KR20180035827A - Photosensitive element, resin composition for forming barrier layer, method for forming resist pattern, and method for producing printed wiring board - Google Patents

Abstract

There is provided a photosensitive element comprising a support film, a barrier layer and a photosensitive layer in this order, with the object of providing a photosensitive element capable of improving the peeling property between the barrier layer and the support film without using a release promoter, Wherein the barrier layer contains a water-soluble resin and an alcohol having 3 or more carbon atoms.

Description

TECHNICAL FIELD [0001] The present invention relates to a photosensitive element, a resin composition for forming a barrier layer, a method of forming a resistor pattern, and a method of manufacturing a printed wiring board. BACKGROUND ART < RTI ID = 0.0 >

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

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

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

Next, a mask film or the like is used, and a desired region of the photosensitive layer is exposed through the support film to generate radicals. The resulting radical contributes to the crosslinking reaction (photocuring reaction) of the photopolymerizable compound through several reaction paths. Then, after the support film is peeled off, the unhardened portion of the photosensitive layer is dissolved or dispersed in a developing solution to form a resistor pattern. Next, a resist pattern is used as a resistor, an etching process or a plating process is performed to form a conductor pattern, and finally the photocurable portion (resist pattern) of the photosensitive layer is peeled off (removed).

However, recently, a method of forming an excellent resist pattern by peeling the support film before exposure and exposing the photosensitive layer has been studied. However, when the photosensitive layer is exposed after the support film is peeled, the generated radicals are brought into contact with oxygen in the air, so that the radicals are rapidly stabilized (inactivated), and the photocuring reaction of the photopolymerizable compound hardly progresses . Therefore, in this method, for the purpose of alleviating the influence of oxygen incorporation when the support film is peeled and exposed, a photosensitive element having a barrier layer (intermediate layer) having gas barrier property between the support film and the photosensitive layer (See, for example, Patent Documents 1 to 3).

Patent Document 1: Japanese Patent No. 5483734 Patent Document 2: JP-A-2013-24913 Patent Document 3: Japanese Patent No. 5551255

In the photosensitive element having the barrier layer containing the water-soluble resin as described in the above Patent Documents 1 to 3, since the affinity between the water-soluble resin and the support film is high, the adhesion between the barrier layer and the support film is strong have. In this case, when the support film is peeled off from the barrier layer of the photosensitive element, it is difficult to separate the support film, and the barrier layer or the photosensitive layer may be defective.

Up to now, the adhesion property between the barrier layer and the support film has been lowered by adding a release promoting agent such as silicon or a fluorine surfactant to the resin composition for forming a barrier layer containing a water-soluble resin to peel off the barrier layer from the support film It is proposed to improve the performance.

However, it has been found that there is a problem that fogging tends to occur in the formed barrier layer by adding a detachment promoter such as a surfactant. Further, since the peel-promoting agent such as a surfactant is present at the interface between the barrier layer and the supporting film, the interfacial composition may change or the adhesiveness between the barrier layer and the supporting film may change at a long- (Peeling property between the barrier layer and the support film) is difficult to maintain.

The present disclosure has been made in view of the above problems of the prior art, and it is an object of the present invention to provide a photosensitive element capable of improving the releasability between the barrier layer and the support film without using a release promoting agent, a resin composition for forming a barrier layer, And a method for producing a printed wiring board.

In order to attain the above object, the present disclosure provides a photosensitive element comprising a support film, a barrier layer, and a photosensitive layer in this order, wherein the barrier layer comprises a photosensitive element containing a water-soluble resin and an alcohol having 3 or more carbon atoms, Lt; / RTI >

The photosensitive element of the present disclosure contains alcohols having 3 or more carbon atoms in the barrier layer, so that the releasability between the barrier layer and the support film can be improved without using a release promoter. According to such a 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. In addition, since the peeling property between the barrier layer and the support film can be improved without using the peeling promoter, the occurrence of the fogging of the barrier layer due to the presence of the peeling promoter and the change in the peelability of the support film over time can be suppressed. Therefore, by using the photosensitive element of the present disclosure, a resist pattern excellent in resolution and resist pattern shape can be formed.

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

[In the general formula (4), R ¹¹ represents an alkyl group, R ¹² represents an alkylene group, and the sum of the carbon number of the group of R ^{11 and} the group of R ¹² is 3 or more.]

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

In the photosensitive element of the present disclosure, the content of the alcohol having 3 or more carbon atoms in the barrier layer may be 0 mass% or more and 2.0 mass% or less based on the total amount of the barrier layers. With such a photosensitive element, it is possible to suppress diffusion of alcohols in a later step.

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

In the photosensitive element of the present disclosure, the support film may be a polyester film. According to such a photosensitive element, it is possible to improve the mechanical strength and resistance to heat of the support film, and to suppress defects such as wrinkles of the barrier layer which are generated when the barrier layer is formed on the support film, Can be improved.

The present disclosure also provides a resin composition for forming a barrier layer, which comprises a water-soluble resin, an alcohol having 3 or more carbon atoms, and water. According to such a resin composition for forming a barrier layer, a barrier layer excellent in peelability from a support film can be formed without using a release promoter.

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

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

In the barrier layer forming resin composition of the present disclosure, the content of the alcohol having 3 or more carbon atoms may be 100 to 500 parts by mass based on 500 parts by mass of water. According to such a resin composition for forming a barrier layer, it is possible to form a barrier layer excellent in peelability from a support film and to improve the solubility of the water-soluble resin, so that the barrier layer can be easily formed.

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

The present disclosure also relates to a method of manufacturing a semiconductor device comprising the steps of disposing a photosensitive layer, a barrier layer and a supporting film in this order on a substrate from the side of the substrate using the photosensitive element of the present disclosure, A step of exposing the photosensitive layer with an actinic ray through a substrate, and a step of removing the unlayered portion of the barrier layer and the photosensitive layer from the substrate. According to such a method of forming a resist pattern, since a resist pattern is formed by using the photosensitive element of the present disclosure, a resist pattern excellent in resolution and resist pattern shape can be formed.

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

According to the present disclosure, it is possible to provide a photosensitive element, a resin composition for forming a barrier layer, a method of forming a resistor pattern, and a method of manufacturing a printed wiring board, which can improve the peeling property between the barrier layer and the support film without using a release promoter have.

BRIEF DESCRIPTION OF DRAWINGS FIG. 1 is a schematic cross-sectional view showing an embodiment of a photosensitive element of the present disclosure;
2 is a diagram schematically showing an example of a manufacturing process of a printed wiring board by a semi-insulating method.

Hereinafter, preferred embodiments of the present disclosure will be described in detail with reference to the drawings as necessary. In the following embodiments, elements (including element steps and the like) are not necessarily essential except when specifically stated and when it can be reasonably considered to be essential in principle. It should be understood that the same is true of the numerical value and the range, and is not to be construed as unduly limiting the present disclosure.

In the present specification, (meth) acrylic acid means at least one of acrylic acid and corresponding methacrylic acid. The same is true for other similar expressions such as (meth) acrylate.

In the present specification, the term " process "is included in this term when not only an independent process but also an intended action of the process can be clearly distinguished from another process.

In the present specification, the numerical range indicated by using "~ " indicates a range including the numerical values before and after" ~ "as the minimum value and the maximum value, respectively. In the numerical range described stepwise in this specification, the upper limit value or the lower limit value of the numerical range of any step may be replaced with the upper limit value or the lower limit value of the numerical range of the other steps. In the numerical range described in the present specification, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the embodiment. In the present specification, the term "layer " includes a structure formed in a part in addition to a structure formed on the entire surface when viewed in a plan view.

[Photosensitive element]

1, the photosensitive element 1 of the present embodiment includes a support film 2, a barrier layer 3, and a photosensitive layer 4 in this order, and the protective layer 5, May be further provided. The barrier layer contains a water-soluble resin and an alcohol having 3 or more carbon atoms. By using the photosensitive element of this embodiment, the peeling property between the barrier layer and the support film can be improved. In addition, the photosensitive element of the present embodiment can suppress the layer separation of the barrier layer, and thus is excellent in practical use. Hereinafter, each layer in the photosensitive element according to this embodiment will be described in detail.

<Support film>

The support film of the present embodiment can be used without particular limitation. For example, polyester films such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT) and polyethylene-2,6-naphthalate (PEN), and polyolefin films such as polypropylene and polyethylene have. Among them, a polyester film may be used. The use of a polyester film as the support film tends to improve the mechanical strength and resistance to heat of the support film. By using a polyester film, it is possible to suppress defects such as wrinkles of the barrier layer which are generated when the barrier layer is formed on the support film, and the workability tends to be improved. Further, from the viewpoint of suppressing the occurrence of a minute omission of the resistor pattern, a polyester film containing particles (e.g., lubricant) may be used. When a polyester film containing particles (such as lubricant) is used, a barrier layer may be formed on the side having particles (such as lubricant). Examples of such a polyester film include a polyester film kneaded with particles (lubricant or the like), a polyester film formed with a layer containing particles (lubricant or the like) on both sides, ) May be used instead of the polyester film. The support film may be a single layer or a multilayer.

Examples of the method of adding particles such as a lubricant to the support film include a method of mixing particles (lubricant or the like) into a support film, a method of coating a layer containing particles (lubricant or the like) , A spray coat, a curtain flow coat, a dip coat, a slit die coat, and the like.

The haze 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 is 0.01% or more, the support film itself tends to be easily produced. When the haze is 5.0% or less, the foreign matter in the photosensitive layer tends to be easily detected when the photosensitive layer of the photosensitive element is formed . Here, "haze" means cloudiness. The haze in this disclosure refers to a value measured using a commercially available haze meter (turbidimeter) in accordance with the method defined in JIS K 7105. The haze can be measured with a commercially available turbidimeter such as NDH-5000 (trade name, manufactured by Nippon Denshoku Kogyo K.K.).

Further, the support film can be used as a support film of a photosensitive element among commercially available general industrial films, and may be appropriately processed and used. Specifically, for example, a PET film "FB-40" (product name, manufactured by Toray Industries, Inc.), "A4100", "A1517" (product name, manufactured by Toyobo Sekiki K.K.), "G2H" Manufactured by Jin-DuPont Film &amp; Chemicals Co., Ltd.).

The support film has a thickness of 1 to 200 m, 1 to 100 m, 1 to 60 m, 5 to 60 m, 10 to 60 m, 10 to 50 m, 10 to 40 m, 10 to 30 m, 25 mu m. When the thickness of the support film is 1 占 퐉 or more, tearing of the support film tends to be suppressed when the support film is peeled off. Further, when the thickness of the support film is 200 占 퐉 or less, economic benefits tends to be obtained.

<Barrier Layer>

The photosensitive element of this embodiment has a barrier layer between the support film and the photosensitive layer. The barrier layer contains a water-soluble resin and an alcohol having 3 or more carbon atoms. According to the photosensitive element of this embodiment, even when the barrier layer does not contain a release promoting agent, the support film can be smoothly peeled off from the barrier layer. Therefore, when the photosensitive layer is exposed through the barrier layer after peeling off the support film, Deterioration of the resolution of the formed resistor pattern can be suppressed. The barrier layer may be a layer formed by using the resin composition for forming a barrier layer of the present embodiment to be described later. The resin composition for forming a barrier layer in the present embodiment may contain a water-soluble resin, an alcohol having 3 or more carbon atoms, . The barrier layer may have water solubility or solubility in a developer. From the viewpoint of further improving the gas barrier property by the barrier layer, the adhesion force between the support film and the barrier layer may be smaller than the adhesion force between the barrier layer and the photosensitive layer. That is, when the support film is peeled from the photosensitive element, unintentional peeling of the barrier layer and the photosensitive layer may be suppressed.

(Water-soluble resin)

Here, "water-soluble resin" means a resin having a solubility of 5 g or less in 100 mL of hexane at 25 ° C. This solubility can be calculated by mixing hexane at 25 占 폚 and a water-soluble resin which has been dried and examining the presence or absence of clouding. Specifically, a sample 1 obtained by adding a mixed solution of a water-soluble resin A (g) and hexane (100 mL-A) after drying to a colorless transparent glass container with a polishing-fitting glass lid and 100 mL of hexane alone were placed, 2, respectively. Subsequently, the sample in the glass container is sufficiently shaken, and it is confirmed that the bubble disappears. Immediately after confirmation, the liquid state of the sample 1 and the liquid state of the sample 2 are compared with each other in parallel under the light of diffuse daylight (light) or light equivalent thereto. The sample 1 and the sample 2 were compared and the addition amount A (g) when the sample 1 was observed to be less cloudy or when the suspension of the solid content began to be observed was added to 100 mL of the water- The solubility is determined.

Examples of the water-soluble resin include polyvinyl alcohol, polyvinyl pyrrolidone, and water-soluble polyimides. The water-soluble resin may contain polyvinyl alcohol from the viewpoint of further improving the gas barrier property of the barrier layer and further suppressing the deactivation of the radicals generated by the active rays used for exposure. The polyvinyl alcohol can be obtained, for example, by saponifying polyvinyl acetate which can be 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. The upper limit of the saponification degree is 100 mol%. By including polyvinyl alcohol having a saponification degree of 50 mol% or more, the gas barrier property of the barrier layer is further improved, and the resolution of the formed resistor pattern can be further improved. In the present specification, the "degree of saponification" refers to a value measured in accordance with JIS K 6726 (1994) (test method of polyvinyl alcohol) specified by Japanese Industrial Standards.

The above-mentioned polyvinyl alcohol may be used in combination of two or more different types such as degree of saponification, viscosity, degree of polymerization, and denatured species. The average degree of polymerization of polyvinyl alcohol may be 300 to 5000, 300 to 3500, or 300 to 2000. The water-soluble resins may be used singly or in combination of two or more. The water-soluble resin may include, for example, polyvinyl alcohol and polyvinyl pyrrolidone. In this case, the mass ratio (PVA: PVP) of polyvinyl alcohol and polyvinylpyrrolidone may be 40:60 to 90:10, 50:50 to 90:10, or 60:40 to 90:10.

The content of the water-soluble resin in the barrier layer-forming resin composition of the present embodiment is preferably from 50 to 300 parts by mass, from 60 to 250 parts by mass, from 70 to 200 parts by mass based on 500 parts by mass of water , 80 to 150 parts by mass, or 80 to 125 parts by mass.

(Alcohols having 3 or more carbon atoms)

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

In the general formula (4), R ¹¹ represents an alkyl group and R ¹² represents an alkylene group. The sum of the carbon numbers of the groups R ¹¹ and R ¹² is 3 or more. The sum of the carbon numbers of the groups R ¹¹ and R ¹² may be 10 or less, 8 or less, 7 or less, 6 or less, or 5 or less from the viewpoint of improving affinity with water. The alkyl group represented by R ^{11 may} be an alkyl group having 1 to 4 carbon atoms, and the alkylene group represented by R ¹² may be an alkylene group having 1 to 3 carbon atoms. The alkyl group represented by R &lt; ¹¹ &gt; and the alkylene group represented by R &lt; ¹² &gt; may each have a substituent or may not have a substituent. If it has a substituent, the carbon number of a group having a carbon number of R ¹² and R ¹¹ of the group is assumed to contain a number of carbon atoms of each substituent. The alcohols having 3 or more carbon atoms represented by the general formula (4) may be 2-butoxyethanol or 1-methoxy-2-propanol.

The above-mentioned alcohols having 3 or more carbon atoms may be used singly or in combination of two or more kinds. The solubility of alcohols having 3 or more carbon atoms in water at 20 占 폚 is preferably 300 ml / 100 ml or more, 500 ml / 100 ml or more, or 1000 ml / 100 ml or more, in view of being able to further suppress the layer separation of the barrier layer .

The "solubility in water at 20 캜 for alcohols having 3 or more carbon atoms" in the present specification can be calculated by mixing the alcohol with water at 20 캜 and examining the presence or absence of clouding. Specifically, a sample 3 obtained by adding a mixed solution of the alcohol AmL and water (100-A) mL to a colorless transparent glass container with a polishing-fitting glass lid and a sample 4 obtained by adding only water (100 mL) Prepare. Subsequently, the sample 3 and the sample 4 in the glass container were sufficiently shaken, respectively, and then it was confirmed that the bubbles disappeared. Immediately after the confirmation, the liquid state in the specimen 3 and the liquid state in the specimen 4 are compared with each other, with the diffusing main light or light equal to the diffusing main light. The sample 3 and the sample 4 are compared, and the addition amount AmL of the alcohol when the sample 3 is observed more blurred is defined as the solubility of the alcohol in water at 20 ° C.

The content of the alcohol having 3 or more carbon atoms in the barrier layer-forming resin composition of the present embodiment is 100 to 500 parts by mass, 110 to 480 parts by mass, 120 to 460 parts by mass, 125 to 440 parts by mass Mass part, 125 to 420 mass parts, or 125 to 400 mass parts. When the content is 100 parts by mass or more, the releasability between the barrier layer to be formed and the support film tends to be improved, and when it is 500 parts by mass or less, the solubility of the water-soluble resin is improved and the barrier layer tends to be easily formed have.

The content of the alcohols having 3 or more carbon atoms in the barrier layer of the present embodiment is preferably more than 0 mass% and 2.0 mass% or less based on the total amount of the barrier layers (the total solid content of the barrier layer forming resin composition forming the barrier layer) 0.001 to 2.0% by mass or 0.005 to 1.0% by mass. When the content is 2.0 mass% or less, the diffusion of alcohols in subsequent steps tends to be suppressed. When the content is more than 0 mass%, the releasability between the barrier layer and the support film tends to be improved, When the content is 0.001% by mass or more, the releasability between the barrier layer and the support film tends to be further improved.

The resin composition for forming a barrier layer in this embodiment may contain an alcohol having less than 3 carbon atoms. When the alcohol contains less than 3 carbon atoms, the content thereof may be 125 to 375 parts by mass or 150 to 325 parts by mass based on 500 parts by mass of water. When the content is more than 125 parts by mass, the solubility of the water-soluble resin is improved and the barrier layer tends to be easily formed. When the content is less than 375 parts by mass, there is a tendency that the releasability of the formed barrier layer and the support film is improved . The content of the alcohol having less than 3 carbon atoms in the barrier layer of the present embodiment is preferably 0.1 to 10 parts by mass based on the total amount of the alcohols in the barrier layer from the viewpoint of improving the releasability between the barrier layer and the support film, To 10 mass%, or 0.1 to 10 mass parts relative to 100 mass parts of the total amount of the alcohols having 3 or more carbon atoms in the barrier layer.

The resin composition for forming a barrier layer of the present embodiment may contain known additives such as plasticizers and surfactants within a range not hindering the effect of the present disclosure. In addition, a release promoting agent may be contained within a range not hindering the effect of the present disclosure.

As the plasticizer, for example, a polyhydric alcohol compound may be contained from the viewpoint of improving stretchability. (Poly) alkyl (meth) acrylates such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, and polypropylene glycol, and glycerin derivatives such as glycerin, diglycerin and triglycerin; And the like, and the like. These plasticizers may be used singly 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 a resin composition for forming a barrier layer of the present embodiment on 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 탆 or less, 10 탆 or less, 8 탆 or less, 7 탆 or 6 탆 or less from the viewpoint of ease of removal of the barrier layer. The thickness of the barrier layer may be 1.0 占 퐉 or more, 1.5 占 퐉 or more, 2 占 퐉 or more, 3 占 퐉 or more, or 4 占 퐉 or more from the viewpoints of ease of formation of the barrier layer and resolution.

Further, the barrier layer in this embodiment may have photosensitivity, but the photosensitivity thereof is lower than that of the photosensitive layer. Further, the barrier layer does not need to be photosensitive. When the barrier layer does not have photosensitivity, the photosensitivity of the photosensitive layer tends to be more stable. The term "photosensitive" means, for example, that when a photosensitive layer is exposed and, if necessary, a heat treatment is performed after exposure, and then a photosensitive layer is developed using a developer for removing the uncured portions of the photosensitive layer, Which is capable of forming a pattern.

<Photosensitive Layer>

The photosensitive layer of the present embodiment is a layer formed by using a photosensitive resin composition described later. The photosensitive resin composition may be used in accordance with a desired purpose if it is a material whose properties are changed (for example, photo-cured) by light irradiation, and may be a negative type or a positive type. The photosensitive resin composition may contain (A) a binder polymer, (B) a photopolymerizable compound and (C) a photopolymerization initiator. If necessary, (D) a photosensitizer, (E) a polymerization inhibitor or other components may be contained. Hereinafter, each component used in the photosensitive resin composition in the present embodiment will be described in more detail.

((A) binder polymer)

(A) a binder polymer (hereinafter also referred to as "component (A)") can be produced, for example, by radical polymerization of a polymerizable monomer. Examples of the polymerizable monomer include polymerizable styrene derivatives substituted in an? -Position or aromatic ring such as styrene, vinyltoluene and? -Methylstyrene, acrylamides such as diacetone acrylamide, acrylonitrile, Ethyl (meth) acrylate, benzyl (meth) acrylate such as benzyl methacrylate, tetrahydrofurfuryl (meth) acrylate, dimethylamino (meth) acrylate Ethyl ester, diethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (Meth) acrylic acid,? -Styryl (meth) acrylic acid, maleic acid, maleic anhydride, maleic anhydride, Resan there may be mentioned monomethyl, monoethyl maleate, monoisopropyl maleate, maleic acid monoester, fumaric acid, cinnamic acid, α- cyano didanosine acid, itaconic acid, crotonic acid and propionic olsan of. These may be used singly or in combination of two or more.

Among them, (meth) acrylic acid alkyl ester may be included in view of improvement of plasticity. Examples of the (meth) acrylic acid alkyl ester include compounds represented by the following general formula (II) and compounds in which the alkyl group of these compounds is substituted with a hydroxyl group, an epoxy group, a halogen group and the like.

H ₂ C = C (R ⁶ ) -COOR ⁷ (II)

In the general formula (II), R ⁶ represents a hydrogen atom or a methyl group, and R ⁷ represents an alkyl group having 1 to 12 carbon atoms. Examples of the 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 nonyl group, a decyl group, And structural isomers of these groups.

Examples of the (meth) acrylic acid alkyl ester represented by the general formula (II) include (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid propyl ester, (meth) (Meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl , Undecyl (meth) acrylate, and dodecyl (meth) acrylate. These may be used singly or in combination of two or more.

The component (A) may contain a carboxyl group from the viewpoint of alkali developability. The component (A) containing a carboxyl group can be produced, for example, by radical polymerization of a polymerizable monomer having a carboxyl group and other polymerizable monomers. The polymerizable monomer having a carboxyl group may be (meth) acrylic acid or methacrylic acid. The acid value of the component (A) containing a carboxyl group may be 50 to 250 mgKOH / g, 50 to 200 mgKOH / g, or 100 to 200 mgKOH / g.

The content of the carboxyl group of the component (A) (the blend ratio of the polymerizable monomer having a carboxyl group to the total amount of the polymerizable monomers used in the binder polymer) is preferably from 12 to 50% by mass, 15 to 35 mass%, 15 to 30 mass%, or 20 to 30 mass%. When the content of the carboxyl group is 12 mass% or more, the alkali developability tends to be improved. When the content of the carboxyl group is 50 mass% or less, the alkali resistance tends to be excellent.

The content of the structural unit derived from the polymerizable monomer having a carboxyl group in the component (A) correlates with the compounding ratio of the polymerizable monomer having the carboxyl group, so that the content of the structural unit derived from the polymerizable monomer having 12 to 50 mass% , 15 to 35 mass%, 15 to 30 mass%, or 20 to 30 mass%.

Further, from the standpoint of adhesion and chemical resistance, the component (A) may use styrene or a styrene derivative as a polymerizable monomer. When the styrene or styrene derivative is a polymerizable monomer, the content thereof (the blending ratio of styrene or styrene derivative to the total amount of the polymerizable monomers used in the component (A)), from the viewpoint of further improving the adhesiveness and chemical resistance, 10 to 60 mass%, 15 to 50 mass%, 30 to 50 mass%, 35 to 50 mass%, or 40 to 50 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, it is possible to suppress the increase in the amount of peeled off at the time of development, and the prolonged time required for peeling tends to be suppressed.

The content of the structural unit derived from the styrene or the styrene derivative in the component (A) is in the range of 10 to 60% by mass, 15 to 50% by mass, 30 to 50% by mass, , 35 to 50 mass%, or 40 to 50 mass%.

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

These binder polymers may be used singly or in combination of two or more. As the component (A) when two or more kinds are used in combination, for example, two or more kinds of binder polymers comprising different polymerizable monomers, two or more different types of binder polymers with different weight average molecular weights, A binder polymer of at least two kinds can be mentioned.

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

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

The content of the component (A) is preferably 30 to 80 parts by mass, 40 to 75 parts by mass, 50 to 70 parts by mass, or 50 to 70 parts by mass, based on 100 parts by mass of the total solid content of the component (A) To 60 parts by mass. When the content of the component (A) is within this range, the film property of the photosensitive resin composition and the strength of the light-cured portion become better.

((B) photopolymerizable compound)

The photosensitive resin composition according to this embodiment may contain a photopolymerizable compound (B) (hereinafter also referred to as "component (B)"). The component (B) can be used as a photopolymerizable compound or a photo-crosslinkable compound without particular limitation, and for example, a compound having at least one ethylenic unsaturated bond in the molecule can be used.

Examples of the component (B) include a compound obtained by reacting a polyhydric alcohol with an alpha, beta -unsaturated carboxylic acid, a bisphenol-type (meth) acrylate compound such as a bisphenol A (meth) acrylate compound, (Meth) acrylate compounds, nonylphenoxyethylene oxy (meth) acrylate, nonylphenoxy octaethylene oxy (meth) acrylate, gamma -chloro-beta-hydroxypropyl- (Meth) acryloyloxyethyl-o-phthalate,? -Hydroxypropyl-? '- (meth) acryloyloxyethyl-o -Phthalate, and (meth) acrylic acid alkyl ester. These may be used singly or in combination of two or more.

Among the above, the component (B) may contain a bisphenol-type (meth) acrylate compound from the viewpoint of improving the resolution, adhesiveness and suppressing the occurrence of the resistor hem. The bisphenol-type (meth) acrylate compound may be a compound represented by the following general formula (III).

In the general formula (III), R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or a methyl group. X and Y each independently represent an ethylene group or a propylene group and XO and YO each independently represent an oxyethylene group (hereinafter may be referred to as "EO group") or an oxypropylene group (hereinafter referred to as "PO group "). &Lt; / RTI &gt; p ₁ , p ₂ , q ₁ and q ₂ independently represent 0 to 40. However, p ₁ + q ₁ and p ₂ + q ₂ are both 1 or more. When X is an ethylene group and Y is a propylene group, p ₁ + p ₂ is 1 to 40, and q ₁ + q ₂ is 0 to 20. When X is a propylene group and Y is an ethylene group, p ₁ + p ₂ is 0 to 20, and q ₁ + q ₂ is 1 to 40. Since p ₁ , p ₂ , q ₁ and q ₂ represent the number of structural units of the EO group or PO group, they represent an integer value in a single molecule and a rational number in an aggregate of a plurality of molecules. The EO group and the PO group may be present in a block form or in a random manner in succession.

When X and Y together represent an ethylene group, p ₁ + p ₂ + q ₁ + q ₂ may be 1 to 20, 1 to 10, or 1 to 7 from the viewpoint of more excellent resolution and adhesiveness .

 Examples of the compound represented by the general formula (III) include 2,2-bis (4 - ((meth) acryloxypolyethoxy) phenyl) propane, 2,2- Bis (4 - ((meth) acryloxypolyethoxypolypropoxy) phenyl) propane, and the like. These may be used singly or in combination of two or more.

Examples of commercially available bisphenol type (meth) acrylate compounds include 2,2-bis (4- (methacryloxy diethoxy) phenyl) propane (Shin-Nakamura Kagaku Kogyo Co., (BPE-500 manufactured by Shin-Nakamura Kagaku Kogyo K.K. or FA-500 manufactured by Hitachi Kasei Kabushiki Kaisha), 2,2-bis (4- (methacryloxypentaethoxy) 321 M "), 2,2-bis (4- (methacryloxypentadecaethoxy) phenyl) propane (BPE-1300 manufactured by Shin Nakamura Kagaku Kogyo K.K.), 2,2- (Methacryloxypolyethoxy) phenyl) propane ("BP-2 EM" (EO group: 2.6 (average value)) manufactured by Kyowa Chemical Industry Co., Ltd.) and the like.

The content of the bisphenol-type (meth) acrylate compound is preferably 1 to 50% by mass, 3 to 40% by mass, and 10 to 50% by mass, based on the total solid content of the component (A) 40% by mass, 20% by mass to 40% by mass, or 30% by mass to 40% by mass.

The content of the bisphenol-type (meth) acrylate compound is preferably from 30 to 99% by mass, from 50 to 97% by mass, from 60 to 95% by mass, , 70 to 95 mass%, or 80 to 90 mass%.

The content of the compound represented by the general formula (III) in which the total number of the EO group and the PO group is 1 to 7 is preferably within a range from the total amount of the solid components of the component (A) and the component (B) , 1 to 50 mass%, 2 to 48 mass%, 3 to 45 mass%, 5 to 40 mass%, 10 to 30 mass%, or 10 to 25 mass%.

Further, from the viewpoint of further improving the followability to the unevenness of the substrate, a compound obtained by reacting an?,? - unsaturated carboxylic acid with a polyhydric alcohol 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, and dipentaerythritol (meth) acrylate having an EO group can be used. Examples of commercially available dipentaerythritol (meth) acrylate having an EO group include "DPEA-12" manufactured by Nippon Kayaku Co., Ltd., and the like. The content of dipentaerythritol (meth) acrylate having an EO group is preferably from 1 to 10 mass%, from 1.5 to 8 mass%, from 2 to 8 mass%, from the viewpoint of improving the resolution, , 2. 5 to 8 mass%, or 3 to 8 mass%.

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

Examples of commercially available polyalkylene glycol di (meth) acrylates having both an EO group and a PO group include a polyalkyl (meth) acrylate having an EO group of 6 (average value) and a PO group of 12 (average value) (FA-023M ", "FA-024M ", manufactured by Hitachi Chemical Co., Ltd.), and the like. The content of the polyalkylene glycol di (meth) acrylate having both the EO group and the PO group is preferably from 1 to 5, more preferably from 1 to 5, from the viewpoint of improving the followability and resolution of the substrate relative to the total amount of the solid content of the component (B) To 15 mass%, 1.5 to 15 mass%, 2 to 13 mass%, or 3 to 13 mass%.

The content of the component (B) may be 20 to 70 parts by mass, 25 to 60 parts by mass, or 30 to 50 parts by mass based on 100 parts by mass of the total solid content of the components (A) and (B). When the content of the component (B) is within the above range, the photosensitive resin composition is superior in the photosensitivity and film resistance in addition to the resolution, adhesiveness, and resistance to the occurrence of the resistor hem.

((C) photopolymerization initiator)

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

As the component (C), for example, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -2-morpholinopropanone-1, quinones such as alkyl anthraquinone, benzoin ether compounds such as benzoin alkyl ether, benzoin compounds such as benzoin and alkylbenzoin, benzyl dimethyl ketal, etc. (O-chlorophenyl) -4,5-diphenylimidazole dimer and 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, Acridine derivatives such as 4,5-triarylimidazole dimer, 9-phenylacridine, and 1,7- (9,9'-acridinyl) heptane. These may be used singly or in combination of two or more.

Among these, 2,4,5-triarylimidazole dimer may be contained from the viewpoint of improving the resolution. Examples of the 2,4,5-triarylimidazole dimer include 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) - A dimer of 4,5-bis- (m-methoxyphenyl) imidazole, and a dimer of 2- (p-methoxyphenyl) -4,5-diphenylimidazole. Among them, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer may be contained in view of improvement of photosensitivity stability.

As the 2,4,5-triarylimidazole dimer, for example, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbisimidazole is preferably represented by B And is commercially available as -CIM (product name, product of Hodogaya Kagaku Kogyo K.K.).

The component (C) may further contain at least one kind of 2,4,5-triarylimidazole dimer in view of further improving light sensitivity and adhesion, and further suppressing light absorption of the component (C) And may include 2- (2-chlorophenyl) -4,5-diphenylimidazole dimer. Further, the 2,4,5-triarylimidazole dimer may be symmetric or asymmetric in structure.

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

((D) photosensitizer)

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

Examples of the component (D) include, but are not limited to, pyrazoles, dialkylaminobenzophenones, anthracenes, coumarins, xanthones, oxazoles, benzoxazoles, thiazoles, benzothiazoles, triazoles, Triazines, thiophenes, naphthalimides, and triarylamines. These may be used singly or in combination of two or more. From the standpoint of more effectively utilizing the absorption wavelength of the active light used for exposure, the component (D) may contain a pyrazoline, an anthracene or a dialkylaminobenzophenone, and among these, Aminobenzophenones may also be included. As the dialkylaminobenzophenones commercially available, for example, "EAB" manufactured by Hodogaya Chemical Industry Co., Ltd. and the like can be mentioned.

(D), the content thereof is preferably 1.0 parts by mass or less, 0.5 parts by mass or less, 0.15 parts by mass or less, and 0.12 parts by mass or less based on 100 parts by mass of the total solid content of the components (A) and (B) , Or 0.10 parts by mass or less. When the content of the component (D) is 1.0 parts by mass or less based on 100 parts by mass of the total solid content of the component (A) and the component (B), deterioration of the resistor pattern shape and the resistance of the resistor skirt can be suppressed, There is a tendency to be able to do. The content of the component (D) may be 0.01 parts by mass or more based on 100 parts by mass of the total amount of the solid components of the component (A) and the component (B) from the viewpoint of obtaining high sensitivity and good resolution.

((E) polymerization inhibitor)

The photosensitive resin composition according to this embodiment may contain a polymerization inhibitor (E) (hereinafter also referred to as "component (E)"). By containing the component (E), there is a tendency that the amount of exposure necessary for photo-curing the photosensitive resin composition can be adjusted to an optimum amount of exposure for exposing with a projection exposure machine.

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

In the general 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 amino group, an aryl group, a mercapto group, M and n are selected such that m is an integer of 2 or more, n is an integer of 0 or more, and m + n = 6, and the alkyl group of the alkyl group is preferably an alkyl group of 1 to 10 carbon atoms, an alkoxy group of 1 to 20 carbon atoms, When n is an integer of 2 or more, R ⁵ may be the same or different. The aryl group may be substituted with an alkyl group having 1 to 20 carbon atoms.

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

Examples of the compound represented by the general formula (I) include catechol, resorcinol (resorcinol), 1,4-hydroquinone, 3-methylcatechol, 4-methylcatechol, , 4-ethylcatechol, 3-propylcatechol, 4-propylcatechol, 3-n-butylcatechol, 4-n-butylcatechol, 3- , 3,5-di-tert-butylcatechol, and the like, 2-methyl resorcinol, 4-methyl resorcinol, 5-methyl resorcinol 4-tert-butyl resorcinol, 2-tert-butyl resorcinol, 2-tert-butyl resorcinol, 2- tert -butyl resorcinol, -Butylresorcinol, alkyl hydroquinone such as methylhydroquinone, ethylhydroquinone, propylhydroquinone, tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone, pyrogallol, . These may be used singly or in combination of two or more.

Among the compounds represented by the general formula (I), alkyl catechol may be used in view of further improving the resolution.

The content of the component (E) is preferably from 0.001 to 0.3 parts by mass, from 0.01 to 0.2 parts by mass, from 0.02 to 0.15 parts by mass, or from 0.03 to 0.1 parts by mass, based on 100 parts by mass of the total solid content of the components (A) . When the content of the component (E) is set to 0.3 parts by mass or less, the exposure time can be shortened and there is a tendency to contribute to improvement in mass production efficiency. When the content of the component (E) is 0.001 parts by mass or more, the photoreaction of the photo-curing portion can be sufficiently advanced, and the resistivity tends to be improved by suppressing the swelling property of the resist by improving the reaction rate .

The content of the component (E) may be 0.03 to 0.4 parts by mass, 0.05 to 0.4 parts by mass, 0.05 to 0.2 parts by mass, or 0.05 to 0.1 parts by mass based on 100 parts by mass of the solid content of the component (A). When the content of the component (E) is 0.05 parts by mass or more based on the component (A), the thermal stability of the photosensitive resin composition tends to be improved. When the content is 0.4 parts by mass or less, the yellowing of the photosensitive resin composition There is a tendency.

(Other components)

The photosensitive resin composition according to the present embodiment may contain a dye such as malachite green, victoria pure blue, brilliant green and methyl violet, tribromophenylsulfone, leuco crystal violet, diphenylamine, benzylamine, triphenyl Coloring agents such as amine, diethylaniline, o-chloroaniline and tertiary butyl catechol, plasticizers such as an antistatic agent and p-toluenesulfonamide, pigments, fillers, antifoaming agents, flame retardants, adhesion promoters, leveling agents, An additive such as an accelerator, an antioxidant, a flavoring agent, an imaging agent and a heat crosslinking agent may be contained in an amount of 0.01 to 20 parts by mass based on 100 parts by mass of the total solid content of the components (A) and (B). These additives may be used singly or in combination of two or more kinds.

The photosensitive resin composition according to the present embodiment may contain at least one organic solvent as needed in order to improve handling properties of the photosensitive composition or to control viscosity and storage stability. As the organic solvent, a commonly used organic solvent may be used without particular limitation. Specific examples of the solvent include organic solvents such as methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N, N-dimethylformamide, propylene glycol monomethyl ether, Solvent. These may be used singly or in combination of two or more.

<Protective layer>

In the photosensitive element of the present embodiment, a protective layer may be laminated on the surface of the photosensitive layer opposite to the surface in contact with the barrier layer. As the protective layer, for example, a polymer film such as polyethylene or polypropylene may be used. Further, the same polymer film as the above-mentioned support film (described above) may be used, or a different polymer film may be used.

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

&Lt; Method of manufacturing photosensitive element &gt;

First, for example, a water-soluble resin containing polyvinyl alcohol is mixed with a mixed solvent of water heated to 70 to 90 占 폚 and alcohols including alcohols having 3 or more carbon atoms such that the solid content is 10 to 20 mass% , And the mixture is stirred for about 1 hour and uniformly dissolved to obtain a resin composition for forming a barrier layer containing polyvinyl alcohol and alcohols having 3 or more carbon atoms. In the present specification, the term "solid content" refers to non-volatile matter excluding volatile substances such as water and organic solvents in the resin composition. That is, it refers to components other than solvents such as water and organic solvents that remain without volatilization in the drying step, and include liquid, syrupy, and waxy forms at room temperature around 25 ° C.

Next, the resin composition for forming a barrier layer is coated on a support film and dried to form a barrier layer. The application of the barrier layer-forming resin composition onto the support film can be carried out by a known method such as roll coating, comma coating, gravure coating, air knife coating, die coating, bar coating, spray coating and the like have.

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

Next, the photosensitive resin composition may be coated and dried on the barrier layer of the support film on which the barrier layer is formed in the same manner as the application of the resin composition for forming a barrier layer, thereby forming the photosensitive layer on the barrier layer. Next, by laminating a protective layer on the photosensitive layer thus formed, a photosensitive element comprising a support film, a barrier layer, a photosensitive layer and a protective layer in this order can be produced. Further, by forming a barrier layer on the support film and forming a photosensitive layer on the protective layer, the support film, the barrier layer, the photosensitive layer having the photosensitive layer and the protective layer in this order Element.

The thickness of the photosensitive layer in the photosensitive element may be appropriately selected depending on the application, but may be 1 to 200 占 퐉, 5 to 100 占 퐉, or 10 to 50 占 퐉 in thickness after drying. When the thickness of the photosensitive layer is 1 占 퐉 or more, industrial coating is easy and productivity tends to be improved. When the thickness of the photosensitive layer is 200 占 퐉 or less, there is a tendency that a resist pattern excellent in resolution and aspect ratio tends to be formed because the photosensitive property is high and the photocurability of the register bottom portion is excellent.

The melting viscosity of the photosensitive layer in the photosensitive element at 110 캜 can be appropriately selected depending on the kind of the base material in contact with the photosensitive layer. After drying, the solubility of the photosensitive layer in the photosensitive element is preferably from 50 to 10000 Pa · s, To 5000 Pa · s, or 200 to 1000 Pa · s. If the melt viscosity at 110 캜 is 50 Pa · s or more, wrinkles and voids do not occur in the lamination step, and the productivity tends to be improved. When the melt viscosity at 110 ° C is 10000 Pa · s or less, adhesion with the undercoat is improved in the lamination step, and the adhesion failure tends to be reduced.

The form of the photosensitive element according to this embodiment is not particularly limited. For example, it may be a sheet-like shape, or a shape obtained by winding in a roll shape on a core. In the case of winding in the roll, the support film may be wound so as to be outside. Examples of the core include plastics such as polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin or ABS resin (acrylonitrile-butadiene-styrene copolymer).

A cross-section separator may be provided on the end face of the roll-shaped photosensitive element roll obtained in this manner from the viewpoint of protection of the cross section, or a moisture-proof cross section separator may be provided in view of edge fusion. As a wrapping method, wrapping may be carried out on a black sheet having low moisture permeability.

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

[Method of forming register pattern]

(I) a step of arranging the photosensitive layer, the barrier layer and the supporting film in this order on the substrate from the substrate side (hereinafter, referred to as " (ii) a step of removing the support film and exposing the photosensitive layer by an actinic ray through the barrier layer (hereinafter referred to as "(ii) exposure " (Hereinafter also referred to as "(iii) developing step")), and the step of removing the unlayered portions of the barrier layer and the photosensitive layer from the substrate Process. The resist pattern may be referred to as a photocured pattern of a photosensitive resin composition, or may be referred to as a relief pattern. Depending on the purpose, the register pattern in the present embodiment may be used as a resistor, or may be used for other purposes such as a protective film.

((i) photosensitive layer and barrier layer forming step)

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

As a method for 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 pressed on the substrate while heating, A photosensitive layer and a barrier layer can be formed on a substrate. Thereby, a laminate having a substrate, a photosensitive layer, a barrier layer and a supporting film in this order can be obtained.

When the photosensitive layer and the barrier layer forming step are carried out using the photosensitive element, it may be carried out under reduced pressure in view of adhesion and followability. Heating at the time of compression is be carried out at a temperature of 70~130 ℃, but the compression is also performed at a pressure of 0.1~1.0MPa (1~10kgf / cm ^2), these conditions may be appropriately selected as needed. When the photosensitive layer of the photosensitive element is heated to 70 to 130 占 폚, it is not necessary to preheat the substrate in advance. However, in order to further improve the adhesion and followability, the substrate may be preheated.

((ii) exposure step)

In the exposure process, the support film is removed, and the photosensitive layer is exposed through the barrier layer with an actinic ray. As a result, the exposed portion irradiated with the actinic light ray is photo-cured to form a photo-cured portion (latent image), and the unexposed portion to which no active ray is irradiated is photo-cured to form a photo-cured 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 and exposed. By exposing the photosensitive layer through the barrier layer, a resist pattern excellent in resolution and resist pattern shape can be formed.

As the exposure method, a known exposure method can be applied. For example, a method of irradiating an actinic ray in a picture image form through a negative or positive mask pattern called an artwork (a mask exposure method ), An LDI (Laser Direct Imaging) exposure method, or a method in which an active light ray projected from a photomask is used to irradiate the image on a screen through a lens (projection exposure method). Among them, a projection exposure system may be used from the viewpoint of excellent resolution. That is, the photosensitive element or the like according to the present embodiment is applied by a projection exposure method. Also, the projection exposure method may be referred to as an exposure method using an active light beam of a damped energy amount.

As the light source of the active light beam, there is no particular limitation as long as it is a commonly used known light source. For example, gas arc such as carbon arc, mercury vapor arc, ultra high pressure mercury lamp, high pressure mercury lamp, xenon lamp, argon laser, And a semiconductor laser such as a gallium nitride-based blue-violet laser, or the like. It is also possible to use a flood bulb for photography, a device for effectively emitting visible light such as a solar lamp, or the like. Among these, a light source capable of emitting i-line monochromatic light with an exposure wavelength of 365 nm, a light source capable of emitting h-monochromatic light having an exposure wavelength of 405 nm, or a light source capable of emitting ihg crossover light Or a light source capable of emitting an i-line monochromatic light with an exposure wavelength of 365 nm may be used. As a light source capable of emitting i-line monochromatic light having an exposure wavelength of 365 nm, for example, ultra high-pressure mercury lamp and the like can be mentioned.

((iii) developing process)

In the developing step, the unlayered portions of the barrier layer and the photosensitive layer are removed from the substrate. By a developing process, a resist pattern is formed on the substrate, the resist pattern being formed of a photo-cured portion in which the photosensitive layer is photo-cured. When the barrier layer is water-soluble, it may be washed with water to remove the barrier layer, and then the uncured portions other than the light-cured portion may be removed by the developer. In the case where the barrier layer is soluble in the developer, The barrier layer may be removed with a developing solution in addition to the un-cured portions. The developing method includes a wet phenomenon.

In the case of the wet phenomenon, the developer can be developed by a known wet developing method using a developer corresponding to the photosensitive resin composition. Examples of the wet developing method include a dip method, a paddle method, a high-pressure spray method, a brushing method, a slapping method, a scrubbing method, a method using a rocking dipping method, or the like , And from the viewpoint of improving the resolution, the high-pressure spraying method is most suitable. These wet developing methods may be performed either singly or in combination of two or more methods.

The developing solution is appropriately selected according to the constitution of the photosensitive resin composition. Examples thereof include alkaline aqueous solutions and organic solvent developers.

An alkaline aqueous solution may be used as the developer in terms of safety, stability, and operability. Examples of the base of the alkaline aqueous solution include alkaline hydroxides such as hydroxides of lithium, sodium or potassium, alkali metal carbonates such as carbonates or bicarbonates of lithium, sodium, potassium or ammonium, alkali metal phosphates such as potassium phosphate, sodium phosphate, Alkali metal pyrophosphate such as sodium phosphate, potassium pyrophosphate and the like, sodium borate, sodium metasilicate, tetramethylammonium hydroxide, ethanolamine, ethylenediamine, diethylenetriamine, 2-amino- Propanediol, 1,3-diamino-2-propanol and morpholine are used.

Examples of the alkaline aqueous solution used for the development include a diluted solution of 0.1 to 5 mass% sodium carbonate, a diluted solution of 0.1 to 5 mass% potassium carbonate, a diluted solution of 0.1 to 5 mass% sodium hydroxide, A dilute solution of sodium borate, or the like can be used. The pH of the alkaline aqueous solution used for the 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. The alkaline aqueous solution may contain, for example, a surface active agent, a defoaming agent, and a small amount of an organic solvent for promoting development. Examples of the organic solvent used in the alkaline aqueous solution include acetone, acetone, ethyl acetate, alkoxyethanol having an alkoxy group of 1 to 4 carbon atoms, ethyl alcohol, isopropyl alcohol, butyl alcohol, diethylene glycol mono Methyl ether, diethylene glycol monoethyl ether and diethylene glycol monobutyl ether.

Examples of the organic solvent used in the organic solvent developer include organic solvents such as 1,1,1-trichloroethane, N-methylpyrrolidone, N, N-dimethylformamide, cyclohexanone, methylisobutylketone, Butyrolactone. From the viewpoint of prevention of ignition, these organic solvents may be added with water so as to be in the range of 1 to 20% by mass to be an organic solvent developer.

(Other processes)

The method for forming a resist pattern according to this embodiment, the resist pattern was removed by a microscope conversion unit in the developing process, subjected to heating or exposure amount of the exposure to the 0.2~10J / cm ² at 60~250 ℃ as needed May be further cured.

[Manufacturing method of printed wiring board]

The method of manufacturing a printed wiring board according to the present embodiment includes a step of forming a conductor pattern by etching or plating a substrate on which a resistor pattern is formed by the method of forming the resistor pattern, And the like. The method of manufacturing 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 by the photosensitive element. Among these methods, a conductor pattern is formed by plating Application to methods is more appropriate. The conductor pattern may be referred to as a circuit.

In the etching process, the conductor pattern of the substrate not covered with the resist is etched off by using the resist pattern formed on the substrate having the conductor layer as a mask, and the conductor pattern is formed.

The method of the etching treatment is appropriately selected according to the conductor layer to be removed. Examples of the etching solution include a cupric chloride solution, a ferric chloride solution, an alkali etching solution, a hydrogen peroxide etching solution, and the like. In view of the excellent etch factor, .

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

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

After the etching treatment or the plating treatment, the resist pattern on the substrate is removed. The resist pattern can be removed by, for example, a strong alkaline aqueous solution more than the alkaline aqueous solution used in the developing step. As the alkaline aqueous solution, for example, 1 to 10 mass% aqueous sodium hydroxide solution and 1 to 10 mass% potassium hydroxide aqueous solution are used. Among these, an aqueous solution of 1 to 5 mass% sodium hydroxide or an aqueous solution of potassium hydroxide may be used.

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

In the case where the resist pattern is removed after the plating process, the conductor layer covered with the resistor by the etching process is further etched 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 according to the conductor layer to be removed. For example, the above-described etching solution can be applied.

The method of manufacturing a printed wiring board according to the present embodiment is applicable not only to the production of a single-layer printed wiring board but also to the production of a multilayer printed wiring board and also to the production of a printed wiring board having a small-diameter through hole It is possible.

The method for producing a printed wiring board according to the present embodiment can be suitably used for the production of a high-density package substrate, particularly for the production of a wiring board by a semi-adhesive method. An example of a manufacturing process of the wiring board by the semi-insulating method is shown in Fig.

2 (a), a substrate (circuit formation substrate) on which a conductor layer 40 is formed on an insulating layer 50 is prepared. The conductor layer 40 is, for example, a copper layer. 2 (b), the photosensitive layer 30 and the barrier layer 20 are formed on the conductive layer 40 of the substrate by the photosensitive layer and the barrier layer forming process. 2C, the photosensitive layer 30 is irradiated with an actinic ray 80, which is an image of the photomask, projected onto the photosensitive layer 30 through the barrier layer 20 by the exposure process, A light curing portion is formed. 2 (d), a resist pattern 32, which is a photocurable portion, is formed on the substrate by removing a region (including a barrier layer) other than the light-cured portion formed by the exposure process by the developing process from the substrate do. 2E, the plating layer 60 is formed on the conductor layer 40 of the substrate which is not covered with the resist by a plating process using the resist pattern 32 as a photocurable portion as a mask. 2F, the resist pattern 32, which is a photocured portion, is peeled off by a strong alkaline aqueous solution, and then the conductive layer 40 masked by the resist pattern 32 is removed by a flash etching process, The conductor pattern 70 including the plated layer 62 after the treatment and the conductor layer 42 after the etching treatment is formed. The conductor layer 40 and the plating layer 60 may be made of the same material or different. When the conductor layer 40 and the plating layer 60 are made of the same material, the conductor layer 40 and the plating layer 60 may be integrated. Although the projection exposure method is described in FIG. 2, the register pattern 32 may be formed by using the mask exposure method and the LDI exposure method in combination.

While the preferred embodiments of the present disclosure have been described above, the present disclosure is not limited to the above embodiments.

Example

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

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

&Lt; Synthesis Example 1 &

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

Further, 1.2 g of azobisisobutyronitrile was dissolved in 100 g of a mixed solution of 60 g of methyl cellosolve and 40 g of toluene (weight ratio 3: 2) to prepare solution b.

On the other hand, 400 g of a mixed solution of methylcellosolve and toluene (hereinafter also referred to as "mixed solution x") having a mass ratio of 3: 2 was added to a flask equipped with a stirrer, a reflux condenser, a thermometer, a dropping funnel, The mixture was stirred while blowing nitrogen gas and heated to 80 占 폚.

The solution a was dropped into the mixed solution x in the flask at a constant dropping rate over 4 hours, followed by stirring at 80 캜 for 2 hours. Subsequently, the solution b was dropped into the solution in the flask at a constant dropping rate over 10 minutes, and then the solution in the flask was stirred at 80 캜 for 3 hours. Further, the solution in the flask was heated to 90 DEG C over 30 minutes, kept at 90 DEG 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 by adding the mixed solution x so that the non-volatile component (solid content) became 50% by mass.

The weight average molecular weight of the binder polymer (A-1) was 50,000, and the acid value was 163 mgKOH / g. The acid value was measured by a neutralization titration method. Specifically, 30 g of acetone was added to 1 g of the binder polymer solution, and the solution was uniformly dissolved. An appropriate amount of phenolphthalein, which is an indicator, was added to the solution of the binder polymer, and titration was performed using a 0.1 N KOH aqueous solution Respectively. The weight average molecular weight was determined by gel permeation chromatography (GPC) and calculated by using a standard polystyrene calibration curve. The conditions of GPC are shown below.

-GPC condition-

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

Column: 3 total of the following (column specifications: 10.7 mm phi x 300 mm, all manufactured by Hitachi Chemical Co., Ltd.)

Gelpack GL-R420

Gelpack GL-R430

Gelpack GL-R440

Eluent: tetrahydrofuran

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

Measuring temperature: 25 ° C

Flow rate: 2.05 mL / min

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

<Preparation of a resin composition for forming a barrier layer>

Next, the components shown in the following Tables 1 to 3 were mixed in an amount (unit: parts by mass) shown in the table to obtain a resin composition for forming a barrier layer. Specifically, the water-soluble resin was slowly added to water and alcohol at room temperature, and the whole amount was added, followed by heating to 90 占 폚. After reaching 90 캜, 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 blending amounts other than the solvents in Tables 1 to 3 are all the blending amounts in the solid content.

&Lt; Preparation of Photosensitive Resin Composition &gt;

Next, the components shown in the following Tables 1 to 3 were mixed in an amount (unit: parts by mass) shown in the table to obtain a photosensitive resin composition.

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

(Water-soluble resin)

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

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

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

* 4: Polyvinyl pyrrolidone K-30 (trade name, product of Nippon Shokubai Co., Ltd.)

(A) Component: Binder polymer

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

Methacrylic acid / methyl methacrylate / benzyl methacrylate / styrene

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

Component (B): Photopolymerizable compound having an ethylenically unsaturated bond

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

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

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

EOPO-modified dimethacrylate

* 8: BPE-200 (product name of Shin-Nakamura Kagaku Kogyo K.K.)

2,2-bis (4- (methacryloxy diethoxy) phenyl) propane

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

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

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

Ethylene oxide-modified dipentaerythritol hexaacrylate

(C): Photopolymerization initiator

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

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

(D) Component: Photosensitizer

* 12: EAB (product name, manufactured by Hodogaya Chemical Industry Co., Ltd.)

4,4'-bis (diethylamino) benzophenone

Component (E): Polymerization inhibitor

* 13: TBC (manufactured by DIC Corporation)

4-tert-butylcatechol

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

&Lt; Preparation of Photosensitive Element &gt;

As the supporting film of the photosensitive element, PET films shown in Tables 1 to 3 were prepared.

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

FB40: biaxially oriented PET film (product name, thickness: 16 mu m, made by TORAY KABUSHIKI KAISHA) having an active layer on the front and back sides,

A1517: A biaxially oriented PET film (product name, thickness: 16 mu m, made by TOYOBO SEIKI KABUSHIKI CO., LTD.) Having a two-layer structure having a lubricant layer on one side,

G2H: biaxially oriented PET film (manufactured by Teijin DuPont Film Co., Ltd., thickness: 15.5 占 퐉 m) having a single layer structure (lubricant kneading type) containing a lubricant,

(Fabrication of barrier layer)

Subsequently, a resin composition for forming a barrier layer was applied on the PET film (support film) so as to have a uniform thickness, and dried with a hot air convection type drier at 95 캜 for 10 minutes to form a barrier layer having a thickness of 5 탆 after drying did. When the barrier layer is formed on the surface of the PET film having less lubricant and the active layer is provided on one side of the PET film when the density of the lubricant is different on both sides of the PET film, Layer.

(Preparation of photosensitive layer)

Next, on the barrier layer of the support film, the photosensitive resin composition was coated so as to have a uniform thickness, and dried with a hot air convection type dryer at 100 캜 for 10 minutes to form a photosensitive layer having a thickness of 10 탆 after drying.

Next, a polyethylene protective film (protective layer) (product name: "NF-15 ", manufactured by TAMARO POLYMER LTD.) Was stuck on this photosensitive layer, and a PET film (support film), a barrier layer, And a protective layer were laminated in this order.

&Lt; Measurement of Residual Alcohol Content &gt;

The amount of residual alcohol in the formed barrier layer was measured by gas chromatography mass spectrometry. The measurement conditions of the gas chromatography mass spectrometry are as follows. The item "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. "&Lt; 1.0" means more than 0 and less than 1.0.

(Measurement conditions of gas chromatography mass spectrometry)

Measurement apparatus: GC / MS QP-2010 (product name of Shimadzu Corporation)

Column: HP-5MS (product name, manufactured by Agilent Technologies, Inc.)

Oven Temp: After heating at 40 占 폚 for 5 minutes, the temperature was raised to 300 占 폚 at a rate of 15 占 폚 / min

Carrier gas: helium, 1.0 mL / min

Interface temperature: 280 ℃

Ion source temperature: 250 ° C

Sample injection amount: 0.1 mL

&Lt; Preparation of laminate &

The copper surface of a copper-clad laminate (substrate: MCL-E-67, manufactured by Hitachi Chemical Co., Ltd.), which is a glass epoxy laminated on both sides of copper foil having a thickness of 12 탆, After washing with water, it was air-dried. The copper clad laminate was heated to 80 DEG C and the photosensitive element was pressed onto the copper clad laminate so that the photosensitive layer was in contact with the copper surface while peeling off the protective layer. The pressing was performed at a roll speed of 1.0 m / min at a pressure of 0.40 MPa using a heat roll at 110 캜. Thus, a laminate obtained by laminating the substrate, the photosensitive layer, the barrier layer, and the supporting film in this order was obtained. These laminated bodies were used as test specimens in the following tests. As the laminator, HLM-3000 (product name, manufactured by Taihei Laminator Co., Ltd.) was used.

<Evaluation of peelability of support film>

The test piece was allowed to stand in an environment of 23 캜 and 50% humidity for 1 hour. Thereafter, a 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 rate of 500 mm / sec, and the peelability of the support film was evaluated on the following evaluation criteria. The results of the evaluation are shown in Tables 4 to 6 below.

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

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

<Evaluation of resolution>

In order to investigate the resolution, a support film was peeled off from the test piece, and then a Hitachi 41-step tablet was placed on the barrier layer of the test piece, and a line width / space width of z / z ( (manufactured by Wako Pure Chemical Industries, Ltd., product name UX-2240SM (trade name, manufactured by Wako Pure Chemical Industries, Ltd.) having a high-pressure mercury lamp with a wavelength of 365 nm was placed in a glass mask having a wiring pattern of z = 2 to 20 -XJ01) was used to expose the photosensitive layer through the barrier layer with an irradiation energy amount that the number of remaining steps after development of the Hitachi 41-step tablet was eight stages. After the exposure, the test piece was rinsed at room temperature to remove the barrier layer. Next, a 1% by mass aqueous sodium carbonate solution was used at 30 캜, and the photosensitive layer was spray-developed for twice the shortest developing time to remove the unexposed portion. Here, the shortest developing time was obtained by measuring the time when the unexposed portion was completely removed by the above developing process. The smallest value (unit: 占 퐉) among the space widths between the line portions (exposed portions) from which the unexposed portions are cleanly removed by the developing process is taken as an index of resolution evaluation. The smaller the numerical value, the better the resolution. The results are shown in Tables 4 to 6 below.

<Evaluation of Resistor Pattern Shape>

The cross-sectional shape of the resist pattern with a line width / space width of 10/10 (unit: 占 퐉) was observed by a scanning electron microscope (SEM) on the substrate evaluated in the evaluation of the resolution. The sectional shapes of the resistor patterns are shown in the following Tables 4 to 6 as evaluation of the register pattern shape.

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

&Lt; Evaluation of transparency of barrier layer solution &

As the reference samples, the same procedures as those of the examples 1 to 15 and the comparative examples 1 to 7 except for using the alcohols in the barrier layer forming resin compositions of the examples 1 to 15 and the comparative examples 1 to 7 The composition was prepared in the same manner as the composition. Thereafter, the transparency of the resin composition solution for barrier layer formation (hereinafter also referred to as "barrier layer solution ") and the reference sample of Examples 1 to 15 and Comparative Examples 1 to 7 was visually observed and evaluated as follows . The evaluation results are shown in Tables 4 to 6 below.

A: The fog of the barrier layer solution is equal to or less than that of the reference sample.

B: As compared with the reference sample, a large amount of fogging occurred in the barrier layer solution.

&Lt; Evaluation of barrier layer transparency &gt;

The barrier layer forming resin compositions of Examples 1 to 15 and Comparative Examples 1 to 7 were applied on the support film so that the thickness became uniform and dried for 10 minutes in a hot air convection type dryer at 95 캜 to give a thickness of 5 Mu m. As the reference samples, the same procedures as those of the examples 1 to 15 and the comparative examples 1 to 7 except for using the alcohols in the barrier layer forming resin compositions of the examples 1 to 15 and the comparative examples 1 to 7 Using the composition prepared in the same manner as the composition, a barrier layer was formed. Thereafter, the appearance of the barrier layer was visually observed and evaluated as follows. The evaluation results are shown in Tables 4 to 6 below.

A: As compared with the reference sample, the degree of occurrence of clouding and voids in the barrier layer is equal or less.

B: As compared with the reference sample, a part or all of the barrier layer is mostly cloudy or voids.

In Examples 1 to 15, when the exposure was performed under a condition that the number of remaining steps was eight and the amount of energy was low using a high resolution image projection exposure apparatus, peeling properties between the support film and the barrier layer were high, 7, it was confirmed that the separability between the support film and the barrier layer was low.

Industrial availability

INDUSTRIAL APPLICABILITY As described above, according to the present disclosure, it is possible to provide a photosensitive element capable of improving the peelability of a barrier layer and a support film without using a release promoter, a resin composition for forming a barrier layer, a method of forming a resistor pattern, Method can be provided.

Explanation of symbols

One… Photosensitive element, 2 ... Support film, 3, 20 ... Barrier layer, 4, 30 ... Photosensitive layer, 5 ... Protective layer, 32 ... Register pattern, 40 ... Conductor layer, 42 ... Conductor layer after etching treatment, 50 ... Insulation layer, 60 ... Plated layer, 62 ... Plating layer after etching treatment, 70 ... Conductor pattern, 80 ... Active rays.

Claims (13)

A photosensitive element comprising a support film, a barrier layer, and a photosensitive layer in this order, wherein the barrier layer contains a water-soluble resin and an alcohol having 3 or more carbon atoms. The method according to claim 1,
Wherein the alcohol having at least 3 carbon atoms contains at least one member selected from the group consisting of a compound represented by the following Chemical Formulas (1) to (3) and a compound represented by the following Chemical Formula (4).

[In the general formula (4), R ¹¹ represents an alkyl group, R ¹² represents an alkylene group, and the sum of the carbon number of the group of R ^{11 and} the group of R ¹² is 3 or more.] The method according to claim 1 or 2,
Wherein the solubility of the alcohol having 3 or more carbon atoms in water at 20 DEG C is 300 mL / 100 mL or more. 4. The method according to any one of claims 1 to 3,
Wherein the content of the alcohol having 3 or more carbon atoms in the barrier layer is more than 0 mass% and 2.0 mass% or less based on the total amount of the barrier layers. 5. The method according to any one of claims 1 to 4,
Wherein the water-soluble resin contains polyvinyl alcohol. 6. The method 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, which comprises a water-soluble resin, an alcohol having 3 or more carbon atoms, and water. The method of claim 7,
Wherein the alcohol having 3 or more carbon atoms is at least one compound selected from the group consisting of compounds represented by the following formulas (1) to (3) and compounds represented by the following formula (4) Composition.

[In the general formula (4), R ¹¹ represents an alkyl group, R ¹² represents an alkylene group, and the sum of the carbon number of the group of R ^{11 and} the group of R ¹² is 3 or more.] The method according to claim 7 or 8,
Wherein the solubility of the alcohol having 3 or more carbon atoms in water at 20 DEG C is 300 mL / 100 mL or more of water. The method according to any one of claims 7 to 9,
Wherein the content of the alcohol having 3 or more carbon atoms is 100 to 500 parts by mass based on 500 parts by mass of water. The method according to any one of claims 7 to 10,
Wherein the water-soluble resin contains polyvinyl alcohol. A step of disposing a photosensitive layer, a barrier layer and a supporting film in this order on a substrate from the substrate side using the photosensitive element according to any one of claims 1 to 6,
Removing the support film to expose the photosensitive layer by an actinic ray through the barrier layer,
Removing the unlayered portions of the barrier layer and the photosensitive layer from the substrate;
And a step of forming the resist pattern. A manufacturing method of a printed wiring board comprising the step of forming a conductor pattern by etching or plating a substrate on which a resistor pattern is formed by the method of forming a resist pattern according to claim 12.

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