alcohol having 3 or more carbon atoms has a solubility in water of 20 ° C of 300 mL/water of 100 mL or more. The resin composition for forming a barrier layer according to any one of the items of the present invention, wherein the content of the alcohol having 3 or more carbon atoms is 100 parts by mass based on 500 parts by mass of water. ~500 parts by mass. The resin composition for forming a barrier layer according to any one of claims 7 to 10, wherein the water-soluble resin contains polyvinyl alcohol. A method of forming a resist pattern, comprising: using the photosensitive element according to any one of claims 1 to 6, wherein a photosensitive layer and a resist are disposed on the substrate in order from the substrate side a barrier layer and a step of supporting the film; removing the support film, exposing the photosensitive layer by using the barrier layer by actinic rays; and disposing the barrier layer and the photosensitive layer The step of removing the hardened portion from the substrate. A method of manufacturing a printed wiring board, comprising: performing an etching treatment or a plating treatment on a substrate on which a resist pattern is formed by a method for forming a resist pattern according to claim 12; The step of the conductor pattern.