JP5056840B2 - Photosensitive resin composition, photosensitive film using the same, method for forming resist pattern, printed wiring board, and method for producing the same - Google Patents

Description

  The present invention relates to a photosensitive resin composition, a photosensitive film using the same, a method for forming a resist pattern, a printed wiring board, and a method for producing the same.

  With the miniaturization, weight reduction, and multifunctionality of electrical and electronic components, photosensitive resins (photosensitive materials) such as dry films for circuit formation and solder resists can be used for high density printed circuit boards. Higher resolution is required. In consideration of environmental problems, an alkali development type using a dilute alkaline aqueous solution as a developing solution has become mainstream.

  Formation of the resist pattern using the photosensitive material is performed by image development after developing the photosensitive resin composition as a raw material after exposure. In such a process, the photosensitive resin composition is photocured by exposure, but in order to increase the resolution, it is necessary to increase the solubility of the unexposed area, that is, to increase the contrast.

  On the other hand, the flame retardant regulations required for electrical and electronic components are not only for global environmental issues and safety issues for the human body, but the focus has shifted to non-polluting, low toxic, and safety. Not only is it difficult to burn, but there is a demand for reducing harmful gases and fuming substances. In response to this, development of non-halogen flame retardants is strongly demanded. For example, in the field of printed wiring boards, copper-clad laminates that are circuit-forming boards and flame-retardant materials that do not use halides as sealing materials have already been developed and put to practical use. In the field of solder resists, there is an urgent need to develop materials that do not contain halides.

  Therefore, the use of phosphorus-based compounds, nitrogen-based compounds, aluminum hydroxide, magnesium hydroxide, and the like as non-halogen flame retardants for imparting flame retardancy to photosensitive materials has been proposed (for example, non-halogen-based flame retardants). (See Patent Document 1).

Latest Flame Retardant / Flame Retardation Technology, Technical Information Association, 1992, pages 105-112

  However, in the case of the photosensitive resin composition using the conventional flame retardant, the solder heat resistance, the electric corrosion resistance, the resin residue after development, and the resolution tend to be insufficient. In particular, when a non-halogen flame retardant is added alone, a large amount of addition is necessary to impart sufficient flame retardancy, and this causes a decrease in developability of unexposed areas, resulting in a decrease in resolution. Will be invited.

  Therefore, the present inventors first examined a method for improving the developability of the unexposed area without increasing the amount of flame retardant added. As a method for improving the developability of the unexposed area, use of a flame retardant (ammonium polyphosphate, melamine polyphosphate, etc.) with a high concentration of phosphorus, nitrogen or the like can be considered. However, many of these flame retardants are filler-type flame retardants that are insoluble in solvents, causing further reduction in solubility in the developer, light fogging due to light scattering, and poor dispersion. Even if it is reduced, the resolution may be significantly reduced.

  Further, as another method for improving the developability of the unexposed area, a method of increasing the solubility of the unexposed area by introducing a hydrophilic group such as a carboxyl group into the photosensitive resin composition is conceivable. In this case, the high hydrophilicity when a carboxyl group is applied can be determined using the acid value as an index, and the higher the acid value resin, the higher the solubility. However, in the case of a permanent resist such as a solder resist, the higher the acid value of the polymer, the higher the water absorption rate. Therefore, the insulation resistance under high-temperature and high-humidity conditions, that is, the resistance to electric corrosion tends to occur.

  In addition, as a method of ensuring high temperature moisture resistance of the photosensitive resin composition, the method of using the reaction material of a novolak-type epoxy compound and unsaturated carboxylic acid for active energy ray-curable resin can be considered. However, since the photosensitive resin composition for solder resist is usually in a liquid state and the carboxyl group easily reacts with the epoxy group, such a product has two liquids (two-pack type of epoxy group-containing solution and carboxyl group-containing solution). It is often sold separately. And such a photosensitive resin composition is accompanied by restrictions of use conditions, such as the pot life at the time of mixing two liquids being as short as several hours to one day. Further, when the two liquids are mixed in advance to form a film, it is difficult to store in a film state.

  The present invention has been made in view of such circumstances, can ensure flame retardancy without using a halogen-based flame retardant, and is excellent in resolution, electric corrosion resistance, and storage stability. It aims at providing the photosensitive resin composition, the photosensitive film using the same, the formation method of a resist pattern, a printed wiring board, and its manufacturing method.

In order to solve the above problems, the photosensitive resin composition of the present invention comprises (A) a polymer having a carboxyl group, (B) a photopolymerizable compound having an ethylenically unsaturated bond, and (C) initiation of photopolymerization. And (D) a phenoxyphosphazene compound, and the content of component (D) is 30 to 70 parts by weight with respect to 100 parts by weight of the total amount of components (A) and (B). And (A) component is a copolymer of (meth) acrylic acid and / or (meth) acrylic acid alkyl ester and (meth) acrylic acid and / or copolymerized vinyl monomer other than (meth) acrylic acid alkyl ester Alternatively, it is characterized by containing a copolymer having an ethylenically unsaturated bond introduced in the side chain and / or terminal of the copolymer .

  According to the photosensitive resin composition of the present invention, by having the above-described configuration, flame retardancy is ensured without using a halogen-based flame retardant, and resolution, electric corrosion resistance, and storage stability are achieved at a high level. It becomes possible to do.

  In addition, the present inventors guess as follows about the reason the above-mentioned effect is acquired by the photosensitive resin composition of this invention. That is, in the case of the photosensitive resin composition of the present invention, by using the above components (A) to (D) as essential components, the flame retardancy of the photosensitive resin composition is enhanced and the varnish for film formation is used. The solubility in solvents such as acetone, methyl ethyl ketone, N, N-dimethylformamide, etc. used in the production of this product is enhanced, resulting in better dispersibility and resolution than conventional photosensitive materials using filler-type flame retardants. This is considered to improve the performance. Further, conventional flame retardants such as phosphate esters have problems in terms of stability such as hydrolysis of ester bonds, but the components (A) to (D) according to the present invention themselves are such hydrolysis. In addition, the components (B) to (D) are substantially reactive to the carboxyl group of the component (A) at room temperature. No. Therefore, the photosensitive resin composition of the present invention is considered to exhibit good storage stability even when a one-pack varnish is used in order to cope with film formation.

  Moreover, since the photosensitive resin composition of the present invention can be a cured product excellent in flame retardancy, insulation resistance and mechanical strength by being photocured by irradiation with actinic rays, an insulating resin for printed wiring boards, It is very useful as a solder resist.

  The photosensitive resin composition of the present invention includes a compound having a cyclic structure represented by the following general formula (1) and / or a chain structure represented by the following general formula (2) as the component (D). It is preferable to contain. The use of the compound having a structure represented by the general formulas (1) and (2) can satisfy the above-described effects of the photosensitive composition of the present invention.

（式（１）中、ｍは１〜２０の整数を示す。）

(In formula (1), m represents an integer of 1 to 20.)

（式（２）中、ｎは１〜２０の整数を示す。）

(In formula (2), n represents an integer of 1 to 20)

  Moreover, the photosensitive resin composition of this invention contains the amine compound represented by following General formula (3) and / or the thioxanthone type compound represented by following General formula (4) as (C) component. It is preferable. By using the compounds represented by the general formulas (3) and (4) as the component (C), the above-described effects of the photosensitive resin composition of the present invention can be further improved, and particularly higher resolution. You will be able to get

（式（３）中、Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４は同一でも異なっていてもよく、それぞれ水素原子又は炭素数１〜１０のアルキル基を示し、Ｒ^５及びＲ^６は同一でも異なっていてもよく、それぞれ水素原子又はアルキル基を示す。）

(In the formula (3), R ¹ , R ² , R ³ and R ⁴ may be the same or different and each represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ⁵ and R ⁶ may be the same. They may be different and each represents a hydrogen atom or an alkyl group.)

（式（４）中、Ｒ^７及びＲ^８は同一でも異なっていてもよく、それぞれ水素原子又は炭素数１〜１０のアルキル基を示し、Ｒ^９及びＲ^１０は同一でも異なっていてもよく、それぞれ水素原子又はアルキル基を示す。）

(In Formula (4), R ⁷ and R ⁸ may be the same or different and each represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ⁹ and R ¹⁰ may be the same or different, Each represents a hydrogen atom or an alkyl group.)

  The improvement in resolution due to the use of the compounds represented by the general formulas (3) and (4) improves the curability of the exposed area by the sensitizing action of these compounds during the formation of the resist pattern. In addition, the present inventors speculate that this is caused by the fact that scattered light, which is extra light for the unexposed portion, is absorbed by these compounds.

  In addition, the photosensitive resin composition of the present invention includes a copolymer of (meth) acrylic acid and / or (meth) acrylic acid alkyl ester and a copolymerized vinyl monomer as the component (A), or the copolymer. It is preferable to contain a copolymer having an ethylenically unsaturated bond introduced in the side chain and / or terminal thereof.

  Moreover, it is preferable that the acid value of (A) component is 90-200 mgKOH / g. Thereby, the resolution and electric corrosion resistance of the photosensitive resin composition can be achieved at a high level with a good balance.

  Moreover, it is preferable that the molecular weight of (B) component is 200-5000. Thereby, sufficient photosensitivity can be achieved, without the tack property of the photosensitive resin composition increasing excessively.

  Furthermore, regarding the compounding quantity of each component in the photosensitive resin composition of this invention, the compounding quantity of the said (B) component is 10-80 weight with respect to 100 weight part of total amounts of (A) component and (B) component. Part.

  Such a photosensitive resin composition of the present invention is very useful as a photosensitive material in the field of production of printed wiring boards, and is particularly preferably used for forming a permanent resist.

  Moreover, the photosensitive film of this invention is equipped with the support body and the photosensitive resin composition layer which consists of the said photosensitive resin composition of this invention formed on this support body, It is characterized by the above-mentioned.

  Since the photosensitive resin composition layer provided in the photosensitive film of the present invention is composed of the photosensitive resin composition of the present invention as described above, while ensuring flame retardancy without using a halogen-based flame retardant, It is very useful as a photosensitive material capable of achieving resolution, electric corrosion resistance and storage stability at a high level.

  It is preferable that the photosensitive film of this invention is further equipped with the peelable protective film provided on the surface on the opposite side to the support body of the photosensitive resin composition layer.

  In the first resist pattern forming method of the present invention, a photosensitive resin composition layer comprising the above-described photosensitive resin composition of the present invention is laminated on a circuit forming substrate, and the photosensitive resin composition layer is formed. A predetermined portion of the above is irradiated with actinic rays to photocur the exposed portion, and then portions other than the exposed portion are removed.

  The second resist pattern forming method of the present invention comprises laminating a photosensitive resin composition layer in the photosensitive film of the present invention on a circuit forming substrate, and a predetermined portion of the photosensitive resin composition layer. The exposed portion is irradiated with actinic light to cure the exposed portion, and then the portion other than the exposed portion is removed.

  In these resist pattern formation methods, the photosensitive resin composition layer is stably laminated on the circuit-forming substrate by using the photosensitive resin composition of the present invention or the photosensitive film of the present invention. Can do. Moreover, since this photosensitive resin composition layer contains the above components (A) to (D), sufficient imparting of flame retardancy to the resist pattern and improvement in resolution and electric corrosion resistance are achieved. It becomes possible.

  Therefore, the first and second resist pattern forming methods described above include, as a circuit forming substrate, an insulating substrate body and a conductor layer having a predetermined circuit pattern formed on the substrate body. This is suitable when a substrate is used. In this case, it is preferable to laminate a photosensitive resin composition layer on the surface of the substrate on which the conductor layer is formed so as to cover the conductive layer.

  Furthermore, in this case, it is preferable to provide an opening so that a part of the conductor layer is exposed when removing the portion other than the exposed portion. The formed opening can be used for so-called surface mounting in which a mounting component such as CSP or BGA is joined to a conductor layer having a circuit pattern by solder or the like.

  In the first and second resist pattern forming methods, the exposed portion may be a permanent resist. The permanent resist functions as a solder resist to prevent solder from adhering to unnecessary parts of the conductor layer when soldering for bonding, and protects the conductor layer after bonding of mounted components To function as a permanent mask. The first and second resist pattern forming methods are very useful as such a permanent resist forming method.

  The printed wiring board manufacturing method of the present invention is characterized by etching or plating a circuit forming substrate on which a resist pattern is formed by the resist pattern forming method of the present invention.

  Moreover, the printed wiring board of this invention is obtained by the manufacturing method of the said printed wiring board of this invention, and is provided with the resist pattern after an etching or plating as a resist layer on a circuit formation board | substrate.

  In the printed wiring board manufacturing method, the resist pattern formed on the circuit forming substrate is formed by the resist pattern forming method of the present invention, that is, the photosensitive resin composition or photosensitive resin of the present invention. It is formed using a sex element. Therefore, it becomes possible to carry out etching or plating with high accuracy, and it is possible to effectively realize a high-density printed wiring board.

  Moreover, the printed wiring board of the present invention thus obtained uses a resist pattern made of a photocured product of the photosensitive resin composition layer as a resist layer without removing it after etching or plating. Since this resist layer is excellent in flame retardancy, electrical insulation and mechanical strength, a highly reliable printed wiring board can be realized.

  According to the present invention, it is possible to ensure flame retardancy without using a halogen-based flame retardant, and further, a photosensitive resin composition excellent in resolution, electric corrosion resistance and storage stability, and the use thereof. It is possible to provide a photosensitive film, a resist pattern forming method, a printed wiring board, and a manufacturing method thereof.

It is sectional drawing which shows one Embodiment of the photosensitive film of this invention. It is a schematic cross section which shows one Embodiment of the printed wiring board of this invention. (A)-(d) is process drawing which shows the manufacturing method of the printed wiring board 2 shown in FIG. 2, respectively.

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings as the case may be. In the drawings, the same or corresponding parts are denoted by the same reference numerals, and redundant description is omitted. In the present invention, (meth) acrylic acid means acrylic acid and methacrylic acid corresponding thereto, (meth) acrylate means acrylate and corresponding methacrylate, (meth) acryloyl group means acryloyl group and The corresponding methacryloyl group is meant.

  First, the photosensitive resin composition of the present invention will be described.

  The component (A) in the photosensitive resin composition of the present invention is a polymer having a carboxyl group (hereinafter sometimes referred to as (A) polymer). (A) The polymer is not particularly limited as long as it has a carboxyl group, but a copolymer of (meth) acrylic acid, a (meth) acrylic acid alkyl ester and a copolymerized vinyl monomer, or a copolymer of the copolymer A copolymer having an ethylenically unsaturated bond introduced in the side chain and / or terminal is preferred.

(Meth) acrylic San'a Le kills esters, e.g., methyl (meth) acrylate, (meth) acrylic acid butyl esters, 2-ethylhexyl (meth) acrylic acid.

  The copolymerized vinyl monomer means a vinyl monomer that can be copolymerized with (meth) acrylic acid alkyl ester and (meth) acrylic acid, for example, (meth) acrylic acid tetrahydrofurfuryl ester, (meth) acrylic acid dimethyl ester. Aminoethyl ester, (meth) acrylic acid diethylaminoethyl ester, methacrylic acid glycidyl ester, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl methacrylate, acrylamide, diacetone Examples include acrylamide, styrene, and vinyl toluene.

  A copolymer obtained from these monomers can be obtained by a known polymerization method such as radical polymerization. Moreover, you may use commercial items, such as SD-600 and SD-900 (all are Hitachi Chemical Industries Ltd. make) as this copolymer.

  Moreover, the copolymer may have an ethylenically unsaturated bond in the side chain and / or the terminal as described above. The ethylenically unsaturated bond can be introduced into the side chain through an ester bond, a urethane bond or the like. Examples of the monomer having a urethane bond include UA-11 and UA-13 (both manufactured by Shin-Nakamura Chemical Co., Ltd.). As a method for introducing a double bond into the side chain, a glycidyl group-containing ethylenically unsaturated monomer is added to the carboxyl group in the copolymer of (meth) acrylic acid, (meth) acrylic acid alkyl ester and copolymerized vinyl monomer. It is mentioned that a monomer is reacted to form an ester bond.

  (A) It is preferable that the acid value of a component is 90-200 mgKOH / g, It is more preferable that it is 100-180 mgKOH / g, It is still more preferable that it is 110-150 mgKOH / g. If the acid value is less than 90 mgKOH / g, the resolution tends to be insufficient, whereas if it exceeds 200 mgKOH / g, the electric corrosion resistance of the resist tends to be insufficient.

  The blending amount of the component (A) is preferably 20 to 90 parts by weight, more preferably 30 to 80 parts by weight, when the total amount of the component (A) and the component (B) is 100 parts by weight. . If the blending amount is less than 20 parts by weight, the tackiness of the surface at the time of coating film formation, cracking of the coating film, developability, and solder heat resistance become poor. When it exceeds 90 parts by weight, there is a tendency that sufficient sensitivity cannot be obtained.

  The component (B) in the photosensitive resin composition of the present invention is a photopolymerizable compound having an ethylenically unsaturated bond (hereinafter sometimes referred to as (B) a photopolymerizable compound). (B) The photopolymerizable compound is a copolymer or monomer having a functional group that can be cross-linked by the action of light or a photopolymerization initiator, and a compound having an ethylenically unsaturated bond polymerizable in the molecule. I just need it. The structure is not particularly limited, and may have any structure such as aliphatic, aromatic, alicyclic, and heterocyclic, and has an ester bond, urethane bond, amide bond, etc. in the molecule. You may do it. As the ethylenically unsaturated bond, an acryloyl group or a methacryloyl group is preferable.

  Examples of the compound having an acryloyl group which is an ethylenically unsaturated bond include acrylic acid, acrylic acid ester having a hydroxyl group such as hydroxylethyl acrylate and hydroxylpropyl acrylate, aliphatic alcohol such as methyl acrylate and butyl acrylate, and acrylic. Acrylic acid ester consisting of an acid, an acrylic acid ester consisting of an alcohol having a heterocyclic ring such as an isocyanurate ring and acrylic acid, an acrylic acid ester having an epoxy group such as glycidyl acrylate, ethylene glycol diacrylate, polypropylene glycol acrylate, Acrylic esters of polyhydric alcohols such as methylolpropane triacrylate and ethoxylated trimethylolpropane triacrylate, tetrahydrofurfryl acrylate Acrylic acid ester having a cyclic ether structure, diglycidyl etherified epoxy acrylate acrylic acid added bisphenols, novolac type epoxy resin to an acrylic-modified novolac-type epoxy resins and acrylic acid was added and the like.

  Examples of the compound having a methacryloyl group which is an ethylenically unsaturated bond include methacrylic acid, methacrylic acid esters having a hydroxyl group such as hydroxylethyl methacrylate and hydroxylpropyl methacrylate, aliphatic alcohols such as methyl methacrylate and butyl methacrylate, and methacrylic acid. Methacrylic acid ester consisting of acid, methacrylic acid ester consisting of alcohol having heterocyclic ring such as isocyanurate ring and methacrylic acid, methacrylic acid ester having epoxy group such as glycidyl methacrylate, ethylene glycol dimethacrylate, polypropylene glycol methacrylate, tri Methacrylates of polyhydric alcohols such as methylolpropane trimethacrylate, ethoxylated trimethylolpropane trimethacrylate, Methacrylic acid ester having a cyclic ether structure such as trahydrofurfuryl methacrylate, epoxy methacrylate in which methacrylic acid is added to diglycidyl ether of bisphenol, methacrylic modified novolac type epoxy resin in which methacrylic acid is added to novolac type epoxy resin, etc. Is mentioned.

  In addition, the photopolymerizable compound obtained by adding (meth) acrylic acid may be modified with saturated and / or carboxylic anhydride within a range not deteriorating physical properties such as resolution and moisture resistance insulation. .

  The blending amount of component (B) is preferably 10 to 80 parts by weight, more preferably 20 to 70 parts by weight, when the total amount of component (A) and component (B) is 100 parts by weight. preferable. When the blending amount of the component (B) is less than 10 parts by weight, the photosensitivity tends to decrease. On the other hand, when it exceeds 80 parts by weight, surface tackiness at the time of coating film formation, cracking of the coating film, developability, solder Heat resistance tends to be insufficient. Moreover, it is preferable that the photopolymerizable compound molecular weight which has an ethylenically unsaturated bond with (B) component is 200-5000, and it is more preferable that it is 300-2000. If the molecular weight is less than 200, the tackiness of the photosensitive resin composition tends to increase, and if it exceeds 5000, the total number of moles of C═C bonds tends to decrease, and the photosensitivity tends to decrease.

  (C) component in the photosensitive resin composition of this invention is a photoinitiator. (C) The photoinitiator should just be match | combined with the light wavelength of the exposure machine to be used, and a well-known thing can be utilized. For example, as a radical photopolymerization initiator, acetophenone, benzophenone, 4,4-bisdimethylaminobenzophenone, 4,4-bisdiethylaminobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzoin ethyl ether, benzoin butyl ether, Benzoin isobutyl ether, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-dimethoxy-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2- Hydroxy-2-methylpropane, azobisisobutylnitrile, 2-methylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2,4-dimethylthioxanthone, Tilbenzoyl formate, 3,3,4,4-tetra (t-butylperoxycarbonyl) benzophenone, 1,2-di-9-acridinylethane, 1,3-di-9-acridinylpropane, 1,4-di-9-acridinylbutane, 1,7-di-9-acridinylheptane, 1,8-di-9-acridinyloctane and the like can be mentioned.

  Moreover, as (C) photoinitiator, the photoinitiator which a Lewis acid generate | occur | produces by light irradiation can also be used. Such photopolymerization initiators are generally known, and examples of cationic photoinitiators include triphenyl sulfone hexafluoroantimonate, triphenyl sulfone hexafluorophosphate, and p-methoxybenzenediazonium hexafluoro. Phosphate, p-chlorobenzenediazonium hexafluorophosphate, diphenyliodonium hexafluorophosphate, 4,4-di-t-butylphenyliodonium hexafluorophosphate, (1-6-n-cumene) (n-dichloropentazini F) Iron hexafluorophosphoric acid and the like.

  As the component (C), among the above photopolymerization initiators, an amine compound represented by the following general formula (3) and a thioxanthone compound represented by the following general formula (4) are preferable.

In general formula (3), R ¹ , R ² , R ³ and R ⁴ may be the same or different and each represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group. The alkyl group having 3 to 10 carbon atoms may be linear or branched. R ⁵ and R ⁶ may be the same or different and each represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom.

  Preferable examples of the amine compound represented by the general formula (3) include 4,4-bisdimethylaminobenzophenone and 4,4-bisdiethylaminobenzophenone.

In the general formula (4), R ⁷ and R ⁸ may be the same or different and each represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. The alkyl group represented by R ⁷ and ^{R 8,} the formula (3) an alkyl group having 1 to 10 carbon atoms which is exemplified in the description of ^R 1 to R ⁴ in the like. R ⁹ and R ¹⁰ may be the same or different and each represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom.

  Preferable examples of the thioxanthone compound represented by the general formula (4) include 2-methylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2,4-dimethylthioxanthone and the like.

  In the present invention, two or more photopolymerization initiators are used as the component (C), and at least one of them is preferably a compound represented by the general formula (3) or (4). ) And / or a compound represented by the general formula (4) and another photopolymerization initiator are more preferably used in combination.

  (C) It is preferable that the compounding quantity of a component shall be 0.1-10 weight% with respect to the total solid of each component in the photosensitive resin composition, and shall be 0.5-5.0 weight%. It is more preferable.

  Furthermore, when using together the amine compound represented by the said General formula (3) with the other photoinitiator of (C) component, the compounding quantity of the said amine compound is each component in the photosensitive resin composition. It is preferable to set it as 0.01-3 weight% with respect to all the solid content of, and it is especially preferable to set it as 0.05-1 weight%. When the blending amount is less than 0.01% by weight, when the photosensitive resin composition layer is formed and photocured by exposure, the light absorption action by the amine compound becomes insufficient, and the effect of improving the resolution is lowered. Tend to. On the other hand, if the blending amount exceeds 3% by weight, the light-absorbing action of this amine compound tends to be excessive, and the photocuring at a site deep from the exposed surface tends to be insufficient.

  Moreover, when using together the thioxanthone type compound represented by General formula (4) with the other photoinitiator of (C) component, the compounding quantity of the said thioxanthone type compound is the amount of each component in the photosensitive resin composition. It is preferable to set it as 0.01-3 weight% with respect to the total solid, and it is especially preferable to set it as 0.05-1 weight%. If it is less than 0.01% by weight, the light absorption action by the thioxanthone compound is insufficient, and the effect of improving the resolution tends to decrease. On the other hand, if the blending amount exceeds 3% by weight, the light absorption action by this compound becomes excessive, and the photocuring in a portion deep from the exposed surface tends to be insufficient.

  The component (D) in the present invention is a phenoxyphosphazene compound. Preferable examples of the (D) phenoxyphosphazene compound include a compound having a cyclic structure represented by the following general formula (1) and a compound having a chain structure represented by the following general formula (2).

  M in the general formula (1) and n in the general formula (2) each represent an integer of 1 to 20. In the present invention, it is preferable to use a phenoxyphosphazene oligomer in which m or n is 2 or more. Examples of such phenoxyphosphazene oligomers include SPS-100, SPB-100, and SPE-100 (all manufactured by Otsuka Chemical Co., Ltd.). These may be used alone or in combination of two or more.

  The blending amount of (D) is preferably 30 to 70 parts by weight, particularly preferably 40 to 60 parts by weight, with respect to 100 parts by weight of the total amount of (D) and (B) components. If the amount is less than 30 parts by weight, the flame retardancy tends to be reduced. If the amount exceeds 70 parts by weight, the resolution may be lowered and the glass transition temperature of the film may be lowered.

  You may add a thermosetting agent to the photosensitive resin composition in the range which does not inhibit the effect obtained by this invention. Such a thermosetting agent is not particularly limited. For example, a thermosetting agent that itself crosslinks by heating, that is, a curing agent that forms a polymer network by applying heat (A And a curing agent that reacts with the carboxyl group of the component to form a three-dimensional structure. A bismaleimide compound is mentioned as a thermosetting agent which bridge | crosslinks itself by heating. Bismaleimide compounds include m-di-N-maleimidylbenzene, bis (4-N-maleimidylphenyl) methane, 2,2-bis (4-N-maleimidylphenyl) propane, and 2,2-bis. (4-N-maleimidyl 2,5-dibromophenyl) propane, 2,2-bis [(4-N-maleimidylphenoxy) phenyl] propane, 2,2-bis [(4-N-malemidyl-2- Various bismaleimide compounds such as methyl-5-ethylphenyl) propane are used as they are or as a mixture. These bismaleimide compounds can be used either alone or modified with various resins. A block isocyanate compound is mentioned as a hardening | curing agent which reacts with the carboxyl group of (A) component by heating and forms a three-dimensional structure. Examples of the blocked isocyanate compound include polyisocyanate compounds blocked with a blocking agent such as an alcohol compound, a phenol compound, ε-caprolactam, an oxime compound, and an active methylene compound. Examples of blocked polyisocyanate compounds include 4,4-diphenylmethane disissocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene 1,5-diisocyanate, o-xylene diisocyanate, and m-xylene. Aromatic polyisocyanates such as diisocyanates and 2,4-tolylene dimers, aliphatic polyisocyanates such as hexamethylene diisocyanate, 4,4-methylenebis (cyclohexyl isocyanate) and isophorone diisocyanate, and alicyclic polyisocyanates such as bicycloheptane triisocyanate An aromatic polyisocyanate is preferable from the viewpoint of heat resistance, and an aliphatic polyisocyanate or an alicyclic polyisocyanate is preferable from the viewpoint of preventing coloring.

  Moreover, you may add a thermosetting resin etc. to the photosensitive resin composition in the range which does not inhibit the effect obtained by this invention. Examples of the thermosetting resin include unsaturated polyester resins, copolymers having functional groups that can be cross-linked by the above radical photopolymerization initiator, and compounds equivalent to monomers. Moreover, resin which can be polymerized by the action of heat or a thermal polymerization initiator can also be used.

  Known thermal polymerization initiators can be used, for example, benzoyl peroxide, ketone peroxides such as methyl ethyl ketone peroxide, alkyl peroxides such as tertiary butyl peroxide, peroxydicarbonates, Peroxyketals, peroxyesters, alkyl peresters and the like can be used. The blending amount of the thermal polymerization initiator is preferably 0.1 to 10% by weight, and preferably 0.5 to 5.0% by weight, based on the total solid content of each component in the photosensitive resin composition. Particularly preferred.

  The photosensitive resin composition may contain a filler as long as resolution and flame retardancy are not deteriorated. Examples of fillers include silica, fused silica, talc, alumina, hydrated alumina, barium sulfate, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, aerosil, calcium carbonate and other inorganic fine particles, powdered epoxy resins, powdered polyimide particles, etc. Organic fine particles, powdered Teflon (registered trademark) particles, and the like. These fillers may be subjected to a coupling treatment in advance. These dispersions are achieved by a known kneading method such as a kneader, ball mill, bead mill, or three rolls. The blending amount of these fillers is preferably 2 to 20% by weight, particularly preferably 5 to 15% by weight, based on the total solid content of each component in the photosensitive resin composition.

  You may add a polymerization stabilizer, a leveling agent, a pigment, dye, and an adhesive improvement agent to the photosensitive resin composition. These selections are made under the same considerations as for ordinary photosensitive resin compositions. The addition amount is such that the characteristics of the photosensitive resin composition of the present invention are not impaired, and each is preferably added in an amount of 0.01 to 10% by weight in the resin composition.

  Moreover, it is preferable that the glass transition temperature after hardening by the exposure process or / and post-heating process mentioned later is 90 degreeC or more, and, as for the photosensitive resin composition, it is more preferable that it is 100-180 degreeC, 100- More preferably, it is 150 degreeC.

  The photosensitive resin composition of the present invention can be diluted with a solvent and used as a coating liquid when forming a resist pattern. Examples of the solvent include ketone compounds such as methyl ethyl ketone, acetone and cyclohexanone, aromatic hydrocarbon compounds such as xylene and toluene, amide compounds such as N, N-dimethylformamide and N, N-dimethylacetamide. These solvents may be used alone or in a mixed system. In order to efficiently dissolve the photosensitive resin composition, ethylene glycol monoethyl ether, ethyl ethoxypropionate or the like may be used as a solvent in accordance with the solubility of the composition, or may be added to other solvents. Good.

  The amount of the solvent is preferably 10 to 200 parts by weight, particularly preferably 30 to 100 parts by weight, based on 100 parts by weight of components other than the solvent in the photosensitive resin composition. When the blending amount of the solvent is less than 10 parts by weight, the viscosity of the photosensitive resin composition tends to increase, and it tends to be difficult to mix uniformly. On the other hand, when the amount of the solvent exceeds 100 parts by weight, it tends to be difficult to control the thickness of the layer when the photosensitive resin composition layer is formed due to a decrease in the viscosity. Since there are many, it tends to be expensive.

  There is no restriction | limiting in particular about the thickness of the photosensitive resin composition layer formed using the photosensitive resin composition of this invention, In the range of 10-150 micrometers, it selects suitably. Examples of the method for applying the photosensitive resin composition include a dip coating method, a roll coating method, a flow coating method, a screen printing method, a spray method, and an electrostatic spray method. As described above, the photosensitive resin composition of the present invention is directly applied onto a substrate or a printed wiring board, and a photosensitive resin composition layer composed of the photosensitive resin composition is easily formed on the substrate or the wiring board. Although it is possible, you may use as a photosensitive film for permanent resists so that it may mention later.

  In addition, the photosensitive resin composition layer formed using the photosensitive resin composition and the photosensitive film of the present invention may be formed by a laser drilling method using a printing method, a carbon dioxide laser, a YΑG laser, an excimer laser, or the like. It is also possible to form an image resin film.

  Next, the photosensitive film of the present invention will be described.

  FIG. 1 is a schematic cross-sectional view showing a preferred embodiment of the photosensitive film of the present invention. A photosensitive film 1 shown in FIG. 1 is a photosensitive film for a permanent resist, and includes a photosensitive resin composition layer 12 on a support (carrier film) 11, and further a carrier for the photosensitive resin composition layer 12. A cover film (protective film) 13 is provided on the surface opposite to the film 11.

  The support 11 is not particularly limited as long as it can support the photosensitive resin composition layer 12 and further the cover film 13. For example, a film such as a polyester film, a polyimide film, a polyamideimide film, a polypropylene film, or a polystyrene film. Are preferably used. The support 11 may have a single layer structure or may have a multilayer structure in which films having a plurality of compositions are laminated. Furthermore, the surface of the support 11 opposite to the photosensitive resin composition layer 12 may be subjected to treatment such as embossing and corona treatment.

  Although the thickness in particular of the support body 11 is not restrict | limited, Preferably it is 5-150 micrometers, More preferably, it is 8-20 micrometers, More preferably, it is 10-16 micrometers. If the thickness is less than 2 μm, the support 11 tends to be broken when the support 11 is peeled and removed from the photosensitive film 1, and if it exceeds 100 μm, the flexibility of the photosensitive film 1 as a whole is lowered and should be laminated. There is a tendency that followability to unevenness on the surface of the object is lowered.

  As a method for forming the photosensitive resin composition layer 12 on the support 11, a coating liquid containing the photosensitive resin composition of the present invention is applied on the support 11 with a comma coater, a blade coater, a lip coater, a rod coater, and a squeeze. Examples thereof include a method of applying a uniform thickness with a coater, reverse coater, transfer roll coater, etc., and heating and drying to volatilize the solvent. There is no restriction | limiting in particular about the thickness of the formed photosensitive resin composition layer, It selects suitably in the range of 10-150 micrometers.

  The cover film 13 is used as a protective film and is peeled off before laminating. Therefore, the cover film 13 is flexible so that it can be peelably adhered to the photosensitive layer and is not damaged at the temperature of the drying furnace. Although not particularly limited, for example, paper, release paper, polyester such as polyethylene terephthalate, polyolefin such as polymethylpentene, polypropylene and polyethylene, halogen-containing vinyl polymer such as polyvinyl fluoride and polyvinyl chloride, polyamide such as nylon, Examples thereof include cellulose such as cellophane, and films such as polystyrene. These may be transparent or non-transparent, and may be subjected to a release treatment. Examples of the available cover film include product name E-200H manufactured by Oji Paper Co., Ltd., and product name NF-13 manufactured by Tamapoli Co., Ltd.

  Although the thickness of the cover film 13 is not particularly limited, it is preferably 10 to 30 μm, more preferably 10 to 25 μm, and more preferably 10 to 20 μm in view of the size when rolled into a roll. It is particularly preferred.

  Next, as a preferred embodiment of the method for forming a resist pattern of the present invention, a case where a resist pattern is formed using the photosensitive film 1 shown in FIG. 1 will be described.

  When forming a resist pattern using the photosensitive film 1 shown in FIG. 1, first, the photosensitive film 1 is overlapped so that the photosensitive resin composition layer 12 faces the circuit forming substrate or the printed wiring board, Laminate using a hot roll laminator. Thereby, the photosensitive resin composition layer 12 can be easily formed on a substrate or a wiring board. In addition, when the photosensitive resin composition layer 12 contains a volatile component such as a solvent, the photosensitive resin composition in which a component after most of the solvent is removed by heating is formed on a substrate or a wiring board. It becomes the main component of the layer 12. There is no restriction | limiting in particular about the thickness of this photosensitive resin composition layer 12, Usually, it selects suitably in the range of 10-150 micrometers.

  After the lamination of the photosensitive resin composition layer 12 is completed in this way, a predetermined portion of the photosensitive resin composition layer 12 is irradiated with actinic rays to be photocured (exposure process). Examples of the exposure method include a method of irradiating an image with an actinic ray through a negative or positive mask pattern called an artwork. At this time, exposure can be performed by placing a mask on the photosensitive resin composition layer 12 after the support 11 is peeled and removed. However, when the support 11 is transparent, the support 11 is interposed through the support 11. Exposure may be performed. Moreover, a mask may be made to contact directly on the photosensitive resin composition, and may be made to contact through a transparent film.

  As the exposure light source, a known light source such as a carbon arc lamp, a mercury vapor arc lamp, an ultra-high pressure mercury lamp, a high-pressure mercury lamp, or a xenon lamp that emits ultraviolet rays effectively is used. Moreover, what emits visible light effectively, such as a photographic flood light bulb and a solar lamp, is also used.

After the exposure, an alkaline aqueous solution is used to remove a portion other than the exposed portion by a known method such as spraying, rocking immersion, brushing, and scraping, and development is performed to form a resist pattern. In addition, after resist pattern formation, you may further perform the postcure by exposure (post-heating process) of 1-5 J / cm < ² > exposure or / and 100-200 degreeC and 30 minutes-12 hours. The developer used in the development process is an alkali developer as a standard, but there is no particular limitation on the type of the developer as long as it does not damage the exposed part and selectively elutes the unexposed part. It is determined depending on the development type of the composition, and general ones such as a semi-aqueous developer and a solvent developer can be used. For example, an emulsion developer containing water and an organic solvent as described in JP-A-7-234524 can be used. Particularly useful emulsion developers include, for example, propylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, 2,2-butoxyethoxyethanol, butyl lactate, cyclohexyl lactate, ethyl benzoate, and 3-methyl-3 as organic solvent components. An emulsion developer containing 10 to 40% by weight of an organic solvent such as methoxybutyl acetate can be mentioned. When an alkaline developer is used, an alkaline aqueous solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, 4-sodium borate, ammonia, amines and the organic solvent are used. It is also possible to use an emulsion developer.

  Such a method for forming a resist pattern according to the present invention is very useful when a resist pattern is formed on an insulating substrate of a laminated substrate having an insulating substrate and a conductor layer having a circuit pattern formed on the insulating substrate. Useful. In this case, the photosensitive resin composition layer composed of the photosensitive resin composition of the present invention or the photosensitive resin composition layer in the photosensitive film of the present invention is laminated so as to cover the conductor layer, and the photosensitive resin is laminated. It is preferable to irradiate a predetermined portion of the composition layer with an actinic ray to form an exposed portion, and then remove a portion other than the exposed portion.

  By the above-described method, a resist pattern can be formed on the photosensitive resin composition layer laminated on the conductor layer on which the circuit pattern is formed. The photosensitive resin composition layer on which the resist pattern is formed can be used as a solder resist for preventing solder from adhering to unnecessary portions on the conductor layer at the time of mounting components. Since this solder resist uses the photosensitive resin composition for permanent resists or the photosensitive film of the present invention, there is no insulation deterioration of the resin under high temperature and high humidity, and it has excellent electric corrosion resistance.

  Next, the printed wiring board and the manufacturing method thereof according to the present invention will be described.

  FIG. 2 is a schematic cross-sectional view showing an embodiment of the printed wiring board of the present invention. The printed wiring board 2 shown in FIG. 2 includes an insulating substrate 22, a conductor layer 23 having a circuit pattern formed on one surface of the insulating substrate 22, and a circuit pattern formed on the other surface of the insulating substrate 22. A conductor layer 21 not provided and a resist layer 24 formed on the insulating substrate 22 so as to cover the conductor layer 23 having a circuit pattern are provided. The resist layer 24 is made of a cured product of the photosensitive resin composition layer in the permanent resist photosensitive film of the present invention, and the resist layer 24 exposes at least a part of the conductor layer 23 having a circuit pattern. Has an opening 26.

  Since the printed wiring board 2 has the opening 26, a mounting component such as CSP or BGA can be joined to the conductor layer 23 having a circuit pattern by solder or the like, and so-called surface mounting becomes possible. The resist layer 24 has a role as a solder resist for preventing solder from adhering to unnecessary portions of the conductor layer during soldering for bonding, and after bonding of mounted components. Functions as a permanent mask for protecting the conductor layer 23.

  FIG. 3 is a process diagram schematically showing a method of manufacturing the printed wiring board 2 shown in FIG. 3A shows an insulating substrate 22 having a conductor layer 23 having a circuit pattern on one side and a conductor layer 21 having no circuit pattern on the other side. FIG. 3B and FIG. And 3 (d) are the printed wiring board 4 after the photosensitive resin composition 24 is laminated on the insulating substrate 22, the state in which the photosensitive resin composition layer 24 is irradiated with actinic rays, and the print after development. The wiring board 2 is shown.

  First, the pattern of the conductor layer 23 is formed on the insulating substrate 22 as shown in FIG. 3A by a known method or the like for etching one side of a double-sided metal laminate (for example, double-sided copper-clad laminate). The printed wiring board 3 on which the conductor layer 23 is formed is obtained. Next, as shown in FIG.3 (b), it consists of the photosensitive resin composition of the photosensitive film of this invention so that the conductor layer 23 may be covered on the double-sided metal-clad laminated board 3 in which the conductor layer 23 was formed. The photosensitive resin composition layer 24 is laminated, and the printed wiring board 4 on which the photosensitive resin composition layer 24 is laminated is obtained. Next, a predetermined portion of the photosensitive resin composition layer 24 is irradiated by irradiating the photosensitive resin composition layer 24 laminated as shown in FIG. 3C with actinic rays through the mask 5 having a predetermined pattern. Is cured. Finally, the unexposed portion is removed (for example, alkali development) to form the resist layer 24 having the opening 26 as shown in FIG. 3D, thereby obtaining the printed wiring board 2. When the photosensitive resin composition contains a volatile component such as a solvent, the resist layer 24 is a cured product of the photosensitive resin composition after most of the volatile component is removed.

  In addition, lamination | stacking of the photosensitive resin composition layer 24 on the insulated substrate 22, irradiation of actinic light, and removal of an unexposed part can be performed by the method similar to the case in the formation method of the above-mentioned resist pattern.

  The resist layer 24 in the printed wiring board 2 thus obtained is made of a cured product of the photosensitive resin composition in the photosensitive film for permanent resist of the present invention, and the resin discoloration in the PCT test and Excellent in suppressing blistering.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example at all.

[Example 1]
A photosensitive resin composition was prepared using the materials shown below.

A copolymer obtained by copolymerizing methacrylic acid, methyl methacrylate and methyl acrylate in a weight ratio of 20:45:35 (weight average molecular weight 70,000, acid value 117 mg / g): 70 parts by weight (solid content)
Urethane bond-containing monomer (UA-11, Shin-Nakamura Chemical Co., Ltd.): 30 parts by weight (solid content)
Photopolymerization initiator (Irgacure 651, manufactured by Ciba Geigy Co., Ltd.): 5 parts by weight Phenoxyphosphazene compound (SPB-100, manufactured by Otsuka Chemical Co., Ltd.): 50 parts by weight Methyl ethyl ketone: 20 parts by weight.

[Example 2]
Other than using 0.2 parts by weight of 4,4-bisdiethylaminobenzophenone (EAB, Hodogaya Chemical Co., Ltd.), which is an amine compound, as a photopolymerization initiator instead of Irgacure 651) used in Example 1. Prepared a photosensitive resin composition in the same manner as in Example 1.

[Example 3]
Except for using 0.5 parts by weight of 2,4-diethylthioxanthone (DETX, manufactured by Nippon Kayaku Co., Ltd.), which is a thioxanthone compound, instead of Irgacure 651 used in Example 1 as a photopolymerization initiator. A photosensitive resin composition was prepared in the same manner as in Example 1.

[Example 4]
As a component (A), a polymer having a double bond in the side chain was synthesized. Specifically, 120 parts by weight of ethylene glycol monomethyl ether acetate was placed in a 1 L four-necked flask and heated to 75 ° C. while nitrogen was sealed. On the other hand, a mixture of 80 parts by weight of methyl methacrylate, 50 parts by weight of acrylic acid, 80 parts by weight of benzyl methacrylate, 120 parts by weight of ethylene glycol monomethyl ether acetate and 1.5 parts by weight of azobisisobutyronitrile is set to 27-30 ° C. in advance. After the temperature of ethylene glycol monomethyl ether acetate in the four-necked flask was stabilized, the solution was added dropwise over 3 hours with stirring in the four-necked flask. Stirring was further continued at 75 ° C. for 7 hours, and then 2 parts by weight of methylhydroquinone was mixed as a polymerization inhibitor to stop nitrogen encapsulation and complete the polymerization.

  Immediately after this, 35 parts by weight of glycidyl acrylate was added, and the reaction was further continued for 5 hours. The number of moles of C bonds was 0.0011 mol / g, and the total number of moles of C = C bonds was 0.08 mol).

  Next, a photosensitive resin composition was prepared in the same manner as in Example 1 except that the polymer obtained above was used as the component (A) instead of the copolymer in Example 1.

[Example 5]
A photosensitive resin composition was prepared in the same manner as in Example 1, and the photosensitive resin composition was applied onto a PET film and dried at 80 ° C. for 20 minutes to produce a photosensitive film.

[Comparative Example 1]
A photosensitive resin composition was prepared in the same manner as in Example 1 except that the phenoxyphosphazene compound (SPB-100) in Example 1 was not used.

[Comparative Example 2]
A photosensitive resin composition was prepared in the same manner as in Example 1 except that the amount of the phenoxyphosphazene compound (SPB-100) in Example 1 was 15 parts by weight.

[Comparative Example 3]
Photosensitive resin composition in the same manner as in Example 1 except that 50 parts by weight of a phosphoric acid ester (Reofes TPP, manufactured by Ajinomoto Co., Inc.) was used instead of the phenoxyphosphazene compound (SPB-100) in Example 1. A product was prepared.

[Comparative Example 4]
In the same manner as in Example 1, except that 50 parts by weight of a phosphate ester (PX-200, manufactured by Daihachi Chemical Co., Ltd.) was used instead of the phenoxyphosphazene compound (SPB-100) in Example 1, A functional resin composition was prepared.

[Comparative Example 5]
Photosensitivity was the same as in Example 1 except that 50 parts by weight of melamine polyphosphate (PMP-100, manufactured by Nissan Chemical Industries, Ltd.) was used instead of the phenoxyphosphazene compound (SPB-100) in Example 1. A resin composition was prepared.

[Comparative Example 6]
A photosensitive resin was prepared in the same manner as in Example 1 except that 50 parts by weight of Al (OH) ₃ (Hydelite H-42M, Showa Denko KK) was used instead of the phenoxyphosphazene compound in Example 1. A composition was prepared.

  The following evaluation tests were performed on the photosensitive resin compositions of Examples 1 to 4 and Comparative Examples 1 to 6 and the photosensitive film of Example 5 thus obtained.

[Biahole resolution]
In Examples 1 to 4 and Comparative Examples 1 to 6, first, a glass cloth base epoxy resin double-sided copper-clad laminate having a double-sided roughened foil on both sides (copper foil thickness 18 μm, MCL manufactured by Hitachi Chemical Co., Ltd.) -BE-67G (trade name)) is etched using a photosensitive dry film, and has a comb-like circuit (circuit layer) having a line width / space width (40 μm / 40 μm) dimension on one side ( Hereinafter, it was referred to as a circuit board). A photosensitive resin composition was applied on the circuit layer side surface of the circuit board thus obtained and dried at 80 ° C. for 20 minutes to form a photosensitive resin composition layer having a thickness of 30 μm.

Next, an ultraviolet ray having an exposure amount of 200 mJ / cm ² is irradiated on the portion to be an opening (via hole) through a photomask having a shielding portion having a diameter of 150 and 100 μm, and the unexposed portion is further 1% by weight. A resist (solder mask) was formed by spraying at 30 ° C. for 1 minute using a developer containing sodium carbonate. The opening of the resist thus formed was evaluated with a metal microscope. The obtained results are shown in Tables 1 and 2. In the table, A means that the developability is good (no resin remains on the substrate surface), and B means that the developability is poor (a little resin remains on the substrate surface).

  In Example 5, a photosensitive film was laminated on a circuit board similar to the above using a laminator so that the photosensitive resin composition layer was in contact with the circuit layer, and a photosensitive resin composition having a film thickness of 30 μm. A physical layer was formed. Thus, except having formed the photosensitive resin composition layer, it carried out similarly to the above, the resist (solder mask) was formed, and the opening part was evaluated. The obtained results are shown in Table 1.

[Flame retardance]
In evaluating the flame retardancy, the photosensitive resin compositions of Examples 1 to 4 and Comparative Examples 1 to 6 were coated on a PET film and dried at 80 ° C. for 20 minutes to obtain a photosensitive film. The photosensitive film of Example 5 was used as it was.

  On the other hand, etching is performed on the entire surface of a glass cloth base epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, Hitachi Chemical Co., Ltd. MCL-BE-67G (trade name)) having double-sided roughened foil on both sides. To produce a substrate without a circuit layer.

  Subsequently, the photosensitive film was laminated | stacked on the board | substrate using the laminator so that the photosensitive resin composition layer might face a board | substrate.

Furthermore, in order to cure the photosensitive resin composition layer, an exposure step and a heat treatment step were performed. Specifically, the entire surface of the photosensitive resin composition layer is irradiated with ultraviolet rays having an exposure amount of 200 mJ / cm ² , and further a metal halide lamp type conveyor type exposure machine (lamp output: 80 W / cm ² , lamp height: 80 cm, Using a cold mirror and a conveyor speed of 1.5 m / min, the photosensitive resin composition layer was irradiated with ultraviolet rays of 1000 mJ / cm ² for post-exposure. And the flame-retardant test piece was produced by performing a post-heating at 160 degreeC for 1 hour.

  Using the thus obtained test piece, a flame retardancy test was performed according to the UL-94 method. The obtained results are shown in Tables 1 and 2.

[Electrical corrosion resistance]
Glass cloth base epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, MCL-BE-67G (trade name) manufactured by Hitachi Chemical Co., Ltd.) having double-sided roughened foil on both sides is etched on one side. A printed wiring board (circuit board) having a comb-shaped circuit (circuit layer) having a line width / space width (40 μm / 40 μm) dimension was produced.

  In Examples 1 to 4 and Comparative Examples 1 to 6, a photosensitive resin composition was applied to the surface of the circuit board on the circuit layer side, dried at 80 ° C. for 20 minutes, and a photosensitive resin composition having a thickness of 30 μm. A physical layer was formed. In Example 5, the photosensitive film was laminated on the circuit board using a laminator so that the photosensitive resin composition layer was in contact with the circuit layer to form a photosensitive resin composition layer having a thickness of 30 μm. did.

Next, the photosensitive resin composition layer on the circuit board is irradiated with ultraviolet light having an exposure amount of 200 mJ / cm ² through a photomask, and a developer containing 1% by weight of sodium carbonate is applied to the unexposed portion. And sprayed at 30 ° C. for 1 minute.

Next, a metal halide lamp type conveyor type exposure machine (lamp output 80 W / cm ² , lamp height 80 cm, no cold mirror, conveyor speed 1.5 m / min) is used for the resist (solder mask) on the substrate. Post-exposure was performed by irradiation with ultraviolet rays of 1000 mJ / cm ² .

  Furthermore, by performing post-heating at 160 ° C. for 1 h, a solder mask corresponding to the negative mask and an evaluation substrate on which the solder mask was formed were obtained.

  With respect to the evaluation substrate thus obtained, the insulation resistance value (initial value) in a normal state and the insulation resistance value after being treated at 130 ° C., 85% RH, 6 V, 200 hours were measured. The obtained results are shown in Tables 1 and 2.

  As shown in Tables 1 and 2, when the photosensitive resin compositions of Examples 1 to 4 and the photosensitive film of Example 5 were used, HAST resistance (High Accelerated) was higher than that of Comparative Examples 1 to 6. It was found that the stress testability was improved. Moreover, in Example 5, it was confirmed that there is no problem in film property and a uniform photosensitive film of 30 μm can be obtained.

  DESCRIPTION OF SYMBOLS 1 ... Photosensitive film for permanent resists, 2, 3, 4 ... Printed wiring board, 5 ... Photomask, 11 ... Support, 12 ... Photosensitive resin composition layer, 13 ... Cover film, 21 ... No circuit pattern Conductor layer, 22 ... insulating substrate, 23 ... conductor layer having a circuit pattern, 24 ... resist layer, 26 ... opening

Claims (7)

(A) a polymer having a carboxyl group, (B) a photopolymerizable compound having an ethylenically unsaturated bond, (C) a photopolymerization initiator, and (D) a phenoxyphosphazene compound, The content of the component (D) is 30 to 70 parts by weight with respect to 100 parts by weight of the total amount of the component (A) and the component (B), and the component (A) is (meth) acrylic acid and / or Or a copolymer of (meth) acrylic acid alkyl ester and (meth) acrylic acid and / or a copolymerized vinyl monomer other than (meth) acrylic acid alkyl ester , or a side chain and / or terminal of the copolymer A photosensitive resin composition comprising a copolymer into which an ethylenically unsaturated bond is introduced. The photosensitive resin composition according to claim 1, wherein the acid value of the component (A) is 90 to 200 mgKOH / g. A photosensitive film comprising: a support; and a photosensitive resin composition layer formed on the support and made of the photosensitive resin composition according to claim 1. A photosensitive resin composition layer comprising the photosensitive resin composition according to claim 1 or 2 is laminated on a circuit forming substrate, and exposure is performed by irradiating a predetermined portion of the photosensitive resin composition layer with an actinic ray. A method for forming a resist pattern, wherein the portion is photocured, and then the portion other than the exposed portion is removed. The photosensitive resin composition layer in the photosensitive film according to claim 3 is laminated on a circuit forming substrate, and a predetermined portion of the photosensitive resin composition layer is irradiated with actinic rays to photocure the exposed area. And then removing the portions other than the exposed portion. A method for producing a printed wiring board, comprising etching or plating a circuit forming substrate on which a resist pattern is formed by the method for forming a resist pattern according to claim 4. A printed wiring board obtained by the method for producing a printed wiring board according to claim 6, wherein the resist pattern after etching or plating is provided as a resist layer.

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