JP5530091B2 - Resin composition for electronic materials - Google Patents

Description

  The present invention relates to a resin composition for electronic materials. More specifically, the present invention relates to a resin composition containing a phosphazene flame retardant which is a non-halogen-containing flame retardant, and particularly relates to a resin composition suitable for a circuit protection film for a circuit board.

  Conventionally, in the field of flexible printed circuit boards, so-called “coverlay films” have been used to protect circuit surfaces. The cover lay film is obtained by applying a thermosetting adhesive having flexibility to a polyimide film. When mounting a component on a protected circuit, a small hole is made in the coverlay film by mold processing and the component is mounted through the hole. Along with the recent miniaturization of mounted components, cases where a coverlay film and a so-called “solder resist” are used in combination are increasing. The solder resist is an acrylic ink-like or film-like material and is patterned with light.

  However, when two types of materials, ie, a coverlay film and a solder resist, are used in combination, the process becomes complicated and the process cost is increased. Accordingly, a material called “photosensitive coverlay” having both functions of a coverlay film and a solder resist has been vigorously developed in recent years.

  On the other hand, since the flexible printed circuit board is used for electronic devices such as mobile phones, high flame resistance is required from the viewpoint of safety. Specifically, it is required to be V-0 or V-1 (VTM-0 or VTM-1 in the case of a thin film) according to UL94 standard (Underwriters Laboratories) which is an international safety standard. The same flame retardancy is also required for the photosensitive coverlay.

  In order to satisfy the high flame retardancy required by the UL94 standard, halogen-based flame retardants have been frequently used in conventional printed circuit board materials. However, due to recent interest in the safety and environmental impact of chemical substances, there is a growing trend to adopt halogen-free materials worldwide. As a typical flame retardant that replaces the halogen flame retardant, a phosphorus flame retardant may be mentioned. However, it is known that the properties of phosphoric acid esters and the like, which are phosphorus-based flame retardants, are significantly deteriorated when blended with a polymer of a printed circuit board material because of their hygroscopicity.

  Similarly, in recent years, phosphazene flame retardants have attracted attention as phosphorus flame retardants. The technique of adding a phosphazene-based flame retardant to an acrylic compound has also been disclosed for use in photosensitive solder resist and photosensitive coverlay (see Patent Documents 1 and 2). In addition, a technique for adding a phosphazene flame retardant to a mixture of polyimide and an acrylic compound has been disclosed (see Patent Documents 3 and 4).

  However, in these technologies, the added phosphazene-based flame retardant is only mixed with an acrylic compound or a polyimide / acrylic compound. It is a problem to liberate and cause so-called “bleed out”.

In order to overcome the problem caused by the phase separation between the resin matrix and the flame retardant, such as “bleed out”, a method of reacting the resin matrix with the flame retardant and immobilizing it is effective. Therefore, a technique using a so-called “reactive phosphazene-based flame retardant” having a polymerizable reactive functional group having an unsaturated bond has recently been studied (see Patent Document 5).
JP 2001-75270 A JP 2002-40633 A JP 2003-177515 A JP 2005-047995 A JP 2003-302751 A

  However, since these “reactive phosphazene flame retardants” have an acryloyl group, a methacryloyl group, or the like which is a polymerizable reactive functional group having an unsaturated bond, the phosphorus concentration in the molecule is low. A decrease in phosphorus concentration reduces flame retardancy. In addition, these reactive functional groups easily undergo a combustion reaction, resulting in a reduction in flame retardancy. As a result, it is necessary to add a large amount of flame retardant in order to impart high flame retardancy satisfying the UL94 standard to the resin composition. Therefore, the matrix resin is diluted with the flame retardant, and the original properties of the matrix resin are significantly impaired.

  Therefore, as a result of intensive studies, the inventors have solved these problems by using a specific phenoxyphosphazene compound as a flame retardant for a resin composition.

The first of the present invention relates to the following resin composition for electronic materials.
[1] A resin composition for electronic materials comprising (A) a phenoxyphosphazene flame retardant and (B) a compound having a photopolymerizable unsaturated double bond, the melting temperature of the (A) phenoxyphosphazene flame retardant Is a resin composition for electronic materials, wherein the average number of functional groups having an unsaturated bond per molecule is 0.1 or less.
[2] A resin composition for electronic materials comprising (A) a phenoxyphosphazene flame retardant and (B) a compound having a photopolymerizable unsaturated double bond, wherein the (A) phenoxyphosphazene flame retardant is The resin composition for electronic materials which is a compound represented by Formula (1).

（Ｒ_１とＲ_２は、互いに同一であっても異なっていてもよく、また繰り返し単位ごとに異なっていてもよいが、水素、メチル基、エチル基、メトキシ基およびエトキシ基からなる群から選択され、一分子中に１つ以上の水素以外の基を含み；ｎは３以上の整数であり、各ベンゼン環は、２つ以上の置換基Ｒ_１またはＲ_２を有していてもよい）

(R ₁ and R ₂ may be the same or different from each other, and may be different for each repeating unit, but are selected from the group consisting of hydrogen, methyl group, ethyl group, methoxy group and ethoxy group. And one or more groups other than hydrogen are contained in one molecule; n is an integer of 3 or more, and each benzene ring may have two or more substituents R ₁ or R ₂ )

  [3] The resin composition for electronic materials according to [1] or [2], which is selected from the group consisting of (C) polyamic acid, (C ′) alkali-soluble resin, and (C ″) an epoxy resin. A resin composition for electronic materials, further comprising at least one kind of resin.

The second of the present invention relates to the following electronic circuit board and the like.
[4] An electronic circuit board obtained by using the resin composition for electronic materials according to any one of [1] to [3].
[5] An electronic circuit board having a resin film formed of a dry film comprising the resin composition for electronic materials according to any one of [1] to [3].
[6] The electronic circuit board according to [4] or [5], which is a printed board.
[7] An electronic / electric apparatus comprising the electronic circuit board according to any one of [4] to [6].

Since the flame retardant used in the resin composition of the present invention is greatly improved in compatibility with the matrix resin, the resin composition of the present invention is a so-called “addition type” flame retardant. At least in general use as a printed circuit board material, problems (bleed out, etc.) due to phase separation between the resin matrix and the flame retardant are not caused.
And since the flame retardant used with the resin composition of this invention does not have the functional group which has the unsaturated bond which reduces a flame retardance substantially, a flame retardance is high enough. Therefore, it is not necessary to add a large amount of flame retardant to the resin composition of the present invention. As a result, a printed circuit board material having excellent characteristics can be obtained, and in particular, a photosensitive coverlay can be provided.

  The characteristics required for the photosensitive coverlay include bending resistance (strip fold resistance), warpage resistance, and insulation reliability in addition to patterning properties by exposure and development. The resin composition of the present invention not only has these excellent characteristics, but can also cause problems when using additive-type flame retardants, such as contamination of the reflow board during solder reflow and migration resistance tests. Problems such as precipitation of flame retardants are also suppressed.

1. Resin Composition of the Present Invention The resin composition of the present invention includes (A) a phenoxyphosphazene flame retardant, and (B) a compound having a photopolymerizable unsaturated double bond.

(A) The phenoxyphosphazene flame retardant is composed of one or more phenoxyphosphazene compounds. The phenoxyphosphazene compound can be represented by the general formula (1). R ₁ and R ₂ in the general formula (1) may be the same or different from each other, and may be different for each repeating unit. N is an integer of 3 or more.

  Although the phenoxyphosphazene compound represented by the general formula (1) is a cyclic compound, the chain phenoxyphosphazene compound represented by the general formula (2) may be mixed with the (A) phenoxyphosphazene flame retardant. Good. Even if it is only a cyclic compound or a mixture with a chain compound, it can be used as a flame retardant.

R ₁ and R ₂ in the general formula (2) may be the same or different, and may be different for each repeating unit. n is an integer of 3 or more. Each benzene ring may have two or more substituents R ₁ or R ₂ .

  Specific examples of the phenoxyphosphazene compound include hexa (phenoxy) cyclotriphosphazenes (for example, CAS No. 53051-41-5) and the like.

When substituents (for example, the substituents R ₁ and R _{2 in} the general formula (1) and the general formula (2)) are introduced into the benzene ring of the phenoxy part of the phenoxyphosphazene compound, the crystallinity and polarity change, and the crystal of the compound , Solubility, compatibility, thermal decomposition resistance, and flame retardancy change.

  For example, when a functional group having an unsaturated bond mainly containing a carbon atom (for example, an acryloyl group or a methacryloyl group) is introduced into the benzene ring of the phenoxy part, the flame retardancy is lowered, which is not preferable as a flame retardant.

  Therefore, the (A) phenoxyphosphazene flame retardant used in the present invention is preferably a phenoxyphosphazene compound which does not substantially contain a functional group having an unsaturated bond. “Substantially free” means that the average number of functional groups having an unsaturated bond contained in one molecule is 0.1 or less.

(A) The presence or absence of a functional group having an unsaturated bond in the flame retardant can be determined from the infrared absorption spectrum of the flame retardant. That is, when there is absorption of unsaturated bonds, for example, absorption having a peak in the vicinity of a wave number of 810 cm ⁻¹ , it can be determined that it has unsaturated bonds. It is also possible to determine the unsaturated bond from the absorption intensity using a known sample having a functional group having an unsaturated bond as a standard sample. Therefore, the number of functional groups having an unsaturated bond per unit amount of the flame retardant can be determined.
On the other hand, the number of molecules per unit amount of the flame retardant can be estimated by quantifying phosphorus atoms by NMR spectrum, atomic absorption analysis or the like, or by combining other measurements. Therefore, the number of functional groups having an unsaturated bond contained in one molecule can be determined.

In addition, when a functional group that enhances crystallinity, such as a cyano group, is introduced into the phenoxyphosphazene compound, compatibility with the resin decreases, which is not preferable. When the compatibility with the resin is lowered, remarkable phase separation occurs in the resin, and desired resin physical properties cannot be obtained.
The degree of crystallinity of the phenoxyphosphazene compound can be determined using the melting temperature as an index. That is, the functional group introduced into the phenoxyphosphazene compound can be selected with reference to the melting temperature. For example, since it can be said that the crystallinity of a compound having a melting temperature exceeding 100 ° C. is particularly high, it is preferable to select the functional group so that the melting temperature becomes 100 ° C. or less, particularly, around 25 ° C. which is room temperature.

  The melting temperature of the phenoxyphosphazene compound can be generally measured by differential scanning calorimetry (DSC) or the like. On the other hand, phenoxyphosphazene compounds have unique thermal properties, and it may be difficult to measure the melting temperature depending on the production conditions of the compounds. For example, in general, when a cyclic phenoxyphosphazene compound is once melted at a high temperature and then rapidly cooled, it becomes a glass state without causing crystallization. Therefore, a clear melting point cannot be obtained. Therefore, it is preferable to measure the melting temperature due to the original crystal of the compound by gradually cooling after melting (for example, the rate of temperature decrease per minute is 10 ° C. or less).

  In addition, even when a functional group that is not a functional group having an unsaturated bond (for example, a functional group with low thermal decomposition resistance such as a long-chain alkyl group) is introduced into the phenoxyphosphazene compound, the thermal decomposition temperature may be lowered. . Lowering the thermal decomposition temperature is not preferable because it ultimately reduces heat resistance when used as an electronic material. The heat resistance can be indicated by using heat decomposition resistance as an index. The thermal decomposition resistance can be expressed by “5% thermogravimetric decrease temperature”, and the 5% thermogravimetric decrease temperature is preferably 340 ° C. or more, more preferably 370 ° C. or more. Using a thermogravimetric measurement device (TG / DTA), the sample weight is measured while raising the temperature from 20 ° C. to 600 ° C. in air at a heating rate of 10 ° C./min, and the sample weight is reduced by 5%. The temperature at that time is the 5% thermogravimetric decrease temperature.

  The 5% thermal weight reduction temperature of the resin composition of the present invention is preferably 340 ° C. or higher, that is, the “10% thermal weight reduction temperature” at which the sample weight further decreases is 370 ° C. to 400 ° C. or higher. Preferably there is. Japanese Patent Application Laid-Open No. 2003-177515 describes that “the 10% thermal weight reduction temperature is preferably between 300 ° C. and 500 ° C. in order to develop flame retardancy” for the thermal weight reduction temperature of the flame retardant. . However, in practice, it has been found that the heat resistance of the resin composition is impaired by thermal decomposition of the flame retardant when the 10% thermogravimetric decrease temperature is about 300 ° C.

From the above, in order to impart appropriate flame retardancy, compatibility, thermal decomposition resistance, etc. to the resin composition, (A) a substituent (general formula (A)) that the phenoxyphosphazene compound contained in the phenoxyphosphazene flame retardant contains 1) and the general formula (substituent R ₁ in 2) and R ₂₎ is preferably a short chain alkoxy group or a short-chain alkyl group; methoxy group or ethoxy group or is preferably a methyl group or an ethyl group; in particular A methoxy group is preferred.

  The short-chain alkoxy group or the short-chain alkyl group may be introduced into the benzene rings of all phenoxy groups contained in the phenoxyphosphazene compound, but is preferably introduced into the benzene rings of some phenoxy groups. This is because the crystallinity of the compound is lowered and the melting temperature is lowered. Of the benzene rings of the phenoxy group of the phenoxyphosphazene compound, 10 to 90% of the benzene rings are preferably introduced with a short-chain alkoxy group or a short-chain alkyl group, and 30 to 70% of the phenoxy group is introduced with a benzene ring. More preferably.

  The phenoxyphosphazene compounds represented by the general formulas (1) and (2) may all have the same number of repeating units n, and the number of different repeating units n (n = 3, 4, 5, 6,. Etc.) may be used. When n is mutually the same, since the crystallinity falls that the one where n is large is preferable. The crystallinity of the compound contained in the mixture of compounds having a different number of repeating units n decreases, and the melting temperature decreases. Thus, a mixture of compounds having different numbers of repeating units n may be preferred.

  Examples of the phenoxyphosphazene compound that can be used in the resin composition of the present invention include phenoxy group and m-tolyloxy group-substituted cyclophosphazene, phenoxy group and p-tolyloxy group-substituted cyclophosphazene, phenoxy group, m-tolyloxy group, and p- Tolyloxy-substituted cyclophosphazenes, phenoxy and m-methoxyphenoxy substituted cyclophosphazenes, phenoxy and p-methoxyphenoxy substituted cyclophosphazenes, phenoxy, m-methoxyphenoxy and p-methoxyphenoxy substituted cyclophosphazenes, and these And the like.

The addition amount of the (A) phenoxyphosphazene flame retardant in the resin composition of the present invention is preferably in the range of 0.1% to 5% as the weight content of phosphorus element with respect to the total weight of the resin composition. A range of 1% to 4% is more preferable. When the phosphorus element conversion content is less than 0.1%, a sufficient flame retardant effect cannot be obtained.
In addition, the weight content of phosphorus element in the (A) phenoxyphosphazene flame retardant is about 10% to about 13%. Therefore, if the phosphorus element equivalent content in the resin composition exceeds 5%, the amount of the (A) flame retardant added exceeds 50% with respect to the total weight of the resin composition, and the resin physical properties are excessively affected.

  Another flame retardant may be further added to the resin composition of the present invention. Although the kind of other flame retardant is not particularly limited, it is usually preferably an organic or inorganic substance other than the halogen-containing organic compound or antimony compound.

  Preferred examples of other flame retardants include aluminum hydroxide, magnesium hydroxide, magnesium carbonate, calcium carbonate, graphite, heat-expandable graphite, melamine, phosphate esters, other phosphazene compounds, ammonium phosphate, 9, Examples include, but are not limited to, adducts of 10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide, silicone compounds, and the like. An organic compound containing a phosphorus atom as a constituent atom has particularly high flame retardancy and exhibits an effect in a small amount. Therefore, sufficient flame retardancy can be obtained without deteriorating the original physical properties of the photosensitive resin, which is more preferable as another flame retardant.

  It is desired that the total content of the flame retardant in the photosensitive resin composition of the present invention is an amount that exhibits the desired flame retardant performance without deteriorating the original physical properties of the resin. The usual total content of a flame retardant is 1-70 mass parts with respect to 100 mass parts of total amounts of a resin component, Preferably it is 1-50 mass parts.

  Examples of the compound (B) having a photopolymerizable unsaturated double bond used in the resin composition of the present invention include monofunctional acrylate compounds and polyfunctional acrylate compounds.

  Examples of monofunctional acrylate compounds include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, phenoxyethyl acrylate, stearyl methacrylate, lauryl acrylate, dicyclopentenyl acrylate, Dicyclopentenyloxyethyl acrylate, dicyclopentanyl acrylate, tetramethylpiperidyl methacrylate, benzyl methacrylate, glycidyl methacrylate, glycerin monomethacrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol (meth) acrylate, methoxypolyethylene glycol mono (meth) Acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, It is included.

  Examples of polyfunctional acrylate compounds include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and 1,3-butylene glycol di (meth). ) Acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl di (meth) acrylate, polypropylene glycol di (meth) acrylate, ethylene oxide modified bisphenol A di (meth) acrylate, ethylene oxide-propylene oxide modified bisphenol A di ( (Meth) acrylate, tetramethylene oxide modified bisphenol A di (meth) acrylate, propylene oxide modified bisphenol A di (meth) acrylate, Propylene oxide-tetramethylene oxide modified bisphenol A di (meth) acrylate, ethylene oxide modified bisphenol F di (meth) acrylate, ethylene oxide-propylene oxide modified bisphenol F di (meth) acrylate, tetramethylene oxide modified bisphenol F di (meth) Acrylate, propylene oxide modified bisphenol F di (meth) acrylate, propylene oxide-tetramethylene oxide modified bisphenol F di (meth) acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, trimethylolpropane triacrylate, trimethylolpropane-propylene oxide Modified triacrylate, ethylene cyanate isocyanurate Side-modified diacrylate, isocyanuric acid ethylene oxide modified diacrylate, glycerin di (meth) acrylate, bifunctional or higher functional (meth) urethane acrylate having an acryloyl group, a urethane (meth) acrylate, and polyester acrylates.

The monofunctional or polyfunctional acrylate compound may be a compound obtained by modifying an epoxy group of an epoxy compound with (meth) acrylic acid, a (meth) acrylate compound having a urethane bond, or the like.
The epoxy compound modified with (meth) acrylic acid is not particularly limited as long as it is an epoxy compound having two or more epoxy groups in one molecule. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl Type epoxy resin, phenol novolak type epoxy resin, o-cresol novolak type epoxy resin, p-cresol novolak type epoxy resin, bisphenol A type novolak epoxy resin, bisphenol F type novolak epoxy resin, biphenyl novolak type epoxy resin, alicyclic epoxy Examples thereof include resins.
Examples of the (meth) acrylate compound having a urethane bond include an addition reaction product of a (meth) acrylic monomer having an OH group at the β-position and an isocyanate compound. Examples of the isocyanate compound include isophorone diisocyanate, 2,6-toluene diisocyanate, 1,6-hexamethylene diisocyanate, EO or PO-modified urethane di (meth) acrylate, and carboxyl group-containing urethane (meth) acrylate. These can be used individually by 1 type or in combination of 2 or more types.

The polyfunctional acrylate may be a compound represented by the formula (3). In the formula (3), R ₃ represents a hydrogen atom or a methyl group, R ₄ represents a hydrogen atom or a monovalent organic group, and l and m each represents an integer of 1 to 5. p represents an integer of 0 to 6, q and r each represents an integer of 0 to 4, and s represents an integer of 0 to 6. The sum of p, q, r, and s is 6, and the sum of p and s is 3-6.

  Of the monofunctional or polyfunctional acrylate compounds, the resin composition of the present invention preferably contains a polyfunctional acrylate, and a compound represented by the formula (3) is particularly preferably used.

  The content of the compound (B) having an unsaturated double bond capable of photopolymerization in the resin composition of the present invention is preferably 10 wt% or more, and more preferably 20 wt% or more.

  The resin composition of the present invention may contain (C) polyamic acid, (C ′) alkali-soluble resin, and (C ″) epoxy resin, depending on the application and required characteristics.

  The (C) polyamic acid contained in the resin composition of the present invention is not particularly limited as long as it is a polyamic acid generally used as a polyimide precursor. The polyamic acid is a polyimide precursor obtained by reacting an acid dianhydride (such as pyromellitic dianhydride) and a diamine compound (such as 1,3-bis (4-aminophenoxy) benzene). .

  Examples of acid dianhydride used as a raw material for polyamic acid include pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetra Carboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 1,1-bis (2,3-dicarboxyl Phenyl) ethane dianhydride, 2,2-bis (2,3-dicarboxylphenyl) ethane dianhydride, 2,2-bis (3,3-dicarboxylphenyl) ethane dianhydride, 2,2-bis [4- (3,4-Dicarboxyphenoxy) phenyl] propane dianhydride, 4,4′-oxydiphthalic anhydride, 2,3,3 ′, 4′-biphenyl ether tetracarboxylic dianhydride, 2, 3,5,6-pyridinetetracarboxylic dianhydride, pyromellitic dianhydride, 3,4,9, 0-perylenetetracarboxylic dianhydride, 2,3,3 ′, 4′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 3,4, And 3 ′, 4′-biphenyltetracarboxylic dianhydride.

  Although it depends on the composition component of the resin composition, preferred examples of the acid dianhydride used as the raw material of the polyamic acid from the viewpoint of compatibility between the polyamic acid and other components include pyromellitic dianhydride, 4,4. Examples include '-oxydiphthalic anhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, 3,4,3 ', 4'-biphenyltetracarboxylic dianhydride, and the like. More preferred examples include pyromellitic dianhydride, 4,4′-oxydiphthalic anhydride, 3,4,3 ′, 4′-biphenyltetracarboxylic dianhydride, and the like.

  On the other hand, aromatic diamine, polyalkylene glycol diamine, alkyl diamine, etc. are mentioned as an example of the diamine compound used as the raw material of polyamic acid. One or two or more diamines may be used in combination to form a raw material diamine.

  Examples of aromatic diamines include 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diamino-3,3 ', 5,5'-tetra Methyldiphenylmethane, 4,4'-diamino-3,3'-diethyl-5,5'-dimethyldiphenylmethane, 4,4'-diaminodiphenyl-2,2'-propane, 4,4'-diaminodiphenylmethane, 3, 4'-diaminobenzanilide, 4,4'-diaminobenzanilide, 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 3,3'-diethyl-4,4'-diaminodiphenyl ether, 3,3 '-Diethoxy-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylpropane, 3,3'-diethyl- 4,4'-diaminodipheny Propane, 3,3′-dimethyl-5,5′-diethyl-4,4′-diaminodiphenylmethane, 3,3′-dimethoxy-4,4′-diaminodiphenyl ether, 3,3′-dimethoxy-4,4 ′ -Diaminodiphenylmethane, 3,3'-dimethoxy-4,4'-diaminodiphenylsulfone, 3,3'-dimethoxy-4,4'-diaminodiphenylpropane, 3,3'-diethoxy-4,4'-diaminodiphenyl Propane, 3,3 ′, 5,5′-tetramethyl-4,4′-diaminodiphenylmethane, 3,3 ′, 5,5′-tetraethyl-4,4′-diaminodiphenylmethane, polytetramethylene oxide-di- p-aminobenzoate, polyethylene oxide-di-p-aminobenzoate, polypropylene oxide-di-p-aminobenzoate, 4,4′-bis (3-aminophenoxy) biphenyl, 4,4′-bis (4-aminophenoxy) ) Biff 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis [3- ( And aminophenoxy) phenoxy] benzene, bis [4- (4-aminophenoxy) phenyl] ether, and 2,2′-bis [4- (4-aminophenoxy) phenyl] propane.

The polyalkylene glycol diamine is represented, for example, by the following general formula (4). In the formula (4), R ₆ represents an aliphatic hydrocarbon group having 1 to ₆ carbon atoms. R ₅ and R ₇ each represents an aliphatic hydrocarbon or polyalkylene glycol having 1 to 6 carbon atoms. j represents an integer of 1 to 30, preferably 2 to 20.

  Examples of polyalkylene glycol diamines include polyethylene glycol diamine, polypropylene glycol diamine, polybutylene glycol diamine, polytetramethylene glycol diamine, polyethylene glycol polypropylene glycol block copolymer diamine, polyethylene glycol polytetramethylene glycol block copolymer Examples thereof include a diamine of a combination, a diamine of a block copolymer of polypropylene glycol polytetramethylene glycol, and a diamine of a block copolymer of polyethylene glycol polypropylene glycol polytetramethylene glycol.

  Preferable examples of the polyalkylene glycol diamine include polypropylene glycol diamine and a diamine of a block copolymer of polypropylene glycol polytetramethylene glycol. Examples of the alkyl diamine include dodecane diamine and hexamethylene diamine.

  (C) Particularly preferred examples of the diamine compound used as a raw material for the polyamic acid include 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis [ 3- (aminophenoxy) phenoxy] benzene, 4,4′-bis (3-aminophenoxy) biphenyl, and polyalkylene glycol diamines such as polypropylene glycol diamine and polybutylene glycol diamine.

  On the other hand, if the diamine compound used as the raw material for the (C) polyamic acid is polyalkylene glycol diamine, improvement in flexibility and warpage of the resulting polyimide can be improved, and low temperature curability can be obtained. Heat resistance may decrease. Therefore, it is usually preferable to copolymerize a polyalkylene glycol diamine and another aromatic diamine compound having heat resistance. The composition ratio (molar ratio) between the polyalkylene glycol diamine and the other diamine compound is preferably 0.05 to 4.9 mol of polyalkylene glycol diamine with respect to 1 mol of the other diamine compound. When the polyalkylene glycol diamine is 5.0 or more (molar ratio) with respect to other diamine compounds, the heat resistance may decrease, which is not preferable. Further, when the molar ratio is 0.05 or more, the flexibility is remarkably improved and the occurrence of warpage can be reduced.

  Polyamic acid is synthesized by a polymerization reaction of the above-described diamine compound and the above-described acid dianhydride. The reaction temperature is usually 10 to 60 ° C., preferably 20 to 55 ° C., and the reaction pressure is not particularly limited. The polyamic acid may be partially imidized. The partially imidized polyamic acid is reacted while being dehydrated at a high temperature of about 100 to 200 ° C., or is synthesized catalytically in order to advance imidization. The reaction time varies depending on the kind of the organic solvent to be used and the reaction temperature, but the time sufficient for the completion of the reaction is usually 2 to 48 hours.

  The content ratio of (C) polyamic acid contained in the resin composition of the present invention is 10 to 90% by mass (in terms of solid content), and preferably 30 to 70% by mass. When the content ratio is 10% by mass or more, solubility by an alkaline solution after exposure in photopatterning is improved, and high resolution can be obtained. Furthermore, the final cured product can be imparted with heat resistance, chemical resistance, electrical insulation, etc., which are characteristic of polyimide. Moreover, by making a content rate into 90 mass% or less, photosensitivity is made to express in a resin composition, energy ray hardening | curing of UV etc. is attained, and the pattern formation by light is attained.

  The (C ′) alkali-soluble resin contained in the resin composition of the present invention is not particularly limited as long as it is soluble in an aqueous alkali solution, and examples thereof include (meth) acrylic acid copolymers. Monomers copolymerizable with (meth) acrylic acid include esters such as (meth) acrylic acid alkyl ester and (meth) acrylic acid hydroxyalkyl ester, acid amides such as (meth) acrylic acid amide, and acrylonitrile. , Styrene, vinylphenol and the like. These can be used individually by 1 type or in combination of 2 or more types. Among these, a copolymer of (meth) acrylic acid and another monomer having a copolymerizable double bond is preferable from the viewpoint of excellent alkali developability.

  The acid value of the (C ′) alkali-soluble resin is preferably 50 to 200 mgKOH / g, and more preferably 60 to 100 mgKOH / g. Within these ranges, developability can be ensured and migration resistance is also good. (C ′) The glass transition temperature of the alkali-soluble resin is preferably 30 to 100 ° C., more preferably 40 to 70 ° C. In such a range, the lamination property is good and the tackiness of the film can be suppressed.

  The weight average molecular weight of the (C ′) alkali-soluble resin is preferably 5,000 to 300,000, and more preferably 10,000 to 150,000. Within this range, good developability and gloss on the film surface can be maintained. This weight average molecular weight is a value measured by gel permeation chromatography and converted to standard polystyrene.

  The content ratio of (C ′) alkali-soluble resin in the resin composition of the present invention is 10 to 90% by mass (in terms of solid content), preferably 30 to 70% by mass. When the content ratio is 10% by mass or more, solubility by an alkaline solution after exposure in photopatterning is improved, and high resolution can be obtained. Moreover, by setting the content ratio to 90% by mass or less, the resin composition can sufficiently exhibit photosensitivity, can be cured with energy rays such as UV, and can be patterned with light.

  The (C ″) epoxy resin contained in the resin composition of the present invention is not particularly limited as long as it is an epoxy compound having two or more epoxy groups in one molecule. For example, bisphenol A type epoxy resin, bisphenol F Type epoxy resin, biphenyl type epoxy resin, phenol novolak type epoxy resin, o-cresol novolak type epoxy resin, p-cresol novolak type epoxy resin, bisphenol A type novolak epoxy resin, bisphenol F type novolak epoxy resin, biphenyl novolak type epoxy resin And alicyclic epoxy resins, and bisphenol type epoxy resins, biphenyl type epoxy resins, and novolac type epoxy resins are preferred. These may be used individually by 1 type and may be used in combination of 2 or more type.

  Examples of the commercially available epoxy resin contained in the resin composition of the present invention include “Epicoat 828”, “Epicoat 1001”, and “Epicoat 1002” (all manufactured by Japan Epoxy Resin Co., Ltd., trade names) and the like. Bisphenol A type epoxy resin; Bisphenol F type epoxy resin such as “Epicoat 807” (trade name, manufactured by Japan Epoxy Resin Co., Ltd.); “EBPS-200” (trade name, manufactured by Nippon Kayaku Co., Ltd.) and “Epiclon EXA-1514” Bisphenol S-type epoxy resin (trade name, manufactured by Dainippon Ink and Chemicals, Inc.).

  Examples of the biphenol type epoxy resin include “YL-6121” (trade name, manufactured by Japan Epoxy Resin Co., Ltd.), and examples of the bixylenol type epoxy resin include “YX-4000” (product name, manufactured by Japan Epoxy Resin Co., Ltd.). Is mentioned.

  Examples of the alicyclic hydrogenated bisphenol A type epoxy resin include “ST-2004” and “ST-2007” (both manufactured by Tohto Kasei Co., Ltd., trade name) and the like. The dibasic acid-modified diglycidyl ether type described above. Examples of the epoxy resin include “ST-5100” and “ST-5080” (both manufactured by Tohto Kasei Co., Ltd., trade names).

  These diglycidyl ether type epoxy compounds have an epoxy equivalent (gram weight of a compound containing 1 equivalent of an epoxy group) of 160 to 3300 in order to improve the developability of the photosensitive resin composition with an alkaline aqueous solution. It is desirable.

  When using an epoxy resin, it is desirable to contain a curing accelerator. Curing accelerators include imidazoles such as 2-methylimidazole, 2-ethyl-4-methylimidazole, and 2-heptadecylimidazole; amines such as triethanolamine, triethylenediamine, and N-methylmorpholine; triphenylphosphine, Organic phosphines such as tolylphosphine; tetraphenylboron salts such as tetraphenylphosphonium tetraphenylborate and triethylammonium tetraphenylborate; 1,8-diaza-bicyclo (5,4,0) undecene-7 and derivatives thereof; naphthene Organic metal salts such as lead acid, lead stearate, zinc naphthenate, tin oleate, manganese naphthenate, cobalt naphthenate, cobalt octylate and the like can be mentioned. These curing accelerators may be used alone or in combination of two or more, and an organic peroxide or an azo compound may be used in combination as necessary.

  The content ratio of the (C ″) epoxy resin contained in the resin composition of the present invention is 5 to 70% by mass (in terms of solid content), and preferably 10 to 50% by mass. When the content ratio is 5% by mass or more, sufficient heat resistance and migration resistance can be obtained. Moreover, by setting the content ratio to 70% by mass or less, the resin composition can sufficiently exhibit photosensitivity, can be cured with energy rays such as UV, and can be patterned with light.

  The photosensitive resin composition of the present invention is a blocked isocyanate compound (compound obtained by adding a blocking agent to an isocyanate group of an isocyanate compound) as a compound that reacts with a carboxyl group contained in (C) or (C ′). It may contain. The blocked isocyanate compound is a compound that is inactive at room temperature but reversibly dissociates when heated to regenerate the isocyanate group.

  The blocked isocyanate compounds include isocyanurate type, biuret type, and adduct type, but isocyanurate type is preferable. These are used alone or in combination of two or more.

  Examples of the blocking agent include at least one compound selected from diketones, oximes, phenols, alkanols, and caprolactams. Specific examples include methyl ethyl ketone oxime and ε-caprolactam.

  Specific examples of the blocked isocyanate include “SUMIDUR BL-3175”, “DESMODULE TPLS-2957”, “TPLS-2062”, “TPLS-2957”, “TPLS-2078”, “BL4165”, “TPLS2117”. , “BL1100”, “BL1265”, “Desmotherm 2170”, “Desmotherm 2265” (manufactured by Sumitomo Bayer Urethane Co., Ltd., trade name), “Coronate 2512”, “Coronate 2513”, “Coronate 2520” (above Nippon Polyurethane) Kogyo Co., Ltd., trade name) etc. are readily available as commercial products. The dissociation temperature of the blocking agent of the blocked isocyanate compound is preferably 120 to 200 ° C.

  The photosensitive resin composition of the present invention preferably contains a photopolymerization initiator. Specific examples of the photopolymerization initiator include benzophenone, Michler's ketone, benzoin, benzoin ethyl ether, benzoin butyl ether, benzoin isobutyl ether, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-phenylacetophenone, and 2-hydroxy. -2-Methylpropiophenone, 2-hydroxy-4-isopropyl-2-methylpropiophenone, 2-ethylanthraquinone, 2-t-butylanthraquinone, diethylthioxanthone, chlorothioxanthone, benzyl, benzyldimethyl ketal, 1-hydroxy Cyclohexyl phenyl ketone, benzoylbenzoic acid, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone -1 Such as 2,4,6-trimethylbenzoyl diphenylphosphine oxide contains.

  Further examples of photopolymerization initiators include equimolar adducts of benzoin and ethylene oxide, 2 to 4 molar additions; equimolar additions of benzoin and propylene oxide, and 2 to 4 molar additions; α- Allyl benzoin; equimolar adduct of 1-hydroxycyclohexyl phenyl ketone and ethylene oxide, 2 to 4 times molar adduct; equimolar adduct of 1-hydroxycyclohexyl phenyl ketone and propylene oxide, and 2 to 4 times molar adduct Benzoylbenzoic acid and ethylene oxide equimolar reactant, 2 to 4 times mole adduct; benzoylbenzoic acid and propylene oxide equimolar reaction, 2 to 4 times mole adduct; hydroxybenzophenone and ethylene oxide equimolar reactant , 2- to 4-fold molar adducts; hydroxybenzophenone and propylene oxide, etc. Reactant, 2- to 4-fold molar adduct; 4- (2-hydroxyethoxy) -phenyl- (2-hydroxy-2-propyl) ketone; 4- (2-acryloxyethoxy) -phenyl- (2-hydroxy 2-propyl) ketone; 4- (2-hydroxyethoxy) -phenyl- (2-hydroxy-2-propyl) ketone and ethylene oxide equimolar reaction product, 2- to 4-fold molar adduct; 4- (2- Hydroxyethoxy) -phenyl- (2-hydroxy-2-propyl) ketone and propylene oxide equimolar reactant, 2-4 fold molar adduct; 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane -1-one; 1- (4-decylphenyl) -2-hydroxy-2-methylpropan-1-one and the like are included. The photopolymerization initiator may be used alone or in combination of two or more.

  Preferred examples of the photopolymerization initiator include diethyl thioxanthone, benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl- 2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2,4,6-trimethylbenzoyldiphenylphosphine oxide and the like are included.

  The resin composition of the present invention may contain a photopolymerization initiation assistant for the purpose of improving the polymerization efficiency. Specific examples of the photopolymerization initiation aid include triethanolamine, diethanolamine, monoethanolamine, tripropanolamine, dipropanolamine, monopropanolamine, ethyl dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and the like. . The photopolymerization initiation assistant may be used alone or in combination of two or more.

  Each content of a photoinitiator and a photoinitiator assistant is 0.05-10% with respect to the weight of the compound which has (B) photopolymerizable unsaturated double bond, Preferably 0.5- 7%, more preferably 0.5 to 5%. By setting the total content of the photopolymerization initiator and the photopolymerization initiation assistant to 0.1% or more, a degree of cure that can achieve the target resolution can be obtained. Further, by setting the total to 20% or less, (B) the degree of polymerization of the photopolymerizable compound having an unsaturated double bond can be adjusted appropriately, and the resolution and flexibility can be controlled. .

  The photosensitive resin composition of the present invention may contain a nitrogen-containing heterocyclic compound. The nitrogen-containing heterocyclic compound has an effect of improving adhesion with a base material such as an electronic circuit board. The nitrogen-containing heterocyclic compound is a compound in which at least one of atoms constituting the heterocyclic ring is a nitrogen atom, and the heterocyclic ring has an aryl group. A nitrogen-containing ring compound may be used independently or may be used in combination of multiple types.

  The heterocyclic ring of the nitrogen-containing heterocyclic compound is preferably a 5-membered ring or a 6-membered ring. Examples of the heterocyclic ring include tetrazole (5-membered ring), imidazole (5-membered ring), triazine (6-membered ring) and the like.

  The aryl group contained in the heterocyclic ring of the nitrogen-containing heterocyclic compound may have a substituent, and examples of the substituent include a hydroxyl group, an alkyl group, an alkoxy group, a formyl group, a carboxyl group, and an amide group. More specific examples include hydroxyl group, methyl group, t-butyl group, methoxy group, ethoxy group, formyl group, carboxyl group, acetamide group and the like. A preferred example of the aryl group that the heterocyclic ring has is a phenyl group.

  Preferred examples of the nitrogen-containing heterocyclic compound include 5-mercapto-1-phenyltetrazole, 1- (3-methylphenyl) -1H-tetrazole-5-thiol, 1- (4-ethoxyphenyl) -1H-tetrazole- 5-thiol, 1- (4-methoxyphenyl) -5-mercaptotetrazole, 1- (4-carboxyphenyl) -5-mercaptotetrazole, 1- (3-acetamidophenyl) -5-mercaptotetrazole, 5-phenyltetrazole 4- (tetrazol-5-yl) benzaldehyde, 5- (4- (t-butyl) phenyl) -2H-1,2,3,4-tetrazole, 5- (3-t-butyl-4-methoxyphenyl) ) -2H-tetrazole, 2- (4-chlorophenyl) -1H-imidazole, 2- (4-fluorophenyl) -1H-imidazole, 4- (1H-imidazol-2-yl) benzoic acid 2,2-phenylimidazole, 2,4-diamino-6-phenyl-1,3,5-triazine, 2,4-diamino-6- (m-toluyl) -1,3,5-triazine, 2, 4-diamino-6- (2,3-xylyl) -1,3,5-triazine, 4′-chlorobenzoguanamine, 3′-trifluoromethylbenzoguanamine and the like are included.

  More preferred examples of the nitrogen-containing heterocyclic compound include 5-mercapto-1-phenyltetrazole, 5-phenyltetrazole, 2-phenylimidazole, 2,4-diamino-6-phenyl-1,3,5-triazine and the like. included.

  The content of the nitrogen-containing heterocyclic compound in the photosensitive resin composition of the present invention is preferably such an amount that does not deteriorate the original physical properties of the resin, and is usually from 0.00 to 100 parts by mass of the solid content of the resin composition. It is 01-10 mass parts, Preferably it is 0.01-5 mass parts.

  The photosensitive resin composition of the present invention usually contains a solvent. The solvent preferably dissolves part or all of the components of the resin composition easily. However, a poor solvent may be included as long as workability (including drying properties) and resin physical properties are not improved or impaired. The content of the solvent in the photosensitive resin composition of the present invention is not particularly limited as long as the workability (including drying properties) and the physical properties of the resin are improved or not impaired. The content of a preferable solvent is 30 to 90% by mass of the photosensitive resin composition, and more preferably 45 to 70% by mass. A solvent having a content in the above range can improve leveling properties when producing a dry film, and can improve the quality of the dry film.

  Examples of solvents are acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, methyl-n-amyl ketone, ketones such as acetonyl acetone, isophorone and acetophenone; ethyl alcohol, isopropyl alcohol, n-butanol, ethylene glycol , Alcohols such as diethylene glycol, triethylene glycol, propylene glycol and hexylene glycol; ethers such as 1,4-dioxane, trioxane, diethyl acetal, 1,2-dioxolane, diethylene glycol dimethyl ether and tetrahydrofuran; ethyl acetate, methyl benzoate , Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl acetate, ethylene glycol Nopropyl acetate, ethylene glycol diacetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol diacetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate Esters such as diethylene glycol diacetate; hydrocarbons such as n-heptane, n-octane, cyclohexane, benzene, toluene, xylene, ethylbenzene and diethylbenzene; dimethyl sulfoxide, N, N-dimethylacetamide, N, N-dimethylformamide , Hexamethyl phosphorami And N, include aprotic polar solvents such as N'- dimethylimidazolidinone.

  Any other solvent may be contained in the photosensitive resin composition as long as the effects of the present invention are not impaired. A solvent may be used independently or may use multiple types together. For example, by mixing a low boiling point solvent and a high boiling point solvent, foaming in a drying process for producing a dry film can be suppressed, and the quality of the dry film can be improved.

2. Dry film A dry film can be produced from the resin composition of the present invention. For example, a dry film is obtained by applying a resin composition having a solid content concentration adjusted to 30 to 90% by mass to a colorless and transparent carrier film having a certain thickness to form a coating film having a certain thickness and then drying it. Get.

  The colorless and transparent carrier film is low density polyethylene, high density polyethylene, polypropylene, polyester, polyethylene terephthalate, polycarbonate, polyarylate, ethylene / cyclodecene copolymer (Mitsui Chemicals, trade name (registered trademark): APEL) ) And the like. Since the photosensitive resin composition is affected by moisture and physical properties and coating conditions, the carrier film is preferably a low moisture-permeable resin film. Therefore, among these, films such as APEL (registered trademark), polyethylene terephthalate, polyethylene, and polypropylene are more preferable.

  The thickness of the carrier film is usually 15 to 100 μm, preferably 15 to 75 μm. A carrier film having a thickness in the above range is excellent in coating property, adhesion, roll property, toughness, cost, and the like. Considering coatability, adhesion, rollability, toughness, cost and the like, a polyethylene terephthalate film having a thickness in the range of 15 to 100 μm, preferably 15 to 40 μm is more preferable.

  Application | coating of the photosensitive resin composition to a carrier film can be performed using well-known means, such as a reverse roll coater, a gravure roll coater, a comma coater, a curtain coater. The coating film may be dried at a temperature of 50 to 200 ° C. (preferably 60 to 150 ° C.) for 0.1 to 30 minutes using a dryer using hot air drying, far infrared rays or near infrared rays. it can.

  A cover film for protecting the photosensitive resin composition layer may be attached to the dry film. The cover film is desirably a low moisture-permeable resin film, like the carrier film, but need not be transparent. Moreover, it is necessary that the cover film can be easily peeled off. Therefore, the adhesive force between the cover film and the photosensitive resin layer is required to be lower than the adhesive force between the carrier film and the photosensitive resin layer.

  Preferably, the cover film is a resin film such as APEL (registered trademark), polyethylene terephthalate, polyethylene and polypropylene having a thickness of 5 to 100 μm.

3. Electronic Circuit Board The resin composition of the present invention can be used as a protective member for an electronic member (particularly an electronic circuit board). For example, the above-mentioned dry film can be bonded to a printed wiring board to form a protective film.

  After peeling the cover film from the dry film, it is superimposed on the surface of the printed wiring board on which the circuit is formed. Further, the photosensitive film can be formed by thermocompression bonding by a known method such as planar pressure bonding or roll pressure bonding. The pressure bonding is usually performed at a pressure of 0.2 to 3 MPa while heating to 40 to 150 ° C., preferably 50 to 120 ° C. When a photosensitive resin layer is formed on a printed wiring board using a vacuum laminator, the embedded state can be improved.

  When the temperature capable of thermocompression bonding is 40 ° C. or higher, it is easy to prevent the occurrence of tack in the alignment before the pressure bonding. When the temperature is 150 ° C. or lower, the excessive curing of the photosensitive resin can be prevented and a sufficient pressure bonding time can be easily obtained. As a result, a large process margin can be obtained. The temperature at which thermocompression bonding is possible is to control the film to such a viscosity that the resin can be sufficiently embedded in the pattern without causing problems such as remaining bubbles and the resin does not flow out of the pattern. Means a possible temperature.

The laminated dry film is exposed through a photomask on which an arbitrary pattern is drawn, and further developed. Thereby, fine holes and fine width lines can be formed in the photosensitive resin layer formed on the printed wiring board. Examples of active energy rays used for exposure include electron beams, ultraviolet rays, and X-rays, and preferably ultraviolet rays. A light source such as a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, or a halogen lamp can be used. The exposure amount is usually 100 to 1000 mJ / cm ² .

  After exposure, development is performed to remove unexposed portions. Development is performed by a dipping method or a spray method. A developer such as an aqueous alkali solution (for example, an aqueous sodium hydroxide solution or an aqueous sodium carbonate solution) can be used. After the development, it is usually washed with water for the purpose of washing the developer. Before washing with water, the developer-containing component may be removed using a dilute aqueous acid solution.

  It is good also as a permanent protective film by converting the photosensitive resin of the pattern part obtained by image development into a hardened | cured material by giving heat processing after image development and water washing. The heat treatment is performed continuously or stepwise at a temperature of 140 to 450 ° C., preferably 150 to 250 ° C., for 0.1 to 5 hours.

  Hereinafter, the present invention will be described in more detail by way of representative examples, but the scope of the present invention is not limited thereto. In the examples and comparative examples, sample evaluation was performed by the following method.

(1) Developability test: A sample for evaluation was obtained by laminating the dry films obtained in Examples and Comparative Examples on a two-layer material of polyimide having a thickness of 25 μm and copper having a thickness of 18 μm. The sample for evaluation was irradiated with UV light through a predetermined mask at an exposure amount of 400 mJ / cm ² . After the exposure, a 1.0% Na ₂ CO ₃ aqueous solution at 30 ° C. was sprayed at a spray pressure of 0.20 MPa to wash away unexposed portions and develop. As a result, when the shape and opening state of the circular opening having a diameter of 200 μm were good, the developability was good, and when there was a resin residue or the like, it was bad.

  (2) Anti-strip test: A base material with a comb-shaped copper circuit of L / S = 50/50 μm was prepared with a two-layer material of polyimide having a thickness of 25 μm and copper having a thickness of 18 μm. The samples for evaluation were obtained by bonding the dry films obtained in Examples and Comparative Examples to the base material. The sample for evaluation was passed through a reflow furnace in an air atmosphere at 260 ° C. in accordance with the later-described (5) reflow test. Then, after peeling off the sample for evaluation from the reflow board, a goblet folding test was performed. Both inner and outer folds were performed under the conditions of a load of 100 g and R = 0.1 mm to make one time. Thereafter, the goby folds were observed with a 40 × microscope, and the number of times until the cracks occurred was taken as the number of goby folds. In order to shorten the test time, the upper limit of the number of goby foldings is 20 times.

  (3) Warpage resistance test: Copper (12 μm) / polyimide (25 μm) / copper (12 μm) three-layer copper-laminated flexible laminate (Neoflex (registered trademark) NFX-2ABEPFE (25T) manufactured by Mitsui Chemicals, Inc.) did. An evaluation sample was obtained in which the dry films obtained in Examples and Comparative Examples were bonded to one side of a polyimide film obtained by etching away the copper foils on both sides of the prepared flexible laminate. The sample for evaluation was cut into 10 cm × 10 cm, and the heights of the four corners of the cut sample were measured with a steel rule and evaluated.

  (4) Elastic modulus measurement: The dry films obtained in Examples and Comparative Examples were pasted on a copper foil that had been subjected to a mold release treatment, peeled after processing, and a film-like sample for evaluation was obtained. A test piece having a width of 15 mm and a length of 15 cm was cut out, a tensile test was performed according to JIS K7127, and the elastic modulus was calculated.

  (5) Reflow test: A comb-shaped polyimide substrate with a copper circuit having a copper thickness of 12 μm and L / S = 35/35 μm was prepared. An evaluation sample was obtained by bonding the dry films obtained in Examples and Comparative Examples to the circuit surface of the polyimide substrate. Reflow furnace (manufactured by Senju Metal Co., Ltd., SX-1508) in which a sample for evaluation was attached to a reflow board (magic resin board) manufactured by Daisho Electronics Co., Ltd. so that the cover surface was in close contact, and peak temperatures were set to 220 ° C. and 260 ° C. ) At a flow rate of 0.4 m / min. After peeling off the sample for evaluation from the reflow board, it was confirmed with a 25 × microscope whether the cover film was peeled off or contaminated on the surface of the reflow board.

  (6) Migration resistance test: A comb-shaped polyimide substrate with a copper circuit having a copper thickness of 12 μm and L / S = 35/35 μm was prepared. The dry film obtained in the example and the comparative example was bonded to the circuit surface of the polyimide substrate to obtain a sample for evaluation. Under 85 ° C. and 85% RH, current was passed for 1000 hours at 30 VDC, and the resistance value after 1000 hours and the surface state (whether something was deposited on the surface) were confirmed.

  (7) Flame retardancy test: Evaluated according to the method of UL94 thin vertical combustion test. A copper (12 μm) / polyimide (25 μm) / copper (12 μm) three-layer copper-laminated flexible laminate (Neoflex (registered trademark) NFX-2ABEPFE (25T) manufactured by Mitsui Chemicals, Inc.) was prepared. The sample for evaluation was prepared and evaluated by bonding the dry films (thickness 30 μm) obtained in Examples and Comparative Examples on both sides of the polyimide film obtained by etching away the copper foils on both sides of the prepared flexible laminate.

The phosphazene compounds used in Examples and Comparative Examples were synthesized according to the procedures of Synthesis Examples 1 to 6 below. The obtained phosphazene compound is based on the results of measurement of ¹ H-NMR spectrum and ³¹ P-NMR spectrum, analysis of elemental chlorine (residual chlorine) by potentiometric titration method using silver nitrate after alkali melting, and TOF-MS analysis. Identified.

[Synthesis Example 1]
(Synthesis of cyclophosphazene compound substituted with phenoxy group, p-tolyloxy group and m-tolyloxy group)
In a 5 L separable flask, a stirrer, a reflux condenser, a dropping funnel and a nitrogen introducing tube were installed. Under a nitrogen atmosphere, a chlorocyclophosphazene oligomer (molecular formula [PNCl ₂ ] _n , where n is a mixture of 3 to 8 and the ratio of n = 3: n = 4: n = 5-8 is 75: 18: 7 348 g of a mixture), 1,000 g of tetrahydrofuran (manufactured by Kishida Chemical Co., Ltd., reagent), and 145 g of metal sodium (manufactured by Kanto Chemical Co., Ltd., reagent) were charged into the flask. While stirring it, 292 g of phenol (made by Kishida Chemical Co., Ltd., reagent), 195 g of p-cresol (made by Kanto Chemical Co., Ltd., reagent) and 130 g of m-cresol (made by Kanto Chemical Co., Ltd., reagent) A 500 g solution was added dropwise at 0 ° C. over 3 hours. Thereafter, the internal temperature was raised to 50 ° C. The reaction was stirred at 50 ° C. for 6 hours, and then cooled to room temperature. After cooling, 800 g of toluene (manufactured by Kishida Chemical Co., Ltd., reagent) and 600 g of water are added and separated, and the organic layer is washed with 400 g of water three times and concentrated under reduced pressure, whereby a phenoxy group and a p-tolyloxy group are obtained. And 722g (yield 98%) of cyclophosphazene compounds substituted with m-tolyloxy group were obtained. The analysis result of this product was as follows.

¹ H-NMR spectrum (300 MHz, CDCl ₃ , δ, ppm): 2.4 (3H, m), 6.5 to 7.1 (9H, m)
³¹ P-NMR spectrum (120 MHz, CDCl ₃ , δ, ppm): −16.8, −12.2, 9.4
MS (MALDI-TOF) m / z: 1255, 1010, 750, 736, 721
Residual chlorine analysis: <0.01%

From the above analysis results, the product obtained in this step is a mixture of cyclophosphazene compounds whose average composition is [NP (OC ₆ H ₅ ) _1.0 (OC ₆ H ₄ Me) _1.0 ]. I confirmed that there was.

[Synthesis Example 2]
(Synthesis of cyclophosphazene compound substituted with phenoxy group and m-tolyloxy group)
In a 5 L separable flask, a stirrer, a reflux condenser, a dropping funnel and a nitrogen introducing tube were installed. Under a nitrogen atmosphere, 348 g of hexachlorocyclotriphosphazene, 1,000 g of acetonitrile (manufactured by Kishida Chemical Co., Ltd., reagent), 414 g of phenol and 260 g of m-cresol were charged into a flask. While stirring at 10 ° C. with cooling, 668 g of triethylamine (manufactured by Kishida Chemical Co., Ltd., reagent) was added dropwise over 1 hour. Thereafter, the internal temperature was raised to 83 ° C. The mixture was refluxed for 9 hours and then cooled to room temperature. After cooling, 800 g of toluene and 600 g of water were added, and the mixture was separated. The organic layer was washed with 400 g of water three times and concentrated under reduced pressure to obtain 693 g of cyclophosphazene compound substituted with a phenoxy group and an m-tolyloxy group (recovery). Rate 96%). The analysis result of this product was as follows.

¹ H-NMR spectrum (300 MHz, CDCl ₃ , δ, ppm): 2.4 (6H, s), 6.6 to 7.3 (28 H, m)
³¹ P-NMR spectrum (120 MHz, CDCl ₃ , δ, ppm): 9.8
MS (MALDI-TOF) m / z: 750, 736, 721
Residual chlorine analysis: <0.01%

From the above analysis results, the products obtained in this step are [N ₃ P ₃ (OC ₆ H ₄ Me) (OPh) ₅ ], [N ₃ P ₃ (OC ₆ H ₄ Me) ₂ (OPh) ₄ ] and [N ₃ P ₃ (OC ₆ H ₄ Me) ₃ (OPh) ₃ ], the average composition of which is [N ₃ P ₃ (OC ₆ H ₄ Me) _2.0 (OPh) _{4. 0} ] was confirmed to be a mixture of cyclophosphazene compounds.

[Synthesis Example 3]
(Synthesis of cyclophosphazene compound substituted with phenoxy group and p-methoxyphenoxy group)
In a 5 L separable flask, a stirrer, a reflux condenser, a dropping funnel and a nitrogen introducing tube were installed. Under a nitrogen atmosphere, a chlorocyclophosphazene oligomer (molecular formula [PNCl ₂ ] _n , where n is a mixture of 3 to 8 and the ratio of n = 3: n = 4: n = 5-8 is 75: 18: 7 348 g of a mixture), 600 g of dimethylformamide (manufactured by Kishida Chemical Co., Ltd., reagent), and 414 g of potassium carbonate (manufactured by Kishida Chemical Co., Ltd., reagent) were charged into a flask. While stirring at 60 ° C., a solution of 292 g of phenol in 200 g of dimethylformamide was added dropwise over 2 hours, and then a solution of 385 g of p-methoxyphenol (made by Kishida Chemical Co., Ltd., reagent) in 300 g of dimethylformamide was added for 1 hour. It was dripped over. Thereafter, the mixture was stirred at an internal temperature of 60 ° C. for 6 hours and then cooled to room temperature. After cooling, 800 g of toluene (manufactured by Kishida Chemical Co., Ltd., reagent) and 1,400 g of water were added, followed by liquid separation, and the organic layer was washed with 400 g of water three times and concentrated under reduced pressure, whereby 769 g (yield 98%) of a cyclophosphazene compound substituted with a methoxyphenoxy group was obtained. The analysis result of this product was as follows.

¹ H-NMR spectrum (300 MHz, CDCl ₃ , δ, ppm): 3.9 (3H, m), 6.4 to 7.1 (9H, m)
³¹ P-NMR spectrum (120 MHz, CDCl ₃ , δ, ppm): −16.6, −12.1, 9.9
MS (MALDI-TOF) m / z: 1246,984,814,784,754
Residual chlorine analysis: <0.01%

From the above analysis results, the product obtained in this step is a mixture of cyclophosphazene compounds whose average composition is [NP (OC ₆ H ₅ ) _1.0 (OC ₆ H ₄ OMe) _1.0 ]. I confirmed that there was.

[Synthesis Example 4]
(Synthesis of cyclophosphazene compounds substituted with phenoxy groups)
In a 5 L separable flask, a stirrer, a reflux condenser, a dropping funnel and a nitrogen introducing tube were installed. Under a nitrogen atmosphere, a chlorocyclophosphazene oligomer (molecular formula [PNCl ₂ ] _n , where n is a mixture of 3 to 8 and the ratio of n = 3: n = 4: n = 5-8 is 75: 18: 7 348 g of a mixture) and 1,000 g of tetrahydrofuran were charged into a flask. While stirring it, sodium phenoxide prepared by dissolving 621 g of phenol and 260 g of sodium hydroxide (manufactured by Kanto Chemical Co., Ltd., reagent) in 650 g of water and drying under reduced pressure was added in portions over 3 hours. After refluxing, it was cooled to room temperature. After cooling, 800 g of toluene (manufactured by Kishida Chemical Co., Ltd., reagent) and 900 g of water are added and separated, and the organic layer is washed with 400 g of water three times and concentrated under reduced pressure to substitute the phenoxy group-substituted cyclophosphazene compound. 675 g (97% yield) was obtained. The analysis result of this product was as follows.

¹ H-NMR spectrum (300 MHz, CDCl ₃ , δ, ppm): 6.7 to 7.1 (10H, m)
³¹ P-NMR spectrum (120 MHz, CDCl ₃ , δ, ppm): −16.9, −16.8, −11.3, 9.9
MS (MALDI-TOF) m / z: 1388, 1156, 925, 694
Residual chlorine analysis: <0.01%

From the above analysis results, it was confirmed that the product obtained in this step was a mixture of cyclophosphazene compounds whose composition was [NP (OC ₆ H ₅ ) ₂ ].

[Synthesis Example 5]
(Synthesis of cyclophosphazene compound substituted with phenoxy group and p-cyanophenoxy group)
In a 5 L separable flask, a stirrer, a reflux condenser, a dropping funnel and a nitrogen introducing tube were installed. Under a nitrogen atmosphere, 348 g of hexachlorocyclotriphosphazene, 800 g of acetone (manufactured by Kishida Chemical Co., Ltd., reagent), 292 g of phenol and 357 g of p-cyanophenol (manufactured by Tokyo Chemical Industry Co., Ltd., reagent) were charged into the flask. While stirring it at 0 ° C. with cooling, 617 g of triethylamine was added dropwise over 1 hour. Thereafter, the internal temperature was raised to the reflux temperature. After refluxing for 12 hours, the mixture was cooled to room temperature. After cooling, 600 g of methanol (manufactured by Kishida Chemical Co., Ltd., reagent) was added, and the deposited precipitate was filtered and dried under reduced pressure to obtain 760 g (yield) of a cyclophosphazene compound substituted with a phenoxy group and a p-cyanophenoxy group. 99%). The analysis result of this product was as follows.

¹ H-NMR spectrum (300 MHz, CDCl ₃ , δ, ppm): 6.8-7.5 (9H, m)
³¹ P-NMR spectrum (120 MHz, CDCl ₃ , δ, ppm): 9.1
MS (MALDI-TOF) m / z: 1330, 1075, 793, 769, 743
Residual chlorine analysis: <0.01%

From the above analysis results, the product obtained in this step is a mixture of cyclophosphazene compounds whose average composition is [NP (OC ₆ H ₅ ) _1.0 (OC ₆ H ₄ CN) _1.0 ]. I confirmed that there was.

[Synthesis Example 6]
(Synthesis of cyclophosphazene compound substituted with 2- (methacryloyloxy) ethyloxy)
In a 5 L separable flask, a stirrer, a reflux condenser, a dropping funnel and a nitrogen introducing tube were installed. Under a nitrogen atmosphere, 348 g of hexachlorocyclotriphosphazene, 900 g of tetrahydrofuran, and 158 g of sodium hydride (manufactured by Kanto Chemical Co., Ltd., reagent) thoroughly washed with heptane were charged into the flask. While stirring it at 0 ° C., a solution of 94 g of phenol in 50 g of tetrahydrofuran was added dropwise over 1 hour, and subsequently, 716 g of 2-hydroxyethyl methacrylate (manufactured by Kishida Chemical Co., Ltd., reagent) was added dropwise over 2 hours. Then, it stirred at internal temperature 0 degreeC for 6 hours. After the reaction, 800 g of toluene and 1,400 g of water were added, liquid separation was performed, and the organic layer was washed with 400 g of water three times and concentrated under reduced pressure to replace the cyclophosphazene compound substituted with phenoxy group and 2- (methacryloyloxy) ethyloxy. 824 g (yield 95%) was obtained. The analysis result of this product was as follows.

¹ H-NMR spectrum (300 MHz, CDCl ₃ , δ, ppm): 1.9 (15 H, m), 4.2 (10 H, m), 4.6 (10 H, m), 5.6 (5 H, m ), 6.2 (5H, m), 6.7-7.1 (5H, m)
³¹ P-NMR spectrum (120 MHz, CDCl ₃ , δ, ppm): 12.0 (2P, m), 19.7 (2P, m)
MS (MALDI-TOF) m / z: 898, 864, 830
Residual chlorine analysis: <0.01%

From the above analysis results, the products obtained in this step are {N ₃ P ₃ [OC ₂ H ₄ OCOC (CH ₃ ) = CH ₂ ] ₄ (OPh) ₂ }, {N ₃ P ₃ [OC ₂ H ₄ OCOC (CH ₃ ) ═CH ₂ ] ₅ (OPh)} and {N ₃ P ₃ [OC ₂ H ₄ OCOC (CH ₃ ) ═CH ₂ ] ₆ }, the average composition of which is {N ₃ It was confirmed to be a mixture of cyclophosphazene compounds of P ₃ [OC ₂ H ₄ OCOC (CH ₃ ) ═CH ₂ ] _5.0 (OPh) _1.0 }.

  The number of unsaturated bonds is determined by setting a silicon wafer with a flame retardant sandwiched in an infrared absorption measurement device, and performing infrared absorption measurement. From the absorption strength of unsaturated bonds, the number of functional groups having unsaturated bonds Asked. The liquid flame retardant was sandwiched between silicon wafers as it was; the solid flame retardant was mixed with liquid paraffin, pulverized with milk dust, and sandwiched between silicon wafers. When the flame retardant was sandwiched between silicon wafers, the sample thickness was adjusted with a spacer.

[Example 1]
(Formulation of resin composition)
As a flame retardant, 20.0 g of methoxy group-introduced phenoxycyclophosphazene synthesized in Synthesis Example 3, and dipentaerythritol hexa / pentaacrylate (trade name; Aronix M-402, manufactured by Toagosei Co., Ltd.) as a photopolymerizable compound. ) 16.7 g, 30.0 g of acid-modified bisphenol A acrylate (product name; Kayrad ZAR-1035, manufactured by Nippon Kayaku Co., Ltd.), 27.7 g of N, N′-dimethylacetamide as a solvent, and a photopolymerization initiator 1.9 g of diethylthioxanthone (manufactured by Nippon Kayaku Co., Ltd., Kayacure DETX-S), and ethyl p-dimethylaminobenzoate (manufactured by Nippon Kayaku Co., Ltd., Kayacure EPA) 3 as a photopolymerization initiation assistant 0.7 g was added. The mixture was stirred for 30 minutes to obtain a brown viscous liquid having a viscosity of about 0.3 Pa · s.

(Manufacture of dry film)
The obtained photosensitive resin solution was applied to a carrier film (polyethylene terephthalate film: M5001 manufactured by Toyobo Co., Ltd.) having a width of 30 cm and a thickness of 19 μm using an applicator, and the coating film was 100 ° C. in a hot air circulating drying furnace. X Dried for 8 minutes. A 30 μm-thick cover film (polyethylene film: GF-130, manufactured by Tamapoly Co., Ltd.) was bonded to the formed photosensitive resin film to obtain a dry film.

(Performance evaluation)
The cover film is peeled off from the produced dry film, and aligned with each substrate as described in each evaluation test. After that, with a vacuum laminator (MVLP600 vacuum laminator manufactured by Meiki Seisakusho), a press temperature of 60 ° C. The sample for evaluation was obtained by pressure bonding at a pressure of 0.5 MPa for 60 seconds.
UV light was irradiated through a predetermined mask at an exposure amount of 400 mJ / cm ² . After the exposure, a 1.0% Na ₂ CO ₃ aqueous solution at 30 ° C. was sprayed at a spray pressure of 0.20 MPa to wash away unexposed portions and develop. Next, it was washed with water, dried, put into a 160 ° C. hot air circulating furnace for 60 minutes, and cured by heating.
Each of the obtained samples for evaluation was subjected to a warp resistance test, a goby folding test, and a flame retardance test. The developability was good. The number of goby folding was 20 times. The amount of warpage was a comparatively low average value of the heights of the four corners of 13 mm, and the flame retardancy was a result of conforming to the VTM-0 standard.

[Comparative Example 1]
Samples for evaluation were obtained in the same manner as in Example 1, except that the flame retardant was cyano group-introduced phenoxycyclophosphazene synthesized in Synthesis Example 5. The obtained sample for evaluation was evaluated. The developability was poor. The number of goby folds was 10. The amount of warpage could not be measured and became curled. The flame retardancy was a result that conformed to the VTM-0 standard. Although the flame retardancy was good, the other physical properties were inferior to those of Example 1.

[Example 2]
(Synthesis of polyamic acid (Synthesis Example A))
In a 3 L separable flask, a stirrer, a Dean-Stark tube, a reflux condenser, a 200 ml dropping funnel, and a nitrogen-introducing tank were installed. Under a nitrogen atmosphere, 1223.7 g of N-methylpyrrolidone (manufactured by Tokyo Chemical Industry Co., Ltd., reagent), 524.4 g of mesitylene (manufactured by Kanto Chemical Co., Ltd., reagent), oxydiphthalic dianhydride (manufactured by Manac Co., Ltd.) 434 .3g was charged to the flask. While stirring it, 303.5 g of terminal aminated poly (propylene glycol-tetramethylene glycol copolymer) (manufactured by Huntsman Corporation; trade name: Jeffamine XTJ542) and 114.9 g of 1,12-diaminododecane were increased. The solution was added dropwise over 1 hour under temperature. Thereafter, the internal temperature was raised to 180 ° C. After refluxing at 180 ° C. for 4 hours, the mixture was cooled to room temperature. After cooling, 109.3 g of 1,3-bis (3-aminophenoxy) benzene (manufactured by Mitsui Chemicals, Inc.) was added. After the addition, stirring was continued in a nitrogen atmosphere for 20 hours to obtain a partially imidized polyamic acid solution (Synthesis Example A) having a solid content of 35% by mass.

(Formulation of resin composition)
As a flame retardant, 9.0 g of methyl group-introduced phenoxycyclophosphazene synthesized in Synthesis Example 1 and dipentaerythritol hexa / pentaacrylate (trade name; Aronix M-402, manufactured by Toagosei Co., Ltd.) as a photopolymerizable compound ) 11.0 g, 73.3 g of the polyamic acid of Synthesis Example A as the polyamic acid, 5.4 g of N, N′-dimethylacetamide as the solvent, and diethylthioxanthone (Nippon Kayaku Co., Ltd.) as the photopolymerization initiator 0.4 g of Kayacure DETX-S) and 0.9 g of ethyl p-dimethylaminobenzoate (manufactured by Nippon Kayaku Co., Ltd., Kayacure EPA) were added as a photopolymerization initiation aid. The mixture was stirred for 30 minutes to obtain a brown viscous liquid (photosensitive resin solution) having a viscosity of about 0.5 Pa · s.

(Manufacture of dry film)
The obtained photosensitive resin solution was applied to a carrier film (polyethylene terephthalate film: M5001 manufactured by Toyobo Co., Ltd.) having a width of 30 cm and a thickness of 19 μm using an applicator, and then dried in a hot air circulating drying oven at 100 ° C. for 8 minutes. did. A 30 μm-thick cover film (polyethylene film: GF-130, manufactured by Tamapoly Co., Ltd.) was bonded to the formed photosensitive resin film to obtain a dry film.

(Performance evaluation)
The cover film is peeled off from the produced dry film, and aligned with each substrate as described in each evaluation test. After that, with a vacuum laminator (MVLP600 vacuum laminator manufactured by Meiki Seisakusho), a press temperature of 60 ° C. The sample for evaluation was obtained by pressure bonding at a pressure of 0.5 MPa for 60 seconds.
UV light was irradiated through a predetermined mask at an exposure amount of 400 mJ / cm ² . After the exposure, a 1.0% Na ₂ CO ₃ aqueous solution at 30 ° C. was sprayed at a spray pressure of 0.20 MPa to wash away unexposed portions and develop. Next, it was washed with water, dried, put into a 160 ° C. hot air circulating furnace for 60 minutes, and cured by heating.
Each of the obtained samples for evaluation was subjected to a developability test, a warp resistance test, a gouge folding test, an elastic modulus measurement (tensile test), a reflow test, a migration test, and a flame retardance test. The developability was good. The number of goby folding was 20 times. The amount of warpage was very good with the average value of the height of the four corners being 0 mm. When the elastic modulus was measured, it was a very low value of 0.3 GPa. In the reflow test, no contamination was observed at a low temperature (220 ° C.) and good results were obtained. However, white precipitates were observed on the reflow board at a high temperature (260 ° C.), and contamination was observed. After the migration test, no precipitate was seen on the substrate surface, which was a good result. The flame retardancy was also a result conforming to the VTM-0 standard.

[Examples 3 and 4, Comparative Examples 2 to 4]
Each evaluation sample was obtained in the same manner as in Example 2 except that the flame retardant was changed as shown in Tables 2 and 3. In particular, in Comparative Examples 3 and 5 using a flame retardant having a high melting temperature, developability was poor. In Comparative Example 2 and Comparative Example 3 using a flame retardant having a high melting temperature, the results of remarkably inferior warping resistance test and gond folding resistance test were observed. This is presumably because the low elastic modulus that can be exhibited if the compatibility is good is not achieved because the flame retardant has low compatibility. Moreover, when the substrate surface after the migration test was observed, in Comparative Example 2 and Comparative Example 3, fine crystalline precipitates were observed. In addition, when a flame retardant containing a polymerizable reactive functional group (methacryloyl group) is added (Comparative Example 4), the results of the goblet fold resistance test and warpage resistance test are very poor, and the flame resistance is remarkably low. It was.

[Example 5]
(Synthesis of polyamic acid (Synthesis Example B))
A stirrer, a Dean-Stark tube, a reflux condenser, a 200 ml dropping funnel, and a nitrogen inlet were installed in a 3 L separable flask. Under a nitrogen atmosphere, N-methylpyrrolidone (Tokyo Kasei Co., Ltd., reagent) 1216.7 g, mesitylene (Kanto Chemical Co., Ltd., reagent) 521.5 g, oxydiphthalic dianhydride (manac Co., Ltd.) 434 .3g was charged to the flask. While stirring it, 75.9 g of terminal aminated polypropylene glycol (manufactured by Huntsman Corporation, trade name: Jeffamine D400) and terminal aminated poly (propylene glycol-tetramethylene glycol copolymer) (manufactured by Huntsman Corporation, product) Name: Jeffamine XTJ542) 227.6 g and 1,12-diaminododecane 56.2 g were added dropwise over 1 hour at elevated temperature. Thereafter, the internal temperature was raised to 180 ° C. After refluxing at 180 ° C. for 4 hours, the mixture was cooled to room temperature. After cooling, 153.3 g of 1,3-bis (3-aminophenoxy) benzene (manufactured by Mitsui Chemicals, Inc.) was added. After the addition, stirring was continued in a nitrogen atmosphere for 20 hours to obtain a partially imidized polyamic acid solution (Synthesis Example B) having a solid content of 35% by mass.

  Using the polyamic acid as the polyamic acid of Synthesis Example B, resin compositions having the composition components shown in Table 2 were obtained. From the obtained resin composition, a dry film was produced in the same manner as in Example 1, and each evaluation sample was produced and evaluated.

[Comparative Example 5]
Using the polyamic acid as the polyamic acid of Synthesis Example B, resin compositions having the composition components shown in Table 3 were obtained. From the obtained resin composition, a dry film was produced in the same manner as in Example 1, and each evaluation sample was produced and evaluated.

  Compared with Comparative Example 5, Example 5 had good numerical values for the goblet folding test and warpage resistance test. Moreover, the resistance value at the time of a migration test was also high, and precipitation on the surface after the test was not seen, and a good result was obtained.

  The compositions and evaluation results of the resin compositions obtained in each Example and each Comparative Example are summarized in Table 2 and Table 3.

[Example 6]
(Synthesis of polyamic acid (Synthesis Example C))
The same equipment as in Synthesis Example B was used except that the flask was a 300 mL separable flask. Under a nitrogen atmosphere, 106.7 g of N-methylpyrrolidone, 45.7 g of mesitylene, and 45.8 g of pyromellitic dianhydride (manufactured by Mitsubishi Gas Chemical Co., Inc.) were charged into the flask. While stirring it, 12.3 g of terminal aminated polypropylene glycol (trade name; Jeffamine D400, manufactured by Huntsman Corporation) and 11.0 g of terminal aminated polypropylene glycol (trade name; Jeffamine D230, manufactured by Huntsman Corporation) And 36.8 g of terminal aminated poly (propylene glycol-tetramethylene glycol copolymer) (manufactured by Huntsman Corporation, trade name: Jeffamine XTJ542) were added dropwise over 1 hour at an elevated temperature. Thereafter, the internal temperature was raised to 180 ° C. After refluxing at 180 ° C. for 4 hours, the mixture was cooled to room temperature. After cooling, 18.6 g of 4,4′-diaminodiphenyl ether (manufactured by JFE Chemical Co., Ltd.) was added. After the addition, stirring was continued for 20 hours under a nitrogen atmosphere to obtain a partially imidized polyamic acid solution (Synthesis Example C) having a solid content of 45% by mass.

  Using the polyamic acid of Synthesis Example C, a resin composition having the composition components of Example 6 shown in Table 5 was obtained. From the obtained resin composition, a dry film was produced in the same manner as in Example 1, and each evaluation sample was produced and evaluated.

[Examples 7 to 14]
(Synthesis of polyamic acid (Synthesis Examples D to G)
A polyamic acid was synthesized in the same manner as in Synthesis Example C using the raw material composition shown in Table 4. Using the polyamic acids of Synthesis Examples D to G, resin compositions having the composition components shown in Tables 5 and 6 were obtained. From the obtained resin composition, a dry film was produced in the same manner as in Example 1, and each evaluation sample was produced and evaluated.

ＰＭＤＡ：ピロメリット酸二無水物（三菱瓦斯化学製）
ＢＰＤＡ：３,４,３',４'-ビフェニルテトラカルボン酸二無水物（宇部興産製）
ＯＤＰＡ：３,４,３',４'−オキシジフタル酸無水物（マナック製）
ＸＴＪ５４２：ジェファーミンＸＴＪ５４２（ハンツマン製）
Ｄ２３０：ジェファーミンＤ２３０（ハンツマン製）
Ｄ４００：ジェファーミンＤ４００（ハンツマン製）
ＯＤＡ：４,４'-ジアミノジフェニルエーテル（ＪＦＥケミカル製）
ＡＰＢ：１,３-ビス（３-アミノフェノキシ）ベンゼン（三井化学製）

PMDA: pyromellitic dianhydride (Mitsubishi Gas Chemical)
BPDA: 3,4,3 ′, 4′-biphenyltetracarboxylic dianhydride (manufactured by Ube Industries)
ODPA: 3,4,3 ′, 4′-oxydiphthalic anhydride (manac)
XTJ542: Jeffermin XTJ542 (manufactured by Huntsman)
D230: Jeffermin D230 (manufactured by Huntsman)
D400: Jeffermin D400 (manufactured by Huntsman)
ODA: 4,4'-diaminodiphenyl ether (manufactured by JFE Chemical)
APB: 1,3-bis (3-aminophenoxy) benzene (Mitsui Chemicals)

アロニックスＭ-４５０：ペンタエリスリトールペンタアクリレート／テトラアクリレート混合物（東亞合成製）
カヤラッドＴＰＡ３２０：トリメチロールプロパン−プロピレンオキサイド変性トリアクリレート（日本化薬製）
ＦＡ-３２１Ｍ：エチレンオキサイド変性ビスフェノールＡジメタクリレート（日立化成製）
光重合開始剤１：カヤキュアＤＥＴＸ-Ｓ（日本化薬製）
光重合開始剤２：ルシリンＴＰＯ（BASF製）
光開始助剤：カヤキュアＥＰＡ（日本化薬製）
含窒素複素環化合物：２-フェニルイミダゾール（和光純薬製）

Aronix M-450: Pentaerythritol pentaacrylate / tetraacrylate mixture (Toagosei Co., Ltd.)
Kayrad TPA320: Trimethylolpropane-propylene oxide modified triacrylate (Nippon Kayaku)
FA-321M: Ethylene oxide modified bisphenol A dimethacrylate (manufactured by Hitachi Chemical)
Photopolymerization initiator 1: Kayacure DETX-S (Nippon Kayaku)
Photoinitiator 2: Lucillin TPO (manufactured by BASF)
Photoinitiator aid: Kayacure EPA (Nippon Kayaku)
Nitrogen-containing heterocyclic compound: 2-phenylimidazole (manufactured by Wako Pure Chemical Industries)

（Ｃ’）アルカリ可溶性樹脂：メタクリル酸／アクリル酸エチル／メタクリル酸メチル／スチレン（質量比：１４／３８／３８／１０）の共重合体の、トルエン／メチルセロソルブ（質量比＝２／３）溶液（重量平均分子量：７万、酸価：９０ｍｇＫＯＨ／ｇ）
エピコート８０７：ビスフェノールF型エポキシ樹脂（ジャパンエポキシレジン製）
ブロック化イソシアネート化合物（ＢＬ３１７５）：ヘキサメチレンジイソアシアネートのイソシアヌレート体をメチルエチルケトンオキシムでブロックした化合物（住化バイエルウレタン社製）

(C ′) Alkali-soluble resin: Toluene / methyl cellosolve (mass ratio = 2/3) of a copolymer of methacrylic acid / ethyl acrylate / methyl methacrylate / styrene (mass ratio: 14/38/38/10) Solution (weight average molecular weight: 70,000, acid value: 90 mgKOH / g)
Epicoat 807: Bisphenol F type epoxy resin (made by Japan Epoxy Resin)
Blocked isocyanate compound (BL3175): A compound obtained by blocking the isocyanurate of hexamethylene diisocyanate with methyl ethyl ketone oxime (manufactured by Sumika Bayer Urethane Co., Ltd.)

The resin composition for electronic materials of the present invention provides, for example, an excellent photosensitive coverlay.

Claims (7)

(A) phenoxyphosphazene seen including Zen flame retardant, and (B) photopolymerizable unsaturated double compounds with binding, and
The resin composition for electronic materials does not include an adduct of an organophosphorus compound represented by the following formula (X) and a compound having four or more (meth) acrylate groups ,

The resin composition for electronic materials, wherein the melting temperature of the (A) phenoxyphosphazene flame retardant is 100 ° C. or lower and the average number of functional groups having an unsaturated bond per molecule is 0.1 or lower. object. (A) phenoxyphosphazene seen including Zen flame retardant, and (B) photopolymerizable unsaturated double compounds with binding, and
The resin composition for electronic materials does not include an adduct of an organophosphorus compound represented by the following formula (X) and a compound having four or more (meth) acrylate groups ,

The resin composition for electronic materials, wherein the (A) phenoxyphosphazene flame retardant is a compound represented by the general formula (1).

(Where
R ₁ and R ₂ may be the same or different from each other, and may be different for each repeating unit, but are selected from the group consisting of hydrogen, methyl group, ethyl group, methoxy group, and ethoxy group. , Containing one or more non-hydrogen groups in one molecule,
n is an integer greater than or equal to 3,
Each benzene ring may have two or more substituents R ₁ or R ₂ ) The resin composition for electronic materials according to claim 1 or 2,
A resin composition for electronic materials, further comprising at least one resin selected from the group consisting of (C) polyamic acid, (C ′) alkali-soluble resin, and (C ″) epoxy resin.   The electronic circuit board obtained using the resin composition for electronic materials as described in any one of Claims 1-3.   The electronic circuit board which has a resin film formed with the dry film containing the resin composition for electronic materials as described in any one of Claims 1-3.   The electronic circuit board according to claim 4, which is a printed board.   An electronic electrical apparatus comprising the electronic circuit board according to any one of claims 4 to 6.