JP6359452B2 - Method for producing photosensitive resin element - Google Patents

Description

  The present invention relates to a method for producing a photosensitive resin element, and the like.

  The manufacturing method of the photosensitive resin composition for producing a printed circuit is a resin for a binder, a photopolymerizable unsaturated compound, a photopolymerization initiator, a dye, etc., a ketone represented by methyl ethyl ketone, and a representative of ethyl acetate. In general, the method includes a step of uniformly stirring and dissolving in a solvent mainly composed of esters such as tetrahydrofuran and ethers typified by tetrahydrofuran. For example, Patent Document 1 describes a photosensitive resin mixed solution prepared by using a mixed solvent of methyl ethyl ketone / 1-methoxy-2-propanol = 2/1 (weight ratio). Also. The obtained preparation liquid can be uniformly coated on a polyester film as a support layer using a die coater or the like, and the solvent can be dried in a drying step to obtain a photosensitive resin laminate. Furthermore, a photosensitive resin laminate having a three-layer structure can be obtained by laminating with a polyethylene film or the like as a protective layer. These laminates are generally called dry film photoresists (hereinafter abbreviated as “DF”).

JP 11-143069 A

However, in the conventional production method using methyl ethyl ketone as the main component of the solvent, the solubility of the binder resin and the unsaturated compound photopolymerizable and the solubility of additives such as dyes are insufficient, and the preparation liquid is filtered. Sometimes the filter was clogged. Further, there is still room for improvement from the viewpoint of reducing minute irregularities on the surface of the manufactured DF and reducing the frequency of observation as unevenness by visual inspection of the appearance.
Therefore, the subject of this invention is providing the manufacturing method of the photosensitive resin element which is excellent in productivity and has a favorable external appearance.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have produced a photosensitive resin composition using a mixed solvent containing acetone when producing the above-mentioned preparation liquid. As a result, the present inventors have found that the appearance of the manufactured DF is good without unevenness and completed the present invention. That is, the present invention is as follows.

[1] The following steps:
(A) Resin for binder whose carboxyl group content is 100-600 in an acid equivalent, and whose weight average molecular weight is 5000-500,000,
(B) a photopolymerizable unsaturated compound,
(C) a photopolymerization initiator,
(D) acetone, and (e) a step of preparing a non-acetone solvent to obtain a preparation solution, wherein the mass of (d) acetone relative to the total mass of (d) acetone and (e) non-acetone solvent The proportion of total solids in the formulation is 30% to 80% by mass; and the formulation is applied onto the support layer and dried. And forming a photosensitive resin element on the support layer;
The manufacturing method of the photosensitive resin element containing this.
[2] The method according to [1], wherein the (e) non-acetone solvent is selected from the group consisting of alcohols, esters, and ethers.
[3] The method according to [2], wherein the alcohol is selected from the group consisting of methanol, ethanol, normal propyl alcohol, isopropyl alcohol, and normal butanol.
[4] The method according to [3], wherein the alcohol is ethanol.
[5] The method according to [2], wherein the ester is ethyl acetate.
[6] The method according to [2], wherein the ether is tetrahydrofuran.
[7] The method according to any one of [1] to [6], wherein a film thickness after drying of the preparation liquid is 5 μm to 50 μm.
In addition, the present invention provides a method for producing the DF by applying the above prepared solution on a support layer and drying, and further laminating a protective layer on the surface of the photosensitive resin layer laminated on the support layer. A method of manufacturing a DF having a three-layer structure is also provided.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the photosensitive resin element which is excellent in productivity and has a favorable external appearance is provided.

FIG. 1 (1) is a photograph showing the appearance of a roll-shaped laminate having an appearance evaluation of S, and FIG. 1 (2) is a photograph showing the appearance of the roll-shaped laminate having an appearance evaluation of A. FIG. 1 (3) is a photograph showing the appearance of a roll-shaped laminate having an appearance evaluation of B.

  The best mode for carrying out the present invention (hereinafter abbreviated as “embodiment”) will be described in detail below. In addition, this invention is not limited to embodiment, It can implement by changing variously within the range of the summary.

In the embodiment, the photosensitive resin element includes the following steps:
(A) Resin for binder whose carboxyl group content is 100-600 in acid equivalent, and whose weight average molecular weight is 5000-500,000,
(B) a photopolymerizable unsaturated compound,
(C) a photopolymerization initiator,
(D) acetone,
(E) a step of preparing a non-acetone solvent, and optionally (f) other additives to obtain a preparation liquid; and applying the preparation liquid on the support layer, drying, and exposing the support layer to the photosensitive layer. Forming a conductive resin element;
Can be manufactured by a method including:

  A photosensitive element refers to a substance that changes its properties by receiving light. The photosensitive element may be in various forms such as a film, a plate, a sheet, a roll, and a molded article, and may include, for example, a photosensitive resin or a material that includes a photosensitive resin. More specifically, by applying a composition containing a photosensitive resin (hereinafter referred to as “photosensitive resin composition”) to a support layer such as a film, a layer made of the photosensitive resin (hereinafter referred to as “photosensitive resin”). A photosensitive resin laminate obtained by laminating a layer ") on a support layer is preferred as the photosensitive element. The photosensitive resin composition may be in any state (for example, liquid, solid, emulsion, suspension, etc.), but is a liquid containing a photosensitive resin (hereinafter also referred to as “preparation liquid”). Is preferred. Further, a photosensitive resin roll obtained by further laminating and winding a protective material (for example, a protective film, an interleaf paper film, etc.) on the exposed portion of the photosensitive resin laminate, It is more preferable as a photosensitive element, and a dry film roll in which the entire photosensitive resin roll or the photosensitive resin layer portion is dried is particularly preferable.

It is preferable that the thickness (film thickness after drying a solvent) of the photosensitive resin element manufactured using the preparation liquid containing component (a)-(f) is 5 micrometers-50 micrometers. The thickness of the photosensitive resin element is preferably adjusted to 5 μm or more from the viewpoint of the accuracy with which the preparation liquid is applied to the support layer, and on the other hand, adjusted to 50 μm or less from the viewpoint of drying properties in the drying process. Is preferred. The thickness of the photosensitive resin element is more preferably 30 μm to 50 μm.
In addition, since the resolution improves as the photosensitive resin layer is thinner, and the film strength improves as the thickness is thicker, the film thickness can be appropriately selected depending on the application.

<Formulation liquid>
The formulation solution comprises (a) a binder resin, (b) a photopolymerizable unsaturated compound, (c) a photopolymerization initiator, (d) acetone, and (e) a non-acetone solvent, and optionally (f) It is preferable to include other additives.

In the manufacturing method of the photosensitive resin element, it is preferable that the ratio of the total solid content in a preparation liquid is 30 mass%-80 mass%. The ratio of the total solid content in the preparation liquid is, for example, solids of the preparation liquid obtained by dissolving the components (a) to (c) and (f) in (d) acetone and (e) non-acetone solvent. In order to obtain the effect of improving the coating speed, the concentration is preferably 30% by mass or more from the viewpoint of controlling the amount of solvent to be dried and evaporated, while 80% from the viewpoint of the uniformity of the prepared solution. It is preferable that it is below mass%. The ratio of the total solid content in the preparation liquid is more preferably 40% by mass to 60% by mass.
Hereinafter, components (a) to (f) will be described in detail.

(A) Resin for binder (a) Resin for binder has a carboxyl group content of 100 to 600 in terms of acid equivalent, a weight average molecular weight of 5000 to 500,000, and is used as a binder.
(A) The carboxyl group in the binder resin is preferable for imparting developability or releasability to an aqueous alkaline solution to the photosensitive resin element. The acid equivalent is preferably 100 or more from the viewpoint of development resistance, resolution, and adhesion, and is preferably 600 or less from the viewpoint of developability and peelability.
The weight average molecular weight of the (a) binder resin is preferably 5,000 or more, more preferably 20,000 or more, from the viewpoint of maintaining a uniform DF thickness and obtaining resistance to the developer. On the other hand, from the viewpoint of maintaining developability, it is preferably 500,000 or less, and more preferably 300,000 or less.
The preferred molecular weight distribution is 1.5 or more, more preferably 2 or more. On the other hand, the upper limit is preferably 7 or less, and more preferably 5 or less.

  Typically, the binder resin (a) is a thermoplastic copolymer containing at least a carboxyl group-containing monomer as a copolymerization component. The thermoplastic copolymer is preferably obtained by copolymerizing at least one first monomer described below and at least one second monomer described below.

  The first monomer is a monomer containing a carboxyl group in the molecule. Examples of the first monomer include (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, and maleic acid half ester. Of these, (meth) acrylic acid is preferred. In this specification, (meth) acryl indicates acrylic or methacrylic.

  The second monomer is a monomer that is non-acidic and has at least one polymerizable unsaturated group in the molecule. Examples of the second monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate. , Tert-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, vinyl acetate, etc. And (meth) acrylonitrile, styrenic monomers (for example, styrene and polymerizable styrene derivatives), and the like. Among them, methyl (meth) acrylate, n-butyl (meth) acrylate, styrene, and benzyl (meth) acrylate are preferable, and styrene is particularly preferable from the viewpoint of resolution.

  (A) The binder resin is prepared by mixing the first and second monomers and diluting with a solvent, for example, acetone, methyl ethyl ketone, or isopropanol, into a radical polymerization initiator, for example, benzoyl peroxide, azoiso It is preferable to synthesize by adding an appropriate amount of butyronitrile and stirring with heating. In some cases, the synthesis is performed while a part of the mixture is dropped into the reaction solution. After completion of the reaction, a solvent may be further added to the (a) binder resin to adjust to a desired concentration. As synthesis means, bulk polymerization, suspension polymerization, or emulsion polymerization may be used in addition to solution polymerization.

  (A) In the binder resin, the preferred copolymerization ratio of the first monomer and the second monomer is such that the first monomer is 10% by mass to 60% by mass and the second monomer The mass is 40% by mass to 90% by mass. More preferably, the first monomer is 15% by mass to 35% by mass, and the second monomer is 65% by mass to 85% by mass.

  (A) More specific examples of the binder resin include, for example, a polymer containing methyl methacrylate, methacrylic acid, and styrene as a copolymerization component, methyl methacrylate, methacrylic acid, and n-butyl acrylate as a copolymerization component. And a polymer containing benzyl methacrylate, methyl methacrylate and 2-ethylhexyl acrylate as a copolymerization component.

  In the embodiment, the content of (a) binder resin in the photosensitive resin element (however, based on the total solid content of the photosensitive resin element. Is the same in the components.) Is in the range of 20% by mass to 90% by mass, the preferred lower limit is 25% by mass, the preferred upper limit is 75% by mass, the more preferred lower limit is 40% by mass, and the more preferred upper limit is 65% by mass. It is. This content is preferably 20% by mass or more from the viewpoint of maintaining alkali developability, and on the other hand, 90% by mass from the viewpoint that the resist pattern formed by exposure sufficiently exhibits the performance as a resist. The following is preferable.

(B) Photopolymerizable unsaturated compound (b) The photopolymerizable unsaturated compound is, for example, a monomer having an addition polymerization property by having an ethylenically unsaturated bond. The ethylenically unsaturated bond is preferably a terminal ethylenically unsaturated group.

  (B) Specific examples of the photopolymerizable unsaturated compound include, for example, polyethylene glycol dimethacrylate in which 1 unit of ethylene oxide is added to both ends of bisphenol A, or 2 units of ethylene in both ends of bisphenol A, respectively. Polyethylene glycol dimethacrylate with oxide added, polyethylene glycol dimethacrylate with an average of 5 units of ethylene oxide at each end of bisphenol A, and polyethylene glycol dimethacrylate with an average of 7 units of ethylene oxide at each end of bisphenol A A polyalkylene glycol dimethacrylate and a bimethacrylate and bisphenol A each having an average of 6 units of ethylene oxide and an average of 2 units of propylene oxide added to both ends. Dimethacrylate phenol A polyalkylene glycols each obtained by adding propylene oxide ethylene oxide and average 2 units of the average 15 units at both ends of the preferred.

  From the viewpoint of high resolution, cured film peeling performance, and cured film flexibility, (b) as the photopolymerizable unsaturated compound, for example, 4-nonylphenylheptaethylene glycol dipropylene glycol acrylate or 4-nonyl Phenyl octaethylene glycol acrylate, 4-nonylphenyl tetraethylene glycol acrylate, 4-octylphenyl pentapropylene glycol acrylate, and the like are preferable.

  Specific examples of the other (b) photopolymerizable unsaturated compound include, for example, reaction of 2-hydroxy-3-phenoxypropyl acrylate, a half ester compound of phthalic anhydride and 2-hydroxypropyl acrylate, and propylene oxide. 1,6-hexanediol di (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, 2-di (p-hydroxyphenyl) propane di (meth) acrylate, pentaerythritol tetra (meth) acrylate, di Pentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethylolpropane triglycidyl ether tri (meth) acrylate, 2,2-bis (4-methacryloxypentaethoxyphenyl) propane, Lise triacrylate, triacrylate was acrylated trimethylol propane, tetraacrylate glycol obtained by adding an average 4 moles of ethylene oxide to pentaerythritol, and the like polyfunctional (meth) acrylate of isocyanuric acid ester compounds. These may be used alone or in combination of two or more.

  The content of (b) the photopolymerizable unsaturated compound in the photosensitive resin element is preferably in the range of 5% by mass to 75% by mass. This content is preferably 5% by mass or more, more preferably 15% by mass or more, and further preferably 30% by mass or more from the viewpoint of suppressing poor curing and delay in development time. On the other hand, this content is preferably 75% by mass or less, more preferably 60% by mass or less, and still more preferably 50% by mass or less from the viewpoint of suppressing cold flow and delayed peeling of the cured resist.

(C) Photopolymerization initiator (c) The photopolymerization initiator is a compound that polymerizes a monomer by light. As the (c) photopolymerization initiator, for example, those usually used as photopolymerization initiators for photosensitive resins can be used as appropriate. In particular, hexaarylbisimidazole (hereinafter also referred to as triarylimidazolyl dimer). Is preferably used.

  Examples of the triarylimidazolyl dimer include 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer (hereinafter referred to as “2,2′-bis (2-chlorophenyl) -4,4 ′, 5”). , 5′-tetraphenyl-1,1′-bisimidazole ”), 2,2 ′, 5-tris- (o-chlorophenyl) -4- (3,4-dimethoxyphenyl) -4 ′, 5 '-Diphenylimidazolyl dimer, 2,4-bis- (o-chlorophenyl) -5- (3,4-dimethoxyphenyl) -diphenylimidazolyl dimer,

  2,4,5-tris- (o-chlorophenyl) -diphenylimidazolyl dimer, 2- (o-chlorophenyl) -bis-4,5- (3,4-dimethoxyphenyl) -imidazolyl dimer, 2, 2′-bis- (2-fluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2′-bis- (2,3-difluoromethyl) Phenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2′-bis- (2,4-difluorophenyl) -4,4 ′, 5 5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer,

  2,2′-bis- (2,5-difluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2′-bis- (2, 6-difluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2′-bis- (2,3,4-trifluorophenyl) -4 , 4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2′-bis- (2,3,5-trifluorophenyl) -4,4 ′, 5,5 '-Tetrakis- (3-methoxyphenyl) -imidazolyl dimer,

  2,2′-bis- (2,3,6-trifluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2′-bis- (2,4,5-trifluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2′-bis- (2,4,6- Trifluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer,

  2,2′-bis- (2,3,4,5-tetrafluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2′- Bis- (2,3,4,6-tetrafluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, and 2,2′-bis- (2 , 3,4,5,6-pentafluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer and the like.

  In particular, 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer is a photopolymerization initiator having a high effect on resolution or the strength of a cured resist film, and is preferably used. The triarylimidazolyl dimers listed above may be used alone or in combination of two or more. The triarylimidazolyl dimers listed above can be used in combination with the following acridine compounds, pyrazoline compounds and the like.

  (C) As the photopolymerization initiator, an acridine compound or a pyrazoline compound is preferably used. Examples of the acridine compound include acridine, 9-phenylacridine, 9- (4-tolyl) acridine, 9- (4-methoxyphenyl) acridine, 9- (4-hydroxyphenyl) acridine, 9-ethylacridine, 9- Chloroethyl acridine, 9-methoxyacridine, 9-ethoxyacridine,

  9- (4-methylphenyl) acridine, 9- (4-ethylphenyl) acridine, 9- (4-n-propylphenyl) acridine, 9- (4-n-butylphenyl) acridine, 9- (4-tert -Butylphenyl) acridine, 9- (4-ethoxyphenyl) acridine, 9- (4-acetylphenyl) acridine, 9- (4-dimethylaminophenyl) acridine, 9- (4-chlorophenyl) acridine,

  9- (4-bromophenyl) acridine, 9- (3-methylphenyl) acridine, 9- (3-tert-butylphenyl) acridine, 9- (3-acetylphenyl) acridine, 9- (3-dimethylaminophenyl) ) Acridine, 9- (3-diethylaminophenyl) acridine, 9- (3-chlorophenyl) acridine, 9- (3-bromophenyl) acridine, 9- (2-pyridyl) acridine, 9- (3-pyridyl) acridine, Examples include 9- (4-pyridyl) acridine. Of these, 9-phenylacridine is preferable.

  Examples of the pyrazoline compound include 1-phenyl-3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline, 1- (4- (benzoxazol-2-yl) Phenyl) -3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-tert-butyl- Phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-tert-octyl-phenyl) -pyrazoline and the like.

  Examples of (c) photopolymerization initiator other than the above include, for example, 2-ethylanthraquinone, octaethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, Quinones such as 1-chloroanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, and 3-chloro-2-methylanthraquinone Benzophenone, Michler's ketone [4,4′-bis (dimethylamino) benzophenone], and aromatic ketones such as 4,4′-bis (diethylamino) benzophenone, benzoin, benzoin ethyl ether, benzoin phenyl ether, methylbenzoin, and Echi Benzoin ethers such as benzoin, benzyl dimethyl ketal, benzyl diethyl ketal, combinations of thioxanthones and alkylaminobenzoic acid, 1-phenyl-1,2-propanedione-2-O-benzoin oxime, 1-phenyl-1,2 -Oxime esters such as propanedione-2- (O-ethoxycarbonyl) oxime.

  Examples of the combination of the above thioxanthones and alkylaminobenzoic acid include, for example, a combination of ethylthioxanthone and ethyl dimethylaminobenzoate, a combination of 2-chlorothioxanthone and ethyl dimethylaminobenzoate, and isopropylthioxanthone and dimethylamino. A combination with ethyl benzoate and the like can be mentioned. Moreover, you may use N-arylamino acid as (c) photoinitiator. Examples of N-aryl amino acids include N-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N-phenylglycine and the like. Among these, N-phenylglycine is particularly preferable.

  The content of the photopolymerization initiator (c) in the photosensitive resin element is in the range of 0.01% by mass to 30% by mass, a more preferable lower limit is 0.05% by mass, and a further preferable lower limit is 0.00. 1 mass%, a more preferred upper limit is 15 mass%, and a more preferred upper limit is 10 mass%. (C) The content of the photopolymerization initiator is preferably 0.01% by mass or more from the viewpoint of obtaining sufficient sensitivity during photopolymerization by exposure, while the bottom surface of the photosensitive resin element ( That is, it is preferably 30% by mass or less from the viewpoint of sufficiently transmitting light to a portion far from the light source and obtaining good resolution and adhesion.

(D) Acetone and (e) Non-acetone solvent The preparation liquid contains (d) acetone and (e) non-acetone solvent. The preparation liquid comprises (a) a binder resin, (b) a photopolymerizable unsaturated compound and / or (c) a photopolymerization initiator in any order or collectively, (d) acetone and / Or (e) It is obtained by dissolving in non-acetone solvent and mixing.

  For example, (d) a binder resin is dissolved in a mixed solvent of (d) acetone and (e) non-acetone solvent to form a varnish, and (b) a photopolymerizable unsaturated compound, (c) light A polymerization initiator and / or (f) other additives are dissolved to obtain a crude preparation liquid. If desired, the crude preparation liquid and (d) acetone and / or (e) a non-acetone solvent are further mixed, You may obtain the preparation liquid which has desired solid content concentration. Therefore, (a) the binder resin is obtained by solution polymerization or suspension polymerization, but (a) the binder resin obtained by solution polymerization is at least one of (d) acetone or (e) a non-acetone solvent as a solvent. One may be included. (A) Since the solvent contained in the binder resin also acts as a solvent for the preparation liquid, when calculating the concentration or viscosity of the solid content in the preparation liquid, the solvent is added to the calculation.

(E) The non-acetone solvent is not particularly limited as long as it is a solvent other than acetone, but (i) an alcohol typified by ethanol, (ii) an ester typified by ethyl acetate, and (iii) It is preferably at least one selected from the group consisting of ethers typified by tetrahydrofuran. Further, (e) the non-acetone solvent is more preferably at least one selected from the group consisting of methanol, ethanol, normal propyl alcohol, isopropyl alcohol, and normal butanol, and particularly preferably ethanol.
In particular, the use of an alcohol typified by ethanol, which is a polar solvent, as (e) a non-acetone solvent is compared to (d) a preparation solution prepared using only acetone or only methyl ethyl ketone. From the viewpoint of improving the solubility of the polymerizable unsaturated compound and / or dye (f) other additives.

  In addition, the use of alcohol as the (e) non-acetone solvent tends to reduce the viscosity of the preparation liquid, and the solid content concentration in the preparation liquid can be set higher, which is preferable from the viewpoint of improving productivity.

  In addition, it is preferable to use alcohol as the (e) non-acetone solvent from the viewpoint of removing the solvent while maintaining a good dry film surface in the drying step. That is, it is preferable from the viewpoint of increasing the coating speed of the preparation liquid and improving the productivity of the photosensitive element. Here, “while maintaining the dry film surface satisfactorily” means that the film surface has high smoothness and little visual unevenness.

The ratio of the mass of (d) acetone to the total mass of (d) acetone and (e) non-acetone solvent is preferably 30% by mass or more, more preferably 40% by mass or more, and still more preferably 50% by mass or more. Especially preferably, it is 60 mass% or more. On the other hand, the upper limit is preferably 98% by mass or less, more preferably 90% by mass or less, still more preferably 80% by mass or less, and particularly preferably 70% by mass or less.
Moreover, as a ratio of the total solid content in a preparation liquid, Preferably it is 30 mass% or more, More preferably, it is 40 mass% or more, More preferably, it is 50 mass% or more. On the other hand, the upper limit is preferably 80% by mass or less, more preferably 70% by mass or less, and still more preferably 60% by mass or less.
Setting these ratios in such a range is to improve the smoothness of the film surface after drying, to reduce uncoated parts such as pinholes in the drying process, and to provide a good coated surface. From the viewpoint of obtaining.

In the present embodiment, the ratio of the mass of (d) acetone to the total mass of (d) acetone and (e) the non-acetone solvent, and the ratio of the total solid content in the preparation liquid are in the above ranges. Is set.
In addition, by combining invention specific matters with other invention specific matters in this way, a method for producing a photosensitive resin element having excellent productivity and good appearance is realized. The details of this mechanism are not detailed, but by setting the acetone ratio or the solid content ratio within a specific range, the drying of the solvent is appropriately controlled, and the smoothness of the film surface during drying is properly maintained. It is thought that it is.

In addition, as said (e) non-acetone solvent, ethanol is a main component (preferably 50 mass% or more, More preferably, it is 70 mass% or more, More preferably, it is 90 mass% or more, 100 mass% may be sufficient. ) Is preferably contained.
The viscosity of the preparation liquid is preferably 500 Pa · sec to 4000 mPa · sec as a viscosity at 25 ° C.

(F) Other additives In addition to the components (a) to (e), (f) other additives can be contained in the preparation liquid. Specifically, (f) other additives include, for example, coloring substances such as dyes and pigments. A base dye can be used as such a coloring substance. Examples of the base dye include basic green 1 [CAS number (hereinafter the same): 633-03-4], malachite green oxalate [2437-29-8], brilliant green [633-03-4], and fuchsin. [632-99-5], methyl violet [603-47-4], methyl violet 2B [8004-87-3], crystal violet [548-62-9], methyl green [82-94-0], Victoria Blue B [2580-56-5], Basic Blue 7 [2390-60-5], Rhodamine B [81-88-9], Rhodamine 6G [989-38-8], Basic Yellow 2 [2465-27-2 ] Etc. are mentioned. Of these, basic green 1, malachite green oxalate, and basic blue 7 are preferable, and basic green 1 and basic blue 7 are particularly preferable from the viewpoint of improving hue stability and exposure contrast.

  The content of the coloring substance in the photosensitive resin element is preferably 0.001% by mass to 1% by mass. When the content of the coloring material is 0.001% by mass or more, it is preferable because of the effect of improving the handleability. On the other hand, when it is 1% by mass or less, the storage stability is maintained. Therefore, it is preferable.

  In addition, a coloring agent such as a coloring dye may be contained in the preparation liquid so that a visible image can be provided by exposure. Examples of such coloring dyes include leuco dyes or combinations of fluorane dyes and halogen compounds.

  Examples of the leuco dye include tris (4-dimethylamino-2-methylphenyl) methane [leuco crystal violet], tris (4-dimethylamino-2-methylphenyl) methane [leucomalachite green], and fluorane dye. Etc. Among these, when leuco crystal violet is used, the contrast is good and preferable.

  Examples of the halogen compound include amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzal bromide, methylene bromide, tribromomethylphenyl sulfone, carbon tetrabromide, tris (2 , 3-dibromopropyl) phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis (p-chlorophenyl) ethane, hexachloroethane, chlorinated triazine compounds and the like. .

  The content of the color former in the photosensitive resin element is preferably independently from 0.1% by mass to 10% by mass.

  Furthermore, in order to improve the thermal stability and storage stability of the photosensitive resin composition, a radical polymerization inhibitor or at least one compound selected from the group consisting of benzotriazoles and carboxybenzotriazoles is prepared. It is preferable to make it contain.

  Examples of the radical polymerization inhibitor include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert-butylcatechol, cuprous chloride, 2,6-di-tert-butyl-p-cresol, 2,2′-methylenebis. (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), nitrosophenylhydroxyamine aluminum salt, diphenylnitrosamine and the like.

  Examples of benzotriazoles include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis (N-2-ethylhexyl) aminomethylene-1,2,3-benzotriazole, Bis (N-2-ethylhexyl) aminomethylene-1,2,3-tolyltriazole, bis (N-2-hydroxyethyl) aminomethylene-1,2,3-benzotriazole and the like can be mentioned.

  Examples of carboxybenzotriazoles include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, (N, N-dibutylamino) carboxybenzotriazole, N- ( N, N-di-2-ethylhexyl) aminomethylenecarboxybenzotriazole, N- (N, N-di-2-hydroxyethyl) aminomethylenecarboxybenzotriazole, N- (N, N-di-2-ethylhexyl) amino And ethylene carboxybenzotriazole.

  The total content of radical polymerization inhibitors, benzotriazoles, and / or carboxybenzotriazoles in the photosensitive resin element is preferably 0.001% by mass to 3% by mass, and a more preferable lower limit is 0.05% by mass. The upper limit is more preferably 1% by mass. The total content is preferably 0.001% by mass or more from the viewpoint of imparting storage stability to the photosensitive resin composition, and preferably 3% by mass or less from the viewpoint of maintaining sensitivity.

  The preparation liquid may contain other plasticizers as necessary. Examples of such plasticizers include polyethylene glycol, polypropylene glycol, polyoxypropylene polyoxyethylene ether, polyoxyethylene monomethyl ether, polyoxypropylene monomethyl ether, polyoxyethylene polyoxypropylene monomethyl ether, and polyoxyethylene monoethyl. Glyceres and esters such as ether, polyoxypropylene monoethyl ether, polyoxyethylene polyoxypropylene monoethyl ether, sorbitan derivatives such as polyoxyethylene sorbitan laurate and polyoxyethylene sorbitan oleate, and phthalates such as diethyl phthalate , O-toluenesulfonic acid amide, p-toluenesulfonic acid amide, tributyl citrate, citric acid Propylene glycol with propylene oxide added to both sides of bisphenol A and ethylene oxide to both sides of bisphenol A and triethyl acetylcitrate, tri-n-propyl acetylcitrate and tri-n-butyl acetylcitrate And ethylene glycol.

  The content of the plasticizer in the photosensitive resin element is preferably 0.1% by mass to 50% by mass, a more preferable lower limit is 1% by mass, and a more preferable upper limit is 30% by mass. This content is preferably 0.1% by mass or more from the viewpoint of suppressing delay in development time and imparting flexibility to the cured film, while being 50% from the viewpoint of suppressing insufficient curing and cold flow. % Or less is preferable.

  You may contain other antioxidant in a liquid preparation as needed. Examples of the antioxidant include triphenyl phosphite, tris (2,4-di-t-butylphenyl) phosphite, tris (monononylphenyl) phosphite, and bis (monononylphenyl) -dinonylphenyl phosphite. For example, fights.

  The content of the antioxidant in the photosensitive resin element is preferably in the range of 0.01% by mass to 0.8% by mass, the more preferable lower limit is 0.01% by mass, and the more preferable upper limit is 0.00. 3% by mass. When the content is 0.01% by mass or more, the effect of excellent hue stability of the photosensitive resin composition is favorably expressed, and the sensitivity at the time of exposure of the photosensitive resin composition is preferable. In the case where the content is 0.8% by mass or less, color developability is suppressed, so that hue stability is improved and adhesion is also improved.

<Support layer>
The support layer is a layer for supporting the photosensitive resin layer formed thereon. Moreover, the manufacturing method of the photosensitive resin element may include the process of forming a protective layer on the opposite side to the support layer side of the photosensitive resin element if desired.

  The support layer is preferably a transparent film that transmits light emitted from the exposure light source. Examples of such films include polyethylene terephthalate film, polyvinyl alcohol film, polyvinyl chloride film, vinyl chloride copolymer film, polyvinylidene chloride film, vinylidene chloride copolymer film, polymethyl methacrylate copolymer film, polystyrene. Examples include films, polyacrylonitrile films, styrene copolymer films, polyamide films, and cellulose derivative films. As these films, stretched films can be used as necessary. The haze of the support layer is preferably 5 or less. A thinner support layer is more advantageous in terms of image formation and economy, but a thickness of 10 μm to 30 μm is preferably used in order to maintain strength.

<Protective layer>
It is preferable that the protective layer has a property that the protective layer is sufficiently smaller than the support layer and can be easily peeled with respect to the adhesive strength with the photosensitive resin layer. For example, a polyethylene film and a polypropylene film can be preferably used as the protective layer. As the protective layer, for example, a film having excellent releasability disclosed in JP-A-59-202457 can be used. The thickness of the protective layer is preferably 10 μm to 100 μm, and more preferably 10 μm to 50 μm.

<Method for producing photosensitive resin element>
In the method for producing a photosensitive resin element, the step of applying the preparation liquid on the support layer and drying to form the photosensitive resin element on the support layer may be performed by a coating means and, optionally, a drying means. it can. As the coating means, for example, a spin coater, a die coater, a spray coater, dipping, printing, a blade coater, a roll coating, or the like can be used. As a drying means, for example, air drying, hot air drying, light irradiation, a hot plate, an inert oven, a temperature rising oven capable of setting a temperature program, or the like can be used. Moreover, the preparation of a plurality of components contained in the preparation liquid and the application and drying of the preparation liquid can be performed in an atmosphere of air or an inert gas such as nitrogen or argon.

The photosensitive resin element manufactured by the above-described manufacturing method is used for the manufacture of printed wiring boards, the manufacture of lead frames for IC chip mounting, the manufacture of metal foils such as the manufacture of metal masks, ball grid arrays (BGA), Manufacturing of packages such as size packages (CSP), manufacturing of tape substrates such as chip-on-film (COF) or tape automated bonding (TAB), manufacturing of semiconductor bumps, indium tin oxide (ITO) electrodes or address electrodes It is preferably used for manufacturing a partition wall of a flat panel display such as an electromagnetic wave shield.
According to the manufacturing method of this embodiment, the productivity of the photosensitive resin element useful for forming a printed circuit can be improved, and the appearance of the DF formed from the photosensitive resin element can be improved satisfactorily.

  Hereinafter, the present embodiment will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to the examples as long as the gist thereof is not exceeded.

[Examples 1 to 12 and Comparative Examples 1 to 8]
The components of the photosensitive resin composition shown in Table 1 or 2 were prepared, stirred and dissolved in a dissolution tank, and the prepared solution was filtered through a filter. Next, the prepared solution was sent to a die coater with a pump and uniformly applied onto a polyethylene terephthalate film as a support layer, and the solvent was sent to a drying zone to dry the solvent. Then, it laminated with the polyethylene film which is a protective layer, and obtained DF which has the thickness of the photosensitive layer described in Table 1 or 2. In the above steps, solubility evaluation, coating speed evaluation, coating property evaluation, and appearance evaluation were performed by the following methods. Moreover, the weight average molecular weight of resin was measured by the method shown below. The results are shown in Table 1 or 2.

  In addition, Teijin's GR-16 (16 μm thickness) is used as the polyethylene terephthalate as the support layer, and Tamapoly Co., Ltd. GF-18 (19 μm thickness) is used as the polyethylene film as the protective layer. used.

(1) Solubility evaluation When the prepared solution was filtered through a filter, the degree of clogging of the filter was evaluated according to the following rank. When there is little clogging, it shows that the solubility is good.
The aperture of the filter is 3 μm.
A: Good with no clogging.
B: Some clogging occurs, but filtration is possible.
C: Filter clogging occurs, and filtration becomes impossible within 1 hour.

(2) Evaluation of coating speed Based on the preparation liquid described in Comparative Example 1 using only methyl ethyl ketone as a solvent, the maximum coating speed at which there was no uncoated portion and was applied uniformly and smoothly was observed.
Next, for each preparation liquid, the maximum coating speed applied uniformly and smoothly without an uncoated part is observed, and the maximum coating speed observed in the preparation liquid of Comparative Example 1 is set to 1, and the ratio to that evaluated. When the evaluation is greater than 1, it indicates that the maximum coating speed of the preparation liquid is faster than that of the preparation liquid when only methyl ethyl ketone is used as a solvent.

(3) Evaluation of coating properties At the maximum coating speed observed in Comparative Example 1, coating of various preparations was performed. Using a die coater, the state of the photosensitive resin layer obtained by applying the prepared solution on the polyester as the support layer was evaluated according to the following rank.
S: There is no uncoated part, and smoothness is high.
A: There is no uncoated part and it is applied smoothly.
B: Some uncoated parts.
C: Most of the uncoated part.

(4) Appearance evaluation After using a die coater to apply the prepared solution onto the polyester serving as the support layer, drying the solvent, laminating with a polyethylene film serving as the protective layer, and supporting layer / photosensitive layer / protective layer 3 Appearance evaluation was performed on the roll-shaped laminate obtained by the layer structure, and the following rank was evaluated (see FIG. 1).
S: The appearance of the roll product having a three-layer structure is uniform without any unevenness on the surface.
A: The appearance of the roll product having a three-layer structure is uniform with almost no unevenness on the surface.
B: The appearance of the roll product having a three-layer structure is not uniform because the entire surface is uneven.

(5) Weight average molecular weight The weight average molecular weight (Mw) of resin was measured by the gel permeation chromatography method (standard polystyrene conversion). The column used for the measurement was a trade name Shodex 805M / 806M series manufactured by Showa Denko KK, the standard monodisperse polystyrene was Shodex STANDARD SM-105 manufactured by Showa Denko KK, and the developing solvent was N-methyl-2- It was pyrrolidone, and the detector used was a trade name Shodex RI-930 manufactured by Showa Denko.

<Symbol explanation>
P-1: Methyl ethyl ketone solution of ternary copolymer of 65% by mass of methyl methacrylate, 25% by mass of methacrylic acid and 10% by mass of butyl acrylate (solid content mass ratio 30%, weight average molecular weight 100,000, acid equivalent 344)
P-2: A mixture of acetone and ethanol of a terpolymer of 65% by mass of methyl methacrylate, 25% by mass of methacrylic acid and 10% by mass of butyl acrylate (mass ratio of solvent: acetone / ethanol = 80/20, solid content) (Mass ratio 40%, weight average molecular weight 100,000, acid equivalent 344)
P-3: A mixture of acetone and ethanol of a terpolymer of 65% by mass of methyl methacrylate, 25% by mass of methacrylic acid and 10% by mass of butyl acrylate (mass ratio of solvent: acetone / ethanol = 80/20, solid content) (Mass ratio 75%, weight average molecular weight 100,000, acid equivalent 344)
P-4 :: 65% by mass of methyl methacrylate, 25% by mass of methacrylic acid, and an acetone solution of a terpolymer of 10% by mass of butyl acrylate (solid content mass ratio 32%, weight average molecular weight 100,000, acid equivalent 344) )
P-5: Methyl ethyl ketone solution of ternary copolymer of methyl methacrylate 67 mass%, methacrylic acid 23 mass%, butyl acrylate 10 mass% (solid content mass ratio 25%, weight average molecular weight 200,000, acid equivalent 374)
P-6: A mixture of acetone and ethanol of a terpolymer of 67% by mass of methyl methacrylate, 23% by mass of methacrylic acid and 10% by mass of butyl acrylate (mass ratio of solvent: acetone / ethanol = 80/20, solid content) (Mass ratio 34%, weight average molecular weight 200,000, acid equivalent 374)
P-7: Methyl ethyl ketone solution of ternary copolymer of methyl methacrylate 50% by mass, methacrylic acid 25% by mass, styrene 25% by mass (solid content mass ratio 35%, weight average molecular weight 50,000, acid equivalent 344)
P-8: A mixed solution of acetone and ethanol of a terpolymer of 50% by mass of methyl methacrylate, 25% by mass of methacrylic acid and 25% by mass of styrene (solvent mass ratio: acetone / ethanol = 75/25, mass ratio of solid content) 47%, weight average molecular weight 50,000, acid equivalent 344)
P-9: Methyl ethyl ketone and ethanol mixed solution of 50% by mass of methyl methacrylate, 25% by mass of methacrylic acid and 25% by mass of styrene (solvent mass ratio: methyl ethyl ketone / ethanol = 75/25, solid content mass ratio 45%, weight average molecular weight 50,000, acid equivalent 344)
M-1: Polyethylene glycol dimethacrylate (BPE-200 manufactured by Shin-Nakamura Chemical Co., Ltd.) obtained by adding an average of 2 moles of ethylene oxide to both ends of bisphenol A.
M-2: Polyethylene glycol dimethacrylate (BPE-500 manufactured by Shin-Nakamura Chemical Co., Ltd.) having an average of 5 moles of ethylene oxide added to both ends of bisphenol A.
M-3: Polyalkylene glycol dimethacrylate having an average of 2 mol of propylene oxide and an average of 6 mol of ethylene oxide added to both ends of bisphenol A, respectively. M-4: An average of 12 mol of propylene oxide was added. Polyalkylene glycol dimethacrylate M-5 in which ethylene oxide is further added to polypropylene glycol at an average of 3 moles at both ends, respectively, and hexamethylene diisocyanate and oligopropylene glycol monomethacrylate (Nippon Yushi Co., Ltd., Bremer-PP1000) Urethane product M-6: acrylate obtained by adding an average of 3 moles of ethylene oxide to trimethylolpropane (A-TMPT-3EO manufactured by Shin-Nakamura Chemical Co., Ltd.)
M-7: 4-nonylphenylheptaethylene glycol dipropylene glycol acrylate I-1: 4,4'-bis (diethylamino) benzophenone I-2: 2- (o-chlorophenyl) -4,5-diphenylimidazole Dimer D-1: Diamond Green D-2: Leuco Crystal Violet A-1: p-Toluenesulfonamide A-2: Benzotriazole A-3: Aluminum salt 3 mol of nitrosophenylhydroxylamine added A-4: An average of 1 mol of propylene oxide is added to both ends of bisphenol A, and an average of 1 mol of glycidyl group is added to each end. A-5: Polypropylene glycol A having an average of 2 mol of propylene oxide added to both ends of bisphenol A -6: Ciba Special Chemicals Co., Ltd. IRGANOX245
A-7: New Coal 3-85 (manufactured by Nippon Emulsifier Co., Ltd.)
S-1: Acetone S-2: Ethanol S-3: Methyl ethyl ketone

  The photosensitive resin element manufactured according to the present invention can be used for the manufacture of printed wiring boards, the manufacture of lead frames for mounting IC chips, the precision processing of metal foils such as the manufacture of metal masks, the manufacture of packages such as BGA or CSP, COF or TAB, etc. It can be used for the production of tape substrates, semiconductor bumps, ITO electrodes or address electrodes, and the partition walls of flat panel displays such as electromagnetic wave shields.

Claims (8)

The following steps:
(A) Resin for binder whose carboxyl group content is 100-600 in an acid equivalent, and whose weight average molecular weight is 5000-500,000,
(B) a photopolymerizable unsaturated compound,
(C) a photopolymerization initiator,
(D) acetone,
(E) a non-acetone solvent, and (f) a step of preparing a benzotriazole not substituted with a carboxy group or a carboxybenzotriazole to obtain a preparation solution, wherein (d) the acetone and the benzotriazole (e) the ratio of the weight of the (d) acetone to the total weight of the non-acetone solvent is 30 wt% to 98 wt%, the ratio of the total solids in該調Goeki is 30 wt% to 80 wt% der is, and the (e) non-acetone solvent is ethanol; and applying the該調if liquid onto the support layer and dried to form a photosensitive resin element for a printed circuit formed on the support layer Process;
For producing a photosensitive resin element for forming a printed circuit. The dried film thickness of preparations is 5 m to 50 m, The method of claim 1. The method according to claim 1 or 2 , wherein the preparation liquid contains benzotriazoles not substituted with a carboxy group. The benzotriazoles not substituted with the carboxy group are 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis (N-2-ethylhexyl) aminomethylene-1, Consists of 2,3-benzotriazole, bis (N-2-ethylhexyl) aminomethylene-1,2,3-tolyltriazole, and bis (N-2-hydroxyethyl) aminomethylene-1,2,3-benzotriazole The method according to claim 3 , wherein the method is at least one compound selected from the group. The method according to claim 1 or 2 , wherein the preparation liquid contains carboxybenzotriazoles. The carboxybenzotriazoles include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, (N, N-dibutylamino) carboxybenzotriazole, N- (N, N-di-2-ethylhexyl) aminomethylenecarboxybenzotriazole, N- (N, N-di-2-hydroxyethyl) aminomethylenecarboxybenzotriazole, and N- (N, N-di-2-ethylhexyl) aminoethylene The method according to claim 5 , wherein the compound is at least one compound selected from the group consisting of carboxybenzotriazole. The following steps:
(A) Resin for binder whose carboxyl group content is 100-600 in an acid equivalent, and whose weight average molecular weight is 5000-500,000,
(B) a photopolymerizable unsaturated compound,
(C) a photopolymerization initiator,
(D) acetone, and (e) a step of preparing a non-acetone solvent to obtain a preparation solution, wherein the mass of (d) acetone relative to the total mass of (d) acetone and (e) non-acetone solvent The proportion of total solids in the formulation is 30% to 80% by weight, and the (e) non-acetone solvent is ethanol; And applying the prepared solution on a support layer and drying to form a photosensitive resin element on the support layer;
The manufacturing method of the photosensitive resin element containing this. The method of Claim 7 whose film thickness after drying of the said preparation liquid is 5 micrometers-50 micrometers.