TW201839517A - Photosensitive film laminate and cured product formed by using same - Google Patents

Abstract

Provided is a photosensitive film laminate capable of barely affecting a surface of a photosensitive film even when the photosensitive film laminate is inflicted by strong impact or pressure due to being overlapped with laminated substrates. To this end, the photosensitive film laminate sequentially includes a support film, an intermediate layer, and a photosensitive film formed of a photosensitive resin composition. The intermediate layer comprises at least one of melamine and a melamine compound.

Description

Photosensitive film laminate and cured product formed by using same

The present invention relates to a photosensitive film laminate and a cured product formed by using the same.

Generally, in printed wiring boards used in electronic equipment and the like, when mounting electronic components on printed wiring boards, in order to prevent solder from being attached to unnecessary portions, they are attached to substrates with circuit patterns except connection holes. Area forms a solder resist layer.

With the recent increase in precision and density of printed wiring boards caused by the thinness and thinness of electronic devices in recent years, currently, solder resist layers are coated with a photosensitive resin composition on a substrate, dried, and exposed and developed to form a pattern. After the molding, the patterned resin is hardened by heating or light irradiation, so-called formed by a photo solder resist is the mainstream.

It is also proposed to form a solder resist layer using a so-called photosensitive film laminate including a photosensitive film instead of the liquid photosensitive resin composition as described above. Such a photosensitive film laminate is generally a photosensitive film formed by a photosensitive resin composition bonded to a supporting film, and a protective film may be bonded to the surface of the photosensitive film as needed. When such a photosensitive film laminate is used, the protective film is peeled off and laminated on the wiring substrate by heat and pressure bonding, and the supporting film is peeled off and developed before exposure or after exposure from the supporting film side. Thereby, a patterned solder resist layer can be formed. By using the photosensitive film laminate, compared with the case of wet coating, a drying step after coating is not required, and the surface smoothness or surface hardness of the obtained solder resist layer is also excellent. Furthermore, in recent years, from the viewpoint of workability, there has been a tendency to reduce the thickness of photosensitive films. Not only photosensitive films, but also support films laminated with photosensitive films tend to be thinner (for example, refer to International Publication 2010/013623). Booklet, Japanese Patent Laid-Open No. 2011-48270, etc.).

In the step of forming a solder resist layer on the wiring substrate as described above, after the photosensitive thin film laminate is laminated on the wiring substrate and before the next step, the laminated support wiring substrate may be sequentially overlapped. And the case of temporary storage. At this time, the surface of the photosensitive film laminate provided on the wiring substrate may be damaged due to the impact when the wiring substrates to which the photosensitive film laminate is laminated are overlapped or the weight of the wiring substrate when it is overlapped. In particular, due to the recent thinning of the photosensitive film laminate, not only the support film, but also the surface of the photosensitive film laminated on the support film may be damaged due to the impact during the overlap or the pressing of the weight itself.

Therefore, an object of the present invention is to provide a photosensitive film laminate which can suppress the influence on the surface of the photosensitive film even if the substrate is laminated with the photosensitive film laminate on a substrate or the like with strong impact or pressing. It is another object of the present invention to provide a cured product formed by using the photosensitive film laminate.

The present inventors have found that the damage to the surface of the photosensitive film caused by impact or pressing when a substrate or the like on which the photosensitive film laminate is laminated is superimposed, not only due to the impact resistance of the photosensitive film itself, but also It is largely related to the material of the layer adjacent to the surface of the photosensitive film, that is, the layer directly contacting the photosensitive film. In addition, the present inventors have found that the laminated body provided between the support film having the intermediate layer containing a specific component and the photosensitive film allows the substrates or the like on which the photosensitive film laminate is laminated to be overlapped. Strong impact or pressing at the same time can also suppress the effect on the surface of the photosensitive film. Furthermore, the present inventors have found that the use of a solder resist layer formed of a photosensitive film laminate having an intermediate layer containing a specific component as described above can improve the surface of the solder resist layer without being affected by impact. Yield. This invention is made based on this knowledge.

[1] The photosensitive film laminate according to the first embodiment of the present invention is a photosensitive film laminate including a support film, an intermediate layer, and a photosensitive film formed of a photosensitive resin composition in this order. It is characterized in that the intermediate layer contains at least any one of melamine and a melamine compound.

[2] The photosensitive film laminate of the second embodiment of the present invention is the photosensitive film laminate of [1], wherein the thickness of the support film is 10 to 150 μm.

[3] The photosensitive film laminate according to the third embodiment of the present invention is the photosensitive film laminate according to [1] or [2], wherein the photosensitive resin composition contains a filler and a crosslinking component.

[4] The photosensitive film laminate according to the fourth embodiment of the present invention is a photosensitive film laminate according to any one of [1] to [3], which is opposite to the intermediate layer of the photosensitive film The front side is further provided with a protective film.

[5] A cured product according to a fifth embodiment of the present invention, which is formed using the photosensitive thin film laminate according to any one of [1] to [4].

According to the present invention, since a photosensitive film laminate including an intermediate layer containing a specific component as described above is provided between the photosensitive film and the support film, even when a substrate or the like on which the photosensitive film laminate is laminated is strong, Impact or pressing can also suppress the effect on the surface of the photosensitive film. In particular, it is effective to use the said photosensitive thin film laminated body when forming a solder resist layer. Moreover, it is effective from a viewpoint that the said support film exhibits the said effect even if it is a thin film. Furthermore, according to another aspect of this invention, the hardened | cured material formed using the said photosensitive film laminated body can be implemented.

The photosensitive film laminated body of this invention is demonstrated, referring drawings. FIG. 1 is a schematic cross-sectional view showing an embodiment of a photosensitive film laminate according to the present invention. The photosensitive film laminate 1 of the present invention has a structure in which a support film 10, an intermediate layer 20, and a photosensitive film 30 formed of a photosensitive resin composition are sequentially laminated. Here, the photosensitive film refers to a person who makes the photosensitive resin composition into a film shape and does not have another layer such as a support film or a protective film laminated. In addition, in the present invention, in addition to the above configuration, other films and the like may be provided. For example, in order to prevent dust and the like from being attached to the surface of the photosensitive film, and considering the operability of the photosensitive film laminate, as shown in FIG. 2, the photosensitive film laminate 1 may be placed between the photosensitive film 30 and the intermediate layer. A protective film 40 is further provided on the opposite surface side. Hereinafter, each component which comprises the thin film laminated body of this invention is demonstrated.

[Support film] 支持 The support film in the photosensitive film laminate of the present invention has a support for a photosensitive film described below, and is adjacent to the support film when the photosensitive film is exposed and developed as described later. The side surface gives a character with a specific surface shape.

The support film in the photosensitive film laminate of the present invention can be used without any particular limitation as long as it is known, for example, it can be suitably used. Polyethylene terephthalate or polyethylene naphthalate can be suitably used. Polyester film, polyimide film, polyimide film, polypropylene film, polystyrene film and other thermoplastic resins. When the thermoplastic resin film is used, a filler may be added to the resin when the film is formed (kneading treatment), or a matte coating (coating treatment) may be performed, and the surface of the film may be subjected to a sandblasting treatment like a sandblasting treatment. Alternatively, it may be a processor that performs hairline processing or chemical etching. Among these, from the viewpoints of heat resistance, mechanical strength, workability, etc., a polyester film is particularly suitably used. The support film may be a single layer, or two or more layers may be laminated.

The thermoplastic resin film described above is preferably used for a film extending in one or two axial directions for the purpose of improving strength.

From the viewpoint of operability, the thickness of the supporting film is preferably in a range of 10 to 150 μm, more preferably in a range of 10 to 100 μm, and even more preferably in a range of 10 to 50 μm.

In addition, a support film in which an intermediate layer described later is provided on the support film by coating and the intermediate layer is integrated may be used.

<Intermediate layer> The intermediate layer in the photosensitive film laminate of the present invention contains at least one of melamine and a melamine compound. As a result of diligent research by the inventors, it was found that the surface of the photosensitive film is not affected by a strong impact by providing an intermediate layer made of a specific material between the support film and the photosensitive film. Although the reason is not necessarily clear, it is presumed that the intermediate layer protects the surface of the laminated photosensitive film from strong impact. As a result, it does not affect the surface state of the photosensitive film, but it is only an estimated range. Is not necessarily limited to this.

The thickness of the intermediate layer is preferably in the range of 0.1 to 10 μm, and more preferably in the range of 1 to 8 μm from the viewpoint of being protected by a photosensitive film.

As a melamine and a melamine compound contained in an intermediate layer, a well-known person can be used. In the present invention, the melamine compound also includes a mixture of the melamine compound and other substances. In addition, the "melamine" in the present invention refers to a resin hardened by the addition condensation of melamine (2,4,6-triamino-1,3,5-triazine) and formaldehyde, but also includes the resin The concept of methylol melamine and its alkylated alkylated methylol melamine as the initial reactants of melamine and formaldehyde. Melamine also includes modified melamine such as methylated methylol melamine, propylated methylol melamine, butylated methylol melamine, isobutylated methylol melamine, and the like. It also includes melamine modified products such as melamine (meth) acrylate.

The melamine compound refers to a mixture of the melamine and other resins such as an acrylic resin, an epoxy resin, and an alkyd resin, and examples thereof include acrylic melamine, alkyd melamine, polyester melamine, and epoxy melamine. Among these, in order to obtain more excellent impact resistance, melamine acrylic acid and epoxy melamine are preferred; melamine acrylic acid is more preferred. Furthermore, the melamine acrylic acid herein refers to a mixture of an acrylic resin and a melamine resin, and is a form in which an acrylic resin is hardened with a melamine resin. The epoxy melamine refers to a mixture of an epoxy resin and a melamine resin, and is a form in which an epoxy resin is hardened with a melamine resin. Specific examples of melamine include AMIDIR J-820-60, L-109-65, L-117-60, L-127-60, 13-548, G-821-60, and L-110 manufactured by DIC Corporation. -60G, L-125-60, L-166-60B, L-105-60, U-VAN 20SE60, 20SB, 22R, 125, 132, 62, 60R, 169, etc. manufactured by Mitsui Chemicals Corporation. In addition, an acrylic resin or an epoxy resin can be used by a publicly known person without particular limitation. Specific examples of the acrylic resin include ACRYDIC 54-172-60, A-322, A-405, and A-452 manufactured by DIC Corporation. Specific examples of the epoxy resin include Epomik R301 manufactured by Mitsui Chemicals Co., Ltd. and the like. The content of the melamine resin is preferably 0.1 to 50% by mass, and more preferably 1 to 40% by mass based on the total amount of the acrylic resin or epoxy resin.

The blending amount of the melamine and the melamine compound contained in such an intermediate layer is preferably 10 to 90% by mass and more preferably 20 to 80% by mass relative to the entire layer.

The intermediate layer may contain other resins as long as the effect is not impaired. It is particularly preferable that a silicone resin is contained in the intermediate layer as a resin component. When the photosensitive film laminate of the present invention hardens the photosensitive film to form a cured film, the supporting film and the intermediate layer must be peeled off from the photosensitive film (cured film). Since the intermediate layer contains a polysiloxane resin, The support film and the intermediate layer can be easily peeled from the photosensitive film, and the adhesion between the support film and the intermediate layer can be maintained. In addition, since the intermediate layer contains the melamine or melamine compound and a silicone resin, it is possible to further suppress the surface damage of the photosensitive film due to impact or pressing. The polysiloxane resin can be used without particular limitation, and examples thereof include SYMACUS-120, US-150, US-270, US-350, and Aron GS-30 manufactured by Toa Synthesis Co., Ltd.

In addition, the intermediate layer may suitably contain fillers, hardening accelerators, additives, antistatic agents, and the like as components other than resin. A known filler can be used without particular limitation, and examples thereof include silicon dioxide and calcium carbonate. Of these, silicon dioxide is particularly preferred. The average particle diameter of the filler is not particularly limited, but is preferably 1.0 to 5.5 μm, more preferably 2.0 to 4.5 μm, and still more preferably 2.0 to 3.0 μm. As the antistatic agent, a conventionally known antistatic agent can be used, and among these, a cationic surfactant having a quaternary ammonium salt represented by the following general formula (I) as a main component can be suitably used. Since the intermediate layer contains a cationic surfactant represented by the following formula, the surface damage of the photosensitive film due to impact or pressing can be further suppressed.

(In the formula, R represents an alkyl group having 8 or more carbon atoms, R ₁ represents a lower alkyl group, and R ₂ represents a lower alkylene group.)

Among the above-mentioned cationic surfactants of the formula (I), it is particularly preferable to use those represented by the following general formula (II). (In the formula, R represents an alkyl group having 8 or more carbon atoms.)

<Photosensitive film> The photosensitive film constituting the photosensitive film laminate of the present invention is patterned by exposure and development, and becomes a hardened film provided on a circuit board. The hardened film is preferably a solder resist layer. Such a photosensitive film is formed using a photosensitive resin composition, and the photosensitive resin composition can be used without limitation with a conventionally known solder resist ink. The following describes the sensitivity of the photosensitive film that can be preferably used in the present invention. An example of a resin composition.

In the present invention, the photosensitive resin composition preferably contains a crosslinking component and a filler. More preferably, it further contains a photopolymerization initiator. The crosslinking component is preferably a photosensitive resin or photosensitive monomer containing a carboxyl group, and when further heated, it is preferable to contain a component that is crosslinked by heat. Each component is explained below.

[Crosslinking component] The crosslinking component is not particularly limited as long as it is a component that can be crosslinked, and a publicly known one can be used. Particularly preferred is a photosensitive resin or a photosensitive monomer containing a carboxyl group. In the case of further heating, it is preferred to contain a component that is crosslinked by heat (hereinafter referred to as a thermal crosslinking component).

The photosensitive resin containing a carboxyl group is a component which is hardened by polymerization or crosslinking by light irradiation, and can be alkali developable by containing a carboxyl group. From the viewpoint of photocurability and development resistance, it is preferable to have an ethylenically unsaturated bond in the molecule other than the carboxyl group. The ethylenically unsaturated double bond is preferably one derived from acrylic acid or methacrylic acid or a derivative thereof.

Moreover, it is preferable that the photosensitive resin containing a carboxyl group uses the photosensitive resin containing a carboxyl group without using an epoxy resin as a starting material. The photosensitive resin containing a carboxyl group, which does not use epoxy resin as a starting material, has very low halide ion content, and can suppress deterioration of insulation reliability. Specific examples of the carboxyl group-containing photosensitive resin include the following compounds (either oligomers or polymers).

Examples include: (1) reacting (meth) acrylic acid with a polyfunctional (solid) epoxy resin having two or more functions, and adding phthalic anhydride and tetrahydrophthalic acid to hydroxyl groups present on a side chain; A carboxyl group-containing photosensitive resin obtained from a dibasic acid anhydride such as formic anhydride, hexahydrophthalic anhydride, etc. (2) The hydroxyl group of (meth) acrylic acid and a bifunctional (solid) epoxy resin is further subjected to epichlorine A polyfunctional epoxy resin obtained by epoxidation of an alcohol, and a photosensitive resin containing a carboxyl group obtained by adding a dibasic acid anhydride to the generated hydroxyl group, (3) has at least one alcoholic hydroxyl group in one molecule and One phenolic hydroxyl compound and (meth) acrylic acid-containing unsaturated monocarboxylic acid react with an epoxy compound having two or more epoxy groups in one molecule, and react with the obtained reaction product Hydroxy group, a carboxyl group-containing photosensitive resin obtained by reacting a polybasic acid anhydride such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipic acid, etc., (4) using Unsaturated monocarboxylic acids such as (meth) acrylic acid, and bisphenol A, bis Phenol F, bisphenol S, novolac-type phenol resin, poly-p-hydroxystyrene, naphthol and aldehyde condensation products, dihydroxynaphthalene and aldehyde condensation products, etc. have more than two phenols in one molecule The hydroxy-containing compound reacts with a reaction product obtained by reacting an alkylene oxide such as ethylene oxide and propylene oxide, and a carboxyl group-containing photosensitive resin obtained by reacting the obtained reaction product with a polybasic acid anhydride. A reaction product obtained by reacting a monocarboxylic acid containing an unsaturated group with a compound having two or more phenolic hydroxyl groups and cyclic carbonate compounds such as ethyl carbonate and propyl carbonate in one molecule A photosensitive resin containing a carboxyl group obtained by reacting the obtained reaction product with a polybasic acid anhydride, and (6) reacting an aliphatic diisocyanate, a branched aliphatic diisocyanate, an alicyclic diisocyanate, an aromatic diisocyanate, etc. Diisocyanate compounds and polycarbonate-based polyols, polyether-based polyols, polyester-based polyols, polyolefin-based polyols, acrylic-based polyols, bisphenol A-based alkylene oxide adducts, and phenols Sex A urethane resin terminal obtained by addition polymerization reaction of a diol compound such as a hydroxyl group, an alcoholic hydroxyl compound, and the like, and a terminal carboxyl group-containing urethane resin obtained by further reacting an acid anhydride with (7) in Diisocyanate; carboxyl-containing diol compounds such as dimethylolpropionic acid, dimethylolbutanoic acid; and carboxyl-containing urethane resins obtained by addition polymerization with diol compounds Add a compound with one hydroxy group and one or more (meth) acrylfluorenyl groups in the molecule such as hydroxyalkyl (meth) acrylate, and a terminal (meth) acrylated carboxyl group-containing urethane Resin, (8) In the synthesis of a diisocyanate, a diol compound containing a carboxyl group, and a carboxyl group-containing urethane resin obtained by addition polymerization with a diol compound, isophorone diisocyanate and pentaerythritol are added. Compounds with one isocyanate group and one or more (meth) acryl fluorene groups in molecules such as moire reactants such as triacrylates, and terminal (meth) acrylated carboxyl group-containing urethane resins , (9) Dicarboxylic acid such as adipic acid, phthalic acid, hexahydrophthalic acid and the like are reacted with a polyfunctional oxetane resin, and a dibasic acid anhydride is added to the generated primary hydroxyl group, and then Glycidyl (meth) acrylate, α-methylglycidyl (meth) acrylate and the like are further added to the carboxyl group-containing polyester resin obtained by the addition described above. A carboxyl group-containing photosensitive resin made of more than one (meth) acrylfluorenyl compound. (10) Add 1 to the carboxyl group-containing photosensitive resin in any one of (1) to (9) above. A carboxyl group-containing photosensitive resin obtained from a compound having a cyclic ether group and a (meth) acrylfluorene group in the molecule, (11) For unsaturated carboxylic acids such as (meth) acrylic acid, styrene, and α -A carboxyl group-containing resin obtained by copolymerizing an unsaturated group-containing compound such as methylstyrene, a lower alkyl (meth) acrylate, isobutylene, etc., to make one of 3,4-epoxycyclohexyl methacrylate, etc. A carboxyl group-containing compound obtained by reacting a compound having a cyclic ether group with a (meth) acryl group in the molecule Photosensitive resin and the like. Here, (meth) acrylate refers to a term that collectively refers to acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions below.

Among the carboxyl group-containing photosensitive resins, a carboxyl group-containing photosensitive resin that does not use epoxy resin as a starting material or a carboxyl group-containing photosensitive resin obtained from a resin other than a synthetic epoxy resin can be suitably used as described above. Resin. Therefore, among the specific examples of the photosensitive resin containing a carboxyl group, any one or more of the photosensitive resins containing a carboxyl group (4) to (8) and (11) may be suitably used, and (4) to ( 8) Exemplified resin. It can have the characteristics required for solder resist for semiconductor packaging, that is, PCT resistance, HAST resistance, and thermal shock resistance.

In this way, by not using an epoxy resin as a starting material, the amount of chloride ions can be suppressed to a very small amount, for example, 100 ppm or less. The content of chloride ion impurities in the photosensitive resin containing a carboxyl group suitably used in the present invention is 0 to 100 ppm, more preferably 0 to 50 ppm, and still more preferably 0 to 30 ppm.

Further, by not using an epoxy resin as a starting material, a resin containing no hydroxyl group (or a reduced amount of hydroxyl group) can be easily obtained. In general, the presence of hydroxyl groups also has excellent characteristics such as improved adhesion caused by hydrogen bonding, but it is known that the moisture resistance will be significantly reduced. By becoming a photosensitive resin containing a carboxyl group that does not contain a hydroxyl group, the resistance can be improved. Wet.

Furthermore, it is also suitable to use a carboxyl group-containing urethane resin synthesized from an isocyanate compound that does not use phosgene as a starting material and a raw material that does not use epihalohydrin, and has a chloride ion content of 0 to 30 ppm. In such a urethane resin, a resin having no hydroxyl group can be easily synthesized by blending the equivalents of a hydroxyl group and an isocyanate group.

When synthesizing a urethane resin, an acrylic epoxy ester modified raw material may be used as the diol compound. Although chloride ion impurities are mixed in, they can be used from the viewpoint of controlling the amount of chloride ion impurities.

Since the photosensitive resin containing a carboxyl group as described above has a large number of carboxyl groups in a skeleton and a polymer side chain, it can be developed with an alkaline aqueous solution.

The acid value of the photosensitive resin containing a carboxyl group is preferably 40 to 150 mgKOH / g. When the acid value of the photosensitive resin containing a carboxyl group is 40 mgKOH / g or more, alkali development becomes favorable. In addition, by setting the acid value to 150 mgKOH / g or less, a normal resist pattern can be easily drawn. More preferably, it is 50 to 130 mgKOH / g.

Although the weight average molecular weight of the photosensitive resin containing a carboxyl group varies depending on the resin skeleton, it is generally preferably 2,000 to 150,000. When the weight average molecular weight is 2,000 or more, non-stick performance or resolution can be improved. In addition, by setting the weight average molecular weight to 150,000 or less, developability and storage stability can be improved. More preferably, it is 5,000 to 100,000.

The blending amount of the photosensitive resin containing a carboxyl group is preferably 20 to 60% by mass based on the solid content. When it is 20% by mass or more, the coating film strength can be improved. Moreover, when it is 60% by mass or less, the viscosity becomes appropriate and the workability improves. More preferably, it is 30 to 50% by mass.

Examples of the compound used as the photosensitive monomer include conventionally known polyester (meth) acrylates, polyether (meth) acrylates, urethane (meth) acrylates, and carbonates (methyl ) Acrylate, (meth) acrylate epoxy, and the like. Specific examples include hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol. Diacrylates; N, N-dimethyl acrylamide, N-methyl methacrylamide, N, N-dimethylaminopropylacrylamide and other acrylamides; acrylic N, N-dimethylaminoethyl acrylate, N, N-dimethylaminopropyl acrylate, and the like; amine alkyl acrylates; hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, and p-hydroxyethyl Polyisocyanates such as polyisocyanates or polyvalent acrylates such as ethylene oxide adducts, propylene oxide adducts, or ε-caprolactone adducts; phenoxy acrylate Esters, bisphenol A diacrylates, and polyvalent acrylates such as ethylene oxide adducts or propylene oxide adducts of phenols; glycerol diglycidyl ether, glycerol triglycidyl ether, Polyvalent acrylic acid esters of glycidyl ethers such as trimethylolpropane triglycidyl ether, triglycidyl isocyanurate, and the like; Polyols such as polyols, polycarbonate diols, hydroxyl-terminated polybutadiene, polyester polyols, etc. are directly acrylated, or urethane acrylates and melamine acrylics are passed through diisocyanates An ester and at least one of each of the methacrylates corresponding to the above-mentioned acrylate are appropriately selected and used.

An acrylic epoxy resin obtained by reacting acrylic acid with a polyfunctional epoxy resin such as a cresol novolac epoxy resin, or a hydroxy acrylate such as pentaerythritol triacrylate and isophorone diisocyanate may also be used. An epoxy urethane acrylate compound or the like obtained by reacting a bis-urethane compound of an isocyanate with a hydroxyl group of the acrylic epoxy resin as a photosensitive monomer. Such an acrylic epoxy resin can improve the photo-hardening property without reducing the touch dryness.

When the amount of the compound having an ethylenically unsaturated group in the molecule as a photosensitive monomer is used, when a resin containing a carboxyl group is included in the composition, the solid content is converted to 100 parts by mass of the resin containing a carboxyl group. The ratio is preferably 5 to 100 parts by mass, and more preferably 5 to 70 parts by mass. When the compounding amount of the compound having an ethylenically unsaturated group is 5 parts by mass or more, the photocurability of the photocurable resin composition is improved. In addition, by setting the blending amount to 100 parts by mass or less, the hardness of the coating film can be increased. The carboxyl group-containing resin referred to herein means any of a photosensitive resin containing a carboxyl group and a non-photosensitive resin containing a carboxyl group. That is, when any one of the compositions is blended alone, it means alone, and when it is blended, it means its total (the same applies to the following paragraphs).

In particular, when a non-photosensitive resin containing a carboxyl group having no ethylenically unsaturated double bond is used, since the composition is photocurable, it is necessary to use a compound having one or more ethylenically unsaturated groups in the molecule (photosensitive Photosensitive monomers), so photosensitive monomers are effective.

Examples of the thermal crosslinking component include a thermosetting resin. As the thermosetting resin, an isocyanate compound, a blocked isocyanate compound, an amine resin, a maleimine compound, a benzoxazine resin, a carbodiimide resin, a cyclic carbonate compound, a polyfunctional epoxy compound, Polyfunctional oxetane compounds, episulfide resins, and the like are commonly known. Among these, a particularly preferable thermal cross-linking component is thermal cross-linking having at least any one of a plurality of cyclic ether groups and cyclic thioether groups in one molecule (hereinafter referred to as a cyclic (thio) ether group).联 组合。 Composition. These thermosetting components having a cyclic (thio) ether group are commercially available in many varieties, and various properties can be imparted depending on the structure.

The thermosetting component having a plurality of cyclic (thio) ether groups in the molecule is a cyclic ether group having a plurality of 3, 4 or 5 member rings, or any one or two of the cyclic thioether groups For example, a compound having a plurality of epoxy groups in a molecule is a polyfunctional epoxy compound; a compound having a plurality of oxetanyl groups in a molecule is a polyfunctional oxetane compound; a molecule The compound having a plurality of thioether groups is an episulfide resin and the like.

Examples of the polyfunctional epoxy compound include jER828, jER834, jER1001, jER1004 manufactured by Mitsubishi Chemical Corporation, Epiclon 840, Epiclon 840-S, Epiclon 850, Epiclon 1050, Epiclon 2055, and Nippon Steel Co., Ltd. Epotohto YD-011, YD-013, YD-127, YD-128, manufactured by Sumitomo Corporation, DER317, DER331, DER661, DER664, manufactured by The Dow Chemical Company, Sumiepoxy, manufactured by Sumitomo Chemical Industry Co., Ltd. ESA-011, ESA-014, ELA-115, ELA-128, AER330, AER331, AER661, AER664, etc. (all trade names) made by Asahi Kasei Industrial Co., Ltd. JERYL903 manufactured by Mitsubishi Chemical Corporation, Epiclon 152, Epiclon 165 manufactured by DIC Corporation, Epotohto YDB-400, YDB-500 manufactured by Nippon Steel & Sumitomo Corporation, DER542 manufactured by Dow Chemical Co., Ltd., Sumitomo Chemical Brominated epoxy resins such as Sumiepoxy ESB-400, ESB-700 manufactured by Industrial Co., Ltd., and AER711, AER714, etc. (all trade names) manufactured by Asahi Kasei Industrial Co., Ltd .; Mitsubishi Chemical Corporation has Limited by jER152, jER154, Dow Chemical Co., DEN431, DEN438, DIC Corporation Epiclon N-730, Epiclon N-770, Epiclon N-865, Nippon Steel & Sumitomo Corporation Epotohto YDCN-701, YDCN-704, EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, NC-3000H, Sumiepoxy manufactured by Sumitomo Chemical Industry Co., Ltd. ESCN-195X, ESCN-220, ARECEN-235, ECN-299, etc. (all trade names) manufactured by Asahi Kasei Industrial Co., Ltd. (both trade names) novolac-type epoxy resins; Epiclon 830 manufactured by DIC Corporation, Mitsubishi Chemical Corporation Bisphenol F-type epoxy resin manufactured by Nippon Steel & Sumitomo Metal Co., Ltd., and Epotohto YDF-170, YDF-175, YDF-2004 (all trade names) manufactured by Nippon Steel & Sumitomo Metal Co., Ltd .; manufactured by Nippon Steel & Sumitomo Metal Co., Ltd. Epotohto ST-2004, ST-2007, ST-3000 (brand name) and other hydrogenated bisphenol A epoxy resins; jER604 manufactured by Mitsubishi Chemical Corporation; Epotohto YH-434 manufactured by Nippon Steel & Sumikin Corporation Sumiepo, manufactured by Sumitomo Chemical Industries, Ltd. Glycidylamine type epoxy resins such as xy ELM-120, etc. (both trade names); alicyclic epoxy resins, such as Celloxide 2021, etc., manufactured by Daicel Corporation; YL- manufactured by Mitsubishi Chemical Corporation 933, TEN, EPPN-501, EPPN-502, etc. (all trade names) made of Dow Chemical Company, trihydroxyphenylmethane type epoxy resin; YL-6056, YX-4000, Mitsubishi Chemical Corporation, YL-6121 (both trade names) bixylenol-type or biphenol-type epoxy resins or mixtures thereof; EBPS-200 manufactured by Nippon Kayaku Co., Ltd. and EPX-30 manufactured by Asahi Kasei Kogyo Co., Ltd. And bisphenol S epoxy resins such as EXA-1514 (trade name) manufactured by DIC Corporation; bisphenol A novolac epoxy resins such as jER157S (trade name) manufactured by Mitsubishi Chemical Corporation; Mitsubishi Chemical Tetraphenol-based ethane type epoxy resins such as jERYL-931 (trade name) manufactured by a joint-stock company; Heterocyclic epoxy resins such as TEPIC (trade name) manufactured by Nissan Chemical Industry Co., Ltd .; Japan Grease Co., Ltd. Diglycidyl phthalate resins such as Blemmer DGT made by the company; Tetraglycidyl xylenol ethane resins such as ZX-1063 manufactured by Nippon Steel & Sumitomo Metal Co., Ltd .; ESN-190, ESN-360, HP-4032, EXA, manufactured by DIC Co., Ltd. -4750, EXA-4700 and other naphthyl-containing epoxy resins; HP-7200, HP-7200H and other dicyclopentadiene skeleton epoxy resins manufactured by DIC Corporation, EXA-4816, EXA-4822, EXA-4850 series of soft and strong epoxy resin; CP-50S, CP-50M and other glycidyl methacrylate copolymer epoxy resins made by Japan Oil Co., Ltd .; Cyclohexylmaleimide and Copolymerized epoxy resin and the like of glycidyl methacrylate, but are not limited thereto. These epoxy resins can be used alone or in combination of two or more.

Examples of the polyfunctional oxetane compound include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, and bis [(3-ethyl-3-oxetane Alkylmethoxy) methyl] ether, 1,4-bis [(3-methyl-3-oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl Methyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3-oxetanyl) acrylate, methyl (3-ethyl-3-oxetan) Butyl) methyl ester, (3-methyl-3-oxetanyl) methacrylate, (3-ethyl-3-oxetanyl) methacrylate, or the Polyfunctional oxetanes such as oligomers or copolymers, oxetanol and novolac resins, poly (p-hydroxystyrene), Cardo-type bisphenols, calixarene , Ethers of resins having a hydroxyl group, such as calorcinol aromatics or silsesquioxane. Other examples include copolymers of unsaturated monomers having an oxetane ring and alkyl (meth) acrylates.

Examples of the episulfide resin include YL7000 (bisphenol A episulfide resin) manufactured by Mitsubishi Chemical Corporation. In addition, an episulfide resin or the like in which an oxygen atom of an epoxy group of a novolak epoxy resin is replaced with a sulfur atom by a similar synthetic method can also be used.

When the composition contains a thermosetting component having a plurality of cyclic (thio) ether groups in the molecule, the blending amount of the thermosetting component having a plurality of cyclic (thio) ether groups in the molecule is a solid component The conversion is preferably in the range of 0.3 to 2.5 equivalents, and more preferably in the range of 0.5 to 2.0 equivalents with respect to 1 equivalent of the carboxyl group of the carboxyl group-containing resin. By setting the blending amount of the thermosetting component having a plurality of cyclic (thio) ether groups in the molecule to 0.3 equivalent or more, the carboxyl group is not left in the hardened film, and heat resistance, alkali resistance, and electrical insulation properties are improved. . In addition, when the molecular weight is 2.5 equivalents or less, a cyclic (thio) ether group having a low molecular weight does not remain in the dry coating film, and the strength of the cured film is improved.

When a thermosetting component having a plurality of cyclic (thio) ether groups in a molecule is used, a thermosetting catalyst is preferably blended. Examples of such thermosetting catalysts include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, and 1-cyanide. Imidazole derivatives such as ethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; dicyandiamine, benzyldimethylamine, 4- (Dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl-N, N-dimethylbenzylamine, etc. Amine compounds; hydrazine compounds such as dihydrazine adipate, dihydrazine sebacate and the like; phosphorus compounds such as triphenylphosphine and the like. Examples of marketers include 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (all are trade names of imidazole compounds) manufactured by Shikoku Chemical Industry Co., Ltd., and U-made by San-Apro Co., Ltd. -CAT (registered trademark) 3503N, U-CAT3502T (both trade names of dimethylamine-blocked isocyanate compounds), DBU, DBN, U-CATSA102, U-CAT5002 (both bicyclic hydrazone compounds and their salts) Wait. It is not particularly limited as long as it is a thermosetting catalyst of an epoxy resin or an oxetane compound, or one that can promote the reaction of an epoxy group and / or an oxetanyl group with a carboxyl group, may be alone Alternatively, two or more kinds may be used in combination. In addition, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloxyethyl-S-triazine, and 2-vinyl-2 can also be used. 2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine / isotricyanic acid adduct, 2,4-diamino-6-formaldehyde S-triazine derivatives such as propylene ethoxyethyl-S-triazine / isocyanuric acid adducts, etc., are preferably compounds and heat which also function as adhesiveness imparting agents. The hardening catalyst is used in combination.

When the composition contains a thermosetting component having a plurality of cyclic (thio) ether groups in the molecule, the blending amount of the thermosetting catalyst is calculated based on the solid content, relative to the molecule having a plurality of cyclic (sulfur) groups. The amount of the thermosetting component of the ether group is preferably 0.1 to 20 parts by mass, and more preferably 0.5 to 15.0 parts by mass.

Examples of the amine-based resin include amine-based resins such as melamine derivatives and benzoguanamine derivatives. For example, there are a methylol melamine compound, a methylol benzoguanamine compound, a methylol acetylene urea compound, and a methylol urea compound. Further, the alkoxymethylated melamine compound, the alkoxymethylated benzoguanamine compound, the alkoxymethylated acetylene urea compound, and the alkoxymethylated urea compound can be obtained by changing the respective hydroxyl groups. A methyl melamine compound, a methylol benzoguanamine compound, a methylol acetylene urea compound, and a methylol urea compound are converted into an alkoxymethyl group. The kind of the alkoxymethyl group is not particularly limited, and examples thereof include methoxymethyl, ethoxymethyl, propoxymethyl, and butoxymethyl. Particularly preferred is a melamine derivative that is mild to humans or the environment with a concentration of formalin of 0.2% or less.

Commercial products of amine resins include Cymel 300, same 301, same 303, same 370, same 325, same 327, same 701, same 266, same 267, same 238, same 1141, same 272, and 202, Same as 1156, Same as 1158, Same as 1123, Same as 1170, Same as 1174, Same as UFR65, Same as 300 (above, made by Mitsui Cyanamid Co., Ltd.), Nikalac Mx-750, Same as Mx-032, Same as Mx-270, Same as Mx-280 , Same Mx-290, same Mx-706, same Mx-708, same Mx-40, same Mx-31, same Ms-11, same Mw-30, same Mw-30HM, same Mw-390, same Mw-100LM , Same as Mw-750LM, (above, made by Sanwa Chemical Co., Ltd.) and so on.

As the isocyanate compound, a polyisocyanate compound having a plurality of isocyanate groups in the molecule can be used. As the polyisocyanate compound, for example, an aromatic polyisocyanate, an aliphatic polyisocyanate, or an alicyclic polyisocyanate can be used. Specific examples of the aromatic polyisocyanate include 4,4'-diphenylmethane diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, naphthalene-1,5-diisocyanate, and o-diene Toluene diisocyanate, m-xylene diisocyanate and 2,4-toluene dimer. Specific examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, and 4,4-methylenebis (cyclo Hexyl isocyanate) and isophorone diisocyanate. Specific examples of the alicyclic polyisocyanate include dicycloheptane triisocyanate. Examples of the adducts, biuret and isotricyanate of the isocyanate compounds mentioned above are also listed.

The blocked isocyanate group contained in the blocked isocyanate compound is a group in which the isocyanate group is protected by a reaction with the blocking agent and is not activated for a while. When heated to a specific temperature, the blocking agent dissociates to form an isocyanate group.

As the blocked isocyanate compound, an addition reaction product of an isocyanate compound and an isocyanate blocking agent can be used. Examples of the isocyanate compound capable of reacting with the blocking agent include isocyanurate type, biuret type, and adduct type. Examples of the isocyanate compound used to synthesize the blocked isocyanate compound include aromatic polyisocyanate, aliphatic polyisocyanate, and alicyclic polyisocyanate. Specific examples of the aromatic polyisocyanate, aliphatic polyisocyanate, and alicyclic polyisocyanate include the compounds exemplified above.

Examples of the isocyanate blocking agent include phenol-based blocking agents such as phenol, cresol, xylenol, chlorophenol, and ethylphenol; ε-caprolactam, δ-valprolactam, and γ-butyrolactam And β-propiolactam endogenous capping agents; active methylene-based end capping agents such as ethyl acetate and ethyl acetone; methanol, ethanol, propanol, butanol, pentanol, Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, benzyl ether, methyl glycolate, ethylene glycol Alcohol-based capping agents such as butyl alkylate, diacetone alcohol, methyl lactate, and ethyl lactate; formaldehyde oxime, acetaldehyde oxime, acetone oxime, methyl ethyl ketoxime, diethylfluorenyl monooxime, cyclohexyl Oxime-based capping agents such as alkoxime; thiol-based capping agents such as butyl mercaptan, hexyl mercaptan, t-butyl mercaptan, thiophenol, methyl mercaptan, and ethyl mercaptan; acetamide Acid benzylamine-based end-capping agents such as benzamidine; acetonitrile succinate and maleimide-based imine based terminals; dimethyltoluidine, aniline, butylamine, dibutylamine, etc. Amine-based blocking agent; imidazole, 2-ethylimidazole, etc. Azole-based capping agent; imine-based capping agent such as methyleneimine and propyleneimine.

The blocked isocyanate compound may also be commercially available, and examples thereof include Sumidur BL-3175, BL-4165, BL-1100, BL-1265, Desmodur TPLS-2957, TPLS-2062, TPLS-2078, TPLS-2117, and Desmotherm 2170. Desmotherm 2265 (above, manufactured by Sumitomo Bayer Carbamate Co., Ltd., trade name), Coronate 2512, Coronate 2513, Coronate 2520 (above, manufactured by Tosoh Corporation, trade name), B-830, B -815, B-846, B-870, B-874, B-882 (above, manufactured by Mitsui Takeda Chemical Co., Ltd., trade name), TPA-B80E, 17B-60PX, E402-B80T (above, Asahi Kasei Chemicals Co., Ltd. Limited company, trade name) and so on. In addition, Sumidur BL-3175 and BL-4265 are obtained by using methyl ethyl oxime as a capping agent.

In order to promote the hardening reaction between the hydroxyl group or the carboxyl group and the isocyanate group, a urethane-forming catalyst may be added to the photosensitive resin composition. The urethane catalyst is preferably an amino formic acid selected from at least one of a tin-based catalyst, a metal chloride, a metal acetone acetone salt, a metal sulfate salt, an amine compound, and an amine salt. Esterification catalyst.

Examples of the tin-based catalyst include organic tin compounds such as stannous octoate and dibutyltin dilaurate, and inorganic tin compounds. Examples of the metal chloride include chlorides of metals selected from the group consisting of Cr, Mn, Co, Ni, Fe, Cu, and Al, and examples thereof include cobalt (III) chloride, nickel (II) chloride, and chloride. Iron (III), etc. Examples of the metal acetoacetone salt include acetoacetone salts of metals selected from the group consisting of Cr, Mn, Co, Ni, Fe, Cu, and Al, such as cobalt acetoacetone, nickel acetoacetone, and acetone. Iron acetone etc. Furthermore, examples of the metal sulfate include sulfates of metals selected from the group consisting of Cr, Mn, Co, Ni, Fe, Cu, and Al, such as copper sulfate.

Examples of the amine compound include conventionally known triethylenediamine, N, N, N ', N'-tetramethyl-1,6-hexanediamine, and bis (2-dimethylaminoethyl) ether. , N, N, N ', N ", N" -pentamethyldiethylenetriamine, N-methylmorpholine, N-ethylmorpholine, N, N-dimethylethanolamine, dimorpholinyl di Ethyl ether, N-methylimidazole, dimethylaminopyridine, triazine, N '-(2-hydroxyethyl) -N, N, N'-trimethylphosphonium bis (2-aminoethyl) ) Ether, N, N-dimethylhexanolamine, N, N-dimethylaminoethoxyethanol, N, N, N'-trimethyl-N '-(2-hydroxyethyl) ethyl Diamine, N- (2-hydroxyethyl) -N, N ', N ", N" -tetramethyldiethylenetriamine, N- (2-hydroxypropyl) -N, N', N ", N "-tetramethyldiethylenetriamine, N, N, N'-trimethyl-N '-(2-hydroxyethyl) propanediamine, N-methyl-N'-(2-hydroxyethyl ) Piperazine, bis (N, N-dimethylaminopropyl) amine, bis (N, N-dimethylaminopropyl) isopropanolamine, 2-aminoquinine ring, 3-amine Quinine ring, 4-aminoquinine ring, 2-quinol, 3-quinol, 4-quinol, 1- (2'-hydroxypropyl) imidazole, 1- (2'-hydroxy Propyl) -2-methylimidazole, 1- (2'-hydroxyethyl) imidazole, 1- (2'- Ethyl) -2-methylimidazole, 1- (2'-hydroxypropyl) -2-methylimidazole, 1- (3'-aminopropyl) imidazole, 1- (3'-aminopropyl) ) -2-methylimidazole, 1- (3'-hydroxypropyl) imidazole, 1- (3'-hydroxypropyl) -2-methylimidazole, N, N-dimethylaminopropyl- N '-(2-hydroxyethyl) amine, N, N-dimethylaminopropyl-N', N'-bis (2-hydroxyethyl) amine, N, N-dimethylaminopropyl -N ', N'-bis (2-hydroxypropyl) amine, N, N-dimethylaminoethyl-N', N'-bis (2-hydroxyethyl) amine, N, N- At least one of dimethylaminoethyl-N ', N'-bis (2-hydroxypropyl) amine, melamine, and benzoguanamine, and the like.

Examples of the amine salt include organic acid salt-based amine salts such as DBU (1,8-diaza-bicyclo [5.4.0] undecene-7).

[Filler] As the filler, well-known and commonly used inorganic or organic fillers can be used. Particularly preferred are barium sulfate, spherical silica, titanium oxide, Newcastle silica particles and talc. Further, for the purpose of imparting flame resistance, aluminum hydroxide, magnesium hydroxide, gibbsite, or the like may be used. Furthermore, it can also be used in a compound of one or more ethylenically unsaturated groups, or NANOCRYL (trade name) manufactured by Hanse-Chemie Co., Ltd., where nano silica is dispersed in the polyfunctional epoxy resin. XP 0396, XP 0596 , XP 0733, XP 0746, XP 0765, XP 0768, XP 0953, XP 0954, XP 1045 (all product grade names), or NANOPOX (trade name) manufactured by Hanse-Chemie Corporation XP 0516, XP 0525, XP 0314 ( (Both product grade names). These may be used alone or in combination of two or more. By including a filler, the physical strength etc. of the hardened | cured material obtained can be improved.

When the resin containing a carboxyl group is contained in the composition, the blending amount of the filler is, in terms of solid content, preferably 500 parts by mass or less, and more preferably 0.1 to 300 parts by mass relative to 100 parts by mass of the resin containing a carboxyl group. And particularly good for 0.1 to 150 parts by mass. When the blending amount of the filler is 500 parts by mass or less, the viscosity of the photocurable thermosetting resin composition does not become too high, the printability is good, and the cured product is not easily brittle.

[Photopolymerization initiator] 中 In the present invention, known photopolymerization initiators for photopolymerizing the above-mentioned photosensitive resin containing a carboxyl group can be used. Among them, an oxime ester system having an oxime ester group is particularly used for photopolymerization. Initiators, α-aminoacetophenone-based photopolymerization initiators, and fluorenylphosphine oxide-based photopolymerization initiators are preferred. The photopolymerization initiator may be used singly or in combination of two or more kinds.

The commercially available oxime ester-based photopolymerization initiators include CGI-325, Irgacure (registered trademark) OXE01, Irgacure OXE02, ADEKA Corporation N-1919, Adeka Arkls (registered trademark) manufactured by BASF JAPAN. Trademark) NCI-831, etc.

In addition, a photopolymerization initiator having two oxime ester groups in the molecule can be suitably used, and specifically, an oxime ester compound having a carbazole structure represented by the following general formula (III) can be used. (Wherein X ₁ represents a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group, and a phenyl group (via an alkyl group having 1 to 17 carbon atoms and 1 to 8 carbon atoms) Alkoxy, amine, alkylamino or dialkylamino substituted with an alkyl group having 1 to 8 carbon atoms), naphthyl (using an alkyl group having 1 to 17 carbon atoms, 1 to 8 carbon atoms) (Alkoxy, amine, alkylamino or dialkylamino substituted with an alkyl group having 1 to 8 carbons), Y ₁ and Z each represent a hydrogen atom, an alkyl group having 1 to 17 carbons, and carbon Alkoxy, halo, phenyl, and phenyl groups with 1 to 8 carbon atoms (via alkyl groups with 1 to 17 carbon atoms, alkoxy groups with 1 to 8 carbon atoms, amine groups, and alkyl groups with 1 to 8 carbon atoms Substituted with alkylamino or dialkylamino), naphthyl (via an alkyl group with 1 to 17 carbon atoms, alkoxy group with 1 to 8 carbon atoms, amine group, and an alkyl group with 1 to 8 carbon atoms Alkylamino or dialkylamino substituted), anthracenyl, pyridyl, benzofuranyl, benzothienyl, Ar represents alkylene, vinylidene, vinylidene, vinylidene Biphenyl, pyridyl, naphthyl, thiophene, anthracenyl, thienyl, furfuryl, 2,5-pyrrole-diyl, 4,4'-stilbyl-diyl, 4,2 '-Styrene-diyl, n is 0 Integers 1).

In the above formula, X ₁ and Y ₁ are methyl or ethyl, Z is methyl or phenyl, n is 0, and Ar is phenylene, naphthyl, thiophene, or thiophene oxime ester. Department of photopolymerization initiator.

As a preferable carbazoxime ester compound, the compound which can be represented by following General formula (IV) is also mentioned.

(In the formula, R ₃ represents an alkyl group having 1 to 4 carbon atoms, or a phenyl group which may be substituted by a nitro group, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. R ₄ represents an alkyl group having 1 to 4 carbon atoms. An alkyl group, an alkoxy group having 1 to 4 carbon atoms, or a phenyl group which may be substituted by an alkyl group or alkoxy group having 1 to 4 carbon atoms. R ₅ means that it may be bonded via an oxygen atom or a sulfur atom and A benzyl group substituted by a phenyl substituted alkyl group having 1 to 20 carbon atoms and an alkoxy group substituted with 1 to 4 carbon atoms. R ₆ represents a nitro group or a fluorenyl group represented by X ₂ -C (= O)-. Table IX. X ₂ represents an aryl group, a thienyl group, a morpholinyl group, a phenylthio group, or a structure represented by the following formula (V) which may be substituted with an alkyl group having 1 to 4 carbon atoms.

Other examples include Japanese Patent Laid-Open No. 2004-359639, Japanese Patent Laid-Open No. 2005-097141, Japanese Patent Laid-Open No. 2005-220097, Japanese Patent Laid-Open No. 2006-160634, Japanese Patent Laid-Open No. 2008-094770, and Japan The carbazoxime ester compounds described in Japanese Patent Application Publication No. 2008-509967, Japanese Patent Application Publication No. 2009-040762, and Japanese Patent Application Publication No. 2011-80036.

When the oxime ester-based photopolymerization initiator is used, when a resin containing a carboxyl group is included in the composition, it is preferably 0.01 to 5 mass based on 100 parts by mass of the resin containing a carboxyl group. Serving. When it is 0.01 parts by mass or more, the photocurability on copper becomes more reliable, and the coating film properties such as chemical resistance are improved. Moreover, when it is 5 parts by mass or less, the light absorption on the surface of the coating film is suppressed, and the hardenability at the deep part tends to be improved. More preferably, it is 0.5-3 mass parts with respect to 100 mass parts of resin containing a carboxyl group.

α-aminoacetophenone-based photopolymerization initiator, and specifically, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinylacetone-1, 2- Benzyl-2-dimethylamino-1- (4-morpholinylphenyl) -butane-1-one, 2- (dimethylamino) -2-[(4-methylphenyl ) Methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, N, N-dimethylaminoacetophenone, and the like. Examples of commercially available products include Omnirad 907, Omnirad 369, and Omnirad 379 manufactured by IGM Resins.

A fluorenylphosphine oxide-based photopolymerization initiator, specifically, 2,4,6-trimethylbenzylfluorenyldiphenylphosphine oxide, and bis (2,4,6-trimethylbenzyl) (Fluorenyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzylidene) -2,4,4-trimethyl-pentylphosphine oxide, and the like. Examples of commercially available products include Omnirad TPO, Omnirad 819, and the like manufactured by IGM Resins.

As the photopolymerization initiator, JMT-784 manufactured by Yueyang Kimoutain Sci-tech Co., Ltd. can also be suitably used.

When a photopolymerization initiator other than the oxime ester-based photopolymerization initiator is used, when a resin containing a carboxyl group is contained in the composition, the solid content is converted to 100 parts by mass of the resin containing a carboxyl group. It is preferably 0.01 to 15 parts by mass. When it is 0.01 parts by mass or more, the photocurability on copper becomes more reliable, and the coating film properties such as chemical resistance are improved. Moreover, when it is 15 parts by mass or less, a sufficient effect of reducing outgassing can be obtained, light absorption on the surface of the cured film is further suppressed, and hardenability in the deep portion is also improved. More preferably, it is 0.5-10 mass parts with respect to 100 mass parts of resin containing a carboxyl group.

A photoinitiator or a sensitizer may be used in combination with the photopolymerization initiator. Photoinitiators or sensitizers include benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, benzophenone compounds, tertiary amine compounds, and xanthone compounds Wait. These compounds may be used as a photopolymerization initiator, but they are preferably used in combination with a photopolymerization initiator. Moreover, a photoinitiator or a sensitizer may be used individually by 1 type, and may use 2 or more types together.

Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether. Examples of the acetophenone compound include acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, and 1, 1-dichloroacetophenone and the like. Examples of the anthraquinone compound include 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, and 1-chloroanthraquinone. Examples of the thioxanthone compound include 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and 2,4-diisopropylthioxanthone. Wait. Examples of the ketal compound include acetophenone dimethyl ketal and benzyl dimethyl ketal. Further, examples of the benzophenone compound include benzophenone, 4-benzylfluorenyldiphenyl sulfide, 4-benzylfluorenyl-4'-methyldiphenylsulfide, and 4-benzene Formamyl-4'-ethyldiphenylsulfide, 4-benzyl-4'-propyldiphenylsulfide, and the like.

Examples of tertiary amine compounds include ethanolamine compounds and compounds having a dialkylaminobenzene structure. Examples of commercially available products include 4,4'-dimethylaminobenzophenone (Nisso, manufactured by Soda Co., Ltd., Japan). Cure (registered trademark) (MABP), 4,4'-diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Industry Co., Ltd.), and 7- (diethyl Diamino group) 4-methyl-2H-1-benzopyran-2-one (7- (diethylamino) -4-methylcoumarin), etc. Coumarin compounds, ethyl 4-dimethylaminobenzoate (Kayacure (registered trademark) EPA, manufactured by Nippon Kayaku Co., Ltd.), ethyl 2-dimethylaminobenzoate (manufactured by International Bio-Synthetics) Quantacure DMB), 4-dimethylaminobenzoic acid (n-butoxy) ethyl ester (Quantacure BEA, manufactured by International Bio-Synthetics), p-dimethylaminobenzoic acid isoamyl ethyl ester (Japanese version) Kayacure DMBI), 4-dimethylaminobenzoic acid 2-ethylhexyl ester (Esolol 507, manufactured by Van Dyk), and the like. A tertiary amine compound, preferably a compound having a dialkylaminobenzene structure. Among them, a dialkylaminobenzophenone compound and a dialkylamino group-containing coumarin with a maximum absorption wavelength of 350 to 450nm Particularly preferred are vegetal compounds and ketocoumarins.

As the dialkylaminobenzophenone compound, 4,4'-diethylaminobenzophenone is preferred because of its low toxicity. Since the coumarin compound containing a dialkylamine group has a maximum absorption wavelength in the ultraviolet region of 350 to 410 nm, it is of course a light-colored, colorless and transparent photosensitive resin composition, and a coloring pigment can be used to reflect the coloring pigment. Color-sensitive photosensitive film. In particular, 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one is preferable because it exhibits excellent sensitizing effect on laser light having a wavelength of 400 to 410 nm.

Among these, thioxanthone compounds and tertiary amine compounds are preferred. In particular, by containing a thioxanthone compound, deep hardenability can be improved.

When a carboxyl group-containing resin is included in the composition, the total amount of the photopolymerization initiator, the photoinitiator, and the sensitizer is, in terms of solid content, more preferably 100 parts by mass of the carboxyl group-containing resin. 35 parts by mass or less. By being 35 parts by mass or less, such light absorption is suppressed, and the hardenability at the deep portion is also improved.

In addition, these photopolymerization initiators, photostarters, and sensitizers may have low sensitivity depending on the specific wavelength due to absorption of specific wavelengths, and function as ultraviolet absorbers. However, these are not only used for the purpose of improving the sensitivity of the composition. It can absorb light of specific wavelength according to the need, improve the light reactivity of the surface, make the line shape and opening of the resist become vertical, tapered, reverse tapered, and improve the processing precision of line width or opening diameter.

The photosensitive resin composition used for the photosensitive film of the present invention may contain other components such as a block copolymer, a colorant, an elastomer, and a thermoplastic resin in addition to the above components. These components are also described below.

The photosensitive resin composition may suitably contain a block copolymer. A block copolymer refers to a copolymer of two or more polymers having different properties and linked by a covalent bond to form a long-chain molecular structure. It is preferably a solid in a range of 20 ° C to 30 ° C. As long as it is solid within this range, it can be solid at temperatures outside this range. Since the above-mentioned temperature range is solid, the adhesiveness is excellent when it is a photosensitive film or when it is applied to a support film and temporarily dried.

The block copolymer is preferably an XYX or XYX 'type block copolymer. Among XYX or XYX'-type block copolymers, Y in the center is a soft block, and the glass transition point Tg is low, preferably less than 0 ° C. Both outer X or X 'are hard blocks, and Tg is high, preferably A polymer unit having a temperature of 0 ° C or higher is preferred. The glass transition point Tg is measured by differential scanning calorimetry (DSC).

Among the XYX or XYX 'type block copolymers, it is more preferable that the copolymers are formed by polymer units having a Tg of X or X' being 50 ° C or higher, and polymer units having a Tg of Y or lower than -20 ° C. Paragraph copolymer. Among the XYX or XYX 'type block copolymers, X or X' is preferably one having high compatibility with a carboxyl group-containing resin, and Y is preferably one having low compatibility with a carboxyl group-containing resin. In this way, it can be considered that by becoming a block copolymer in which the blocks at both ends are compatible with the matrix, and the block at the center is incompatible with the matrix, it is easy to show a specific structure in the matrix.

The block copolymer is not limited to the XYX or XYX 'type, and may be used without particular limitation as long as the hard block and soft block components each have at least one type.

As the X or X ′ component, polymethyl methacrylate (PMMA), polystyrene (PS), and the like are preferable, and as the Y component, poly n-butyl acrylate (PBA) and polybutadiene ( PB) and so on. In addition, a resin having a carboxyl group such as a styrene unit, a hydroxyl group-containing unit, a carboxyl group-containing unit, an epoxy group-containing unit, an N-substituted acrylamide unit, or the like may be introduced into a part of the X or X 'component A hydrophilic unit with excellent compatibility further improves compatibility. The present inventors have found that the block copolymer obtained in this way has particularly good compatibility with the carboxyl group-containing resin described above. Surprisingly, it can improve the resistance to cold and heat shock, and more surprisingly, an elastomer is added. On the other hand, the glass transition temperature (Tg) tends to decrease. On the other hand, in the case where the block copolymer is added, the Tg does not decrease.

Examples of the method for producing the block copolymer include the methods described in Japanese Patent Application No. 2005-515281 and Japanese Patent Application No. 2007-516326. Examples of commercially available block copolymers include acrylic triblock copolymers produced by living polymerization by Arkema. Examples include SBM type represented by polystyrene-polybutadiene-polymethyl methacrylate, MAM type represented by polymethyl methacrylate-polybutyl acrylate-polymethyl methacrylate, and further MAM N type or MAM A type treated with carboxylic acid or hydrophilic group. Examples of the SBM type include E41, E40, E21, E20, etc., examples of the MAM type include M51, M52, M53, M22, etc., examples of the MAM N type include 52N, 22N, and types of the MAM A type include SM4032XM10. In addition, Kurarity manufactured by Kuraray Co., Ltd. is a block copolymer derived from methyl methacrylate and butyl acrylate.

The block copolymer is preferably a ternary block copolymer or more. In order to obtain the effect of the present invention, it is more preferable that the molecular structure synthesized by the living polymerization method is a precisely controlled block copolymer. This is considered to be because the molecular weight distribution of the block copolymer synthesized by the living polymerization method is narrow, and the respective unit characteristics become clear. The molecular weight distribution of the block copolymer used is preferably 2.5 or less, and more preferably 2.0 or less.

The weight average molecular weight of the block copolymer is generally from 20,000 to 400,000, and more preferably from 30,000 to 300,000. When the weight-average molecular weight is less than 20,000, the intended effects of toughness and flexibility are not obtained, and the adhesiveness is also poor. On the other hand, when the weight average molecular weight exceeds 400,000, the viscosity of the photocurable resin composition becomes high, and printability and developability are significantly deteriorated.

When the blending amount of the block copolymer includes a resin containing a carboxyl group in the composition, it is preferably 1 to 50 parts by mass, more preferably 5 to 100 parts by mass of the resin containing a carboxyl group. ~ 35 parts by mass. The effect is expected to be 1 part by mass or more, and 50 parts by mass or less is good in developability or coatability as a photocurable resin composition.

The photosensitive resin composition may contain a colorant. As the colorant, known colorants such as red, blue, green, and yellow can be used, and pigments, dyes, and pigments can be used. However, from the standpoint of reducing the environmental load and the impact on the human body, it is preferable not to contain halogen.

Red colorants are monoazo, diazo, azo lake, benzimidazolone, hydrazone, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridone. Specific examples include those with a color index (CI; issued by The Society of Dyers and Colourists) as follows.

Monoazo-based red colorants include Pigment Red 1, 2, 3, 4, 5, 6, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 112, 114, 146, 147, 151, 170, 184, 187, 188, 193, 210, 245, 253, 258, 266, 267, 268, 269, etc. Examples of the disazo red colorant include Pigment Red 37, 38, and 41. Examples of the monoazo lake-based red colorant include Pigment Red 48: 1, 48: 2, 48: 3, 48: 4, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53: 1, 53: 2, 57: 1, 58: 4, 63: 1, 63: 2, 64: 1, 68, and so on. Examples of the benzimidazolone red colorant include Pigment Red 171, 175, 176, 185, and 208. Examples of the actinic red colorants include Solvent Red 135, 179, Pigment Red 123, 149, 166, 178, 179, 190, 194, and 224. The diketopyrrolopyrrole-based red colorants include Pigment Red 254, 255, 264, 270, and 272. Examples of the condensed azo-based red colorant include Pigment Red 220, 144, 166, 214, 220, 221, and 242. Examples of the anthraquinone-based red colorants include Pigment Red 168, 177, and 216, Solvent Red 149, 150, 52, and 207. Examples of the quinacridone-based red colorant include Pigment Red 122, 202, 206, 207, and 209.

Blue colorants are phthalocyanine and anthraquinone. Pigments include compounds classified as pigments. For example, Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 60. As the dye system, Solvent Blue 35, 63, 68, 70, 83, 87, 94, 97, 122, 136, 67, 70 and the like can be used. In addition to the above, metal-substituted or unsubstituted phthalocyanine compounds can also be used.

Examples of the yellow colorant include monoazo-based, disazo-based, condensed azo-based, benzimidazolone-based, isoindolinone-based, and anthraquinone-based. For example, anthraquinone-based yellow colorants include Solvent Yellow 163, Pigment Yellow 24, 108, 193, 147, 199, 202, etc. Isoindolinone-based yellow colorants include Pigment Yellow 110, 109, 139, 179, 185, and the like. Examples of the condensed azo-based yellow colorant include Pigment Yellow 93, 94, 95, 128, 155, 166, 180, and the like. Examples of benzimidazolone yellow colorants include Pigment Yellow 120, 151, 154, 156, 175, and 181. Examples of the monoazo yellow colorant include Pigment Yellow 1, 2, 3, 4, 5, 6, 9, 10, 12, 61, 62, 62: 1, 65, 73, 74, 75, 97, 100, 104, 105, 111, 116, 167, 168, 169, 182, 183, etc. Examples of the disazo yellow colorant include Pigment Yellow 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152, 170, 172, 174, 176, 188, 198 and so on.

In addition, you can add purple, orange, brown, black, white and other coloring agents. Specifically, Pigment Black 1, 6, 7, 8, 9, 10, 11, 12, 13, 18, 20, 25, 26, 28, 29, 30, 31, 32; Pigment Violet 19, 23, 29, 32, 36, 38, 42; Solvent Violet 13, 36; CIPigment Orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61 , 63, 64, 71, 73; Pigment Brown 23, 25; titanium oxide, carbon black, etc.

The blending amount of the colorant is not particularly limited. When a resin containing a carboxyl group is contained in the composition, it is preferably 10 parts by mass or less, more preferably 0.1, based on 100 parts by mass of the resin containing a carboxyl group. ~ 7 parts by mass. However, the blending amount of the white colorant such as titanium oxide is in terms of solid content, and is preferably 0.1 to 200 parts by mass, more preferably 1 to 100 parts by mass, more based on 100 parts by mass of the carboxyl group-containing resin. It is preferably 3 to 80 parts by mass.

In addition, an elastomer can be blended into the photosensitive resin composition for the purpose of imparting flexibility to the obtained cured product, improving the brittleness of the cured product, and the like. Examples of the elastomer include polyester elastomers, polyurethane elastomers, polyester polyurethane elastomers, polyamide elastomers, polyester elastomers, and acrylic elastomers. Body, olefin-based elastomer. In addition, a resin obtained by modifying a part or all of epoxy groups of epoxy resins having various skeletons with both terminal carboxylic acid-modified butadiene-acrylonitrile rubbers and the like can also be used. Furthermore, a polybutadiene-based elastomer containing an epoxy group, a polybutadiene-based elastomer containing acrylic, a polybutadiene-based elastomer containing a hydroxyl group, and isoprene containing a hydroxyl group can also be used. Department of elastomers and so on. The elastomer may be used singly or as a mixture of two or more kinds.

Moreover, conventionally well-known adhesive polymers can be used for the purpose of improving the flexibility and touch-drying property of the obtained hardened | cured material. The binder polymer is preferably a cellulose-based, polyester-based, or phenoxy resin-based polymer. Examples of the cellulose-based polymer include cellulose acetate butyrate (CAB) and cellulose acetate propionate (CAP) series manufactured by Eastman. The polyester polymer is preferably Vylon manufactured by Toyobo Co., Ltd. In the series, the phenoxy resin-based polymer is preferably a phenoxy resin of bisphenol A, bisphenol F, and hydrogenated compounds thereof.

When a carboxyl group-containing resin is contained in the composition, the blending amount of the binder polymer is, in terms of solid content, preferably 50 parts by mass or less, more preferably 1 to 100 parts by mass of the carboxyl group-containing resin. 30 parts by mass, and particularly preferably 5 to 30 parts by mass. When the blending amount of the binder polymer is 50 parts by mass or less, the alkali-developability of the photosensitive resin composition is more excellent, and the development time can be lengthened.

Moreover, the photosensitive resin composition can further mix components, such as an adhesion promoter, an antioxidant, an ultraviolet absorber, as needed. These can be used in well-known fields in the field of electronic materials. In addition, it is possible to blend well-known and commonly used thickening agents such as fine powdered silica, hydrotalcite, organic bentonite, montmorillonite, etc .; polyfoam-based, fluorine-based, polymer-based antifoaming agents and leveling agents. At least any one of them; at least any one of well-known and commonly used additives such as imidazole-based, thiazole-based, triazole-based silane coupling agents, and rust inhibitors and fluorescent brighteners.

The photosensitive film can be formed by coating the photosensitive resin composition on one side of the supporting film and drying it. Considering the applicability of the photosensitive resin composition, the photosensitive resin composition can be diluted with an organic solvent and adjusted to a suitable viscosity. The notch wheel applicator, doctor blade applicator, lip applicator, and rod coating can be used. Cloth spreader, squeeze coater, reverse coater, transfer roll coater, gravure coater, spray coater are applied on one side of the support film to a uniform thickness, usually at a temperature of 50 to 130 ° C Dry for 1 to 30 minutes to volatilize the organic solvent to obtain a non-sticky coating film. The coating film thickness is not particularly limited. Generally speaking, it is appropriately selected in a range of 5 to 150 μm, preferably 10 to 60 μm, based on the film thickness after drying.

The organic solvent that can be used is not particularly limited, and examples thereof include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, and petroleum-based solvents. More specifically, ketones such as methyl ethyl ketone (MEK) and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; Kisangsu, carbitol, methylcarbitol, butylcarbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether, etc. Glycol ethers; ethyl acetate, butyl acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate , Propylene glycol butyl ether acetate and other esters; alcohols, propanol, ethylene glycol, propylene glycol and other alcohols; aliphatic hydrocarbons such as octane, decane; petroleum ether, petroleum brain, hydrogenated petroleum brain, solvents Petroleum solvents such as petroleum brain. Such organic solvents may be used alone or as a mixture of two or more.

Volatile drying of organic solvents, such as hot air circulation drying furnace, IR furnace, heating plate, convection oven, etc. Support blowing method).

[Protective film] The photosensitive film laminate of the present invention can provide a protective film on the surface of the photosensitive film opposite to the intermediate layer for the purpose of preventing dust and the like from adhering to the surface of the photosensitive film and improving the operability.

The protective film can be, for example, a polyester film, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, or a surface-treated paper. The adhesive force between the selected protective film and the photosensitive resin layer is preferably smaller than that of the supporting film and the photosensitive property. Adhesive material for resin layer. When the photosensitive film laminate is used, in order to easily peel off the protective film, the surface of the protective film adjacent to the photosensitive resin layer may be subjected to the above-mentioned release treatment.

The thickness of the protective film is not particularly limited, but is appropriately selected depending on the application in a range of about 10 to 150 μm.

<The manufacturing method of a hardened | cured material and a printed wiring board> 硬化 The hardened | cured material is formed using the photosensitive film or photosensitive film laminated body of this invention. A method for forming the cured product and a method for producing a printed wiring board including the cured product (cured film) on a substrate on which a circuit pattern is formed will be described. A method of manufacturing a printed wiring board using a photosensitive film laminate having a protective film will be described as an example. First, i) the protective film is peeled from the photosensitive film laminate to expose the photosensitive film, ii) the photosensitive film of the photosensitive film laminate is bonded to the substrate on which the circuit pattern is formed, and iii ) Exposure is performed on the support film of the aforementioned photosensitive film laminate, iv) the support film is peeled off from the aforementioned photosensitive film laminate, and development is performed to form a patterned photosensitive film on the substrate, v) The patterned photosensitive film is hardened by light irradiation or heat to form a hardened film; thereby forming a printed wiring board. In addition, when a photosensitive film laminate without a protective film is used, the peeling step (i step) of the protective film is of course not required. Each step is described below.

First, the protective film is peeled off from the photosensitive film laminate to expose the photosensitive resin layer, and the photosensitive resin layer of the photosensitive film laminate is bonded to a substrate on which a circuit pattern is formed. Examples of the substrate on which the circuit pattern is formed include a printed wiring board or a flexible printed wiring board in which a circuit is formed in advance. In addition, the use of paper phenol, epoxy paper, glass cloth epoxy resin, glass polyimide, Glass cloth / non-woven epoxy resin, glass cloth / epoxy paper, synthetic fiber epoxy resin, fluororesin / polyethylene / polyphenylene ether, polyphenylene ether / cyanate, etc. The materials are copper-clad laminates of all grades (FR-4, etc.), other polyimide films, PET films, glass substrates, ceramic substrates, wafer boards, etc.

If the photosensitive film of the photosensitive film laminate is to be bonded to a circuit board, it is preferable to use a vacuum laminator or the like, and to bond them under pressure and heating. By using such a vacuum laminator, the photosensitive resin composition layer is closely adhered to the circuit board, so that no bubbles are mixed in, and the hole filling property to the substrate surface is also improved. The pressing conditions are preferably about 0.1 to 2.0 MPa, and the heating conditions are preferably 40 to 120 ° C.

Next, exposure is performed on the support film of the photosensitive thin film laminate (irradiation with active energy rays). With this step, only the exposed photosensitive resin layer is hardened. The exposure step is not particularly limited. For example, the contact (or non-contact) method can be used to selectively expose the active energy rays by forming a photomask with a desired pattern. It is desired that the pattern is exposed with active energy rays.

The exposure machine used for active energy ray irradiation may be a device equipped with a high-pressure mercury lamp, ultra-high pressure mercury lamp, metal halide lamp, etc., which irradiates ultraviolet rays in the range of 350 to 450 nm. Further, a direct drawing device (such as from a computer The CAD data is a laser direct imaging device that directly depicts the image with a laser). As long as the laser light source of the direct scan machine uses laser light with a maximum wavelength in the range of 350 to 410 nm, gas lasers and solid lasers can be used. Although the amount of exposure used to form an image varies depending on the film thickness, etc., it can generally be in the range of 20 to 800 mJ / cm ² , preferably 20 to 600 mJ / cm ² .

After the exposure, the support film and the intermediate layer are separated and developed by the photosensitive film laminate to form a patterned photosensitive film on the substrate. After the support film and the intermediate layer are peeled off, the surface of the photosensitive film hardened by exposure is given the form of the surface of the intermediate layer. In addition, as long as it does not impair the characteristics, the support film may be peeled off from the photosensitive film laminate before exposure, and the exposed photosensitive film may be exposed and developed.

The developing step is not particularly limited, and a dipping method, a spray method, a spray method, a brush method, or the like can be used. As the developing solution, an alkali aqueous solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, or amines can be used.

Next, the patterned photosensitive film is cured by irradiation with active energy rays (light) or heat to form a cured product (cured film). This step is called formal hardening or additional hardening, which can promote the polymerization of unreacted monomers in the photosensitive film, and then thermally harden the photosensitive resin containing carboxyl group and epoxy resin to reduce the amount of remaining carboxyl group. The active energy ray irradiation can be performed in the same manner as the above-mentioned exposure, but it is preferably performed under conditions that are stronger than the irradiation energy during exposure. For example, it may be 500 to 3000 mJ / cm ² . In addition, heat curing can be performed under heating conditions of 100 to 200 ° C. for about 20 to 90 minutes. It is to be noted that the hardening is preferably performed after the light hardening. By performing light hardening first, the resin flow is also suppressed during heat hardening, and it is possible to maintain the surface given the shape.

The photosensitive film laminate of the present invention can be suitably used as a printed wiring board, can be more suitably used for the formation of a solder resist layer, and can be particularly suitably used for the formation of a solder resist layer for IC packaging. [Example]

Examples are given next to explain the present invention in more detail, but the present invention is not limited to these examples.

<Preparation of carboxyl group-containing photosensitive resin> A novolac-type cresol resin (Shonol CRG951 manufactured by Showa Denko Corporation, OH equivalent: 119.4) 119.4 g, 1.19 g of potassium hydroxide, and 119.4 g of toluene. The nitrogen in the system was replaced while stirring, and the temperature was raised by heating. Next, 63.8 g of propylene oxide was slowly dropped, and reacted at 125 to 132 ° C. and 0 to 4.8 kg / cm ² for 16 hours. Thereafter, the mixture was cooled to room temperature, and 1.56 g of 89% phosphoric acid was added to the reaction solution to neutralize potassium hydroxide to obtain an epoxy of a novolac cresol resin having a nonvolatile content of 62.1% and a hydroxyl value of 182.2 g / eq. Propane reaction solution. The obtained novolac-type cresol resin was obtained by adding an average of 1.08 mole alkylene oxide per equivalent of phenolic hydroxyl group.

293.0 g of the alkylene oxide reaction solution of the obtained novolac-type cresol resin, 43.2 g of acrylic acid, 11.53 g of methanesulfonic acid, 0.18 g of methylhydroquinone, and 252.9 g of toluene were fed into a container equipped with a stirrer, a thermometer, and an air blowing tube. In the reactor, air was blown in at a rate of 10 ml / minute, and the reaction was carried out at 110 ° C. for 12 hours while stirring. The water produced by the reaction was used as an azeotropic mixture with toluene, and 12.6 g of water was distilled off. After that, it was cooled to room temperature, and the obtained reaction solution was neutralized with 35.35 g of a 15% sodium hydroxide aqueous solution, followed by washing with water. Thereafter, toluene was replaced with 118.1 g of diethylene glycol monoethyl ether acetate with an evaporator and distilled off to obtain a novolac type acrylate resin solution. Next, 332.5 g of the obtained novolak-type acrylate resin solution and 1.22 g of triphenylphosphine were fed into a reactor equipped with a stirrer, a thermometer, and an air blowing tube, and air was blown in at a rate of 10 ml / minute while stirring. While slowly adding 62.3 g of tetrahydrophthalic anhydride and reacting at 95 to 101 ° C. for 6 hours, a photosensitive resin paint 1 containing a carboxyl group with an acid value of 88 mgKOH / g as a non-volatile component and 71% was obtained.

<Preparation of photosensitive resin composition> The photosensitive resin containing a carboxyl group obtained as described above is painted 1. Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) as a photosensitive monomer of an acrylate compound. KAYARAD DPHA), bisphenol A epoxy resin (EPICLON840-S, manufactured by DIC Corporation) as a thermosetting epoxy resin, and biphenol novolak epoxy resin (NC-made by Nippon Kayaku Co., Ltd.) 3000H), as a photopolymerization initiator, Omnirad TPO manufactured by IGM Resins, or IRGACURE OXE02 manufactured by BASF JAPAN, barium sulfate as a filler (B-30 manufactured by Sakai Chemical Industry Co., Ltd.), and / or spherical silica ( Admafine SO-E2, manufactured by Admatechs Co., Ltd.), melamine as a thermosetting catalyst, carbon black M-50 manufactured by Mitsubishi Chemical Co., Ltd., dioxazine violet CIPigment Violet 23, CIPigment Yellow 147, Each component selected in CIPigment Blue 15: 3 and CIPigment Red 177, and diethylene glycol monoethyl ether acetate as an organic solvent are used in a ratio (mass ratio) shown in Table 1 below. ) Blended in a mixer after preliminary mixing, kneading with a triple roll mill to prepare a photosensitive resin composition 1 and 2.

<Preparation of acrylic melamine resin 1> Amidir G-821-60 (iso-butylated melamine resin, solid content 60%) manufactured by DIC Corporation and ACRYDIC A-405 (acrylic resin for melamine firing) manufactured by DIC Corporation (Solid content 50%) In terms of mass ratio converted to solid content, it is blended so that it becomes 25:75, and it is kneaded with a three-roll mill after preparation with a stirrer to prepare acrylic melamine resin 1.

<Preparation of Epoxy Melamine Resin 2> U-VAN 62 (iso-butylated melamine resin, solid content 60%) manufactured by Mitsui Chemical Co., Ltd. and Epomik R301MIBK solution (bisphenol A ring) manufactured by Mitsui Chemical Co., Ltd. Oxygen resin, solid content 60%), blended in such a way that the solid content becomes 25:75 in terms of mass ratio conversion. After preliminary stirring with a stirrer, it is kneaded with a 3-roll mill to prepare epoxy melamine resin 2.

<Production of the support film 1 having the intermediate layer 1> (1) The acrylic melamine resin 1 obtained as described above was diluted with methyl ethyl ketone to prepare a resin solution having a solid content concentration of 35% by mass. To this resin solution, methyl ethyl ketone was further added to obtain a suitable solid content concentration according to the thickness of the coating film, and then a polysiloxane resin (SYMACUS-270 manufactured by Toa Synthesis Co., Ltd.) and silicon dioxide were added. The mass ratios of the acrylic melamine resin 1, the polysiloxane resin, and the silicon dioxide having an average particle diameter of 2.3 μm were set to 59.7: 0.3: 40, and the mixture was sufficiently stirred at room temperature to obtain a uniform coating solution. This coating liquid was applied to one side of a polyethylene terephthalate film (Lumirror T60 manufactured by Toray Co., Ltd.) on a support film by a gravure roll method, and dried at 130 ° C. for 20 seconds to produce an intermediate film. Support film 1 of layer 1 (thickness of the intermediate layer is 3 μm, thickness of the support film is 25 μm, and total thickness is 28 μm).

<Production of the support film 2 having the intermediate layer 2> The same as the above except that the epoxy melamine resin 2 obtained as described above is used instead of the acrylic melamine resin 1 in the production of the support film 1 having the intermediate layer 1. A support film 2 having an intermediate layer 2 (thickness of the intermediate layer of 3 μm, thickness of the support film of 25 μm, and total thickness of 28 μm) was produced.

[Table 1]

Example 1 <Production of photosensitive film laminate> 300 g of methyl ethyl ketone was added to the photosensitive resin composition 1 obtained as described above, diluted, and stirred with a stirrer for 15 minutes to obtain a coating solution. The coating liquid was applied to the surface on the intermediate layer side of the supporting film 1 having the intermediate layer 1 and dried at a temperature of 80 ° C. for 15 minutes to form a photosensitive film having a thickness of 20 μm. Next, a 18 μm-thick polypropylene film (OPP-FOA manufactured by Futaura Chemical Co., Ltd.) was bonded to the photosensitive film to prepare a photosensitive film laminate.

＜ Production of test substrate ＞ 表面 The surface of FR-4 copper-clad laminate (100mm × 150mm × 0.8mmt, double-sided copper foil, and copper foil thickness 18μm) on which the circuit is formed is chemically treated with MEZ Co., Ltd. CZ8101 Polishing, bonding the exposed surface of the photosensitive film by peeling the polypropylene film from the photosensitive film laminate obtained as described above on the chemically polished surface of the substrate, and then using a vacuum laminator (manufactured by Meiki Seisakusho) MVLP-500) The laminate was heated and laminated under the conditions of pressure: 0.8Mpa, 70 ° C., 1 minute, and vacuum: 133.3 Pa to make the substrate and the photosensitive film adhere to each other to produce a test substrate 1.

Example 2 中 In Example 1, a test substrate 2 was produced in the same manner as in Example 1 except that the photosensitive resin composition 2 was used instead of the photosensitive resin composition 1.

Example 3 中 In Example 1, a test substrate 3 was produced in the same manner as in Example 1 except that a polyethylene terephthalate film 2 having an intermediate layer 2 was used instead of the support film 1 having an intermediate layer 1.

Example 4: In Example 3, except that the photosensitive resin composition 2 was used instead of the photosensitive resin composition 1, a test substrate 4 was produced in the same manner as in Example 3.

Comparative Example 1 Example 1 was the same as Example 1 except that a polyethylene terephthalate film (Lumirror T60, manufactured by Toray Industries, Ltd.) was used instead of the support film 1 having an intermediate layer 1 in a thickness of 25 μm. Ground test substrate 5 is produced.

Comparative Example 2 In Comparative Example 1, except that the photosensitive resin composition 2 was used instead of the photosensitive resin composition 1, a test substrate 6 was produced in the same manner as in Comparative Example 1.

Comparative Example 3 Example 1 was the same as Example 1 except that a polyethylene terephthalate film (Lumirror T60 manufactured by Toray Industries, Ltd.) was used instead of the support film 1 having an intermediate layer 1 in a thickness of 38 μm. Ground test substrate 7 was produced.

Comparative Example 4: In Comparative Example 3, a test substrate 8 was produced in the same manner as in Comparative Example 3 except that the photosensitive resin composition 2 was used instead of the photosensitive resin composition 1.

<Drop resistance of test hammer> The test substrates of Examples 1 to 4 and Comparative Examples 1 to 4 produced as described above were placed on concrete, and a brass ball having a diameter of 30 mm and a weight of 120 g was used as a test hammer. The direction perpendicular to the surface of the polyethylene terephthalate film dropped from the height of 30 cm on the surface of the polyethylene terephthalate film of each of the aforementioned test substrates. Next, a parallel light exposure device equipped with a short-arc high-pressure mercury lamp was used to uniformly expose the polyethylene terephthalate film through the exposure mask, and then the polyethylene terephthalate film and the intermediate layer were peeled off. To expose the photosensitive film. It should be noted that the exposure amount is a 7-segment exposure amount when a Stouffer 41-segment exposure is performed on a polyethylene terephthalate film adjacent to the photosensitive film. The cavity formed by the drop hammer was visually evaluated on the surface of the exposed photosensitive film. The drop of the hammer was performed on each of the test substrates of Examples 1 to 4 and Comparative Examples 1 to 4 by 10 pieces each. The evaluation criteria are as follows. In addition, each test substrate was subjected to this test and evaluation 5 minutes after the heating lamination in the above-mentioned <Preparation of a test substrate>. The test and evaluation were performed under a test environment of 23 ° C and a relative humidity of 50%. ○: No cavities were confirmed on the exposed surfaces of the 10 thin films ×: A cavity was confirmed on more than 10 of the exposed photosensitive films. The evaluation results are shown in Table 2 below.

As a method for easily confirming the impact resistance of the surface of a photosensitive film, a hammer drop resistance test was performed to evaluate it. As is apparent from the examples, the use of the photosensitive film laminate in the present invention can realize a photosensitive film layer that does not affect the surface of the photosensitive film even if a strong impact is caused when the laminated substrates are overlapped. Fit. On the other hand, it is clear from the comparative example that the above-mentioned effects cannot be achieved at all even by using a photosensitive film laminate that does not satisfy the requirements of the present invention.

1‧‧‧ photosensitive film laminate

10‧‧‧ support film

20‧‧‧ middle layer

30‧‧‧ photosensitive film

40‧‧‧ protective film

[Fig. 1] A schematic cross-sectional view showing an embodiment of a photosensitive film laminate according to the present invention. [FIG. 2] A schematic cross-sectional view showing another embodiment of the photosensitive film laminate of the present invention.

Claims (5)

A photosensitive film laminate comprising a support film, an intermediate layer, and a photosensitive film laminated with a photosensitive film formed of a photosensitive resin composition in this order, wherein the intermediate layer contains melamine and It is made of at least any one kind of melamine compound. For example, the photosensitive film laminate of claim 1, wherein the thickness of the support film is 10 to 150 μm. The photosensitive film laminate according to claim 1 or 2, wherein the photosensitive resin composition contains a filler and a crosslinking component. The photosensitive film laminate according to claim 1 or 2, further comprising a protective film on the side of the photosensitive film opposite to the intermediate layer. A cured product formed by using the photosensitive thin film laminate according to any one of claims 1 to 4.