TW201405247A - Method for producing photosensitive resin element - Google Patents

Abstract

The present invention addresses the problem of providing a method for producing a photosensitive resin element that has excellent productivity and good appearance. The present invention provides a method for producing a photosensitive resin element, which comprises: a step for obtaining a liquid blend by blending (a) a binder resin that has a weight average molecular weight of 5,000-500,000 and a carboxyl group content of 100-600 in terms of acid equivalent, (b) a photopolymerizable unsaturated compound, (c) a photopolymerization initiator, (d) acetone and (e) a non-acetone solvent, with the mass ratio of (d) the acetone to the total mass of (d) the acetone and (e) the non-acetone solvent being 30-98% by mass and with the ratio of the total solid content in the liquid blend being 30-80% by mass; and a step wherein the liquid blend is applied onto a supporting layer and dried thereon, thereby forming a photosensitive resin element on the supporting layer.

Description

Method for producing photosensitive resin element

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

The method for producing a photosensitive resin composition for producing a printed circuit generally comprises the steps of: a resin for a binder, a photopolymerizable unsaturated compound, a photopolymerization initiator, and a dye equal to methyl ethyl ketone. A solvent such as an ester represented by a ketone or an ethyl acetate or an ether represented by tetrahydrofuran is uniformly stirred and dissolved in a solvent. For example, Patent Document 1 discloses a photosensitive resin preparation liquid prepared by using a mixed solvent of methyl ethyl ketone / 1-methoxy-2-propanol = 2 / 1 (weight ratio). In addition, the obtained preparation liquid can be uniformly applied to a polyester film or the like as a support layer by a die coater or the like, and the solvent can be dried in a drying step to obtain a photosensitive resin laminate. Further, it is also possible to obtain a photosensitive resin laminate having a three-layer structure by lamination with a polyethylene film or the like as a protective layer. These laminates are generally referred to as dry film photoresists (hereinafter referred to as "DF (Dry Film)").

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. Hei 11-143069

However, in the prior manufacturing method using methyl ethyl ketone as a main component of the solvent, the solubility of the binder resin and the photopolymerizable unsaturated compound and the dye are added. The solubility of the agent is not sufficient, so that filter plugging often occurs when the blending solution is filtered. Further, there is still room for improvement in terms of reducing the minute irregularities on the surface of the manufactured DF and lowering the frequency of unevenness observed in the visual inspection of the appearance.

Therefore, an object of the present invention is to provide a method for producing a photosensitive resin element which is excellent in productivity and excellent in appearance.

In order to solve the above problems, the inventors of the present invention have conducted intensive studies. As a result, it has been found that when a photosensitive resin composition is prepared by using a mixed solvent containing acetone in the preparation of the above-mentioned preparation liquid, the productivity is improved, and the appearance of the produced DF is all the same. It is equally good and thus completes the present invention. That is, the present invention is as follows.

[1] A method for producing a photosensitive resin element, comprising the steps of: (a) a binder resin having a carboxyl group content of from 100 to 600 in terms of acid equivalent, and a weight average molecular weight of from 5,000 to 500,000, (b) a step of obtaining a blending solution by blending a photopolymerizable unsaturated compound, (c) a photopolymerization initiator, (d) acetone, and (e) a non-acetone solvent, wherein the mass of the (d) acetone is relative to The ratio of the total mass of the (d) acetone to the (e) non-acetone solvent is 30% by mass to 98% by mass, and the ratio of the total solid content in the blending liquid is 30% by mass to 80% by mass; The preparation liquid is applied to the support layer and dried to form a photosensitive resin member on the support layer.

[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 above alcohol is selected from the group consisting of methanol, ethanol, n-propanol, and isopropyl a group consisting of alcohol and n-butanol.

[4] The method according to [3], wherein the above alcohol is ethanol.

[5] The method according to [2], wherein the above ester is ethyl acetate.

[6] The method according to [2], wherein the above ether is tetrahydrofuran.

[7] The method according to any one of [1] to [6] wherein the film thickness after drying of the above-mentioned preparation liquid is 5 μm to 50 μm.

Moreover, the present invention also provides a method of producing DF by applying the above-mentioned preparation liquid to a support layer and drying it, and further, by manufacturing a surface layer protective layer of a photosensitive resin layer laminated on the support layer, The method of DF of structure.

According to the present invention, there is provided a method for producing a photosensitive resin element which is excellent in productivity and excellent in appearance.

Fig. 1 (1) is a photograph showing the appearance of a rolled laminated body having an appearance evaluation of S, and Fig. 1 (2) is a photograph showing the appearance of a rolled laminated body having an appearance evaluation of A, and Fig. 1 (3) is a photograph. A photograph showing the appearance of the rolled laminated body of the appearance evaluation B.

Hereinafter, the best mode for carrying out the invention (hereinafter, simply referred to as "the form of implementation") will be described in detail. The present invention is not limited to the embodiment, and various modifications can be made without departing from the spirit and scope of the invention.

In the embodiment, the photosensitive resin element can be produced by a method comprising the steps of: (a) a binder resin having a carboxyl group content of from 100 to 600 in terms of acid equivalent, and a weight average molecular weight of from 5,000 to 500,000. (b) photopolymerizable unsaturated compound, (c) photopolymerization initiator, (d) acetone, (e) a non-acetone solvent, and a step of blending according to the desired (f) other additives to obtain a blending solution; and applying the blending solution to the support layer and drying on the support layer A step of forming a photosensitive resin element.

The term "photosensitive element" refers to a person who changes its properties by receiving light. The photosensitive element can be, for example, a film, a plate, a sheet, a roll, a molded article, or the like, and may be, for example, a photosensitive resin or a photosensitive resin. More specifically, a composition containing a photosensitive resin (hereinafter referred to as "photosensitive resin composition") is applied onto a support layer such as a film to thereby form a layer containing a photosensitive resin (hereinafter referred to as " The photosensitive resin layer ") is preferably a photosensitive resin layer obtained by laminating the support layer. Further, the photosensitive resin composition may be in any state (for example, liquid, solid, emulsion, suspended matter, etc.), but is preferably a liquid containing a photosensitive resin (hereinafter also referred to as "mixing solution"). Further, a portion of the photosensitive resin layer of the photosensitive resin laminate is exposed, and a protective material (for example, a protective film or a spacer film) is laminated and wound up, whereby the photosensitive resin roll obtained as a photosensitive element is further used. Preferably, it is in the form of a dry film roll in which the photosensitive resin roll is entirely or the photosensitive resin layer is partially dried.

The thickness of the photosensitive resin element produced by using the preparation liquid containing the components (a) to (f) (thickness after drying the solvent) is preferably 5 μm to 50 μm. From the viewpoint of the accuracy of applying the preparation liquid to the support layer, the thickness of the photosensitive resin element is preferably adjusted to 5 μm or more, and on the other hand, from the viewpoint of the drying property in the drying step, it is preferred. The thickness of the photosensitive resin element is adjusted to 50 μm or less. The thickness of the photosensitive resin element is more preferably from 30 μm to 50 μm.

In addition, the thinner the photosensitive resin layer is, the higher the resolution is, and the thicker the photosensitive resin layer is, the higher the film strength is. Therefore, the film thickness can be appropriately selected depending on the application.

<mixing solution>

The blending solution preferably contains (a) a binder resin, (b) a photopolymerizable unsaturated compound, (c) a photopolymerization initiator, (d) acetone, and (e) a non-acetone solvent, and as needed Contains (f) other additives.

In the method for producing a photosensitive resin element, the ratio of the total solid content in the preparation liquid is preferably from 30% by mass to 80% by mass. The ratio of the total solid content in the blending liquid is, for example, the solid content of the blending liquid obtained by dissolving the components (a) to (c) and (f) in (d) acetone and (e) a non-acetone solvent. In order to obtain the effect of improving the coating speed and controlling the amount of solvent to be evaporated and evaporated, the ratio of the total solid content in the preparation liquid is preferably 30% by mass or more. On the other hand, the preparation liquid is used. From the viewpoint of uniformity, the ratio of the total solid content in the preparation liquid is preferably 80% by mass or less. The ratio of the total solid content in the blending liquid is more preferably 40% by mass to 60% by mass.

Hereinafter, the components (a) to (f) will be described in detail.

(a) Resin for resin

(a) The carboxyl group content of the binder resin is from 100 to 600 in terms of acid equivalent, and the weight average molecular weight is from 5,000 to 500,000, and the resin for the binder can be used as a binder.

(a) The carboxyl group in the resin for a binder is preferably provided to the photosensitive resin element for developability or releasability to an alkaline aqueous solution. The acid equivalent is preferably 100 or more from the viewpoint of development resistance, resolution, and adhesion. On the other hand, the acid equivalent is preferably 600 or less from the viewpoint of developability and peelability.

In addition, the weight average molecular weight of the resin for the adhesive (a) is preferably 5,000 or more, and more preferably 20,000 or more, from the viewpoint of maintaining the uniformity of the thickness of the DF and obtaining the resistance to the developer. On the other hand, the weight average molecular weight of the (a) binder resin is preferably 500,000 or less, and more preferably 300,000 or less, from the viewpoint of maintaining developability.

Further, a preferred molecular weight distribution is 1.5 or more, and more preferably 2 or more. On the other hand, the upper limit is preferably 7 or less, 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 of the following first monomers and at least one of the following second monomers.

The first single system is a monomer having 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. Among them, (meth)acrylic acid is preferred. In the present specification, the term "(meth)acrylic acid" means acrylic acid or methacrylic acid.

The second single system 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, and (meth)acrylic acid. Butyl ester, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, (meth)acrylic acid ring An ester of vinyl alcohol such as hexyl ester, 2-ethylhexyl (meth)acrylate, benzyl (meth)acrylate or vinyl acetate; (meth)acrylonitrile, styrene monomer (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 preferred, and from the viewpoint of resolution, styrene is particularly preferably used.

(a) The resin for the binder is preferably added by adding a proper amount of radical polymerization to the solution in which the first and second monomers are mixed and diluted in a solvent such as acetone, methyl ethyl ketone or isopropyl alcohol. An initiator such as benzamidine peroxide or azoisobutyronitrile is synthesized by heating and stirring. There is also a case where one part of the mixture is added dropwise to the reaction liquid for synthesis. After the completion of the reaction, the solvent is further added to the (a) binder resin to adjust the concentration to the desired concentration. As the synthesis method, in addition to solution polymerization, bulk polymerization, suspension polymerization, or emulsion polymerization may also be used.

In (a) the resin for a binder, a preferred copolymerization ratio of the first monomer to the second monomer is 10% by mass to 60% by mass of the first monomer, and 40% by mass to 90% of the second monomer. quality %. 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.

More specific examples of the (a) binder resin include a polymer containing methyl methacrylate, methacrylic acid, and styrene as a copolymerization component; and methyl methacrylate and methacrylic acid; A polymer of 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 amount of the resin for the adhesive (a) in the photosensitive resin element (the total amount of the solid content of the adhesive resin element) is hereinafter, unless otherwise specified. The same in the composition is in the range of 20% by mass to 90% by mass, preferably the lower limit is 25% by mass, the upper limit is preferably 75% by mass, the lower limit is more preferably 40% by mass, and the upper limit is more preferably 65% by mass. In view of maintaining the alkali developability, the content is preferably 20% by mass or more. On the other hand, the photoresist pattern formed by exposure sufficiently exhibits the performance as a photoresist. It is preferably 90% by mass or less.

(b) Photopolymerizable unsaturated compounds

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

Specific examples of the (b) photopolymerizable unsaturated compound are, for example, polyethylene glycol dimethacrylate in which an average of one unit of ethylene oxide is added to both ends of bisphenol A, or Adding an average of 2 units of ethylene glycol to the bisphenol A to form a polyethylene glycol dimethacrylate, respectively, and adding an average of 5 units of ethylene oxide to the bisphenol A Diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate with an average of 7 units of ethylene oxide added to both ends of bisphenol A, respectively, added to both ends of bisphenol A An average of 6 units of ethylene oxide with an average of 2 units of propylene oxide of a polyalkylene glycol dimethyl group The acrylate was added to the both ends of bisphenol A to form an average of 15 units of ethylene oxide and an average of 2 units of propylene oxide of a polyalkylene glycol dimethacrylate.

As the (b) photopolymerizable unsaturated compound, for example, 4-nonylphenylheptyl glycol dipropylene glycol is preferred from the viewpoint of high resolution, peeling property of the cured film, and softness of the cured film. Acrylate or 4-mercaptophenyl octylene glycol acrylate, 4-mercaptophenyltetraethylene glycol acrylate, 4-octylphenyl pentylene glycol acrylate, and the like.

Specific examples of the other (b) photopolymerizable unsaturated compound include, for example, 2-hydroxy-3-phenoxypropyl acrylate, a half ester compound of phthalic anhydride and 2-hydroxypropyl acrylate. Reactive reactant of propylene oxide, 1,6-hexanediol di(meth)acrylate, 1,4-cyclohexanediol di(meth)acrylate, 2-di(p-hydroxyphenyl)propane di Methyl) acrylate, pentaerythritol tetra(meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethylolpropane triglycidyl ether tri(meth) acrylate Ester, 2,2-bis(4-methylpropenyloxypentyloxyphenyl)propane, glycerol triacrylate, triacrylate which acrylates trimethylolpropane, and pentaerythritol A tetraacrylate having an average of 4 moles of ethylene oxide diol, and a polyfunctional (meth) acrylate of an isomeric cyanurate compound. These may be used alone or in combination of two or more.

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

(c) Photopolymerization initiator

(c) A photopolymerization initiator is a compound which polymerizes a monomer by light. As the (c) photopolymerization initiator, for example, a photopolymerization initiation of a usual user as a photosensitive resin can be suitably used. The agent, but particularly preferably a hexaarylbisimidazole (hereinafter, also referred to as a triarylimidazolyl dimer) can be preferably used.

Examples of the triarylimidazolyl dimer include 2-(o-chlorophenyl)-4,5-diphenylimidazolyl dimer (hereinafter, also referred to as "2,2'-bis(2- Chlorophenyl)-4,4',5,5'-tetraphenyl-1,1'-bisimidazolium), 2,2',5-tris-(o-chlorophenyl)-4-(3, 4-Dimethoxyphenyl)-4',5'-diphenylimidazolyl dimer, 2,4-bis-(o-chlorophenyl)-5-(3,4-dimethoxybenzene Bis-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-difluoromethylphenyl)-4,4',5,5'-tetra-(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'-tetra-(3-methoxyphenyl)-imidazolyl dimer, 2,2' - bis-(2,6-difluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-imidazolyl dimer, 2,2'-bis-( 2,3,4-Trifluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-imidazolyl dimer, 2,2'-bis-(2, 3,5-trifluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-imidazolyl dimer,

2,2'-bis-(2,3,6-trifluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-imidazolyl dimer, 2, 2'-bis-(2,4,5-trifluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-imidazolyl dimer, 2,2' - bis-(2,4,6-trifluorophenyl)-4,4',5,5'-tetra-(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 Polymer, etc.

Especially 2-(o-chlorophenyl)-4,5-diphenylimidazolyl dimers for resolution or hardening A photopolymerization initiator having a high effect of the strength of the photoresist film can be preferably used. The triaryl imidazolyl dimers listed above may be used singly or in combination of two or more. Further, the above-mentioned triaryl imidazolyl dimer may be used in combination with the following acridine compound, pyrazoline compound or the like.

As the (c) photopolymerization initiator, an acridine compound or a pyrazoline compound can be preferably used. Examples of the acridine compound include acridine, 9-phenyl acridine, 9-(4-methylphenyl)acridine, 9-(4-methoxyphenyl)acridine, and 9-(4-hydroxyl group. Phenyl) acridine, 9-ethyl acridine, 9-chloroethyl acridine, 9-methoxyacridine, 9-ethoxy acridine,

9-(4-methylphenyl)acridine, 9-(4-ethylphenyl)acridine, 9-(4-n-propylphenyl)acridine, 9-(4-n-butylphenyl) Acridine, 9-(4-t-butylphenyl) acridine, 9-(4-ethoxyphenyl)acridine, 9-(4-ethylphenylphenyl)acridine, 9-( 4-dimethylaminophenyl)acridine, 9-(4-chlorophenyl)acridine,

9-(4-bromophenyl)acridine, 9-(3-methylphenyl)acridine, 9-(3-tert-butylphenyl)acridine, 9-(3-ethylmercaptophenyl 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, 9-(4-pyridyl)acridine, and the like. Among them, 9-phenyl acridine is preferred.

As the pyrazoline compound, for example, 1-phenyl-3-(4-t-butyl-styryl)-5-(4-t-butyl-phenyl)-pyrazoline, 1- (4-(benzoxyl) Zin-2-yl)phenyl)-3-(4-t-butyl-styryl)-5-(4-t-butyl-phenyl)-pyrazoline, 1-phenyl-3- (4-biphenyl)-5-(4-t-butyl-phenyl)-pyrazoline, 1-phenyl-3-(4-biphenyl)-5-(4-t-octyl -Phenyl)-pyrazoline and the like.

Examples of the photopolymerization initiator other than the above (c) include 2-ethyl hydrazine, octaethyl hydrazine, 1,2-benzopyrene, 2,3-benzopyrene, and 2- Phenylhydrazine, 2,3-diphenylfluorene, 1-chloroindole, 1,4-naphthoquinone, 9,10-phenanthrenequinone, 2-methyl-1,4-naphthoquinone, 2,3 - quinones such as dimethyl hydrazine and 3-chloro-2-methyl hydrazine, benzophenone, and miscene [4,4'-bis(dimethylamino)benzophenone], And aromatic ketones such as 4,4'-bis(diethylamino)benzophenone, benzoin, benzoin ether, benzoin phenyl ether, methyl benzoin, and ethyl benzoin and other benzoin ethers, benzoin Ketal ketone, benzoin diethyl ketal, 9-oxo sulfur Combination with alkylaminobenzoic acid, 1-phenyl-1,2-propanedione-2-O-benzoin, 1-phenyl-1,2-propanedione-2-(O-B An oxocarbonyl group such as oxycarbonyl.

Furthermore, as the above 9-oxygen sulfur A combination of a class and an alkylaminobenzoic acid, for example, ethyl 9-oxosulfuric acid Combination with ethyl dimethylaminobenzoate, 2-chloro 9-oxosulfur Combination with ethyl dimethylaminobenzoate and isopropyl 9-oxosulfur Combination with ethyl dimethylaminobenzoate and the like. Further, as the (c) photopolymerization initiator, an N-arylamino acid can also be used. Examples of the N-arylamino acid include N-phenylglycine, N-methyl-N-phenylglycine, and N-ethyl-N-phenylglycine. Among them, particularly preferred is N-phenylglycine.

The content of the (c) photopolymerization initiator in the photosensitive resin element is in the range of 0.01% by mass to 30% by mass, more preferably 0.05% by mass, and further preferably 0.1% by mass, more preferably 15% by mass. %, and further preferably, the lower limit is 10% by mass. The content of the (c) photopolymerization initiator is preferably 0.01% by mass or more from the viewpoint of obtaining sufficient sensitivity when photopolymerization by exposure, and on the other hand, the light is sufficiently transmitted to the photosensitive layer during photopolymerization. The content of the photopolymerization initiator (c) is preferably 30% by mass or less from the viewpoint of obtaining a good resolution and adhesion of the bottom surface of the resin element (that is, a portion farther from the light source).

(d) acetone and (e) non-acetone solvent

The blending solution contains (d) acetone and (e) a non-acetone solvent. The blending solution can be prepared by dissolving the above (a) binder resin, the above (b) photopolymerizable unsaturated compound, and/or the above (c) photopolymerization initiator in (d) by any order or once. Obtained by mixing acetone and/or (e) a non-acetone solvent.

For example, (a) a binder resin can be dissolved in a mixed solvent of (d) acetone and (e) a non-acetone solvent to form a varnish, (b) a photopolymerizable unsaturated compound, and (c) photopolymerization. The initiator and/or (f) other additives are dissolved in the varnish to obtain a crude solution, and the crude solution is mixed with (d) acetone and/or (e) non-acetone solvent as needed to obtain A blending solution of the concentration of solid components required. Therefore, although (a) the binder resin can be obtained by solution polymerization or suspension polymerization, the (a) binder resin can also contain (d) acetone or (e) non-acetone solvent. At least one of them is used as a solvent. (a) The solvent contained in the resin for the binder also functions as a solvent for the preparation liquid. Therefore, when the concentration or viscosity of the solid content in the preparation liquid is determined, the amount of 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, and is preferably selected from the group consisting of (i) an alcohol represented by ethanol, (ii) an ester represented by ethyl acetate, and (iii) tetrahydrofuran. At least one of the group consisting of ethers. Further, the (e) non-acetone solvent is more preferably at least one selected from the group consisting of methanol, ethanol, n-propanol, isopropanol, and n-butanol, and particularly preferably ethanol.

The solubility of (b) photopolymerizable unsaturated compound and/or dye, etc. (f) other additives is improved as compared with a preparation liquid prepared by using only (d) acetone or only methyl ethyl ketone. In view of the above, it is particularly preferred to use an alcohol represented by ethanol as a polar solvent as the (e) non-acetone solvent.

Further, in order to reduce the viscosity of the preparation liquid, it is preferable to use alcohol as the (e) non-acetone solvent from the viewpoint of higher setting of the solid content concentration in the preparation liquid and further improvement of productivity.

Further, from the viewpoint of maintaining the surface of the dried film well and removing the solvent in the drying step, it is preferred to use an alcohol as the (e) non-acetone solvent. That is, it is preferable from the viewpoint of improving the coating speed of the preparation liquid and improving the productivity of the photosensitive element. In addition, "preserving the surface of the dried film well" means that the smoothness of the surface of the film is high, and the appearance unevenness by visual observation is small.

(d) The ratio of the mass of acetone to the total mass of the above (d) acetone and the above (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. The mass% or more is particularly preferably 60% by 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, the ratio of the total solid content in the preparation liquid is preferably 30% by mass or more, more preferably 40% by mass or more, and still more preferably 50% by mass or more. On the other hand, the upper limit is preferably 80% by mass or less, more preferably 70% by mass or less, still more preferably 60% by mass or less.

From the viewpoint of improving the smoothness of the surface of the film after drying, the viewpoint of reducing the uncoated portion such as pinholes in the drying step, and the viewpoint of obtaining a good coated surface, it is preferable to set the ratio to As in the above range.

In the present embodiment, the ratio of the mass of (d) acetone to the total mass of the above (d) acetone and the (e) non-acetone solvent, and the ratio of the total solid content in the preparation liquid are set as described above. range.

In addition, as described above, the invention-specific matters are combined with other invention-specific matters, thereby realizing a method for producing a photosensitive resin element which is excellent in productivity and excellent in appearance. Although the details of the mechanism are not clear, it is considered that by setting the acetone ratio or the solid content ratio to a specific range, the drying of the solvent can be appropriately controlled, and the smoothness of the film surface during drying can be appropriately maintained. .

Further, the (e) non-acetone solvent preferably contains ethanol as a main component (preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 90% by mass or more, or 100%). quality%).

Further, the viscosity of the blending liquid is preferably 500 Pa sec to 4000 mPa sec at a viscosity at 25 ° C.

(f) Other additives

In the blending solution, in addition to the components (a) to (e), (f) other additives may be contained. Specifically, in (f) other additives, for example, a coloring matter such as a dye or a pigment is contained. quality. As such a coloring substance, a matrix dye can be used. Examples of the matrix dye include basic green 1 [CAS number (hereinafter, the same): 633-03-4], peacock green grass salt [2437-29-8], and bright green [633-03-4] , Poinsettia [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], Rose Red B [81-88-9], Rose Red 6G [989-38-8], alkali Sexual yellow 2 [2465-27-2] and so on. Among them, alkaline green 1, peacock green grass, and basic blue 7 are preferable, and alkali green 1, and basic blue 7 are particularly preferable from the viewpoint of improving hue stability and exposure contrast.

The content of the coloring matter in the photosensitive resin element is preferably 0.001% by mass to 1% by mass. When the content of the coloring matter is 0.001% by mass or more, the operability is improved, and it is preferable. On the other hand, when the content of the coloring matter is 1% by mass or less, the effect of maintaining storage stability is preferable.

Further, a color developing agent such as a chromogenic dye or the like may be contained in the blending liquid to provide a visible light image by exposure. Examples of such a color-developing dye include a leuco dye, a combination of a fluoran dye and a halogen compound, and the like.

As the leuco dye, for example, tris(4-dimethylamino-2-methylphenyl)methane [leuco crystal violet], tris(4-dimethylamino-2-methylphenyl)methane [Hidden Malachite Green], and fluoran dyes. Among them, in the case where leuco crystal violet is used, the contrast is good, which is preferable.

Examples of the halogen compound include bromopentane, bromoisopentane, 1,2-dibromo-2-methylpropane, 1,2-dibromoethane, diphenylbromomethane, and dibrominated toluene. Dibromomethane, tribromomethylphenylhydrazine, carbon tetrabromide, tris(2,3-dibromopropyl)phosphate, trichloroacetamide, iodopentane, iodoisobutane, 1,1,1 -Trichloro-2,2-bis(p-chlorophenyl)ethane, hexachloroethane, chlorine trichloride Compounds, etc.

The content of the color developing agent in the photosensitive resin element is independent, and is preferably from 0.1% by mass to 10% by mass.

Further, in order to improve the thermal stability and storage stability of the photosensitive resin composition, Preferably, the preparation liquid contains a radical polymerization inhibitor or at least one compound selected from the group consisting of benzotriazoles and carboxybenzotriazoles.

Examples of the radical polymerization inhibitor include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, t-butylcatechol, cuprous chloride, and 2,6-di- Tributyl-p-cresol, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-third Butylphenol), nitrosophenylhydroxylamine aluminum salt, N-nitrosodiphenylamine, and the like.

Examples of the benzotriazoles include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, and bis(N-2-ethylhexyl)aminone. Methyl-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-toluenetriazole, bis(N-2-hydroxyethyl) Aminomethylene-1,2,3-benzotriazole and the like.

Examples of the carboxybenzotriazoles include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, and (N,N-dibutyl). Amino)carboxybenzotriazole, N-(N,N-di-2-ethylhexyl)aminomethylenecarboxybenzotriazole, N-(N,N-di-2-hydroxyethyl) Aminomethylenecarboxybenzotriazole, N-(N,N-di-2-ethylhexyl)amine-based ethylcarboxybenzotriazole, and the like.

The total content of the radical polymerization inhibitor, the benzotriazole, and/or the carboxybenzotriazole in the photosensitive resin element is preferably 0.001% by mass to 3% by mass, and more preferably 0.05% by mass or less. The upper limit is preferably 1% by mass. In view of the storage stability of the photosensitive resin composition, the total content is preferably 0.001% by mass or more, and the total content is preferably 3% by mass or less from the viewpoint of maintaining sensitivity.

Other plasticizers may be included in the blending solution as needed. Examples of such a plasticizer include polyethylene glycol, polypropylene glycol, polyoxypropylene polyoxyethylene ether, polyoxyethylene monomethyl ether, polyoxypropylene monomethyl ether, and polyoxyethylene polyoxypropylene monomethyl ether. Polysorbate such as polyoxyethylene monoethyl ether, polyoxypropylene monoethyl ether, polyoxyethylene polyoxypropylene monoethyl ether, ‧ esters, polyoxyethylene sorbitan laurate, polyoxyethylene sorbitan oleate, etc. Derivatives, phthalic acid esters such as diethyl phthalate, decyl o-toluenesulfonate, p-toluene Sulfonic acid decylamine, tributyl citrate, triethyl citrate, ethyl triethyl citrate, tri-n-propyl citrate, and tri-n-butyl citrate, respectively, in bisphenol A The propylene glycol of propylene oxide is added to both sides, and ethylene glycol of ethylene oxide is added to both sides of bisphenol A, respectively.

The content of the plasticizer in the photosensitive resin element is preferably from 0.1% by mass to 50% by mass, more preferably, the lower limit is 1% by mass, and even more preferably, the upper limit is 30% by mass. The content is preferably 0.1% by mass or more from the viewpoint of suppressing the delay of the development time and imparting flexibility to the cured film. On the other hand, the content is preferably 50% from the viewpoint of suppressing insufficient hardening and cold flow. %the following.

Other antioxidants may also be included in the blending solution as needed. Examples of the antioxidant include triphenyl phosphite, tris(2,4-di-t-butylphenyl) phosphite, tris(monodecylphenyl) phosphite, and bis (single) Nonylphenyl)-didecylphenylphosphite, and the like.

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, more preferably 0.01% by mass, and still more preferably 0.3% by mass. When the content is 0.01% by mass or more, the effect of excellent color stability of the photosensitive resin composition is excellent, and the sensitivity of the photosensitive resin composition at the time of exposure is improved, which is preferable. When the content is 0.8% by mass or less, the color developability is suppressed, so that the hue stability is improved and the adhesion is also improved, which is preferable.

<Support layer>

The above support layer is for supporting a layer of the photosensitive resin layer formed thereon. Further, the method for producing a photosensitive resin element may include a step of forming a protective layer on the side opposite to the support layer side of the photosensitive resin element as needed.

As the support layer, a film transparent to light radiated from the exposure light source is preferable. Examples of such a film include a polyethylene terephthalate film, a polyvinyl alcohol film, a polyvinyl chloride film, a vinyl chloride copolymer film, a polyvinylidene chloride film, a vinylidene chloride copolymer film, and Polymethyl methacrylate copolymer film, polystyrene film, polyacrylonitrile film, styrene copolymerization A film, a polyamide film, a cellulose derivative film, or the like. As such films, an extender can also be used as needed. The haze of the support layer is preferably 5 or less. The thinner support layer is advantageous in terms of image formation and economy, but it is preferable to use 10 μm to 30 μm in order to maintain strength.

<protection layer>

The protective layer preferably has such a property that the protective layer is sufficiently smaller than the support layer and can be easily peeled off with respect to the adhesion to the photosensitive resin layer. For example, a polyethylene film, a polypropylene film, or the like can be preferably used as the protective layer. As the protective layer, for example, a film excellent in peelability as shown in JP-A-59-202457 can be used. The thickness of the protective layer is preferably from 10 μm to 100 μm, more preferably from 10 μm to 50 μm.

<Method of Manufacturing Photosensitive Resin Element>

In the method for producing a photosensitive resin element, the step of applying the preparation liquid to the support layer and drying the photosensitive resin element on the support layer can be carried out by a coating mechanism and a drying mechanism according to the necessity. As the coating means, for example, spin coating, die coating, spray coating, dipping, printing, blade coating, roll coating, or the like can be applied. As the drying means, for example, air drying, hot air drying, light irradiation, a heating plate, an oxidation-free oven, a temperature-increasing oven capable of setting a temperature control program, or the like can be applied. Further, the blending of the plurality of components contained in the blending solution and the application and drying of the blending solution can be carried out in an atmosphere of air or an inert gas such as nitrogen or argon.

The photosensitive resin element manufactured by the above-described production method is preferably used for the production of a printed circuit board, the manufacture of a lead frame for IC chip mounting, the fabrication of a metal mask, and the like, and the ball grid array (BGA, Ball Grid Array). , or manufacturing of packages such as chip size package (CSP), fabrication of tape substrates such as chip on film (COF) or tape automated bonding (TAB), semiconductor bumps Manufacture, manufacture of the partition walls of flat-panel displays such as indium tin oxide (ITO) electrodes, address electrodes, and electromagnetic wave masks.

According to the production method of the present embodiment, the productivity of the photosensitive resin element for forming a printed circuit can be improved, and the appearance of the DF formed of the photosensitive resin element can be favorably improved.

[Examples]

The embodiments of the present invention will be more specifically described below by way of examples and comparative examples, and the present invention is not limited to the embodiments as long as they do not deviate from the gist.

[Examples 1 to 12 and Comparative Examples 1 to 8]

The components of the photosensitive resin composition described in Table 1 or 2 were blended, stirred and dissolved in a dissolution tank, and the preparation liquid was filtered through a filter. Then, the conditioned liquid was transferred to a die coater by a pump, uniformly applied to a polyethylene terephthalate film as a support layer, and sent to a drying zone to dry the solvent. Thereafter, lamination was carried out using a polyethylene film as a protective layer, and DF having the thickness of the photosensitive layer described in Table 1 or 2 was obtained. In the above steps, the solubility evaluation, the coating speed evaluation, the coating property evaluation, and the appearance evaluation were carried out by the methods described below. Further, the weight average molecular weight of the resin was measured by the method shown below. The results are shown in Table 1 or 2.

Further, as the polyethylene terephthalate as the support layer, GR-16 (16 μm thickness) manufactured by Teijin Co., Ltd. was used, and as the polyethylene film as a protective layer, GF manufactured by Tamapoly was used. -18 (19 μm thickness).

(1) Solubility evaluation

When the preparation liquid was filtered through a filter, the clogging condition of the filter was evaluated at the following level. A case where the clogging is small indicates that the solubility is good.

Furthermore, the mesh of the filter was 3 μm.

A: Not blocked at all, good.

B: Slightly clogged but filterable.

C: The filter is clogged and cannot be filtered within 1 hour.

(2) Coating speed evaluation

Using the blending liquid described in Comparative Example 1 using only methyl ethyl ketone as a solvent, the maximum coating speed in which no uncoated portion was applied and uniformly and smoothly applied was observed.

Then, with respect to each blending liquid, the maximum coating speed in which no uncoated portion was applied and uniformly and smoothly applied was observed, and the maximum coating speed observed in the blending liquid of Comparative Example 1 was set to 1, in relation to The ratio is evaluated. When the evaluation is more than 1, it means that the maximum coating speed of the preparation liquid is faster than the preparation liquid when only methyl ethyl ketone is used as a solvent.

(3) Evaluation of coating properties

The coating of various blending solutions was carried out at the maximum coating speed observed in Comparative Example 1. The state of the photosensitive resin layer obtained by applying the preparation liquid to the polyester which is a support layer by the use of a die coater was evaluated by the following grade.

S: There is no uncoated portion and the smoothness is high.

A: There is no uncoated portion and it is smoothly coated.

B: A part of the uncoated portion exists.

C: Most are uncoated parts.

(4) Appearance evaluation

The preparation liquid is applied onto the polyester as a support layer by using a die coater, and after drying the solvent, the polyethylene film as a protective layer is laminated to obtain a three-layer structure of the support layer/photosensitive layer/protective layer. The rolled laminated body was evaluated for appearance by the rolled laminated body, and evaluated by the following grade (see FIG. 1).

S: The appearance of the roll of the 3-layer structure is completely uneven and uniform.

A: The appearance of the three-layered web has almost no unevenness and uniformity.

B: The appearance of the roll of the 3-layer structure is uneven and uneven on almost the entire surface of the surface.

(5) Weight average molecular weight

The weight average molecular weight (Mw) of the resin was measured by gel permeation chromatography (standard polystyrene conversion). The column used for the measurement is the brand name Shodex manufactured by Showa Denko Co., Ltd. 805M/806M series, standard monodisperse polystyrene selected Shodex STANDARD SM-105 manufactured by Showa Denko Electric Co., Ltd., developed solvent N-methyl-2-pyrrolidone, and the detector was brand name made by Showa Denko. Shodex RI-930.

<mark description>

P-1: methyl ethyl ketone solution of a terpolymer of 65 mass% of methyl methacrylate, 25% by mass of methacrylic acid, and 10 mass% of butyl acrylate (solid content mass ratio 30%, weight average molecular weight) 100,000, acid equivalent 344)

P-2: a mixed solution of acetone and ethanol of a ternary copolymer of methyl methacrylate 65 mass%, methacrylic acid 25 mass%, and butyl acrylate 10 mass% (solvent mass ratio: acetone/ethanol = 80/20, Solid content component mass ratio 40%, weight average molecular weight 100,000, acid equivalent 344)

P-3: a mixture of acetone and ethanol of a ternary copolymer of methyl methacrylate 65 mass%, methacrylic acid 25 mass%, and butyl acrylate 10 mass% (solvent mass ratio: acetone/ethanol = 80/20, Solid content component mass ratio 75%, weight average molecular weight 100,000, acid equivalent 344)

P-4: an acetone solution of a ternary copolymer of 65 mass% of methyl methacrylate, 25% by mass of methacrylic acid, and 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 a terpolymer of 67% by mass of methyl methacrylate, 23% by mass of methacrylic acid, and 10% by mass of butyl acrylate (solid content ratio 25% by weight average molecular weight) 200,000, acid equivalent 374)

P-6: a mixed solution 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 (solvent mass ratio: acetone/ethanol = 80/20, Solid content component mass ratio 34%, weight average molecular weight 200,000, acid equivalent 374)

P-7: a methyl ethyl ketone solution of a terpolymer of 50% by mass of methyl methacrylate, 25% by mass of methacrylic acid, and 25% by mass of styrene (solid content ratio of mass fraction 35%, weight average molecular weight 5 10,000, acid equivalent 344)

P-8: 50% by mass of methyl methacrylate, 25% by mass of methacrylic acid, and styrene 25 Mass% terpolymer of acetone and ethanol mixed solution (solvent mass ratio: acetone / ethanol = 75 / 25, solid component mass ratio 47%, weight average molecular weight 50,000, acid equivalent 344)

P-9: a mixed solution of methyl ethyl ketone 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: methyl ethyl ketone) /ethanol = 75 / 25, solid content of the mass ratio of 45%, weight average molecular weight of 50,000, acid equivalent 344)

M-1: polyethylene glycol dimethacrylate (except BPE-200 manufactured by Shin-Nakamura Chemical Co., Ltd.) with an average of 2 moles of ethylene oxide added to both ends of bisphenol A

M-2: polyethylene glycol dimethacrylate (additional BPE-500 manufactured by Shin-Nakamura Chemical Co., Ltd.) with an average of 5 moles of ethylene oxide added to both ends of bisphenol A

M-3: an average of 2 moles of propylene oxide and an average of 6 moles of ethylene oxide of a polyalkylene glycol dimethacrylate added to both ends of bisphenol A

M-4: Dimethyl methacrylate of a polyalkylene glycol of an ethylene oxide having an average of 3 moles of ethylene oxide added to both ends of an average of 12 moles of propylene oxide polypropylene glycol

M-5: urethane of hexamethylene diisocyanate and oligomeric polypropylene glycol monomethacrylate (Blemmer PP1000 manufactured by Nippon Oil & Fats Co., Ltd.)

M-6: an average of 3 moles of ethylene oxide acrylate in trimethylolpropane (A-TMPT-3EO manufactured by Shin-Nakamura Chemical Co., Ltd.)

M-7: 4-mercaptophenylheptyl 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: addition of nitrosophenylhydroxylamine 3 molar aluminum salt

A-4: Adding an average of 1 mole of propylene oxide to both ends of bisphenol A, and respectively adding an average of 1 mole of glycidyl group

A-5: Adding an average of 2 moles of propylene oxide to polypropylene glycol at both ends of bisphenol A

A-6: IRGANOX245 manufactured by Ciba Specialty Chemicals

A-7: Newcol 3-85 (manufactured by Japan Emulsifier)

S-1: Acetone

S-2: ethanol

S-3: methyl ethyl ketone

[Industrial availability]

The photosensitive resin element produced by the present invention can be applied to the manufacture of a printed circuit board, the manufacture of a lead frame for IC chip mounting, the metal foil precision processing such as metal mask manufacturing, the manufacture of a package such as BGA or CSP, or the COF or TAB. Manufacture of a substrate with a substrate, manufacture of a semiconductor bump, manufacture of a partition wall of a flat panel display such as an ITO electrode or an address electrode, and an electromagnetic wave mask.

Claims (7)

A method for producing a photosensitive resin element, comprising the steps of: (a) a resin having a carboxyl group content of from 100 to 600 in terms of acid equivalent, and a weight average molecular weight of from 5,000 to 500,000, and (b) photopolymerizable a step of obtaining a blending solution by blending an unsaturated compound, (c) a photopolymerization initiator, (d) acetone, and (e) a non-acetone solvent, where the mass of the (d) acetone is relative to the (d) a ratio of the total mass of the acetone to the (e) non-acetone solvent is 30% by mass to 98% by mass, and the ratio of the total solid content in the blending liquid is 30% by mass to 80% by mass; and the blending liquid A step of applying a photosensitive resin element to the support layer by applying it to the support layer. The method of claim 1, wherein the (e) non-acetone solvent is selected from the group consisting of alcohols, esters, and ethers. The method of claim 2, wherein the alcohol is selected from the group consisting of methanol, ethanol, n-propanol, isopropanol, and n-butanol. The method of claim 3, wherein the alcohol is ethanol. The method of claim 2, wherein the ester is ethyl acetate. The method of claim 2, wherein the ether is tetrahydrofuran. The method of any one of claims 1 to 6, wherein the film thickness after drying of the blending solution is 5 μm to 50 μm.