JP2005148236A - Dry film photoresist - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a dry film photoresist having high resolution equipped with a photosensitive resin composition layer capable of forming a high strength cured layer (tent film). <P>SOLUTION: The dry film photoresist is equipped with the photosensitive resin composition layer containing a binder, a polymerizable monomer component, a photopolymerization initiator, and inorganic fine particles having polymerizable groups on a support. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a dry film photoresist particularly useful for producing a printed wiring board. The present invention also relates to a method for producing a printed wiring board using the dry film photoresist.

  In the field of manufacturing printed wiring boards, a dry film photoresist comprising a wiring pattern comprising a support (particularly a flexible transparent film support) and a photosensitive resin composition layer formed on the support. It is performed by the photolithographic technique using this. For example, in the case of a printed wiring board having a through hole, a through hole is formed in a printed wiring board forming substrate (for example, a copper-clad laminate), a metal layer is formed on the inner side wall portion of the through hole, and then the substrate surface is dried. The photosensitive resin composition layer of the film photoresist is overlaid, and the photosensitive resin composition layer is cured by irradiating light in a predetermined pattern on the area including the wiring pattern formation area and the through-hole opening, and then dried. The film photoresist support is peeled off, and the uncured photosensitive resin composition layer region other than the cured layer on the wiring pattern formation region and the cured layer (called a tent film) on the through-hole opening region is removed. Then, the exposed metal layer portion is etched, and then the hardened layer is removed to form a wiring pattern on the substrate surface.

  A dry film photoresist used for manufacturing a printed wiring board having a hole portion such as a through hole or a via hole is required to have a high resolution and to be able to form a tent film that is not easily torn. Research and development of a dry film photoresist capable of forming a tent film with high resolution and high strength has been actively conducted so far, and the results are disclosed as follows.

  For example, Patent Document 1 discloses that at least one of α, β-unsaturated carboxyl group-containing monomers having 3 to 15 carbon atoms is 15 to 35% by mass, butyl acrylate is 5 to 30% by mass, and carbon atoms. A binder composed of 35 to 80% by mass of a methacrylic acid ester having an alkyl group of 1 to 8 and having a mass average molecular weight in the range of 20,000 to 200,000. A dry film photoresist having a photosensitive resin composition layer comprising a monomer component having a saturated group and a photopolymerization initiator is disclosed.

  Patent Document 2 discloses a dry film photoresist having a photosensitive resin composition layer comprising a binder having a carboxyl group, a monomer component containing a specific vinylurethane compound and a specific acrylate compound, and a photopolymerization initiator. ing.

Japanese Patent Laid-Open No. 7-271032 Japanese Patent Laid-Open No. 10-142789

  As a result of the above research and development, dry film photoresists have been widely used in the production of printed wiring boards with through-holes and via holes such as multilayer printed wiring boards. However, it is difficult to sufficiently respond to demands for higher density printed wiring boards and thinner wiring patterns due to weight reduction. That is, in order to increase the density of the printed wiring board and make the wiring pattern thinner, it is necessary to further increase the resolution of the dry film photoresist. In order to meet this requirement, it is effective to reduce the thickness of the photosensitive resin composition layer of the dry film photoresist. However, when the thickness of the photosensitive resin composition layer is reduced, the thickness of the tent film is also reduced, so that there is a problem that the tent film is easily broken in the wiring pattern manufacturing process.

  An object of the present invention is to provide a dry film photoresist provided with a photosensitive resin composition layer having a high resolution and capable of forming a high-strength cured layer (tent film). Another object of the present invention is to provide a method capable of industrially advantageously producing a printed wiring board having a through hole or a via hole using the dry film photoresist.

  The inventor has found that a tent film having high strength can be formed by adding inorganic fine particles having a polymerizable group to the photosensitive resin composition layer, and has reached the present invention.

  Accordingly, the present invention is a dry film photoresist comprising a photosensitive resin composition layer comprising a binder, a polymerizable monomer component, a photopolymerization initiator, and inorganic fine particles having a polymerizable group on a support.

Preferred embodiments of the dry film photoresist of the present invention are shown below.
(1) The inorganic fine particles are silica fine particles.
(2) The binder is a carboxyl group-containing vinyl copolymer in which the content of repeating units having a carboxyl group is in the range of 10 to 40 mol%.
(3) The photosensitive resin composition layer has a binder of 30 to 90 mass%, a polymerizable monomer component of 5 to 60 mass%, a photopolymerization initiator of 0.1 to 30 mass%, and inorganic fine particles of 0.1. -10 mass%.
(4) The photosensitive resin composition layer contains 0.1 to 4% by mass of inorganic fine particles.
(5) The thickness of the photosensitive resin composition layer is 5 μm or more and less than 35 μm.
(6) A protective film layer is provided on the photosensitive resin composition layer.
(7) For printed circuit board production.

The present invention also resides in a method for manufacturing a printed wiring board having a through hole or a via hole including the following steps.
(1) A step of preparing a printed wiring board forming substrate having a through hole or a via hole and having a surface covered with a metal layer;
(2) The dry film photoresist of the present invention is pressure-bonded to the surface of the printed wiring board forming substrate so that the photosensitive resin composition layer is in contact with the metal layer, and the printed wiring board forming substrate and the photosensitive resin composition are bonded. A layering step of obtaining a layered body in which the physical layer and the support are laminated in this order;
(3) The photosensitive resin composition layer is cured by irradiating light from the support-side surface of the laminated body to cure the photosensitive resin composition layer, and an opening region of a through hole or a via hole An exposure step of forming a cured product pattern comprising a cured resin region covering the substrate;
(4) The support peeling process which peels a support body from a laminated body before or after the process of said (3);
(5) A development step of dissolving and removing the uncured region of the photosensitive resin composition layer on the printed wiring board forming substrate to expose the metal layer of the uncured region on the substrate surface;
(6) an etching step of dissolving and removing the metal layer in the exposed region with an etching solution; and
(7) A cured resin removing step of removing the cured resin from the printed wiring board forming substrate.

  The present invention further includes inorganic fine particles having a binder, a polymerizable monomer component, a photopolymerization initiator, and a polymerizable group on a printed wiring board forming substrate having a through hole or a via hole and having a surface covered with a metal layer. There is also a laminate in which a photosensitive resin composition layer containing is laminated in this order.

  The present invention further includes a first photosensitive resin composition layer containing a binder, a polymerizable monomer component, and a photopolymerization initiator on a support, and a binder, a polymerizable monomer component, and a photopolymerization initiator, A first photosensitive resin composition layer or a second photosensitive resin composition layer, in which a second photosensitive resin composition layer exhibiting a relatively higher photosensitivity than the one photosensitive resin composition layer is laminated in this order. There is also a dry film photoresist characterized in that at least one of them contains inorganic fine particles having a polymerizable group.

The present invention also resides in a method for manufacturing a printed wiring board having a through hole or a via hole including the following steps.
(1) A step of preparing a printed wiring board forming substrate having a through hole or a via hole and having a surface covered with a metal layer;
(2) The dry film photoresist of the present invention is pressure-bonded to the surface of the printed wiring board forming substrate so that the second photosensitive resin composition layer is in contact with the metal layer, and the printed wiring board forming substrate, second A lamination step of obtaining a laminate in which the photosensitive resin composition layer, the first photosensitive resin composition layer, and the support are laminated in this order;
(3) From the side opposite to the printed wiring board forming substrate of the laminate, the light amount necessary for curing the second photosensitive resin composition layer is formed in the wiring pattern forming region of the printed wiring board forming substrate. Is irradiated in a predetermined pattern to form a cured resin region of a predetermined pattern, and in a region including an opening of a through hole or a via hole, a first photosensitive resin composition layer and a second photosensitive resin composition layer An exposure step of forming a cured resin region that covers an opening region of a through hole or a via hole by irradiating a predetermined pattern with light of a light amount necessary for curing both of
(4) The support peeling process which peels a support body from a laminated body before or after the process of said (3);
(5) Dissolving and removing uncured regions of the first photosensitive resin composition layer and the second photosensitive resin composition layer on the printed wiring board forming substrate to expose the uncured metal layer on the substrate surface. Developing process;
(6) an etching step of dissolving and removing the metal layer in the exposed region with an etching solution; and
(7) A cured resin removing step of removing the cured resin from the printed wiring board forming substrate.

  The present invention further includes a second photosensitive resin having a binder, a polymerizable monomer component, and a photopolymerization initiator on a printed wiring board forming substrate having a through hole or a via hole and having a surface covered with a metal layer. A composition layer, and a first photosensitive resin composition layer including a binder, a polymerizable monomer component, and a photopolymerization initiator, and having a lower photosensitivity than the first photosensitive resin composition layer are laminated in this order. In addition, there is also a laminate in which at least one of the first photosensitive resin composition layer or the second photosensitive resin composition layer includes inorganic fine particles having a polymerizable group.

  Since the dry film photoresist of the present invention can form a tent film that is not easily torn even if the thickness of the photosensitive resin composition layer is reduced, it is possible to increase the resolution by reducing the thickness of the photosensitive resin composition layer. . Therefore, the dry film photoresist of the present invention can be advantageously used for the production of high-density printed wiring boards, and particularly for printed wiring boards having through holes and via holes such as double-sided printed wiring boards and multilayer printed wiring boards. It can be advantageously used for manufacturing.

FIG. 1 is a cross-sectional view of an example of the dry film photoresist of the present invention.
In FIG. 1, a dry film photoresist 10 is laminated in the order of a support 11, a photosensitive resin composition layer 12, and a protective film 13. The photosensitive resin composition layer 12 is formed from a photosensitive resin composition containing a binder, a polymerizable monomer component, a photopolymerization initiator, and inorganic fine particles having a polymerizable group. The thickness of the photosensitive resin composition layer 12 is 5 μm or more and less than 35 μm, and preferably in the range of 10 to 30 μm.

FIG. 2 is a cross-sectional view of an example of the dry film photoresist of the present invention.
In FIG. 2, the dry film photoresist 20 is laminated | stacked in order of the support body 21, the 1st photosensitive resin composition layer 22, the 2nd photosensitive resin composition layer 23, and the protective film 24. In FIG. The first photosensitive resin composition layer 22 and the second photosensitive resin composition layer 23 are each formed from a photosensitive resin composition containing a binder, a polymerizable monomer component, and a photopolymerization initiator. At least one of the first photosensitive resin composition layer 22 or the second photosensitive resin composition layer 23 includes inorganic fine particles having a polymerizable group. The thickness of the second photosensitive resin composition layer 23 is preferably in the range of 1 to 10 μm. The thickness of the first photosensitive resin composition layer 22 is preferably 50 μm or less and thicker than the thickness of the second photosensitive resin composition layer.

  Between the first photosensitive resin composition layer and the second photosensitive resin composition layer, the constituent materials (binder, polymerizable monomer component) of the first photosensitive resin composition layer and the second photosensitive resin composition layer In order to prevent the photopolymerization initiator) from moving to each other, that is, in order to stabilize the sensitivity of the first photosensitive resin composition layer and the second photosensitive resin composition layer over a long period of time, an intermediate layer may be provided. Good. As the intermediate layer, a water-soluble polymer or an alkali-soluble polymer can be used, and water-soluble and alcohol-soluble polymers such as polyvinyl alcohol, polyvinyl pyrrolidone, water-soluble polyamide, and cellulose can be used. These polymers may be used alone or in combination of two or more. Various polymers such as an acrylic polymer, an azide polymer, and an ester polymer may be added as long as water solubility and alcohol solubility are not impaired.

  In the dry film photoresist having two photosensitive resin composition layers shown in FIG. 2, the second photosensitive resin composition layer has a relatively higher photosensitivity than the first photosensitive resin composition layer, that is, It is preferable that the curing of the second photosensitive resin composition layer starts with a light irradiation amount smaller than that of the first photosensitive resin composition layer. The sensitivity of the dry film photoresist will be described with reference to the drawings.

  FIG. 3 is a graph showing a sensitivity curve representing the relationship between the light irradiation amount and the thickness of the cured layer obtained when the dry film photoresist of FIG. 2 is irradiated with light from the support side. In FIG. 3, the horizontal axis represents the amount of light irradiation, and the vertical axis represents the thickness of the photosensitive resin composition layer cured by light irradiation. D on the vertical axis represents the thickness of the second photosensitive resin composition layer, and E represents a photosensitive resin obtained by adding the thickness of the first photosensitive resin composition layer and the thickness of the second photosensitive resin composition layer. It represents the thickness of the entire composition layer.

As shown in FIG. 3, the light irradiated from the support side of the dry film photoresist proceeds in the order of the support 21, the first photosensitive resin composition layer 22, and the second photosensitive resin composition layer 23. First, the curing of the second photosensitive resin composition layer is started with a smaller amount of light before the first photosensitive resin composition layer. The light amount S at which the second photosensitive resin composition layer starts to be cured is preferably in the range of 0.1 to 10 mJ / cm ² . The amount of curing of the second photosensitive resin composition layer 23 increases as the amount of light increases, and eventually the entire second photosensitive resin composition layer is cured. The amount of light A necessary for curing the second photosensitive resin composition layer is preferably 20 mJ / cm ² or less (particularly in the range of ^{2 to} 15 mJ / cm ² ).

  After the entire second photosensitive resin composition layer is cured, if the amount of light is increased, the curing of the first photosensitive resin composition layer 21 starts. If the amount of light is further increased, the first photosensitive resin composition layer is cured. The entire layer is cured. The ratio A / B between the light amount A necessary for curing the second photosensitive resin composition layer and the light amount B necessary for curing the first photosensitive resin composition layer is 0.01 to 0.5. It is preferable that it exists in the range.

  The dry film photoresist having the sensitivity curve as described above is obtained by increasing the content of the photopolymerization initiator in the second photosensitive resin composition layer more than that in the first photosensitive resin composition layer. It can be obtained by adding a sensitizer to the photosensitive resin composition layer.

[binder]
The binder used in the dry film photoresist of the present invention is preferably soluble in an alkaline aqueous solution or at least swellable. Examples of such a binder include those having an acidic group (carboxyl group, sulfonic acid group, phosphoric acid group, etc.), and particularly binders having a carboxyl group are typical, for example, a carboxyl group-containing vinyl. Copolymer, carboxyl group-containing polyurethane copolymer, polyamic acid resin, modified epoxy resin, etc. are mentioned, but solubility in coating solution, solubility in alkaline developer, synthesis suitability, ease of adjustment of film properties From the above, a carboxyl group-containing vinyl copolymer is preferred. The carboxyl group-containing vinyl copolymer is obtained by copolymerization of at least (1) a carboxyl group-containing vinyl monomer and (2) another monomer copolymerizable with these.

  Examples of the carboxyl group-containing vinyl monomer include (meth) acrylic acid, vinyl benzoic acid, maleic acid, itaconic acid, crotonic acid, cinnamic acid, acrylic acid dimer, and the like. In addition, addition reaction products of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a cyclic anhydride such as maleic anhydride or phthalic anhydride can also be used. Or you may use the monomer containing anhydrides, such as maleic anhydride and itaconic anhydride, as a precursor of a carboxyl group. Of these, (meth) acrylic acid is particularly preferred from the viewpoints of copolymerizability, cost, solubility and the like.

  The other monomer is preferably one having no chemical reactivity with the carboxyl group. For example, (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, (meth) acrylamides, styrenes, and vinyl ethers are preferred. Examples of such compounds include the following compounds.

  Examples of (meth) acrylic acid esters 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, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2- Methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2- (2-methoxyethoxy) ethyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, diethylene glycol Examples include coal monomethyl ether (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, diethylene glycol monophenyl ether (meth) acrylate, triethylene glycol monomethyl ether (meth) acrylate, and triethylene glycol monoethyl ether (meth) acrylate. It is done.

  Examples of crotonic acid esters include butyl crotonate and hexyl crotonate. Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, vinyl benzoate, and the like. Examples of maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate. Examples of the fumaric acid diesters include dimethyl fumarate, diethyl fumarate, and dibutyl fumarate.

  Examples of itaconic acid diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate. Examples of (meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, Nn butylacryl (meth) amide, N -Tertbutyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N -Phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) acryloylmorpholine, etc. are mentioned.

  Examples of styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, hydroxy styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chloro styrene, dichloro styrene, bromo styrene, chloromethyl Examples include styrene, methyl vinylbenzoate, and α-methylstyrene. Examples of vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, and methoxyethyl vinyl ether.

  In addition, vinyl pyridine, vinyl pyrrolidone, vinyl carbazole, (meth) acrylonitrile, and the like can be used. Furthermore, a vinyl monomer having a group that induces a hydrogen bond such as a urethane group, a urea group, a phenol group, and a sulfonamide group can also be used.

  These compounds may be used alone or in combination of two or more. Other preferable compounds as copolymerizable monomers include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, benzyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and styrene. , Α-methylstyrene, chlorostyrene, bromostyrene, and hydroxystyrene.

  The carboxyl group-containing vinyl copolymer can be obtained by copolymerizing corresponding monomers according to a conventional method by a conventional method. For example, it can be obtained by using a method (solution polymerization method) in which the above monomer is dissolved in a suitable solvent and a radical polymerization initiator is added thereto to polymerize in a solution. Alternatively, the polymerization may be carried out by so-called emulsion polymerization in a state where the above monomer is dispersed in an aqueous medium.

  Examples of suitable solvents used in the solution polymerization method can be arbitrarily selected according to the monomers used and the solubility of the copolymer to be produced. For example, methanol, ethanol, propanol, isopropanol, 1-methoxy-2- Examples include propanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, methoxypropyl acetate, ethyl lactate, ethyl acetate, acetonitrile, tetrahydrofuran, dimethylformamide, chloroform, and toluene. These solvents may be used as a mixture of two or more.

  Examples of the radical polymerization initiator include azo compounds such as 2,2′-azobis (isobutyronitrile) (AIBN) or 2,2′-azobis (2,4′-dimethylvaleronitrile), and benzoyl peroxide. Peroxides such as and persulfates can be used.

  It is preferable that the content rate of the repeating unit which has a carboxyl group in a carboxyl group-containing vinyl copolymer exists in the range of 10-40 mol% in all the repeating units of a copolymer, More preferably, it is 15-40 mol%. The range of 20 to 35 mol% is particularly preferable. If the content of the carboxyl group-containing repeating unit is less than 10 mol%, the developability to an alkaline aqueous solution may be insufficient, and if it exceeds 40 mol%, the developer resistance of the cured portion (image portion) may be insufficient. is there.

  Although the molecular weight of the said vinyl copolymer can be adjusted arbitrarily, it is preferable in the range of 1000-300000 as a mass mean molecular weight, and it is especially preferable that it exists in the range of 4000-150,000. When the mass average molecular weight is less than 1000, the strength of the film is insufficient, and stable production tends to be difficult. On the other hand, if the molecular weight exceeds 300,000, the developability tends to decrease.

  Two or more kinds of vinyl copolymers may be used.

  In the dry film photoresist of the present invention, a known polymer binder used in the photosensitive resin composition is used in combination with the above-mentioned carboxyl group-containing vinyl copolymer as a binder within a range not deteriorating the performance. It doesn't matter. Examples of such polymer binders include JP-B No. 46-32714, JP-B No. 55-38961, JP-B No. 56-33413, JP-A No. 58-1142, and JP-B No. 7-7208. And alkali-soluble resins described in JP-A-10-161309, JP-B-8-20733, JP-2706858, JP2756623, and JP-A-10-161309.

  In the dry film photoresist of the present invention, the binder content of the photosensitive resin composition layer is generally in the range of 30 to 90% by mass, preferably in the range of 40 to 80% by mass, particularly preferably 45 to 65%. It is the range of mass%. If the binder content is too low, the alkali developability and the adhesion to the printed wiring board forming substrate (for example, copper-clad laminate) will be reduced. If the binder content is too high, the stability against the development time and the cured film ( There is a tendency for the strength of the tent film to decrease. The content of the carboxyl group-containing vinyl copolymer in the binder is generally 30% by mass or more, preferably 50% by mass or more, and more preferably 70% by mass or more.

[Polymerizable monomer component]
As the polymerizable monomer used in the dry film photoresist of the present invention, a monomer (polyfunctional monomer) containing two or more polymerizable groups (ethylenically unsaturated bonds) or an oligomer (polyfunctional oligomer) should be used. preferable. Examples of the polymerizable group include (meth) acryloyl group, (meth) acrylamide group, styryl group, vinyl group such as vinyl ester and vinyl ether, allyl group such as allyl ether and acrylic ester.

  Examples of polyfunctional monomers and polyfunctional oligomers include esters of unsaturated carboxylic acids (eg acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid) with aliphatic polyhydric alcohol compounds, unsaturated Examples include amides of carboxylic acids and aliphatic polyvalent amine compounds.

  Specific examples of esters of acrylic acid and methacrylic acid and aliphatic polyhydric alcohol compounds [(meth) acrylic acid esters] include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, and triethylene glycol di (meth) ) Acrylate, tetraethylene glycol di (meth) acrylate, nonaethylene glycol di (meth) acrylate, dodecaethylene glycol di (meth) acrylate, tetradecaethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol Di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate Polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri ((meth) acryloyloxypropyl) Ether, trimethylolethane tri (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, 1,4-cyclohexanediol Di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol Pentyl (meth) acrylate, dipentaerythritol hexa (meth) acrylate, sorbitol tri (meth) acrylate, sorbitol tetra (meth) acrylate, sorbitol penta (meth) acrylate, sorbitol hexa (meth) acrylate, tri ((meth) acryloyloxy Ethyl) isocyanurate, polyester (meth) acrylate oligomer, bis [p- (3- (meth) acryloxy-2-hydroxypropoxy) phenyl] dimethylmethane, and bis [p-((meth) acryloxyethoxy) phenyl] There are dimethylmethane and the like.

  Examples of esters of itaconic acid and aliphatic polyhydric alcohol compounds (itaconic acid esters) include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, and 1,4-butanediol. Examples include diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate, and sorbitol tetritaconate. Examples of esters of crotonic acid and aliphatic polyhydric alcohol compounds (crotonate esters) include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate. .

  Examples of esters of isocrotonic acid and aliphatic polyhydric alcohol compounds (isocrotonate) include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate. Examples of esters of maleic acid and aliphatic polyhydric alcohol compounds (maleic acid esters) include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.

  Examples of amides of aliphatic polyvalent amine compounds and unsaturated carboxylic acids include methylene bis (meth) acrylamide, ethylene bis (meth) acrylamide, 1,6-hexamethylene bis (meth) acrylamide, and diethylenetriamine tris (meth) acrylamide. And xylylene bis (meth) acrylamide.

  Moreover, (meth) acrylates containing a urethane group can also be used as the polymerizable monomer component. Examples of such compounds are described in JP-B-48-41708, JP-A-51-37193, and JP-B-7-7208, and two or more isocyanates per molecule. A polyisocyanate compound having a nate group (for example, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, xylene diisocyanate, toluene diisocyanate, norbornene diisocyanate or a trimer thereof, And vinyl monomers containing a hydroxyl group in the molecule (for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4) and adducts thereof with polyfunctional alcohols such as trimethylolpropane. -Hydroxybutyl (meth) acrylate , Diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, dipropylene glycol mono (meth) acrylate, tripropylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate And the like, for example, vinyl urethane compounds containing two or more polymerizable vinyl groups in one molecule.

  Furthermore, as polymerizable monomer components, polyester acrylates such as those described in JP-A-48-64183, JP-B-49-43191, and JP-B-52-30490, epoxy resins and (meth) Mention may be made of polyfunctional acrylates and methacrylates such as epoxy acrylates reacted with acrylic acid. In addition, esterified products obtained from phthalic acid, trimellitic acid and the like and a vinyl monomer containing a hydroxyl group in the molecule are also included. Further, those introduced as photocurable monomers and oligomers in Journal of Japan Adhesion Association vol.20, No.7, pages 300 to 308 (1984) can also be used.

  A polyfunctional monomer containing a urea group, a urethane group, a phenol group, or a sulfonamide group can also be used as the polymerizable monomer component. Polyfunctional monomers having a bisphenol structure can also be used.

  These polyfunctional monomers can be used alone or in combination of two or more.

  In the dry film photoresist of the present invention, if necessary, a polymerizable compound (monofunctional monomer) containing one ethylenically unsaturated bond in the molecule can be used in combination as a polymerizable monomer component. Specific examples of the monofunctional monomer include those exemplified as monomers for vinyl copolymer synthesis used in the above-mentioned binder.

In the dry film photoresist of the present invention, the content of the polymerizable monomer component in the photosensitive resin composition layer is generally in the range of 5 to 60% by mass, preferably in the range of 10 to 50% by mass, particularly preferably. It is in the range of 20 to 45% by mass. When the content of the polymerizable monomer component is less than the above range, the strength of the cured film is deteriorated, and when it is large, edge fusion during storage (bleed out from the end of the roll) is likely to occur.
The content of the polymerizable compound containing two or more ethylenically unsaturated bonds in the polymerizable monomer component is generally 50% by mass or more, preferably 70% by mass, and more preferably 80% by mass.

[Photopolymerization initiator]
As the photopolymerization initiator used in the dry film photoresist of the present invention, any compound having the ability to initiate polymerization of the polymerizable compound (polymerizable monomer component) can be used. As long as it has photosensitivity, it can be suitably used. The photopolymerization initiator preferably contains at least one component having a molecular extinction coefficient of at least about 50 within a range of about 300 to 800 nm (more preferably 330 to 500 nm). The photopolymerization initiator may also be an activator that generates an active radical by generating some action with the photoexcited sensitizer.

  Examples of the photopolymerization initiator preferably used in the dry film photoresist of the present invention include halogenated hydrocarbon derivatives (preferably those having a triazine skeleton), hexaarylbiimidazoles, ketoxime derivatives, and organic peroxides. Thio compounds, ketoxime esters, ketone compounds, aromatic onium salts, ketoxime ethers and the like. Of these, the use of a halogenated hydrocarbon having a triazine skeleton, a ketoxime derivative, a hexaarylbiimidazole, a ketoxime ester, and a ketone compound is particularly sensitive to the sensitivity, storage stability, and photosensitive resin composition of the photosensitive resin composition layer. This is preferable from the viewpoint of adhesion between the layer and the printed wiring board forming substrate.

Examples of the halogenated hydrocarbon compound having a triazine skeleton include the following compounds:
Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), for example, 2-phenyl 4,6-bis (trichloromethyl) -s-triazine, 2- (p-chlorophenyl)- 4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (Trichloromethyl) -s-triazine, 2- (2 ′, 4′-dichlorophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2,4,6-tris (trichloromethyl) -s -Triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2-n-nonyl-4,6-bis (trichloromethyl) -s-triazine, and 2- (α, α, β -Trichloroethyl) -4,6- Scan (trichloromethyl) -s-triazine;

Compounds described in GB 1388492, for example 2-styryl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methylstyryl) -4,6-bis (trichloromethyl) -s -Triazine, 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, and 2- (p-methoxystyryl) -4-amino-6-trichloromethyl-s-triazine;
Compounds described in JP-A-53-133428, such as 2- (4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxy-naphtho) -1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- [4- (2-ethoxyethyl) -naphth-1-yl] -4,6-bis (trichloromethyl) -s -Triazine, 2- (4,7-dimethoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, and 2- (acenaphth-5-yl) -4,6-bis ( Trichloromethyl) -s-triazine;

  The compounds described in DE 33 37 024, for example 2- (4-styrylphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-p-methoxystyrylphenyl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (1-naphthylvinylenephenyl) -4, 6-bis (trichloromethyl) -s-triazine, 2-chlorostyrylphenyl-4,6-bis (trichloromethyl) ) -S-triazine, 2- (4-thiophene-2-vinylenephenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-thiophene-3-vinylenephenyl) -4,6- Bis (trichloromethyl) -s-triazine, 2- (4-furan-2-vinylenephenyl) -4,6-bis (trichloromethyl) -s-tri Jin, and 2- (4-benzofuran-2-vinylene) -4,6-bis (trichloromethyl) -s-triazine;

FC Schaefer et al., J. Org. Chem .; 29, 1527 (1964) described compounds such as 2-methyl-4,6-bis (tribromomethyl) -s-triazine, 2,4,6-tris (tri Bromomethyl) -s-triazine, 2,4,6-tris (dibromomethyl) -s-triazine, 2-amino-4-methyl-6-tri (bromomethyl) -s-triazine, and 2-methoxy-4- Methyl-6-trichloromethyl-s-triazine;
Compounds described in JP-A-62-258241 such as 2- (4-phenylacetylenephenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-naphthyl-1-acetylenephenyl- 4,6-bis (trichloromethyl) -s-triazine, 2- (4-p-tolylacetylenephenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-p-methoxyphenylacetylene) Phenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-p-isopropylphenylacetylenephenyl) -4,6-bis (trichloromethyl) -s-triazine, and 2- (4- p-ethylphenylacetylenephenyl) -4,6-bis (trichloromethyl) -s-triazine;

Compounds described in JP-A-5-281728, for example, 2- (4-trifluoromethylphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2,6-difluorophenyl) -4 , 6-Bis (trichloromethyl) -s-triazine, 2- (2,6-dichlorophenyl) -4,6-bis (trichloromethyl) -s-triazine, and 2- (2,6-dibromophenyl) -4 , 6-Bis (trichloromethyl) -s-triazine;
JP-A-5-34920, for example, 2,4-bis (trichloromethyl) -6- [4- (N, N-diethoxycarbonylmethylamino) -3-bromophenyl] -s-triazine; And a halogenated hydrocarbon compound having a triazine skeleton of an electron transfer type initiation system described in JP-A No. 2001-305734.
All of these can be suitably used.

  Examples of the ketoxime compound suitably used in the present invention include compounds represented by the following general formula (I).

In the formula (I), R ¹ and R ² each independently represents a hydrocarbon group which may have a substituent and may contain an unsaturated bond, or a heterocyclic group. R ³ and R ⁴ are each independently a hydrogen atom, a hydrocarbon group which may have a substituent and may contain an unsaturated bond, a heterocyclic group, a hydroxyl group, a substituted oxy group, a mercapto group, And a substituted thio group. Alternatively, R ³ and R ⁴ are bonded to each other to form a ring, and —O—, —NR ⁷ — (R ⁷ is hydrogen or a hydrocarbon group which may have a substituent), —O It represents an alkylene group having 2 to 8 carbon atoms, which may contain —CO—, —NH—CO—, —S—, and / or —SO ₂ — in the connecting main chain of the ring.
R ⁵ and R ⁶ each independently represent a hydrogen atom, a hydrocarbon group which may have a substituent and may contain an unsaturated bond, or a substituted carbonyl group.

  Specific examples of ketoxime derivatives include p-methoxyphenyl 2-N, N-dimethylaminopropylketone oxime-O-allyl ether, p-methylthiophenyl 2-morpholinopropylketone oxime-O-allyl ether, p- Methylthiophenyl 2-morpholinopropyl ketone oxime-O-benzyl ether, p-methylthiophenyl 2-morpholinopropyl ketone oxime-On-butyl ether, p-morpholinophenyl 2-morpholinopropyl ketone oxime-O-allyl ether P-methoxyphenyl 2-morpholinopropylketone oxime-O-n-dodecyl ether, p-methylthiophenyl 2-morpholinopropylketone oxime-O-methoxyethoxyethyl ether, p-methylthiol Nyl 2-morpholinopropyl ketone oxime-Op-methoxycarbonylbenzyl ether, p-methylthiophenyl 2-morpholinopropyl ketone oxime-O-methoxycarbonyl methyl ether, p-methylthiophenyl 2-morpholinopropyl ketone oxime-O -Ethoxycarbonylmethyl ether, p-methylthiophenyl 2-morpholinopropylketone oxime-O-4-butoxycarbonylbutyl ether, p-methylthiophenyl 2-morpholinopropylketone oxime-O-2-ethoxycarbonylethyl ether, p-methylthio Phenyl 2-morpholinopropyl ketone oxime-O-methoxycarbonyl-3-propenyl ether and p-methylthiophenyl 2-morpholinopropyl ketone Shim -O- benzyloxycarbonyl ether can be exemplified, but not limited thereto.

  Examples of the hexaarylbiimidazole used in the present invention include 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole and 2,2′-bis (o-bromo). Phenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o, p-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2 '-Bis (o-chlorophenyl) -4,4', 5,5'-tetra (m-methoxyphenyl) biimidazole, 2,2'-bis (o, o'-dichlorophenyl) -4,4 ', 5 , 5′-tetraphenylbiimidazole, 2,2′-bis (o-nitrophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-methylphenyl)- 4,4 ', 5 '- tetraphenyl biimidazole, and 2,2'-bis (o-trifluoromethylphenyl) -4,4', 5,5'-tetraphenyl biimidazole. These biimidazoles can be easily synthesized by the methods disclosed in, for example, Bull. Chem. Soc. Japan, 33,565 (1960), and J. Org. Chem, 36 (16) 2262 (1971). it can.

  Examples of ketoxime esters include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentane-3-one, 2 -Acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-p-toluenesulfonyloxyiminobutan-2-one, and 2-ethoxycarbonyloxyimino Examples include -1-phenylpropan-1-one.

  Examples of the ketone compound include benzophenone, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4-methoxy-4′-dimethylaminobenzophenone, 4,4′-dimethoxybenzophenone, 4 -Dimethylaminobenzophenone, 4-dimethylaminoacetophenone, benzyl, anthraquinone, 2-tert-butylanthraquinone, 2-methylanthraquinone, phenanthraquinone, xanthone, thioxanthone, 2-chloro-thioxanthone, 2,4-diethylthioxanthone, fluorenone , And acridone.

  In addition, benzoin or benzoin ethers (for example, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin phenyl ether, etc.), polyhalogen compounds (for example, carbon tetrabromide, phenyl triphenyl, etc.) Bromomethyl sulfone, phenyltrichloromethyl ketone, etc.), coumarins (for example, 3- (2-benzofuroyl) -7-diethylaminocoumarin, 3- (2-benzofuroyl) -7- (1-pyrrolidinyl) coumarin, 3-benzoyl- 7-diethylaminocoumarin, 3- (o-methoxybenzoyl) -7-diethylaminocoumarin, 3- (p-dimethylaminobenzoyl) -7-diethylaminocoumarin, 3,3′-carbonylbis (5,7-di-n- The (Ropoxycoumarin), 3,3′-carbonylbis (7-diethylaminocoumarin), 3-benzoyl-7-methoxycoumarin, 3- (2-furoyl) -7-diethylaminocoumarin, 3- (p-diethylaminocinnamoyl) -7 -Diethylaminocoumarin, 7-methoxy-3- (3-pyridylcarbonyl) coumarin, 3-benzoyl-5,7-dipropoxycoumarin, etc.), amines (for example, ethyl p-dimethylaminobenzoate, p-dimethylaminobenzoate) N-butyl acid, phenethyl p-dimethylaminobenzoate, 2-phthalimidoethyl p-dimethylaminobenzoate, 2-methacryloyloxyethyl p-dimethylaminobenzoate, pentamethylenebis (p-dimethylaminobenzoate), m-dimethyl Phenethyl and aminobenzoic acid Pentamethylene ester, p-dimethylaminobenzaldehyde, 2-chloro-4-dimethylaminobenzaldehyde, p-dimethylaminobenzyl alcohol, ethyl (p-dimethylamino) benzoyl acetate, p-piperidinoacetophenone, 4-dimethylaminobenzoin, N, N-dimethyl-p-toluidine, N, N-diethyl-m-phenetidine, tribenzylamine, dibenzylphenylamine, N-methyl-N-phenylbenzylamine, p-bromo-N, N-dimethylaniline, Tridodecylamine, leuco crystal violet, etc.), compounds disclosed in JP-A Nos. 53-133428, 57-1819, 57-6096, and US Pat. No. 3,615,455. Can be mentioned.

  These photopolymerization initiators can be used alone or in combination of two or more. It is also possible to use two or more compounds in combination between different species. The use amount of the photopolymerization initiator content is in the range of 0.1 to 30% by mass, preferably in the range of 0.5 to 20% by mass, particularly preferably relative to all components of the photosensitive resin composition layer. It is in the range of 1 to 15% by mass.

[Sensitizer]
A so-called sensitizer can be added to the exposure of the dry film photoresist when a visible ray or ultraviolet laser is used as a ray (active energy ray). Examples of the sensitizer include known polynuclear aromatics (eg, pyrene, perylene, triphenylene), xanthenes (eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), cyanines (eg, thiacarbocyanine, oxaxene). Carbocyanine), merocyanines (eg merocyanine, carbomerocyanine), thiazines (eg thionine, methylene blue, toluidine blue), acridines (eg acridine orange, chloroflavin, acriflavine), anthraquinones (eg anthraquinone) Squariums (for example, squalium) can be preferably used.

  The addition amount of the sensitizer is generally in the range of 0.05 to 30% by mass, preferably in the range of 0.1 to 20% by mass, particularly preferably 0.8%, based on all components of the photosensitive resin composition layer. It is in the range of 2 to 10% by mass. If the amount of the sensitizer added is too large, it may precipitate from the photosensitive resin composition layer during storage, and if it is too small, the sensitivity to active energy rays will be reduced, and the exposure process will take a long time. Productivity may be reduced.

[Inorganic fine particles having a polymerizable group]
Examples of the inorganic fine particles include oxide particles of elements such as silicon, aluminum, titanium, zirconium, tin, and zinc. Among these, silica particles (such as colloidal silica and powdered silica) are preferable because of availability of raw materials, cost, ease of introduction of polymerizable groups, and the like. The average particle diameter of the inorganic fine particles is preferably 1 nm to 2 μm, more preferably 1 nm to 500 nm, and particularly preferably 1 nm to 200 nm. If it is larger than 2 μm, the dispersion stability and resolution of the particles in the coating solution may deteriorate.

  Examples of the polymerizable group include a (meth) acryloyl group, a (meth) acrylamide group, a styryl group, a vinyl group, an allyl group, and a propenyl group, and it is preferable to have one or more of any one of these groups. Among these, a (meth) acryloyl group is preferred from the viewpoint of the polymerizability of the polymerizable group and the availability of raw materials.

The inorganic fine particles having a polymerizable group can be obtained, for example, by reacting a functional group having reactivity with a functional group on the surface of the inorganic fine particles and a compound containing a polymerizable group in the molecule with the inorganic fine particles. Examples of the functional group reactive with the functional group on the surface of the inorganic fine particle include an alkoxysilyl group, an aryloxysilyl group, an acetoxysilyl group, an aminosilyl group, and a halogenated silyl group.
In addition, as the inorganic fine particles containing a polymerizable group, a form in which the fine particles are dispersed in a solvent, or a composition into which a photopolymerization initiator or the like is further introduced may be used. The addition amount of the inorganic fine particles is preferably 0.1 to 10% by mass, more preferably 0.1 to 4% by mass with respect to all components of the photosensitive resin composition layer. If the content is less than 0.1% by mass, the tent strength may be insufficient. On the other hand, if it exceeds 10% by mass, adhesion to the substrate, developability, resolution and the like may be deteriorated.

[Other ingredients]
In the dry film photoresist of the present invention, if necessary, the photosensitive resin composition layer, thermal polymerization inhibitor, plasticizer, discoloring agent, colorant, further adhesion promoter to the printed circuit board production substrate surface, and Other auxiliaries may be added. By adding these, properties such as the stability, photographic properties, print-out properties, and film properties of the intended dry film photoresist can be adjusted.

[Thermal polymerization inhibitor]
The thermal polymerization inhibitor is added to prevent thermal polymerization or polymerization with time of the polymerizable monomer component of the photosensitive resin composition layer. Examples of the thermal polymerization inhibitor include p-methoxyphenol, hydroquinone, alkyl or aryl-substituted hydroquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone, 4-methoxy-2-hydroxybenzophenone, cuprous chloride, phenothiazine, Examples include chloranil, naphthylamine, β-naphthol, 2,6-di-t-butyl-p-cresol, pyridine, nitrobenzene, dinitrobenzene, picric acid, p-toluidine, methylene blue, organic copper, methyl salicylate, and phenothiazine. .

  The addition amount of the thermal polymerization inhibitor is preferably in the range of 0.001 to 5 mass%, more preferably 0.01 to 2 mass% with respect to the polymerizable monomer component content of the photosensitive resin composition layer. The range is particularly preferably 0.05 to 1% by mass. When the addition amount of the thermal polymerization inhibitor exceeds this range, the sensitivity to active energy rays tends to decrease, and when it exceeds this range, the stability during storage tends to decrease.

[Plasticizer]
The plasticizer is added to control the film physical properties (flexibility) of the photosensitive resin composition layer. Examples of plasticizers include phthalates such as dimethyl phthalate, dibutyl phthalate, diisobutyl phthalate, diheptyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, ditridecyl phthalate, butyl benzyl phthalate, diisodecyl phthalate, and diallyl phthalate; triethylene glycol Glycol esters such as diacetate, tetraethylene glycol diacetate, dimethylglycol phthalate, ethyl phthalyl ethyl glycolate, methyl phthalyl ethyl glycolate, butyl phthalyl butyl glycolate, and triethylene glycol dicabrylate; Phosphate esters such as zircyl phosphate and triphenyl phosphate; p-toluenesulfonamide, Amines such as zensulfonamide and Nn-butylacetamide; aliphatic dibasic acid esters such as diisobutyl adipate, dioctyl adipate, dimethyl sebacate, dibutyl sepacate, dioctyl sepacate, dioctyl azelate, and dibutyl malate Class: Triethyl citrate, tributyl citrate, glycerin triacetyl ester, butyl laurate, and dioctyl 4,5-diepoxycyclohexane-1,2-dicarboxylate.

  The addition amount of the plasticizer is preferably in the range of 0.1 to 50% by mass, more preferably in the range of 0.5 to 40% by mass, particularly preferably relative to all components of the photosensitive resin composition layer. It is the range of 1-30 mass%.

[Discoloring agent]
The color changing agent is added to give a visible image (printing function) to the photosensitive resin composition layer after exposure. Examples of the color changing agent include tris (p-dimethylaminophenyl) methane (leuco crystal violet), tris (p-diethylaminophenyl) methane, tris (p-dimethylamino-o-methylphenyl) methane, and tris (p-diethylamino). -O-methylphenyl) methane, bis (p-dibutylaminophenyl)-[p- (2-cyanoethyl) methylaminophenyl] methane, bis (p-dimethylaminophenyl) -2-quinolylmethane, and tris (p-di Aminotriarylmethanes such as propylaminophenyl) methane; 3,6-bis (dimethylamino) -9-phenylxanthine, and 3-amino-6-dimethylamino-2-methyl-9- (o-chlorophenyl) xanthine Aminoxanthines such as 3,6-bis (die Aminothioxanthenes such as (lamino) -9- (o-ethoxycarbonylphenyl) thioxanthene and 3,6-bis (dimethylamino) thioxanthene; 3,6-bis (diethylamino) -9,10-dihydro-9 -Amino-9,10-dihydroacridines such as phenylacridine and 3,6-bis (benzylamino) -9,10-dihydro-9-methylacridine; amino such as 3,7-bis (diethylamino) phenoxazine Phenoxazines; aminophenothiazines such as 3,7-bis (ethylamino) phenothiazone; aminodihydrophenazines such as 3,7-bis (diethylamino) -5-hexyl-5,10-dihydrophenazine; bis (p- Aminophenylmethanes such as dimethylaminophenyl) anilinomethane; 4 Aminohydrocinnamic acids such as amino-4′-dimethylaminodiphenylamine and 4-amino-α, β-dicyanohydrocinnamic acid methyl ester; hydrazines such as 1- (2-naphthyl) -2-phenylhydrazine; 1,4-bis (ethylamino) -2,3-dihydroanthraquinones amino-2,3-dihydroanthraquinones; phenethylanilines such as N, N-diethyl-p-phenethylaniline; 10-acetyl-3, Acyl derivatives of leuco dyes containing basic NH, such as 7-bis (dimethylamino) phenothiazine; have no oxidizable hydrogen, such as tris (4-diethylamino-o-tolyl) ethoxycarbonylmentane, but are oxidized to chromogenic compounds Possible leuco-like compound; leucoin digoid pigment; US Pat. No. 3,425,515 And organic amines (for example, 4,4′-ethylenediamine, diphenylamine, N, N-dimethylaniline, 4,4′-methylene which can be oxidized to a colored form as described in US Pat. No. 3,425,517. Diamine triphenylamine, N-vinylcarbazole). A particularly preferred discoloring agent is leuco crystal violet.

  The addition amount of the color changing agent is preferably in the range of 0.01 to 20% by mass, more preferably in the range of 0.05 to 10% by mass, and particularly preferably with respect to all the components of the photosensitive resin composition layer. It is the range of 0.1-5 mass%.

[dye]
In the present invention, a dye can be used in the photosensitive resin composition layer for the purpose of coloring the composition for improving handleability or imparting storage stability. Examples of suitable dyes include brilliant green sulfate, eosin, ethyl violet, erythrosine B, methyl green, crystal violet, basic fuchsin, phenolphthalein, 1,3-diphenyltriazine, alizarin red S, thymolphthalein, methyl Violet 2B, quinaldine red, rose bengal, methanyl yellow, thymol sulfophthalein, xylenol blue, methyl orange, orange IV, diphenyltylocarbazone, 2,7-dichlorofluorescein, paramethyl red, Congo red, benzopurpurin 4B, α-naphthyl-red, Nile blue A, phenacetalin, methyl violet, malachite green oxalate, parafuchsin, oil blue # 603 (Orient Manufactured by Manabu Industry Co., Ltd.), it may be mentioned rhodamine B, and Rhodamine 6G and the like. A particularly preferred dye is malachite green oxalate.

  A preferable addition amount of the dye is in a range of 0.001 to 10% by mass with respect to all components of the photosensitive resin composition layer. More preferably, it is the range of 0.01-5 mass%, Most preferably, it is the range of 0.1-2 mass%.

[Adhesion promoter]
In the dry film photoresist of the present invention, a known so-called adhesion promoter can be added to the photosensitive resin composition layer in order to improve adhesion to the printed wiring board manufacturing substrate. As the adhesion promoter, those described in JP-A-5-11439, JP-A-5-341532, and JP-A-6-43638 can be preferably used. Specifically, benzimidazole, benzoxazole, benzothiazole, 2-mercaptobenzoimidazole, 2-mercaptobenzoxanol, 2-mercaptobenzothiazole, 3-morpholinomethyl-1-phenyl-triazole-2-thione, 3- Specific examples include morpholinomethyl-5-phenyl-oxadiazole-2-thione, 5-amino-3-morpholinomethyl-thiadiazole-2-thione, and 2-mercapto-5-methylthio-thiadiazole. Among these, 3-morpholinomethyl-1-phenyltriazole-2-thione is particularly preferable.

  A preferable addition amount of the adhesion promoter is in the range of 0.001 to 20% by mass with respect to all components of the photosensitive resin composition layer. More preferably, it is the range of 0.01-10 mass%, Most preferably, it is the range of 0.1 mass%-5 mass%.

[Production of dry film photoresist]
The dry film photoresist of the present invention is prepared by, for example, preparing a photosensitive resin composition solution by dissolving the above-described various constituents in a solvent, which is a known method on a support (flexible transparent film). It can manufacture by apply | coating by and drying. The coating method of the photosensitive resin composition solution is not particularly limited, and for example, spray method, roll coating method, spin coating method, slit coating method, extrusion coating method, curtain coating method, die coating method, wire bar coating method. And various methods such as a knife coating method can be employed. As drying conditions, although it changes also with each component, the kind of solvent, a usage rate, etc., it is about 30 seconds-15 minutes at the temperature of 60-110 degreeC normally.

  Examples of the solvent for the photosensitive resin composition solution include alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, and n-hexanol; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclogexanone, And ketones such as diisobutyl ketone; esters such as ethyl acetate, butyl acetate, n-amyl acetate, methyl sulfate, ethyl propionate, dimethyl phthalate, ethyl benzoate, and methoxypropyl acetate; toluene, xylene, benzene, And aromatic hydrocarbons such as ethylbenzene; halogenated hydrocarbons such as carbon tetrachloride, trichloroethylene, chloroform, 1,1,1-trichloroethane, methylene chloride, and monochlorobenzene; tetrahydride Furan, diethyl ether, ethylene glycol monomethyl ether, ethers such as ethylene glycol monoethyl ether, and 1-methoxy-2-propanol; dimethylformamide, and the like dimethyl sulfoxide.

[Support and protective film]
The support is preferably a flexible transparent film. The flexible transparent film needs to be able to peel the photosensitive resin composition layer and to have good light transmittance. Moreover, it is desirable that the surface smoothness is good. Examples of the support include polyethylene terephthalate, polyethylene naphthalate, polypropylene, polyethylene, cellulose triacetate, cellulose diacetate, poly (meth) acrylic acid alkyl ester, poly (meth) acrylic acid ester copolymer, polyvinyl chloride, Examples include various plastic films such as polyvinyl alcohol, polycarbonate, polystyrene, cellophane, polyvinylidene chloride copolymer, polyamide, polyimide, vinyl chloride / vinyl acetate copolymer, polytetrafluoroethylene, and polytrifluoroethylene. it can. Furthermore, a composite material composed of two or more of these can also be used. Among these, a polyethylene terephthalate film is particularly preferable. As for the thickness of a support body, the range of 5-150 micrometers is common, and the range of 10-100 micrometers is preferable.

  In the dry film photoresist of the present invention, a protective film layer can be further provided on the photosensitive resin composition layer. Examples of the protective film include a plastic film used for the support and paper, or a paper laminated with a plastic film such as a polyethylene film or a polypropylene film. In particular, a polyethylene film and a polypropylene film are preferable. The thickness of the protective film is generally in the range of 5 to 100 μm, and preferably in the range of 10 to 50 μm. In that case, it is preferable that the adhesive force A between the photosensitive resin composition layer and the support and the adhesive force B between the photosensitive resin composition layer and the protective film satisfy the relationship of A> B. Examples of the support / protective film combination include polyethylene terephthalate / polypropylene, polyethylene terephthalate / polyethylene, polyvinyl chloride / cellophane, and polyimide / polypropylene. In addition to the method of selecting the support and the protective film from different types as described above, the above adhesive force relationship can be satisfied by surface-treating at least one of the support and the protective film. . The surface treatment of the support is generally performed in order to increase the adhesive strength with the photosensitive resin composition layer. For example, coating of a primer layer, corona discharge treatment, flame treatment, ultraviolet irradiation treatment , High frequency irradiation treatment, glow discharge irradiation treatment, active plasma irradiation treatment, laser beam irradiation treatment, and the like. In addition, for example, when a long dry film photoresist is manufactured and stored and transported in a roll, the coefficient of static friction between the support and the protective film is also important. The static friction coefficient is preferably in the range of 0.3 to 1.4, and particularly preferably in the range of 0.5 to 1.2. If it is less than 0.3, it slips too much, so that it may cause a winding deviation when it is rolled. Moreover, when it exceeds 1.4, it may become difficult to wind in a roll shape.

  Moreover, you may surface-treat a protective film. The surface treatment is performed to reduce the adhesion between the protective film and the photosensitive resin composition layer. For example, an undercoat layer made of a polymer such as polyorganosiloxane, fluorinated polyolefin, polyfluoroethylene, and polyvinyl alcohol is provided on the surface of the protective film. The undercoat layer is generally formed by applying the polymer coating solution onto the surface of the protective film and then drying at a temperature of 30 to 150 ° C. (especially 50 to 120 ° C.) for 1 to 30 minutes.

[Method of manufacturing printed wiring board]
A method for producing a printed wiring board using the dry film photoresist of the present invention will be described with reference to the accompanying drawings, taking as an example the production of a printed wiring board having through holes.

FIG. 4 is a diagram schematically showing a method for producing a printed wiring board using a dry film photoresist having a single photosensitive resin composition layer (the dry film photoresist of FIG. 1).
As shown in FIG. 4A, a printed wiring board forming substrate 30 having a through hole 31 and having a surface covered with a metal layer 32 is prepared.

  Next, as shown in FIG. 4B, while the protective film of the dry film photoresist 10 is peeled off, the pressure-sensitive adhesive roller 40 is used for pressure bonding so that the photosensitive resin composition layer is in contact with the metal layer. (Lamination process). Thereby, the laminated body by which the printed wiring board formation board | substrate 30, the photosensitive resin composition layer 12, and the support body 11 were laminated | stacked in this order is obtained.

  Next, as shown in FIG. 4C, the photosensitive resin composition layer is cured by irradiating light from the surface of the laminated body on the support 11 side to form a predetermined pattern. A cured product pattern including the cured resin region 14 and the cured resin region 15 covering the through hole or the via hole is formed (exposure process).

Next, as shown in FIG. 4D, the support 11 is peeled off from the laminate (support peeling process).
In addition, you may peel a support body before the said exposure process.

  Next, as shown in FIG. 4E, the uncured region of the photosensitive resin composition layer 12 on the printed wiring board forming substrate 30 is dissolved and removed with an appropriate developer to form a wiring pattern. The cured resin region 14 and the cured resin region 15 for protecting the metal layer of the through hole are developed to expose the metal layer 32 on the substrate surface (development process).

Next, as shown in FIG. 4F, the exposed metal layer 32 on the substrate surface is dissolved and removed with an etching solution (etching step). As a result, the wiring pattern 33 is formed on the printed wiring board forming substrate 30.
Next, as shown in FIG. 4G, the cured resin regions 14 and 15 are removed from the printed wiring board forming substrate as a release piece 16 with a strong alkaline aqueous solution (cured product removing step).

FIG. 5 is a diagram schematically showing a method for producing a printed wiring board using a dry film photoresist having two photosensitive resin composition layers (the dry film photoresist of FIG. 2).
As shown in FIG. 5A, a printed wiring board forming substrate 30 having a through hole 31 and having a surface covered with a metal layer 32 is prepared.
Next, as shown in FIG. 5B, the pressure-sensitive roller 40 is used so that the second photosensitive resin composition layer 23 is in contact with the metal layer 32 while peeling off the protective film of the dry film photoresist 20. And crimping (lamination process). Thereby, the laminated body by which the printed wiring board formation board | substrate 30, the 2nd photosensitive resin composition layer 23, the 1st photosensitive resin composition layer 22, and the support body 21 was laminated | stacked in this order is obtained.

  Next, as shown in FIG. 5C, the photosensitive resin composition layer is cured by irradiating light from the side of the laminate opposite to the printed wiring board forming substrate 30. A wiring pattern forming region of the printed wiring board forming substrate is irradiated with light of a light amount necessary for curing the second photosensitive resin composition layer 23 in a predetermined pattern, so that a cured resin for forming the wiring pattern Region 25 is formed (wiring portion exposure step). Light of the amount of light necessary for curing the first photosensitive resin composition layer 22 and the second photosensitive resin composition layer 23 is applied to the opening of the through hole of the printed wiring board forming substrate and the periphery thereof. Irradiation is performed to form a cured resin region 26 for protecting the through hole metal layer (hole exposure step).

  Next, as shown in FIG. 5D, the support 21 is peeled from the laminate (support peeling process). In addition, you may peel a support body before the said exposure process.

  Next, as shown in FIG. 5 (E), the uncured regions of the first photosensitive resin composition layer 22 and the second photosensitive resin composition layer 23 on the printed wiring board forming substrate are treated with an appropriate developer. Then, the cured resin region 25 for forming the wiring pattern and the cured resin region 26 for protecting the metal layer of the through hole are developed to expose the metal layer on the substrate surface (developing step).

Next, as shown in FIG. 5F, the exposed metal layer on the substrate surface is dissolved and removed with an etching solution (etching step). Thereby, the wiring pattern 34 is formed on the printed wiring board forming substrate.
Next, as shown in FIG. 5G, the cured resin region is removed from the printed wiring board forming substrate with a strong alkaline aqueous solution as a peeled piece (cured product removing step).

  In the production of the printed wiring board described above, as a printed wiring board manufacturing substrate, a copper-clad laminate and a substrate in which a copper plating layer is formed on an insulating base material such as glass-epoxy, or a plurality of substrates through an interlayer insulating film The board | substrate (laminated board | substrate) which laminated | stacked and formed the copper plating layer can be used.

  The lamination step can be performed at room temperature (15 to 30 ° C.) or under heating (30 to 180 ° C.). In particular, it is preferable to carry out under heating at 60 to 140 ° C.

  As a method of irradiating light in a pattern in the exposure step, a method of irradiating the entire surface with ultraviolet light through a photomask, or a method of irradiating according to a pattern signal with a laser scanning exposure apparatus having a wavelength in the ultraviolet to visible light region It is preferable to use this. In particular, the latter method using a laser scanning exposure apparatus is suitable for the production of a small variety of products because the pattern can be formed without using an expensive mask, and the process problems caused by the mask are eliminated. . As a light source used for the exposure, an electromagnetic wave that is transmitted through a dry film photoresist support and is active with respect to the photopolymerization initiator to be used, an ultraviolet having a wavelength of 310 to 700 nm (preferably 350 to 500 nm). A light source that generates light in the visible region is used. For example, a known light source such as an (ultra) high pressure mercury lamp, a xenon lamp, a carbon arc lamp, a halogen lamp, a copying fluorescent tube, or a semiconductor laser can be used. In addition, an electron beam or an X-ray may be used.

  Examples of the developer used in the development step include an alkaline aqueous solution (for example, sodium carbonate solution), an alkaline aqueous solution containing an organic solvent, and an organic solvent.

  The etchant used in the etching process varies depending on the material of the metal layer. When the material of the metal layer 23 is copper, a ferrous chloride aqueous solution, a copper chloride aqueous solution, and a cupric chloride aqueous solution can be used as the etching solution.

  The strong alkaline aqueous solution used in the cured product removing step preferably has a pH in the range of 13-14. As the strong alkaline aqueous solution, an aqueous solution of sodium hydroxide or potassium hydroxide can be used.

  The printed wiring board may be a multilayer printed wiring board. Further, the dry film photoresist of the present invention may be used not only in the above etching process but also in a plating process. Examples of plating methods include copper plating such as copper sulfate plating and copper pyrophosphate plating, solder plating such as high-throw solder plating, nickel plating such as watt bath (nickel sulfate-nickel chloride) plating, nickel sulfamate plating, and hard gold plating. There are gold plating such as soft gold plating.

[Example 1]
A photosensitive resin composition solution having the following composition was applied to a 20 μm-thick polyethylene terephthalate film so that the dry film thickness was 20 μm and dried to form a photosensitive resin composition layer.

[Composition of photosensitive resin composition solution]
────────────────────────────────────────
35% by mass solution of methacrylic acid / methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate copolymer (composition ratio 29/55/12/4 (molar ratio), mass average molecular weight 116,000 (polystyrene conversion)) (Solvent is methyl ethyl ketone / 1-methoxy-2-propanol = 2/1 (mass ratio)) 51.9 parts by mass Dodecapropylene glycol diacrylate 8.56 parts by mass Tetraethylene glycol dimethacrylate 2.14 parts by mass UV curable inorganic / Organic hybrid hard coat (manufactured by JSR Corporation, DeSolite Z7501, composition containing colloidal silica fine particles having acryloyl group on the surface, 50% by mass methyl ethyl ketone solution) 0.22 parts by mass 4,4′-bis (diethylamino) benzophenone 0.06 parts by mass 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole 1.4 parts by mass Phenyltribromomethylsulfone 0.02 parts by mass Leucocrystal violet 0.02 parts by mass Malachite Green oxalate 0.02 parts by weight p-Toluenesulfonamide 0.63 parts by weight Methyl ethyl ketone 9.3 parts by weight 1-methoxy-2-propanol 5.9 parts by weight ───────────── ────────────────────────────

  Next, a 12 μm thick polypropylene film was laminated on the photosensitive resin composition layer. The shortest development time, resolution, adhesion, number of tent tears, and peeling time of the dry film resist thus obtained were evaluated by the following methods. The results are shown in Table 1.

(1) Measuring method of shortest development time The surface of the surface is dried and the photosensitive resin composition layer is laminated on the surface of a dry copper-clad laminate (without through holes) while peeling the dry film photoresist polypropylene film. (MODEL8B-720-PH, Taisei Laminator Co., Ltd.) is used for pressure bonding to produce a laminate composed of a copper-clad laminate, a photosensitive resin composition layer, and a polyethylene terephthalate film. The pressure bonding conditions are a laminated plate temperature of 70 ° C., a pressure roller temperature of 105 ° C., a pressure roller pressure of 3 kg / cm ² , and a pressure bonding speed of 1.2 m / min. The polyethylene terephthalate film is peeled off from the laminate, and a 1 mass% sodium carbonate aqueous solution at 30 ° C. is sprayed at a pressure of 0.1 MPa over the entire surface of the photosensitive resin composition layer on the copper clad laminate. The time required from the start of spraying the aqueous sodium carbonate solution until the photosensitive resin composition layer on the copper clad laminate is dissolved and removed is measured, and this is defined as the shortest development time.

(2) Resolution measurement method Under the same conditions as in the shortest development time evaluation method of (1) above, a laminate comprising a copper-clad laminate, a photosensitive resin composition layer, and a polyethylene terephthalate film was prepared, and room temperature ( (23 ° C., 55% RH) for 10 minutes. Ultrahigh pressure mercury lamp (3kW ultra high pressure mercury lamp double-sided simultaneous exposure device HMW-6-N type, oak through a photomask (line / space = 1/1, line width 10 μm to 100 μm) on the surface of the polyethylene terephthalate film of the laminate The photosensitive resin composition layer is exposed by irradiating light of 40 mJ / cm ² using a product manufactured by Co., Ltd. After leaving still at room temperature for 10 minutes, a polyethylene terephthalate film is peeled off from a laminated body. A 1 mass% sodium carbonate aqueous solution at 30 ° C. is sprayed over the entire surface of the resin composition layer on the copper clad laminate at a spray pressure of 0.1 MPa for 1.5 times the shortest development time obtained in (1) above. Then, the uncured resin composition is dissolved and removed, and the cured resin pattern is developed. Thereafter, 20 ° C. water is sprayed at a spray pressure of 0.05 MPa for 80 seconds, and the cured resin pattern is washed with water and dried. The surface of the copper-clad laminate with the cured resin pattern thus obtained was observed with an optical microscope, and the minimum line width without any abnormalities such as tsumari and twisting was measured on the cured resin pattern line. To do.

(3) Adhesion measurement method Except for using a photomask with a line / space of 1/3 and a line width of 10 μm to 100 μm, the same operation as the resolution evaluation method of (2) above was performed, and a cured resin pattern line Measure the minimum line width without any abnormalities such as peeling and twisting, and make this the close contact.

(4) Method for measuring the number of tent film tears The shortest development of (1) above, except that a copper-clad laminate having 200 copper-plated through-holes with a diameter of 3 mm is used instead of a copper-clad laminate having no through-holes. Under the same conditions as the time evaluation method, a laminate comprising a copper clad laminate, a photosensitive resin composition layer, and a polyethylene terephthalate film is prepared and allowed to stand at room temperature (23 ° C., 55% RH) for 10 minutes. . The surface of the laminated polyethylene terephthalate film is irradiated with light of 50 mJ / cm ² using an ultrahigh pressure mercury lamp to expose the entire surface of the photosensitive resin composition layer. After leaving at room temperature for 10 minutes, the polyethylene terephthalate film is peeled off from the laminate. A sodium carbonate aqueous solution is sprayed on the entire surface of the resin composition layer on the copper clad laminate under the same conditions as in the resolution evaluation method of (2) except that the spray pressure of the sodium carbonate aqueous solution is 0.2 MPa. The cured resin pattern is developed, washed with water and dried. The copper clad laminate with a cured resin pattern thus obtained was sprayed with a 45 ° C. aqueous cupric chloride solution (etching solution) at a spray pressure of 0.1 MPa for 60 seconds to obtain a copper clad laminate. Etch. The total number of holes in which the tent film has been torn is counted up to this point (the smaller number is better).

(5) Peeling time measurement method Under the same conditions as the evaluation method for the shortest development time in (1) above, a laminate comprising a copper clad laminate, a photosensitive resin composition layer, and a polyethylene terephthalate film was prepared, and the room temperature ( (23 ° C., 55% RH) for 10 minutes. The entire surface of the photosensitive resin composition layer is exposed by irradiating the surface of the polyethylene terephthalate film of the laminate with 40 mJ / cm ² of light using an ultrahigh pressure mercury lamp. After leaving still at room temperature for 10 minutes, a polyethylene terephthalate film is peeled off from a laminated body. Under the same conditions as the resolution evaluation method of (2) above, an aqueous solution of sodium carbonate is sprayed on the entire surface of the resin composition layer on the copper clad laminate to develop a cured resin pattern, washed with water and dried. The copper-clad laminate with a cured resin pattern thus obtained is immersed in a 3% by mass aqueous sodium hydroxide solution. The time required from the start of immersion of the copper-clad laminate to the complete removal of the cured resin pattern on the copper-clad laminate is measured, and this is taken as the peeling time. The peeling time is within 30 seconds.

[Example 2]
In Example 1, 8.56 parts by mass of dodecapropylene glycol diacrylate is 8.22 parts by mass, 2.14 parts by mass of tetraethylene glycol dimethacrylate is 2.05 parts by mass, UV curable inorganic / organic hybrid hard coat 0 A dry film resist was obtained in the same manner as in Example 1 except that .22 parts by mass was changed to 1.08 parts by mass. Table 1 shows the results of evaluating the shortest development time, resolution, number of tent tears, and peeling time of this dry film resist.

[Comparative Example 1]
In Example 1, 8.56 parts by mass of dodecapropylene glycol diacrylate was changed to 8.65 parts by mass, and 2.14 parts by mass of tetraethylene glycol dimethacrylate was changed to 2.16 parts by mass. A dry film resist was obtained in the same manner as in Example 1 except that no coat was used. Table 1 shows the results of evaluating the shortest development time, resolution, number of tent tears, and peeling time of this dry film resist.

[Comparative Example 2]
A dry film resist was obtained in the same manner as in Comparative Example 1 except that the dry film thickness of the photosensitive resin composition layer in Comparative Example 1 was 40 μm. Table 1 shows the results of evaluating the shortest development time, resolution, number of tent tears, and peeling time of this dry film resist.

[Comparative Example 3]
The 35 weight% solution 51.9 parts by mass of the copolymer in Comparative Example 1 was changed to 20.8 parts by mass to obtain a styrene / acrylic acid copolymer (copolymerization composition: 73 mol% / 37 mol%, mass average molecular weight). : 10,000) 35% by weight solution (solvent is methyl ethyl ketone / 1-methoxy-2-propanol = 2/1 (mass ratio)) 31.1 parts by weight A resist was obtained. Table 1 shows the results of evaluating the shortest development time, resolution, number of tent tears, and peeling time of this dry film resist.

[Table 1]
Table 1
────────────────────────────────────────
Minimum development time Resolution Adhesion Number of tent film tears Peeling time ──────────────────────────────────────── ─
Example 1 15 seconds 40 μm 20 μm 3 or less Passed Example 2 20 seconds 50 μm 20 μm 3 or less Passed ─────────────────────────── ────────────
Comparative Example 1 20 seconds 50 μm 30 μm 26 Passed Comparative Example 2 25 seconds 70 μm 30 μm 3 or less Fails Comparative Example 3 11 seconds 40 μm 20 μm 158 Passed ────────────────── ──────────────────────

[Example 3]
(Evaluation of resolution and adhesion of cured product pattern formed by laser exposure)
The surface of the dried copper-clad laminate was prepared and the photosensitive resin composition layer of the dry film photoresist produced in Example 1 was peeled off from the polypropylene film on the photosensitive resin composition layer. The laminate was composed of a copper-clad laminate, a photosensitive resin composition layer, and a polyethylene terephthalate film. Using a laser exposure apparatus having a laser light source with a wavelength of 400 to 415 nm on the polyethylene terephthalate film of this laminate, a pattern with line / space = 1/1 and a line width of 10 μm to 100 μm, and line / space = 1/3 The photosensitive resin composition layer was exposed by irradiating a laser beam of 105 mJ / cm ² with a pattern having a line width of 10 μm to 100 μm. After leaving still at room temperature for 10 minutes, the polyethylene terephthalate film was peeled off from the laminated body. The entire surface of the resin composition layer on the copper-clad laminate is sprayed with a 1 mass% sodium carbonate aqueous solution at 30 ° C. for 17 seconds at a pressure of 0.1 MPa to dissolve and remove the uncured resin composition. Developed. Thereafter, water at 20 ° C. was sprayed for 80 seconds at a spray pressure of 0.05 MPa, and the cured resin pattern was washed with water and dried. When the surface of the copper-clad laminate with a cured resin pattern thus obtained was observed with an optical microscope, the line of the cured resin pattern formed with line / space = 1/1 had no abnormality such as tsumari and twist. The line width (resolution) of the film was peeled off to the line of the cured resin pattern formed with 40 μm and line / space = 1/3, and the minimum line width (adhesion) without abnormality such as twisting was 20 μm.

[Example 4]
(Evaluation of the number of tent film tears formed by laser exposure)
The photosensitive resin composition layer of the dry film photoresist produced in Example 1 was coated on the surface of a copper-clad laminate having 200 copper-plated through-holes having a diameter of 3 mm and dried. The polypropylene film on the resin composition layer was pressure-bonded while peeling to prepare a laminate composed of a copper-clad laminate, a photosensitive resin composition layer, and a polyethylene terephthalate film. The entire surface of the polyethylene terephthalate film of the laminate was irradiated with a laser beam of 105 mJ / cm ² using a laser exposure apparatus having a laser light source having a wavelength of 400 to 415 nm to expose the photosensitive resin composition layer. After leaving still at room temperature for 10 minutes, the polyethylene terephthalate film was peeled off from the laminated body. The entire surface of the resin composition layer on the copper clad laminate is sprayed with a 1 mass% sodium carbonate aqueous solution at 30 ° C. for 17 seconds at a pressure of 2 MPa to dissolve and remove the uncured resin composition and develop the cured resin pattern. Washed with water and dried. The copper clad laminate with a cured resin pattern thus obtained was sprayed with a 45 ° C. aqueous cupric chloride solution (etching solution) at a spray pressure of 0.1 MPa for 60 seconds to obtain a copper clad laminate. Etched. When the total number of holes to which the tent film was torn was counted in the processing so far, the number of tent film torn was 3 or less.

[Example 5]
(Evaluation of peeling time of cured product pattern formed by laser exposure)
The surface of the dried copper-clad laminate was prepared and the photosensitive resin composition layer of the dry film photoresist produced in Example 1 was peeled off from the polypropylene film on the photosensitive resin composition layer. The laminate was composed of a copper-clad laminate, a photosensitive resin composition layer, and a polyethylene terephthalate film. The polyethylene terephthalate film of this laminate is irradiated with a laser beam of 105 mJ / cm ^{2 on} the entire surface of the polyethylene terephthalate film of this laminate using a laser exposure apparatus having a laser light source having a wavelength of 400 to 415 nm. The resin composition layer was exposed. After leaving still at room temperature for 10 minutes, the polyethylene terephthalate film was peeled off from the laminated body. A 1 mass% sodium carbonate aqueous solution at 30 ° C. was sprayed for 17 seconds at a pressure of 2 MPa over the entire surface of the resin composition layer on the copper clad laminate, and the cured resin pattern was developed, washed with water and dried. The copper-clad laminate with a cured resin pattern thus obtained was immersed in a 3% by mass aqueous sodium hydroxide solution so that the cured resin pattern on the copper-clad laminate was obtained from the start of immersion of the copper-clad laminate. As a result, the time required to completely remove was measured, and the time was within 30 seconds.

[Example 6]
The photosensitive resin composition solution of Example 1 was applied to a 20 μm thick polyethylene terephthalate film so that the dry film thickness was 25 μm, and dried to form a first photosensitive resin composition layer.

  Next, an intermediate layer forming solution having the following composition was applied onto the first photosensitive resin composition layer so that the dry film thickness was 2 μm and dried to form an intermediate layer.

[Composition of intermediate layer forming solution]
────────────────────────────────────────
Polyvinyl alcohol (PVA205) 2.0 parts by weight Water 21.0 parts by weight Methanol 17.0 parts by weight ──────────────────────────── ────────────

  Next, on the intermediate layer, a second photosensitive resin composition solution having the following composition is applied so as to have a dry film thickness of 5 μm and dried to form a second photosensitive resin composition layer. did.

[Composition of second photosensitive resin composition solution]
────────────────────────────────────────
Methacrylic acid / methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate copolymer (composition ratio: 28.8 / 40 / 26.7 / 4.5 (molar ratio), mass average molecular weight: 116000 (polystyrene conversion) ) 15 parts by mass Monomer having a bisphenol structure represented by the following formula (II) 8 parts by mass 4,4′-bis (diethylamino) benzophenone 0.4 parts by mass Benzophenone 3.0 parts by mass p-toluenesulfonamide 0.5 Parts by weight malachite green oxalate 0.02 parts by weight 1,2,4-triazole 0.01 parts by weight leuco crystal violet 0.2 parts by weight tribromomethylphenylsulfone 0.1 parts by weight methyl ethyl ketone 30 parts by weight ──── ──────────────────────────────── ────

[但し、ｍ＋ｎは４を表す。]

[However, m + n represents 4. ]

Finally, a 12 μm-thick polypropylene film was laminated on the second photosensitive resin composition layer. As a result of measuring the sensitivity of the dry film photoresist thus obtained by the following method, the amount of light A required to cure the second photosensitive resin composition layer was 4 mJ / cm ² , and the first photosensitive resin composition The amount of light B required to cure the physical layer is 40 mJ / cm ² , and the amount of light C required until the first photosensitive resin composition layer is cured is 14 mJ / cm ² (the amount of light C and the amount of light A The difference was 10 mJ / cm ² ).

[Measurement method of sensitivity]
The photosensitive resin composition layer of the dry film photoresist, by using a high-pressure mercury lamp from the polyethylene terephthalate film side was irradiated with light of different light intensity up to 100 mJ / cm ² at 2 ^1/2 times the interval from 0.1 mJ / cm ² Then, the photosensitive resin composition layer is cured. Next, the polyethylene terephthalate film is peeled off, the unexposed portion of the photosensitive resin composition layer is removed by dissolution with an aqueous sodium carbonate solution, the cured layer is developed, and the thickness of the cured layer is measured. Next, a sensitivity curve is obtained by plotting the relationship between the light irradiation amount and the thickness of the cured layer. From the sensitivity curve thus obtained, the amount of light (light amount A) when the thickness of the cured layer is 5 μm, the amount of light (light amount B) when the thickness of the cured layer is 30 μm, and the thickness of the cured layer is 5 μm. The amount of light (light amount C) is read when exceeding.

  The shortest development time, the number of tent tears, and the peeling time of the dry film photoresist were measured under the same conditions as in Example 1. As a result, the shortest development time was 30 seconds, the number of tent film tears was 3 or less, and the peeling time was acceptable (within 30 seconds). Further, when the resolution and adhesion were evaluated by the following methods, the resolution was 15 μm and the adhesion was 15 μm.

[Measurement method of resolution and adhesion]
Except that the 10 mJ / cm ² light dose 40 mJ / cm ² in the resolution and the measuring method of the adhesion in Example 1, in (this dose of evaluating resolution and adhesion in the same manner as in Example 1, the second photosensitive Only the functional resin composition layer is cured).

1 is a cross-sectional view of an example of a dry film photoresist according to the present invention. FIG. 4 is a cross-sectional view of another example of a dry film photoresist according to the present invention. It is a graph which shows the sensitivity curve showing the relationship between the irradiation amount of light when the light is irradiated to the dry film photoresist shown in FIG. 2 from the support body side, and the thickness of the hardened layer obtained. It is a figure which shows roughly the manufacturing method of the printed wiring board using the dry film photoresist shown in FIG. It is a figure which shows roughly the manufacturing method of the printed wiring board using the dry film photoresist shown in FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Dry film photoresist 11 Support body 12 Photosensitive resin composition layer 13 Protective film 14 Hardening resin area | region for wiring pattern formation 15 Curing resin area | region for metal layer protection of a through hole 16 Peeling piece 20 Dry film photoresist 21 Support body 22nd One photosensitive resin composition layer 23 Second photosensitive resin composition layer 24 Protective film 25 Cured resin region for wiring pattern formation 26 Cured resin region for metal layer protection of through hole 27 Peeling piece 30 Printed wiring board forming substrate 31 Through Hole 32 Metal layer 33 Wiring pattern 40 Pressure roller

Claims (14)

  A dry film photoresist comprising a photosensitive resin composition layer comprising a binder, a polymerizable monomer component, a photopolymerization initiator, and inorganic fine particles having a polymerizable group on a support.   The dry film photoresist according to claim 1, wherein the inorganic fine particles are silica fine particles.   The dry film photoresist according to claim 1 or 2, wherein the binder is a carboxyl group-containing vinyl copolymer having a content of repeating units having a carboxyl group in the range of 10 to 40 mol%.   The photosensitive resin composition layer has a binder of 30 to 90% by mass, a polymerizable monomer component of 5 to 60% by mass, a photopolymerization initiator of 0.1 to 30% by mass, and inorganic fine particles of 0.1 to 10% by mass. The dry film photoresist according to any one of claims 1 to 3, comprising:   The dry film photoresist of Claim 4 in which the photosensitive resin composition layer contains 0.1-4 mass% of inorganic fine particles.   The dry film photoresist according to any one of claims 1 to 5, wherein the photosensitive resin composition layer has a thickness of 5 µm or more and less than 35 µm.   The dry film photoresist according to any one of claims 1 to 6, further comprising a protective film layer on the photosensitive resin composition layer.   The dry film photoresist according to any one of claims 1 to 7, which is used for manufacturing a printed circuit board. A manufacturing method comprising the following steps of a printed wiring board having a through hole or a via hole:
(1) A step of preparing a printed wiring board forming substrate having a through hole or a via hole and having a surface covered with a metal layer;
(2) The dry film photoresist according to any one of claims 1 to 6 is pressure-bonded to the surface of the printed wiring board forming substrate so that the photosensitive resin composition layer is in contact with the metal layer, A laminating step of obtaining a laminate in which a printed wiring board forming substrate, a photosensitive resin composition layer, and a support are laminated in this order;
(3) The photosensitive resin composition layer is cured by irradiating light from the support-side surface of the laminated body to cure the photosensitive resin composition layer, and an opening region of a through hole or a via hole An exposure step of forming a cured product pattern comprising a cured resin region covering the substrate;
(4) The support peeling process which peels a support body from a laminated body before or after the process of said (3);
(5) A development step of dissolving and removing the uncured region of the photosensitive resin composition layer on the printed wiring board forming substrate to expose the metal layer of the uncured region on the substrate surface;
(6) an etching step of dissolving and removing the metal layer in the exposed region with an etching solution; and
(7) A cured resin removing step of removing the cured resin from the printed wiring board forming substrate.   The method for manufacturing a printed wiring board according to claim 9, wherein the light used in the step (3) is laser light.   Photosensitive resin containing inorganic fine particles having a binder, a polymerizable monomer component, a photopolymerization initiator, and a polymerizable group on a printed wiring board forming substrate having a through hole or a via hole and having a surface covered with a metal layer A laminate in which composition layers are laminated.   A first photosensitive resin composition comprising a binder, a polymerizable monomer component, and a photopolymerization initiator on a support, and a first photosensitive resin composition comprising a binder, a polymerizable monomer component, and a photopolymerization initiator. A second photosensitive resin composition layer having a higher photosensitivity than the physical layer is laminated in this order, and at least one of the first photosensitive resin composition layer and the second photosensitive resin composition layer A dry film photoresist characterized by comprising inorganic fine particles having a polymerizable group. A manufacturing method comprising the following steps of a printed wiring board having a through hole or a via hole:
(1) A step of preparing a printed wiring board forming substrate having a through hole or a via hole and having a surface covered with a metal layer;
(2) The dry film photoresist according to claim 12 is pressure-bonded to the surface of the printed wiring board forming substrate so that the second photosensitive resin composition layer is in contact with the metal layer, the printed wiring board forming substrate, A lamination step for obtaining a laminate in which the second photosensitive resin composition layer, the first photosensitive resin composition layer, and the support are laminated in this order;
(3) From the side opposite to the printed wiring board forming substrate of the laminate, the light amount necessary for curing the second photosensitive resin composition layer is formed in the wiring pattern forming region of the printed wiring board forming substrate. Is irradiated in a predetermined pattern to form a cured resin region of a predetermined pattern, and in a region including an opening of a through hole or a via hole, a first photosensitive resin composition layer and a second photosensitive resin composition layer An exposure step of forming a cured resin region that covers an opening region of a through hole or a via hole by irradiating a predetermined pattern with light of a light amount necessary for curing both of
(4) The support peeling process which peels a support body from a laminated body before or after the process of said (3);
(5) Dissolving and removing uncured regions of the first photosensitive resin composition layer and the second photosensitive resin composition layer on the printed wiring board forming substrate to expose the uncured metal layer on the substrate surface. Developing process;
(6) an etching step of dissolving and removing the metal layer in the exposed region with an etching solution; and
(7) A cured resin removing step of removing the cured resin from the printed wiring board forming substrate.   A second photosensitive resin composition layer comprising a binder, a polymerizable monomer component, and a photopolymerization initiator on a printed wiring board forming substrate having a through hole or a via hole, the surface of which is covered with a metal layer; And the 1st photosensitive resin composition layer which contains a binder, a polymerizable monomer component, and a photoinitiator, and shows the photosensitivity relatively lower than the 2nd photosensitive resin composition layer is laminated in this order, At least one of the 1st photosensitive resin composition layer or the 2nd photosensitive resin composition layer contains the inorganic fine particle which has a polymeric group, The laminated body characterized by the above-mentioned.

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