JP5614389B2 - Resin composition, prepreg, metal-clad laminate, sealing material, photosensitive film, resist pattern forming method and printed wiring board - Google Patents

Description

  The present invention relates to a phosphorus-containing polymer, a resin composition using the same, a prepreg, a metal-clad laminate, a sealing material, a photosensitive film, a resist pattern forming method, and a printed wiring board.

  The demand for electronic devices and electronic components is increasing in terms of non-pollution, low toxicity, and safety, as well as global environmental issues and increasing interest in human safety. Among them, reduction of harmful gases when electronic devices and electronic components are incinerated is being demanded. In particular, it is said that the halogen-based flame retardants used in these may generate highly toxic dioxins and the like when burned. In response to this, development of non-halogen flame retardants is strongly demanded.

  In the field of printed wiring boards used in these electronic devices and electronic components, halogen-based flame retardants have been used for copper-clad laminates, circuit-forming boards, insulating resins, solder resists, and the like. Conventionally, most of the halogen compounds used as flame retardants are bromine-based, and brominated epoxy resins such as tetrabromobisphenol A are widely used. As a brominated epoxy resin, for example, an acid pendant brominated epoxy acrylate is known (see, for example, Patent Document 1). In an example in which this is used as a flame retardant for a solder resist, it is used at a high temperature for a long time. In this case, the halide may be dissociated to cause wiring corrosion. From the viewpoint of avoiding the occurrence of defects due to such dissociation of halides, there is an urgent need to develop a printed wiring board material that does not contain a halogen compound.

  Therefore, the use of nitrogen compounds, phosphorus compounds, and inorganic compounds such as aluminum hydroxide and magnesium hydroxide as non-halogen flame retardants for imparting flame retardancy to resin compositions has been proposed. Yes. Among these, in particular, phosphorus flame retardants have been extensively studied, and many uses of aromatic phosphates have been proposed (see, for example, Patent Documents 2 to 4).

Japanese Patent Laid-Open No. 11-181050 JP-A-48-90348 JP 59-45351 Japanese Patent Laid-Open No. 5-70671

  Non-halogen flame retardants as described above include filler-type flame retardants that are insoluble in solvents and flame retardants that are soluble in solvents and can be mixed with other resin components. However, with the former flame-retardant that is insoluble in the solvent, when the B-stage film state is used as the insulating material, the flexibility is lowered and the handling is hindered. As a result, cracks are likely to occur, and the reliability of electronic parts using the cracks is problematic. In the latter solvent-soluble flame retardants, low molecular weight aromatic phosphates are typical examples, but when added to a resin composition, the molecular weight is small and the volatility is high. There is a problem that it is easy to out.

  The present invention has been made in view of the above-described problems of the prior art, and can obtain a cured product having sufficient elongation that can ensure sufficient flame retardancy without using a halogen-based flame retardant. And a phosphorus-containing polymer in which the problem of bleed-out is sufficiently reduced, a resin composition using the same, and a prepreg, a metal-clad laminate, a sealing material using the resin composition, It aims at providing the formation method of a photosensitive film, a resist pattern, and a printed wiring board.

  In order to achieve the above object, the present invention provides a phosphorus-containing polymer having a monomer unit represented by the following general formula (1).

［式（１）中、Ｘは単結合、炭素数１〜１０の脂肪族炭化水素基、フェニレン基、下記一般式（２）で表される２価の基、下記一般式（３）で表される２価の基、下記一般式（４）で表されるエステル結合を含む基、又は、下記一般式（５）で表されるエステル結合を含む基を示し、Ｒ^１及びＲ^２は各々独立に、水酸基、炭素数１〜６の脂肪族炭化水素基、炭素数１〜３のアルキルオキシ基、下記一般式（６）で表されるアリール基、又は、下記一般式（７）で表されるアリールオキシ基を示し、Ｒ^３及びＲ^４は各々独立に、水素原子又はメチル基を示す。］

[In the formula (1), X is a single bond, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, a phenylene group, a divalent group represented by the following general formula (2), and a general formula (3) below. A divalent group, a group containing an ester bond represented by the following general formula (4), or a group containing an ester bond represented by the following general formula (5), wherein R ¹ and R ² are each Independently, it is represented by a hydroxyl group, an aliphatic hydrocarbon group having 1 to 6 carbon atoms, an alkyloxy group having 1 to 3 carbon atoms, an aryl group represented by the following general formula (6), or the following general formula (7). R ³ and R ⁴ each independently represents a hydrogen atom or a methyl group. ]

［式（２）中、Ｌ^１は炭素数１〜３のアルキレン基を示す。］

Wherein (2), ^{L 1} represents an alkylene group having 1 to 3 carbon atoms. ]

［式（３）中、Ｌ^２は炭素数１〜３のアルキレン基を示す。］

Wherein (3), ^{L 2} represents an alkylene group having 1 to 3 carbon atoms. ]

［式（４）中、ａは１〜１０の整数を示す。］

[In Formula (4), a shows the integer of 1-10. ]

［式（５）中、ｂは１〜１０の整数を示す。］

[In Formula (5), b shows the integer of 1-10. ]

［式（６）中、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８及びＲ^９は各々独立に、水素原子、炭素数１〜３の脂肪族炭化水素基、又は、水酸基を示す。］

[In Formula (6), R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 3 carbon atoms, or a hydroxyl group. ]

［式（７）中、Ｒ^１０、Ｒ^１１、Ｒ^１２、Ｒ^１３及びＲ^１４は各々独立に、水素原子、炭素数１〜３の脂肪族炭化水素基、又は、水酸基を示す。］

[In Formula (7), R < ¹⁰ >, R < ¹¹ >, R < ¹² >, R < ¹³ > and R < ¹⁴ > show a hydrogen atom, a C1-C3 aliphatic hydrocarbon group, or a hydroxyl group each independently. ]

  According to the phosphorus-containing polymer of the present invention, by having the above configuration, sufficient flame retardancy can be ensured without using a halogen-based flame retardant, and the problem of bleed-out can be sufficiently reduced and sufficient. A cured product having an elongation can be obtained.

  Here, the present inventors speculate as follows about the reason why the above-described effect is obtained by the phosphorus-containing polymer of the present invention. That is, the phosphorus-containing polymer of the present invention exhibits sufficient flame retardancy by having the monomer unit represented by the general formula (1) having a side chain having a structure containing phosphorus. Can be considered. In addition, the phosphorus-containing polymer has high solubility in solvents such as acetone, methyl ethyl ketone, N, N-dimethylformamide and the like because of having the monomer unit represented by the general formula (1). It is thought that it has. And since it is highly soluble in the above-mentioned solvent, it becomes easy to mix with other resin components, and the handleability in the B-stage film state and the elongation rate of the cured product, which has become a problem with filler-type flame retardants It is considered that the decrease in the temperature can be sufficiently suppressed. In addition, since the phosphorus-containing polymer has a sufficiently high molecular weight Mw (for example, 1,000 or more), it is caused by high volatility often found in monomers and low molecular weight aromatic phosphates. It is considered that the occurrence of bleed out is sufficiently suppressed.

  The phosphorus-containing polymer of the present invention preferably has a weight average molecular weight Mw of 1,000 to 1,000,000. When the weight average molecular weight is less than 1,000, the bleed suppression effect tends to be lower than when the weight average molecular weight is within the above range, and the weight average molecular weight exceeds 1,000,000. And compared with the case where a weight average molecular weight is in the said range, it exists in the tendency for the removal (development) of the resin of the unexposed part after the photocuring mentioned later to become difficult. In addition, a thing with a large molecular weight has a film forming ability, and it is easy to produce a functional film.

  This invention also provides the resin composition characterized by including 10-80 mass% of said phosphorus containing polymers of this invention, and the bismaleimide compound or block isocyanate compound which is a thermosetting agent. The phosphorus-containing polymer of the present invention can be made into a material having properties according to the application by using a resin composition containing the polymer. And according to the resin composition of the present invention, by including the phosphorus-containing polymer having the above configuration, sufficient flame retardancy can be ensured without using a halogen-based flame retardant, and there is a problem of bleeding out. A cured product that is sufficiently reduced and has a sufficient elongation can be obtained.

  The resin composition of the present invention is preferably cured by light and / or heat. Hereinafter, the resin composition is referred to as “resin composition” or “curable resin composition”.

  The resin composition of the present invention preferably further contains a photopolymerizable compound having an ethylenically unsaturated bond and a photopolymerization initiator. That is, the resin composition of the present invention may be a photocurable resin composition, and can be used as a functional material that can be partially irradiated with light to cure only a desired portion.

  The resin composition of the present invention is preferably used for forming a permanent resist. When the resin composition of the present invention is used for a photosensitive permanent resist, the phosphorus-containing polymer having the monomer unit represented by the general formula (1) is soluble in a solvent, so that a partial Only a desired portion can be cured by exposure by light irradiation, and then the resin in the unexposed portion can be removed with a developer containing a solvent. Furthermore, in the case of a filler-type flame retardant that is insoluble in the solvent, light wraparound occurs due to light scattering caused by the flame retardant at the boundary between the exposed part and the unexposed part. According to the invention, since the compatibility with other resins is good, high resolution can be expected.

  The present invention also provides a prepreg obtained by impregnating a base material with the resin composition of the present invention and making the resin composition into a B-stage. This makes it possible to provide a prepreg that is less likely to generate resin powder and has good handleability in the B-stage state. Furthermore, the prepreg can obtain a high elongation rate. In addition, when a metal-clad laminate is produced by applying heat to the prepreg and pressing it, generation of bleed can be sufficiently suppressed.

  In the prepreg of the present invention, the substrate is preferably a glass woven fabric. As a result, the prepreg can be further toughened, and heat resistance and dimensional stability can be improved when a metal-clad laminate is produced by applying heat to the prepreg and pressing it. it can.

  The present invention also provides a metal-clad laminate, wherein a metal foil is disposed on at least one surface of a substrate comprising one or more prepregs of the present invention and heated and pressed. In such a metal-clad laminate, the problem of bleed-out is sufficiently reduced and flame retardancy is sufficiently imparted. In addition, a metal-clad laminate free from defects due to resin powder can be obtained.

  The present invention also provides a sealing material comprising the resin composition of the present invention. According to such a sealing material, it is possible to sufficiently suppress the occurrence of cracks in the sealing material, which becomes a problem when a large amount of filler-type flame retardant is contained, and sufficient flame retardancy and elongation rate. Can be obtained.

  The present invention also provides a photosensitive film comprising a support and a photosensitive resin composition layer comprising the resin composition of the present invention formed on the support. According to such a photosensitive film, by providing the photosensitive resin composition layer comprising the resin composition of the present invention, sufficient flame retardancy can be ensured without using a halogen-based flame retardant. A resist (permanent resist) having an elongation rate can be formed.

  The photosensitive film of the present invention preferably further includes a protective film on the surface of the photosensitive resin composition layer opposite to the support.

  The present invention also provides the resin composition of the present invention so as to cover the conductor layer on the insulating substrate of a multilayer substrate comprising an insulating substrate and a conductor layer having a circuit pattern formed on the insulating substrate. Forming a photosensitive resin composition layer, irradiating a predetermined portion of the photosensitive resin composition layer with actinic rays to form an exposed portion, and forming a portion other than the exposed portion of the photosensitive resin composition layer. A method for forming a resist pattern is provided. Here, the photosensitive resin composition layer comprising the resin composition of the present invention is obtained by laminating the photosensitive resin composition layer in the photosensitive film on an insulating substrate using the photosensitive film of the present invention. It may be. According to such a resist pattern forming method of the present invention, sufficient flame retardancy can be ensured without using a halogen-based flame retardant, and a resist pattern having a sufficient elongation can be formed.

  The present invention also provides a printed wiring board comprising a circuit formed on the metal-clad laminate of the present invention.

  The present invention also provides an inner layer circuit board in which an inner layer circuit is formed, a resin layer made of the resin composition of the present invention formed on the inner layer circuit board, a through hole penetrating the resin layer, and the through hole. A metal plating layer formed on the inner wall of the substrate, and a circuit conductor formed on the surface of the resin layer opposite to the inner circuit board and electrically connected to the inner circuit via the metal plating layer; The printed wiring board characterized by having these.

  The present invention further provides a printed wiring board comprising an insulating substrate, a conductor layer having a circuit pattern formed on the insulating substrate, and a resist layer formed on the insulating substrate so as to cover the conductor layer. The printed wiring board is characterized in that the resist layer is made of a cured product of the resin composition of the present invention, and has an opening so that a part of the conductor layer is exposed.

  According to these printed wiring boards, since the cured product constituting the printed wiring board such as a resist layer is formed by curing the resin composition of the present invention, the cured product does not use a halogen-based flame retardant. In addition, it is possible to ensure a sufficient flame retardancy and to realize a printed wiring board having a sufficient elongation.

  According to the present invention, sufficient flame retardancy can be ensured without using a halogen-based flame retardant, and during heating caused by the high volatility often found in low molecular weight aromatic phosphates. Phosphorus-containing polymer capable of reducing the problem of bleed-out and capable of obtaining a cured product having sufficient elongation, a resin composition using the same, and a prepreg and a metal using the resin composition A tension laminate, a sealing material, a photosensitive film, a resist pattern forming method, and a printed wiring board can be provided.

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.

  The phosphorus-containing polymer of the present invention is characterized by having a structure (monomer unit) represented by the above general formula (1).

  That is, the phosphorus-containing polymer of the present invention is characterized by having a phosphorus compound structure containing phosphorus in the side chain, and such a phosphorus-containing polymer has, for example, a phosphorus compound structure in the side chain. It can be produced by homopolymerization of monomers. Examples of the monomer having a phosphorus compound structure in the side chain include 2-acryloyloxyethyl phosphate (manufactured by Shin Nippon Chemical Co., Ltd., trade name: Z-100), diphenyl- (2-methacryloyloxyethyl) phosphate (Daihachi Chemical). Manufactured by Kogyo Co., Ltd., trade name: MR-260), 2-methacryloyloxyethyl phosphate (manufactured by Daihachi Chemical Industry Co., Ltd., trade name: MR-200), vinyl phosphonate compound, vinyl phosphinate compound, vinyl phosphine oxide Compounds and the like.

  In the above general formula (1), as the vinyl phosphonate compound, vinyl phosphinate compound, and vinyl phosphine oxide compound in which X is a single bond, Japanese Patent No. 2775426, Japanese Patent No. 3041396, Japanese Patent No. 3390399, As described in Japanese Patent No. 3665501 and Japanese Patent Application Laid-Open No. 2004-026655, etc., using a metal catalyst such as Pd, Rh, Ni, hydrogen phosphonate, hydrogen phosphinate and phosphine oxide It can be synthesized by addition reaction to acetylenes. Examples of these are, for example, vinyl dimethyl phosphonate, vinyl diethyl phosphonate, vinyl diphenyl phosphonate, methyl vinyl methyl phosphinate, ethyl vinyl ethyl phosphinate, phenyl vinyl phenyl phosphinate, vinyl dimethyl phosphine oxide, vinyl diethyl phosphine oxide. Vinyl diphenylphosphine oxide and the like, but are not limited thereto.

  The phosphorus-containing polymer in the present invention does not have a monomer having a phosphorus compound structure in the side chain and a monomer having a phosphorus compound structure in the side chain, or a monomer having a phosphorus compound structure in the side chain and no phosphorus in the side chain. Any of the monomers can be copolymerized. Such a monomer is not particularly limited as long as it is a compound copolymerized with a monomer having a phosphorus compound structure in the side chain. Moreover, as a monomer which does not have phosphorus in a side chain, a C1-C20 alkyl group, an alicyclic group, a glycidyl group, a C1-C6 alkyl group containing a hydroxyl group, a nitrogen-containing cyclic compound, etc. are included in an ester chain. Examples thereof include acrylic acid esters and methacrylic acid esters. Here, as the methacrylic acid ester, for example, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, isobutyl acrylate, ethylene glycol methyl ether acrylate, acrylic acid Glycidyl, cyclohexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isobornyl acrylate, amide amide, isodecyl acrylate, octadecyl acrylate, lauryl acrylate, allyl acrylate, N-vinylpyrrolidone acrylate , Methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, isobutyl methacrylate Ethylene glycol methyl ether methacrylate, glycidyl methacrylate, cyclohexyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, isobornyl methacrylate, methacrylamide, isodecyl methacrylate, octadecyl methacrylate, lauryl methacrylate, methacryl Examples include allyl acid and N-vinylpyrrolidone methacrylate. In addition, as a monomer having no phosphorus in the side chain, a non-acrylic acid monomer such as acrylonitrile or dimethylaminoethyl can be used.

  In general, acrylic acid esters and methacrylic acid esters can carry out addition polymerization of double bonds by generating radicals. Also in the present invention, polymerization and copolymerization of a monomer having a phosphorus compound structure in the side chain of the ethylene chain can be performed by a general method.

  Examples of radical polymerization initiators that generate radicals include azobisisobutyronitrile (AIBN), tert-butyl perbenzoate (PBOC), benzoyl peroxide, lauroyl peroxide, peroxides such as potassium persulfate, cumene hydro Peroxide, t-butyl hydroperoxide, dicumyl peroxide, di-t-butyl peroxide, 2,2′-azobis-2,4-dimethylvaleronitrile, t-butyl perisobutyrate, t-butyl perpivalate, peroxide Examples include hydrogen / ferrous salt, persulfate / acidic sodium sulfite, cumene hydroperoxide / ferrous salt, benzoyl peroxide / dimethylaniline, and the like. Moreover, you may combine these.

  The amount of radical polymerization initiator varies depending on the type of initiator used, but the polymerization rate decreases if the amount of initiator is small, and the molecular weight tends to decrease if the amount of initiator is large. 0.0001 to 5 parts by mass is preferable, and 0.001 to 3 parts by mass is more preferable with respect to 100 parts by mass as a whole.

  Polymerization or copolymerization can be carried out by uniformly dissolving a monomer having a phosphorus compound structure in the side chain of the ethylene chain in an organic solvent, or by emulsifying or suspending it in an aqueous solution. The organic solvent to be uniformly dissolved is not particularly limited as long as the monomer having a phosphorus compound structure in the side chain of the raw ethylene chain, the polymer to be formed, and the initiator are dissolved, but toluene, methyl ethyl ketone, dimethylformamide, etc. Can be illustrated.

  The reaction temperature for the polymerization or copolymerization varies depending on the boiling point of the raw material and solvent, the radical generation temperature and half-life of the initiator, but is preferably −15 ° C. to 150 ° C. from the viewpoint of production equipment and efficiency, and is preferably room temperature (25 It is particularly preferable to carry out at a temperature of from 100 ° C. The produced polymer can be used as it is unless particularly required, but can also be purified by removing impurities by filtration, precipitation with a poor solvent, or the like. Further, in suspension polymerization and emulsion polymerization, polymerization can be performed more efficiently by using a chain transfer agent such as a dispersant, an emulsifier, and α-styrene dimer.

Thus, the phosphorus-containing polymer of the present invention having the monomer unit represented by the general formula (1) can be obtained. Here, in the general formula (1), X represents a single bond, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, a phenylene group, a divalent group represented by the general formula (2), the general formula ( A divalent group represented by 3), a group containing an ester bond represented by the general formula (4), or a group containing an ester bond represented by the general formula (5), a single bond, The divalent group represented by the general formula (4) or the divalent group represented by the general formula (5) is preferable, and the divalent group represented by the general formula (5) is preferable. More preferably, it is a group. R ¹ and R ² are each independently a hydroxyl group, an aliphatic hydrocarbon group having 1 to 6 carbon atoms, an alkyloxy group having 1 to 3 carbon atoms, an aryl group represented by the general formula (6), or The aryloxy group represented by the general formula (7) is preferably an aryl group represented by the general formula (6) or an aryloxy group represented by the general formula (7). .

Moreover, in said general formula (4) and (5), a and b are the integers of 1-10 each independently, and it is preferable that it is an integer of 1-6. In the general formulas (6) and (7), R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are each independently a hydrogen atom. , An aliphatic hydrocarbon group having 1 to 3 carbon atoms or a hydroxyl group, preferably a hydrogen atom.

In addition, when X in the general formula (1) is an aliphatic hydrocarbon group having 1 to 10 carbon atoms (preferably an aliphatic hydrocarbon group having 1 to 6 carbon atoms), the aliphatic hydrocarbon group is specifically exemplified. Examples include methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group and the like. When X in the general formula (1) is a divalent group represented by the general formula (2), specific examples of the group include a methyleneoxy group, an ethyleneoxy group, and a propyleneoxy group. When X in the general formula (1) is a divalent group represented by the general formula (3), specific examples of such a group include a methyleneamino group (—CH ₂ —NH—) and an ethyleneamino group. _(-C 2 _H 4 -NH-), propylene amino group _{(-C 3 H 6 -NH -,} - CH (CH 3) CH 2 -NH -, - CH 2 CH (CH 3) -NH-) include It is done.

  Specific examples of the methylene chain of the group containing an ester bond represented by the general formula (4) include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, and an octylene. Group, nonylene group, decylene group and the like. Specific examples of the methylene chain of the group containing an ester bond represented by the general formula (5) include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, and an octylene. Group, nonylene group, decylene group and the like.

  The molecular weight of the phosphorus-containing polymer of the present invention is preferably 1,000 to 1,000,000 in terms of weight average molecular weight (styrene conversion value by GPC method), considering heat resistance. More preferably, it is ˜500,000, more preferably 3,000 to 200,000, particularly preferably 10,000 to 150,000, and more preferably 20,000 to 100,000. Most preferred. If the molecular weight is less than 1,000, problems such as bleed out and B-stage tack (stickiness) tend to occur in the resin composition. Further, when the molecular weight is larger than 1,000,000, the residual resin after development tends to increase.

  The resin composition of the present invention contains the phosphorus-containing polymer of the present invention and is preferably cured by light and / or heat. In the curable resin composition of the present invention, the content of the phosphorus-containing polymer of the present invention is preferably 10 to 80% by mass based on the total solid content in the curable resin composition, and is preferably 20 to 70%. More preferably, it is mass%. If this content is less than 10% by mass, the flame retardancy of the resulting cured product tends to be reduced, and if it exceeds 80% by mass, the heat and / or photocurability in the case of a resin composition is reduced. Thus, the resolution and physical properties after curing tend to be insufficient.

  In the curable resin composition of the present invention, known thermal polymerization initiators can be used. For example, ketone peroxides such as benzoyl peroxide and methyl ethyl ketone peroxide, alkyl peroxides such as tertiary butyl peroxide, peroxydicarbonates, peroxyketals, peroxyesters, alkylperesters, etc. Can be used.

  The content of the thermal polymerization initiator in the curable resin composition is preferably 0.1 to 10% by mass, based on the total solid content in the curable resin composition, and preferably 0.5 to 5.0% by mass. It is particularly preferable that

  In the curable resin composition of the present invention, the photopolymerization initiator may be any photopolymerization initiator as long as it matches the light wavelength of the exposure machine used for curing, and known ones can be used. Examples of the photopolymerization initiator include acetophenone, benzophenone, 4,4-bisdimethylaminobenzophenone, 4,4-bisdiethylaminobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzoin ethyl ether, benzoin butyl ether, and 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, 2-methylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2,4-dimethylthioxanthone, methylbenzoylformate, 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, 2,4,5-triarylimidazole dimer or derivatives thereof .

  The content of the photopolymerization initiator in the curable resin composition is preferably 0.1 to 10% by mass based on the total solid content in the curable resin composition, and is preferably 0.5 to 5.0% by mass. It is particularly preferred that

  You may add resin to the curable resin composition of this invention in the range by which the effect of this invention does not fall. This resin is not particularly limited, and a thermoplastic resin, a thermosetting resin, and a photocurable resin can be used alone or in combination of two or more. Among these, the heat resistance of the curable resin composition can be improved by using a thermosetting resin or a photocurable resin.

  Examples of the thermoplastic resin include acrylic resin, methacrylic resin, phenoxy resin, polyamide, polyamideimide, polyarylate, polyetherimide, polyetheretherketone, polyethylene, polyethylene terephthalate, polysulfone, polyethersulfone, polystyrene, and polyphenylene. Examples include ether, polyphenylene sulfide, and polymethyl methacrylate. In addition, when using an alkali developing solution, the solubility of resin can be improved by using resin which contains a carboxyl group.

  There is no restriction | limiting in particular as a thermosetting resin, A well-known thermosetting resin can be utilized. Specifically, for example, an epoxy resin, a phenol resin, an alkyd resin, a melamine resin, an isocyanate resin, or the like can be used, and those curing agents or curing accelerators are appropriately blended. For example, when an epoxy resin is used as the thermosetting resin, the curing agent is not particularly limited, and amines, phenols, acid anhydrides, and the like are used. Here, as amines, dimethylamine, diethylenetriamine, triethylenetetramine, diethylaminopropylamine, aminoethylpiperazine, mensendiamine, metaxylylenediamine, dicyandiamide, diaminodiphenylmethane, diaminodiphenylsulfone, methylenedianiline, metaphenylenediamine Etc. Examples of the phenols include biphenol, bisphenol-A, bisphenol-F, phenol novolak, cresol novolak, bisphenol A novolak, and alkyl group-substituted products thereof. Acid anhydrides include hexahydrophthalic anhydride (HPA), tetrahydrophthalic anhydride (THPA), pyromellitic anhydride (PMDA), dodenyl succinic anhydride (DDSA), phthalic anhydride (PA), methylhexahydrophthalic anhydride Examples include acid (MeHPA) and maleic anhydride. These curing agents may be used alone or in combination of two or more.

  Moreover, as an accelerator when using an epoxy resin as a thermosetting resin, an imidazole compound, an organophosphorus compound, a tertiary amine, a quaternary ammonium salt, a secondary amino group with acrylonitrile, isocyanate, melamine, acrylate The imidazole compound etc. which were masked by etc. can be used, and it is preferable that the addition amount shall be 0.1-6 mass parts with respect to 100 mass parts of epoxy resins. If this addition amount is less than 0.1 parts by mass, the effect of promoting curing is small, and if it exceeds 6 parts by mass, the storage stability of the curable resin composition tends to decrease. As the imidazole compound used here, imidazole, 2-methyl-imidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 1-benzyl-2-methylimidazole, 4,5 -Diphenylimidazole, 2-methylimidazoline, 2-ethyl-4methylimidazoline, 2-phenylimidazoline, 2-undecylimidazoline, 2-heptadecylimidazoline, 2-isopropylimidazole, 2,4-dimethylimidazole, 2-phenyl- Examples include 4-methylimidazole, 2-methylimidazoline, 2-isopropylimidazoline, 2,4-dimethylimidazoline, 2-phenyl-4-methylimidazoline.

  In addition, as a resin used in the curable resin composition, an unsaturated polyester resin or a photocurable resin having a functional group that can be cross-linked by the above-described photopolymerization initiator can be used.

  The photocurable resin is not particularly limited as long as it has a functional group that can be cross-linked by a photopolymerization initiator. Examples of the resin having a functional group that can be cross-linked by a photopolymerization initiator include compounds having an ethylenically unsaturated bond polymerizable in the molecule. Such a compound is not particularly limited, but a compound having an acryloyl group and / or a methacryloyl group is preferably used. The photocurable resin may have any structure such as aliphatic, aromatic, alicyclic, heterocyclic, etc., and has an ester bond, urethane bond, amide bond, etc. in the molecule. It may be.

  Specific examples of the photo-curable resin include epoxy (meth) acrylate obtained by adding acrylic acid and / or methacrylic acid to a diglycidyl ether compound of bisphenols, and acrylic acid and / or methacrylic acid added to a novolac type epoxy resin ( Examples thereof include a (meth) acryl-modified novolak type epoxy resin, a resin obtained by adding glycidyl acrylate and / or glycidyl methacrylate to an acrylic resin having a carboxyl group.

  In addition, when the curable resin composition of the present invention is used for photolithography, a range in which physical properties such as resolution and moisture resistance are not lowered after acrylic acid and / or methacrylic acid is added to the epoxy resin. Then, modification may be performed with an acid anhydride. Examples of the acid anhydride include carboxylic acid anhydride, maleic acid anhydride, tetrahydrophthalic acid anhydride, itaconic acid anhydride, hexahydrophthalic acid anhydride, succinic acid anhydride, naphthalic acid anhydride, citraconic acid anhydride. Methylphthalic anhydride, butenyltetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, alkenyl anhydride, tricarbanilic anhydride, and the like.

  Moreover, the curable resin composition of this invention may contain the polymeric compound which has an ethylenically unsaturated group. Examples of the polymerizable compound having an ethylenically unsaturated group include a compound obtained by reacting a polyhydric alcohol with an α, β-unsaturated carboxylic acid, 2,2-bis (4-((meth) acryloxypoly). Ethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypolypropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) propane, etc. Bisphenol A-based (meth) acrylate compounds, compounds obtained by reacting glycidyl group-containing compounds with α, β-unsaturated carboxylic acids, urethane monomers such as (meth) acrylate compounds having a urethane bond, γ-chloro-β -Hydroxypropyl-β '-(meth) acryloyloxyethyl-o-phthalate, β-hydroxyethyl-β' (Meth) acryloyloxyethyl -o- phthalate, beta-hydroxypropyl-beta '- (meth) acryloyloxyethyl -o- phthalate, and (meth) acrylic acid alkyl ester.

  Examples of the compound obtained by reacting the polyhydric alcohol with an α, β-unsaturated carboxylic acid include, for example, polyethylene glycol di (meth) acrylate having 2 to 14 ethylene groups and 2 to 2 propylene groups. Polypropylene glycol di (meth) acrylate being 14, polyethylene polyethylene glycol di (meth) acrylate having 2 to 14 ethylene groups and 2 to 14 propylene groups, trimethylolpropane di (meth) acrylate, Trimethylolpropane tri (meth) acrylate, trimethylolpropane ethoxytri (meth) acrylate, trimethylolpropane diethoxytri (meth) acrylate, trimethylolpropane triethoxytri (meth) acrylate, trimethylolpropane tetraeth Xyltri (meth) acrylate, trimethylolpropane pentaethoxytri (meth) acrylate, tetramethylolmethanetri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, polypropylene glycol di (meth) having 2 to 14 propylene groups ) Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like.

  Examples of the 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane include 2,2-bis (4-((meth) acryloxydiethoxy) phenyl) propane, 2,2 -Bis (4-((meth) acryloxytriethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytetraethoxy) phenyl) propane, 2,2-bis (4-((meta ) Acryloxypentaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyhexaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyheptaethoxy) phenyl) Propane, 2,2-bis (4-((meth) acryloxyoctaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxynonane) Xyl) phenyl) propane, 2,2-bis (4-((meth) acryloxydecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyundecaethoxy) phenyl) propane, 2 , 2-bis (4-((meth) acryloxydodecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytridecaethoxy) phenyl) propane, 2,2-bis (4- ((Meth) acryloxytetradecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypentadecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxy) Hexadecaethoxy) phenyl) propane and the like, and 2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane is BPE- 00 (made by Shin-Nakamura Chemical Co., Ltd., product name) and 2,2-bis (4- (methacryloxypentadecaethoxy) phenyl) propane is BPE-1300 (Shin-Nakamura Chemical) It is commercially available as a product name manufactured by Kogyo Co., Ltd.

  Examples of the urethane monomer include a (meth) acryl monomer having an OH group at the β-position and a diisocyanate compound such as isophorone diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, and 1,6-hexamethylene diisocyanate. Addition reaction product, tris ((meth) acryloxytetraethylene glycol isocyanate) hexamethylene isocyanurate, EO-modified urethane di (meth) acrylate, EO, PO-modified urethane di (meth) acrylate, and the like. “EO” represents ethylene oxide, and an EO-modified compound has a block structure of an ethyleneoxy group. “PO” represents propylene oxide, and the PO-modified compound has a propyleneoxy group block structure. As the EO-modified urethane di (meth) acrylate, for example, a product name “UA-11” manufactured by Shin-Nakamura Chemical Co., Ltd. is commercially available. Further, as EO, PO-modified urethane di (meth) acrylate, for example, a product name “UA-13” manufactured by Shin-Nakamura Chemical Co., Ltd. is commercially available.

  You may use these individually or in combination of 2 or more types.

  Moreover, the curable resin composition of this invention may contain the copolymer and / or monomer which have the functional group which can be bridge | crosslinked with a cationic photoinitiator. Such a copolymer and / or monomer is not particularly limited as long as it performs cationic polymerization, and examples thereof include a compound having a polymerizable vinyl ether group, propenyl ether group, epoxy group, oxetanyl group in the molecule. Can be mentioned.

  Examples of the cationic photoinitiator include known ones such as triphenyl sulfone hexafluoroantimonate, triphenyl sulfone hexafluorophosphate, p-methoxybenzenediazonium hexafluorophosphate, p-chlorobenzenediazonium hexafluorophosphate, diphenyl. Examples include iodonium hexafluorophosphate, 4,4-di-t-butylphenyl iodonium hexafluorophosphate, (1-6-n-cumene) (n-dicopentadiniel) iron hexafluorophosphate, and the like. The content of these radical photoinitiators or cationic photoinitiators is preferably 0.1 to 10% by mass, based on the total solid content in the curable resin composition, respectively. It is particularly preferably 5.0% by mass.

  Moreover, you may add a thermosetting agent to the curable resin composition of this invention 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, or a curable resin composition. In the case where a resin having a carboxyl group is used as the resin used in the above, a curing agent that reacts with the carboxyl group of the resin by heating to form a three-dimensional structure is exemplified.

  A bismaleimide compound is mentioned as a thermosetting agent which bridge | crosslinks itself by heating. As bismaleimide compounds, m-di-N-maleimidylbenzene, bis (4-N-maleimidylphenyl) methane, 2,2-bis (4-N-maleimidylphenyl) propane, 2,2 -Bis (4-N-maleimidyl 2,5-dibromophenyl) propane, 2,2-bis [4- (4-N-maleimidylphenoxy) phenyl] propane, 2,2-bis (4-N-malemidyl) Various bismaleimide compounds such as -2-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.

  Moreover, when using resin which has a carboxyl group as resin used for curable resin composition, a block isocyanate compound is mentioned as a hardening | curing agent which reacts with the carboxyl group of the said resin by heating and forms a three-dimensional structure. It is done. 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 diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-xylene diisocyanate, and m-xylene diisocyanate. Aromatic polyisocyanates such as 2,4-tolylene dimer, aliphatic polyisocyanates such as hexamethylene diisocyanate, 4,4-methylenebis (cyclohexyl isocyanate), 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 filler to the curable resin composition of this invention in the range which does not reduce resolution, a flame retardance, and the elongation rate of hardened | cured material. 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 And organic fine particles such as powdered polytetrafluoroethylene particles. These fillers may be subjected to a coupling treatment in advance. Dispersion of these fillers is achieved by a known kneading method such as a kneader, a ball mill, a bead mill, or a three roll. The content of these fillers is preferably 2 to 20% by mass, particularly preferably 5 to 15% by mass, based on the total solid content in the curable resin composition.

  The curable resin composition of the present invention can be used by diluting in a solvent when forming a resin composition layer. 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, and the like. . These solvents can be used alone or in admixture of two or more. In order to efficiently dissolve the curable 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, and these may be used as other solvents. May be added.

  It is preferable that the compounding quantity of the solvent in curable resin composition is 10-200 mass parts with respect to 100 mass parts of components (solid content) other than the solvent in curable resin composition, and is 30-100 mass parts. It is particularly preferred. When the amount of the solvent is less than 10 parts by mass, the viscosity of the curable 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 200 parts by mass, it tends to be difficult to control the thickness of the layer when the curable resin composition layer is formed due to a decrease in viscosity, and the use of the solvent There is a tendency to be expensive due to the large amount.

  A polymerization stabilizer, a leveling agent, a pigment, a dye, and an adhesion improver may be further added to the curable resin composition. These selections are made under the same considerations as for ordinary curable resin compositions. These addition amounts are such that the properties of the curable resin composition of the present invention are not impaired, and each content is 0.01 to 10% by mass based on the total solid content in the curable resin composition. It is preferable to add to.

  Moreover, it is preferable that the glass transition temperature after hardening of a curable resin composition is 90 degreeC or more, It is more preferable that it is 100-180 degreeC, It is still more preferable that it is 100-150 degreeC.

  There is no restriction | limiting in particular about the thickness of the resin composition layer formed using the curable resin composition of this invention, In the range of 10-150 micrometers, it selects suitably. The curable resin composition is applied directly on a substrate or printed wiring board by a conventional method such as dip coating, roll coating, flow coating, screen printing, spraying, electrostatic spraying, etc. Although it is possible to easily form a resin composition layer comprising the curable resin composition on a wiring board, it may be used as a photosensitive film for a permanent resist as described later.

  The curable resin composition of the present invention can be used for the formation of resist patterns such as prepregs, metal-clad laminates, sealing materials, photosensitive films, permanent resists, and printed wiring boards. In addition, the curable resin composition of the present invention preferably has thermosetting and / or photocurable properties, and at least has photocurable properties, thereby forming the above-described photosensitive film and resist pattern, And it can be used conveniently for a printed wiring board.

  Here, the prepreg is impregnated with a curable resin composition of the present invention having at least thermosetting, for example, on a substrate such as a glass woven fabric, and the curable resin composition is heated and dried to form a B stage. It is made up of.

  The metal-clad laminate is obtained by placing a metal foil on at least one surface of a laminate comprising one or more prepregs of the present invention and heating and pressing the laminate.

  Furthermore, the sealing material is made of the curable resin composition of the present invention.

  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 made of the resin composition of the present invention on a support (carrier film) 11, and further a photosensitive film. A cover film (protective film) 13 is provided on the surface of the conductive resin composition layer 12 opposite to the carrier 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 curable 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 being laminated. Therefore, the cover film 13 has flexibility and can be releasably adhered to the photosensitive resin composition layer 12 and is damaged at the temperature of the drying furnace. Although it will not restrict | limit especially if it is not, For example, a polyethylene film, a polypropylene film, a polytetrafluoroethylene film, surface-treated paper etc. are mentioned. In order to make the cover film 13 easily peelable from the photosensitive resin composition layer 12, the resin composition layer 12 and the cover film 13 rather than the adhesive force between the photosensitive resin composition layer 12 and the support 11. It is preferable that the adhesive strength is smaller.

  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.

  According to the photosensitive film 1, the photosensitive resin composition layer 12 is overlaid on a substrate or a printed wiring board, and pasted using a hot roll laminator or the like, whereby the photosensitive film of the permanent resist film is exposed on the substrate or the wiring board. The functional resin composition layer 12 can be easily formed.

  Moreover, exposure and image development of the formed photosensitive resin composition layer 12 can be performed by a conventional method. For example, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, or the like is used as a light source, and imagewise exposure can be performed through a negative mask directly on the resin composition layer 12 or through a transparent film such as a polyethylene terephthalate film. When a transparent film remains after exposure, it is preferable to develop the film after peeling it off.

  The curable resin composition of the present invention can also form an image resin film by a printing method, a laser drilling method using a carbon dioxide laser, a YAG laser, an excimer laser, or the like.

  The curable resin composition and the photosensitive film described above are free from the problem of bleeding when heated without using a halide, can ensure flame retardancy, and further, have improved resolution and elongation of the cured product. An excellent permanent resist can be formed.

  In addition, the photosensitive film of this invention is not limited to the above-mentioned thing, For example, what does not have the cover film 13 may be used.

  Next, the resist pattern forming method of the present invention will be described.

  The method for forming a resist pattern of the present invention is at least photosensitive so as to cover a conductive layer on an insulating substrate of a multilayer substrate comprising an insulating substrate and a conductive layer having a circuit pattern formed on the insulating substrate. Forming a photosensitive resin composition layer comprising the curable resin composition of the present invention having the above, and irradiating a predetermined portion of the photosensitive resin composition layer with an actinic ray to form an exposed portion; This is a method of removing portions other than the exposed portion of the physical layer.

  As a method for laminating the photosensitive resin composition layer, a method of directly coating the photosensitive resin composition of the present invention on an insulating substrate, and a photosensitive resin composition layer in the photosensitive film 1 of the present invention described above. For example, a method of laminating 12 by pressure-bonding to an insulating substrate while heating can be exemplified. Therefore, when the curable resin composition contains a volatile component such as a solvent, the photosensitive resin composition layer laminated on the substrate is mainly composed of the components after most of the solvent is removed.

  After the lamination is completed in this manner, an exposed portion is formed by irradiating a predetermined portion of the photosensitive resin composition layer with actinic rays (exposure step). Examples of the method for forming the exposed portion include a method of irradiating actinic rays in an image form through a negative or positive mask pattern called an artwork. At this time, the mask may be directly contacted on the photosensitive resin composition layer, or may be contacted via a transparent film.

  As the actinic ray light source, a known light source is used. For example, a light source that effectively emits ultraviolet rays, such as a carbon arc lamp, a mercury vapor arc lamp, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, or a xenon lamp, 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, a developer is used to remove a portion other than the exposed portion by a known method such as spraying, rocking dipping, brushing, scraping, etc., and a resist pattern is formed (developing step). Note that after the resist pattern is formed, post-curing may be further performed by exposure at 1 to 5 J / cm ² and / or heating at 100 to 200 ° C. for 30 minutes to 12 hours (post-heating step).

  The developer used in the development process is not particularly limited as long as it selectively elutes the unexposed part without damaging the exposed part, and is determined by the development type of the resin composition, Commonly used ones such as an alkali developer, 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 mass of an organic solvent such as methoxybutyl acetate can be mentioned. When an alkali developer is used, an alkaline aqueous solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, sodium 4-borate, ammonia, amines and the above organic solvent are used. It is also possible to use an emulsion developer.

  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.

  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. A 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 formed on the other surface of the insulating substrate 22. A conductor layer 21 having no pattern 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 photosensitive film of the present invention, and the resist layer 24 has an opening so that at least a part of the conductor layer 23 having a circuit pattern is exposed. 26. The resist layer 24 may be formed by applying and curing the curable resin composition of the present invention on the insulating substrate 22.

  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 FIG. 3D shows a state in which the printed wiring board 4 and the photosensitive resin composition layer 24 after the photosensitive resin composition 24 are laminated on the insulating substrate 22 are irradiated with actinic rays and after development, respectively. The printed 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 printed wiring board 2 is obtained by removing the unexposed portions to form the resist layer 24 having the openings 26 as shown in FIG. 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.

  In addition, the printed wiring board of this invention is not limited to the above-mentioned thing, For example, you may form a circuit in the metal-clad laminated board of the said invention. The printed wiring board of the present invention includes an inner layer circuit board having an inner layer circuit formed thereon, a resin layer made of the curable resin composition of the present invention formed on the inner layer circuit board, and penetrating the resin layer. The through hole, the metal plating layer formed on the inner wall of the through hole, and the resin layer are formed on the surface opposite to the inner circuit board, and are electrically connected to the inner circuit through the metal plating layer. And a circuit conductor. Even in these printed wiring boards, the cured product as the constituent material is made of the curable resin composition of the present invention, so that sufficient flame retardancy can be secured without using a halogen-based flame retardant. In addition, sufficient electric corrosion resistance and sufficient elongation can be obtained, and a highly reliable printed wiring board can be realized.

  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.

[Synthesis Example 1]
50 parts by mass of methyl ethyl ketone was placed in a 500 ml four-necked flask and heated to 80 ° C. with stirring under a nitrogen stream. On the other hand, phosphorus-containing acrylic acid ester (diphenyl- (2-methacryloyloxyethyl) phosphate having a structure represented by the general formula (1) as a P compound bonded to the ethylene side chain, Daihachi Chemical Co., Ltd. 100 parts by mass, trade name: MR-260), 1 part by mass of AIBN (azobisisobutyronitrile) as a radical polymerization initiator, and 0.1 part by mass of PBOC (tert-butyl perbenzoate) It was dissolved in 50 parts by mass of methyl ethyl ketone, which is an organic solvent, at room temperature, and dropped into the four-necked flask over 240 minutes while maintaining the liquid temperature at 80 ° C., and further reacted at the same temperature for 120 minutes. An MEK (methyl ethyl ketone) solution of a phosphorus-containing polymer having a repeating unit represented by the following formula (8) was obtained. The synthesized phosphorus-containing polymer had a weight average molecular weight of 30,000.

  The weight average molecular weight of the polymer was converted from a calibration curve using standard polystyrene by gel permeation chromatography (GPC). The conditions for GPC are as follows.

(GPC conditions)
Pump: Hitachi L-6000 type (manufactured by Hitachi, Ltd.),
Column: Gelpack GL-R420 + Gelpack GL-R430 + Gelpack GL-R440 (3 in total) (above, manufactured by Hitachi Chemical Co., Ltd., trade name)
Eluent: tetrahydrofuran,
Measurement temperature: room temperature (25 ° C.)
Flow rate: 2.05 mL / min,
Detector: Hitachi L-3300 RI (manufactured by Hitachi, Ltd.).

[Example 1]
As shown below, the phosphorus-containing polymer of Synthesis Example 1 and various materials were blended to prepare a photo / thermosetting resin composition.

Phosphorus-containing polymer of Synthesis Example 1 (weight average molecular weight 30,000): 40 parts by mass (solid content)
Epoxy acrylate anhydride (ZFR-1158, manufactured by Nippon Kayaku Co., Ltd., acid value 97 mg / g): 30 parts by mass (solid content),
Urethane bond-containing monomer (UA-11, manufactured by Shin-Nakamura Chemical Co., Ltd.): 30 parts by mass (solid content),
Photopolymerization initiator (Irgacure 651, manufactured by Ciba Geigy Corporation): 5 parts by mass (solid content),
Thermal polymerization initiator (Perhexin 25B, manufactured by NOF Corporation): 2 parts by mass (solid content),
Thermosetting agent (2,2-bis [4- (4-N-maleimidinylphenoxy) phenyl] propane, manufactured by Hitachi Chemical Co., Ltd.): 10 parts by mass (solid content),
Methyl ethyl ketone: 20 parts by mass.

[Reference Example 1]
As shown below, the phosphorus-containing polymer of Synthesis Example 1 and various materials were blended to prepare a thermosetting resin composition.

Phosphorus-containing polymer of Synthesis Example 1 (weight average molecular weight 30,000): 50 parts by mass (solid content)
Cresol novolac type epoxy resin (ESCN-195, manufactured by Sumitomo Chemical Co., Ltd.): 45 parts by mass (solid content),
Bisphenol A type epoxy resin (EP-1001, manufactured by Yuka Shell Co., Ltd.): 15 parts by mass (solid content),
Phenol novolac resin (TD-2131, manufactured by Dainippon Ink Co., Ltd.): 40 parts by mass (solid content),
Curing accelerator (2-phenylimidazole): 0.2 parts by mass (solid content)
Methyl ethyl ketone: 50 parts by mass.

[Example 3]
A photo / thermosetting resin composition was prepared in the same manner as in Example 1, and the obtained resin composition was coated on a PET film and dried at 80 ° C. for 20 minutes, whereby a photosensitive resin having a film thickness of 30 μm. A photosensitive film having a composition layer formed on a PET film was obtained.

[Comparative Example 1]
In Example 1, the phosphorus-containing polymer of Synthesis Example 1 was not blended. Other than that was carried out similarly to Example 1, and prepared the photo / thermosetting resin composition.

[Comparative Example 2]
In Example 1, instead of 40 parts by mass (solid content) of the phosphorus-containing polymer of Synthesis Example 1, a copolymer obtained by polymerizing methacrylic acid, methyl methacrylate and methyl acrylate in a mass ratio of 20:45:35 (Weight average molecular weight 70,000, acid value 110 mg / g) 40 parts by mass (solid content) was used. Other than that was carried out similarly to Example 1, and prepared the photo / thermosetting resin composition.

[Comparative Example 3]
In Example 1, instead of 40 parts by mass (solid content) of the phosphorus-containing polymer in Synthesis Example 1, 40 parts by mass (solid) of Rhephos TPP (manufactured by Ajinomoto Co., Inc.), which is a phosphate ester represented by the following formula (9) Min) was used. Other than that was carried out similarly to Example 1, and prepared the photo / thermosetting resin composition.

[Comparative Example 4]
In Example 1, instead of 40 parts by mass (solid content) of the phosphorus-containing polymer of Synthesis Example 1, 40 parts by mass (solid content) of PMP-100 (manufactured by Nissan Chemical Co., Ltd.) that is melamine polyphosphate was used. Other than that was carried out similarly to Example 1, and prepared the photo / thermosetting resin composition.

[Comparative Example 5]
In Example 1, instead of 40 parts by mass (solid content) of the phosphorus-containing polymer of Synthesis Example 1, 40 parts by mass (solid content) of Heidilite H-42M (manufactured by Showa Denko KK) which is Al (OH) ₃ Was used. Other than that was carried out similarly to Example 1, and prepared the photo / thermosetting resin composition.

  The following evaluation tests were performed on the curable resin compositions of Example 1, Reference Example 1 and Comparative Examples 1 to 5 obtained as described above, and the photosensitive film of Example 3.

(Flame retardancy evaluation test)
First, 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 a double-sided roughened foil on both sides. Thus, a substrate having no circuit layer was produced.

  Next, in Example 1, Reference Example 1 and Comparative Examples 1 to 5, the curable resin composition was applied to the etched side of the substrate and dried at 80 ° C. for 20 minutes. A 30 μm resin composition layer was formed. In Example 3, the photosensitive film was laminated on the substrate using a laminator so that the photosensitive resin composition layer was in contact with the etched surface of the substrate, and the film thickness was 30 μm. A photosensitive resin composition layer was formed.

Next, in Examples 1 and 3 and Comparative Examples 1 to 5, the resin composition layer on the substrate was irradiated with ultraviolet rays having an exposure amount of 200 mJ / cm ² , and in Example 3, the PET film was then peeled off. Next, a metal halide lamp type conveyor exposure machine (lamp output 80 W / cm ² , lamp height 80 cm, no cold mirror, conveyor speed 1. 5 m / min) was used to irradiate ultraviolet rays of 1000 mJ / cm ² to perform post-exposure. Furthermore, the resin composition layer was completely cured by post-heating at 160 ° C. for 1 hour to obtain a cured product. And the flame retardant test piece of Examples 1, 3 and Comparative Examples 1-5 was obtained by cut | disconnecting the obtained hardened | cured material to width 13mm and length 130mm.

  In Reference Example 1, the substrate on which the resin composition layer was formed was post-heated at 170 ° C. for 2 hours to completely cure the resin composition layer to obtain a cured product. And the flame retardant test piece of the reference example 1 was obtained by cut | disconnecting the obtained hardened | cured material to width 13mm and length 130mm.

  Using the test pieces (5 pieces each) thus obtained, the vertical combustion test was conducted 5 times in accordance with the UL94 standard. The total combustion time (seconds) is obtained by summing up the five combustion times, and according to the criteria of UL94 standard, V-0, V-1, V-2 and burned (burned up to the specimen clamp) Judged by rank. The obtained results are shown in Table 1.

(Resolution of the opening)
First, etching is performed on 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, A circuit board having a circuit layer in which a comb-shaped circuit having a line width / space width (40 μm / 40 μm) dimension was formed on one surface was produced.

  Next, in Example 1 and Comparative Examples 1 to 5, a curable 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 resin composition having a thickness of 30 μm. A layer was formed. In Example 3, 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, thereby forming a photosensitive resin composition layer having a thickness of 30 μm. did.

Next, UV light having an exposure amount of 200 mJ / cm ² was irradiated to the resin composition layer through a photomask having a shielding part having a diameter of 150 μm in the opening part, and in Example 3, after peeling the PET film A resist pattern was prepared by spraying at 30 ° C. for 1 minute using a developer containing 10% by volume of 2,2-butoxyethoxyethanol and 8 g / l of sodium tetraborate. The openings of the resist pattern thus formed were evaluated by observing with a metal microscope. The results obtained are shown in the table. 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). .

(Elongation rate evaluation test)
First, an 18 μm-thick copper foil (manufactured by Furukawa Electric Co., Ltd., GTS-18 (trade name)) was prepared. Next, in Example 1, Reference Example 1 and Comparative Examples 1 to 5, a curable resin composition was applied to one side of the copper foil, dried at 80 ° C. for 20 minutes, and a resin composition having a thickness of 30 μm. A layer was formed. In Example 3, a photosensitive film was laminated on one side of a copper foil using a laminator so that the photosensitive resin composition layer was in contact with the copper foil, and a photosensitive resin composition layer having a thickness of 30 μm. Formed.

Next, in Examples 1 and 3 and Comparative Examples 1 to 5, in order to cure the resin composition, the entire surface of the resin composition layer was irradiated with ultraviolet rays having an exposure amount of 200 mJ / cm ^2. Peeled the PET film. Thereafter, 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) is applied to the resin layer (resist) obtained by curing the resin composition layer on the copper foil. 5 m / min) was used to irradiate 1000 mJ / cm ² of ultraviolet rays, and post-exposure was performed. Further, after heating at 160 ° C. for 1 hour, the copper foil was etched with ammonium persulfate to obtain a cured film.

  In Reference Example 1, in order to cure the resin composition, the copper foil on which the resin composition layer was formed was post-heated at 170 ° C. for 2 hours and then etched with ammonium persulfate. And a cured film was obtained.

  The cured film thus obtained was measured for elongation at room temperature using Autograph AG-100C (manufactured by Shimadzu Corporation). The obtained results are shown in Table 1.

(Measurement of weight loss rate)
With respect to the phosphorus-containing polymer of Synthesis Example 1, phosphate ester (Reophos TPP), melamine polyphosphate (PMP-100), and Al (OH) ₃ (Hydriite H-42M), respectively, under the following conditions in an air atmosphere TG-DTA was measured and the weight loss rate at 350 ° C. was determined. The weight loss rate was evaluated as A when the weight loss rate was 60% or less, B when exceeding 60% and less than 95%, and C when exceeding 95%. . The results are shown in Table 2. In addition, since a highly volatile flame retardant causes bleed-out, the bleed-out is sufficiently suppressed as the weight reduction rate is lower.
Measuring device: TG-DTA 2020 (R) (Bruker AXS Co., Ltd.),
Measurement temperature: 30-350 ° C.
Temperature increase rate: 10 ° C./min.

  As is clear from the results shown in Table 1, when the curable resin composition of Example 1 and Reference Example 1 and the photosensitive film of Example 3 were used, compared to Comparative Examples 1-3, 5 It was confirmed that sufficient flame retardancy can be ensured without using a halide. Moreover, when the curable resin composition of Example 1 and the photosensitive film of Example 3 are used, the resolution of the opening (via hole) is better than that of Comparative Examples 4 to 5. Was confirmed. Furthermore, when the curable resin composition of Example 1 and Reference Example 1 and the photosensitive film of Example 3 are used, a sufficient elongation can be obtained as a cured product as compared with Comparative Examples 4 to 5. It was confirmed that it was possible. In addition, when the curable resin composition of the comparative example 4 was used, although flame retardance was favorable, it was confirmed that resolution and elongation rate fall. Further, as apparent from the results shown in Table 2, the curable resin composition of Example 1 and Reference Example 1 containing the phosphorus-containing polymer of Synthesis Example 1 as a flame retardant and the photosensitive film of Example 3 were used. In this case, it was confirmed that the occurrence of bleed out was sufficiently suppressed.

DESCRIPTION OF SYMBOLS 1 ... Photosensitive film, 2, 3, 4 ... Printed wiring board, 5 ... Photomask, 11 ... Support body, 12 ... Photosensitive resin composition layer, 13 ... Cover film, 21 ... Conductor layer which does not have a circuit pattern, 22 ... Insulating substrate, 23 ... Conductor layer having a circuit pattern, 24 ... Resist layer (photosensitive resin composition layer), 26 ... Opening.

Claims (13)

It is composed of a monomer unit represented by the following general formula (1), 10-80% by mass of a phosphorus-containing polymer which is a homopolymer or copolymer of a monomer having a phosphorus compound structure in the side chain, and a thermosetting agent. A bismaleimide compound, a photopolymerizable compound having an ethylenically unsaturated bond, and a photopolymerization initiator,
The phosphorus-containing polymer has a weight average molecular weight of 1,000 to 1,000,000,
A resin composition which is cured by light and heat.

[In the formula (1), X is a single bond, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, a phenylene group, a divalent group represented by the following general formula (2), and a general formula (3) below. A divalent group, a group containing an ester bond represented by the following general formula (4), or a group containing an ester bond represented by the following general formula (5), wherein R ¹ and R ² are each Independently, it is represented by a hydroxyl group, an aliphatic hydrocarbon group having 1 to 6 carbon atoms, an alkyloxy group having 1 to 3 carbon atoms, an aryl group represented by the following general formula (6), or the following general formula (7). R ³ and R ⁴ each independently represents a hydrogen atom or a methyl group. ]

Wherein (2), ^{L 1} represents an alkylene group having 1 to 3 carbon atoms. ]

Wherein (3), ^{L 2} represents an alkylene group having 1 to 3 carbon atoms. ]

[In Formula (4), a shows the integer of 1-10. ]

[In Formula (5), b shows the integer of 1-10. ]

[In Formula (6), R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 3 carbon atoms, or a hydroxyl group. ]

[In Formula (7), R < ¹⁰ >, R < ¹¹ >, R < ¹² >, R < ¹³ > and R < ¹⁴ > show a hydrogen atom, a C1-C3 aliphatic hydrocarbon group, or a hydroxyl group each independently. ]   The resin composition according to claim 1, further comprising a thermal polymerization initiator.   The resin composition according to claim 1 or 2, which is used for forming a permanent resist.   A prepreg obtained by impregnating the resin composition according to claim 1 or 2 into a base material and forming the resin composition into a B-stage.   The prepreg according to claim 4, wherein the base material is a glass woven fabric.   A metal-clad laminate comprising a metal foil disposed on at least one surface of a substrate made of the prepreg according to claim 4 or 5 and heated and pressed.   A sealing material comprising the resin composition according to claim 1.   A photosensitive film comprising: a support; and a photosensitive resin composition layer comprising the resin composition according to any one of claims 1 to 3 formed on the support. .   The photosensitive film according to claim 8, further comprising a protective film on a surface of the photosensitive resin composition layer opposite to the support.   The insulating substrate and a conductor layer having a circuit pattern formed on the insulating substrate, the multilayer substrate including the insulating substrate, and covering the conductor layer so as to cover the conductor layer. Forming a photosensitive resin composition layer composed of the resin composition described in the above, irradiating a predetermined portion of the photosensitive resin composition layer with an actinic ray to form an exposed portion, and forming the exposed portion of the photosensitive resin composition layer. A method for forming a resist pattern, wherein a portion other than an exposed portion is removed.   A printed wiring board comprising a circuit formed on the metal-clad laminate according to claim 6.   The inner layer circuit board which formed the inner layer circuit, The resin layer which consists of a resin composition as described in any one of Claims 1-3 formed on this inner layer circuit board, and the penetration which penetrates this resin layer A hole, a metal plating layer formed on the inner wall of the through-hole, and a surface of the resin layer opposite to the inner layer circuit board, and electrically connected to the inner layer circuit through the metal plating layer And a circuit conductor connected to the printed wiring board. A printed wiring board comprising an insulating substrate, a conductor layer having a circuit pattern formed on the insulating substrate, and a resist layer formed on the insulating substrate so as to cover the conductor layer,
The said resist layer consists of hardened | cured material of the resin composition as described in any one of Claims 1-3, and has an opening part so that a part of said conductor layer may be exposed. Wiring board.

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