JP6845772B2 - Photosensitive film laminate and cured product formed using it - Google Patents

Description

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

Generally, in a printed wiring board used for electronic devices and the like, when mounting electronic components on the printed wiring board, on a substrate on which a circuit pattern is formed in order to prevent solder from adhering to unnecessary parts. A solder resist layer is formed in the region other than the connection hole of the above.

With the recent increase in precision and density of printed wiring boards due to lighter, thinner, shorter and smaller electronic devices, the solder resist layer is currently coated with a photosensitive resin composition on a substrate, dried, and then patterned by exposure and development. The mainstream is that the patterned resin is formed by a so-called photosolder resist, which is mainly cured by heating or light irradiation.

It has also been proposed to form a solder resist layer using a so-called photosensitive film laminate provided with a photosensitive film without using the liquid photosensitive resin composition as described above. Such a photosensitive film laminate is generally formed by laminating a photosensitive film formed of a photosensitive resin composition on a support film, and protects the surface of the photosensitive film as necessary. The film may be stuck together. Such a photosensitive film laminate is developed by peeling off the protective film at the time of use, laminating it on a wiring substrate by heat bonding, and peeling off the support film before exposure or after exposure from the support film side. Therefore, a patterned solder resist layer can be formed. By using the photosensitive film laminate, in addition to eliminating the need for a drying step after coating, the surface smoothness and surface hardness of the obtained solder resist layer are also excellent as compared with the case of wet coating. Further, in recent years, from the viewpoint of workability, the photosensitive film tends to be thinned, and not only the photosensitive film but also the support film on which the photosensitive film is laminated tends to be thinned.

International Publication 2010/013623 Pamphlet Japanese Unexamined Patent Publication No. 2011-48270

In the step of forming the solder resist layer on the wiring board as described above, after laminating the photosensitive film laminate on the wiring board, the laminated wiring boards are sequentially stacked and temporarily before proceeding to the next step. May be stored as a target. In that case, the surface of the photosensitive film laminate provided on the wiring board may be damaged by the impact when stacking the wiring boards to which the photosensitive film laminates are laminated or the weight of the wiring boards when the photosensitive film laminates are laminated. 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 is damaged due to the impact at the time of stacking and the pressing due to its own weight. There is.

Therefore, an object of the present invention is a photosensitive film laminate capable of suppressing an influence on the photosensitive film surface even by a strong impact or pressure when a substrate or the like on which the photosensitive film laminate is laminated is laminated. Is to provide. Another object of the present invention is to provide a cured product formed by using the photosensitive film laminate.

The present inventors have now said that the damage to the surface of the photosensitive film due to impact or pressing when the substrates or the like on which the photosensitive film laminates are laminated is caused only by the impact resistance of the photosensitive film itself. However, it was found that it is largely related to the material of the layer in contact with the surface of the photosensitive film, that is, the layer in direct contact with the photosensitive film. Then, the present inventors have made a substrate or the like on which the photosensitive film laminate is laminated by forming a laminate provided between the support film having an intermediate layer containing a specific component and the photosensitive film. It was found that the influence on the surface of the photosensitive film can be suppressed even by a strong impact or pressure when the films are overlapped.
Furthermore, the present inventors have determined that the solder resist layer formed by using the photosensitive film laminate provided with the intermediate layer containing the above-mentioned specific component does not affect the surface thereof due to impact, and therefore the yield is high. It was found that it can be improved. The present invention is based on such findings.

That is, the photosensitive film laminate according to the present invention is a photosensitive film laminate comprising a support film, an intermediate layer, and a photosensitive film formed of a photosensitive resin composition in that order.
The intermediate layer is characterized by containing at least one of melamine and a melamine compound.

In the aspect of the present invention, the thickness of the support film is preferably 10 to 150 μm.

In the aspect of the present invention, it is preferable that the photosensitive resin composition contains a filler and a cross-linking component.

In the aspect of the present invention, it is preferable that the photosensitive film is further provided with a protective film on the side opposite to the intermediate layer.

Further, the cured product according to another aspect of the present invention is characterized in that it is formed by using the above-mentioned photosensitive film laminate.

According to the present invention, a substrate in which a photosensitive film laminate is laminated by forming a photosensitive film laminate in which an intermediate layer containing a specific component as described above is provided between the photosensitive film and a support film. It is possible to suppress the influence on the surface of the photosensitive film even by a strong impact or pressing when the above is superposed. In particular, it is effective when the above-mentioned photosensitive film laminate is used for forming a solder resist layer. Further, even if the support film is a thin film, it is effective in that the above effect is obtained. Further, according to another aspect of the present invention, a cured product formed by using the photosensitive film laminate can be realized.

It is the schematic sectional drawing which showed one Embodiment of the photosensitive film laminate by this invention. It is the schematic sectional drawing which showed the other embodiment of the photosensitive film laminate by this invention.

The photosensitive film laminate according to the present invention will be described with reference to the 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 according to 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 laminated in this order. Here, the photosensitive film refers to a film in which the photosensitive resin composition is formed into a film shape, and other layers such as a support film and a protective film are not laminated. Further, in the present invention, another film or the like may be provided in addition to the above configuration. For example, as shown in FIG. 2, the photosensitive film laminate 1 is photosensitive in consideration of the handleability of the photosensitive film laminate while preventing dust and the like from adhering to the surface of the photosensitive film. A protective film 40 may be further provided on the surface side of the film 30 opposite to the intermediate layer 20. Hereinafter, each component constituting the film laminate according to the present invention will be described.

[Support film]
The support film in the photosensitive film laminate of the present invention supports the photosensitive film described later, and is predetermined on the surface of the photosensitive film on the side in contact with the support film during exposure and development as described later. It has a role of shaping the surface morphology.

As the support film in the photosensitive film laminate of the present invention, any known one can be used without particular limitation. For example, a polyester film such as polyethylene terephthalate or polyethylene naphthalate, a polyimide film, a polyamideimide film, or polypropylene can be used. A film made of a thermoplastic resin such as a film or a polystyrene film can be preferably used. When the thermoplastic resin film is used, a filler is added (kneaded) into the resin when the film is formed, a matte coating (coating treatment) is applied, and the film surface is sandblasted. It may be blasted, hairlined, or chemically etched. Among these, a polyester film can be preferably used from the viewpoints of heat resistance, mechanical strength, handleability and the like. The support film may be a single layer, or two or more layers may be laminated.

Further, as the thermoplastic resin film as described above, it is preferable to use a film stretched in the uniaxial direction or the biaxial direction for the purpose of improving the strength.

The thickness of the support film is preferably in the range of 10 to 150 μm, more preferably in the range of 10 to 100 μm, and even more preferably in the range of 10 to 50 μm from the viewpoint of handleability.

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

<Middle 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, the present inventors have 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 supporting film and the photosensitive film. The reason is not always clear, but it is presumed that the intermediate layer protects the surface of the laminated photosensitive film from strong impact, and as a result, it does not affect the surface condition of the photosensitive film. It is a range, not necessarily this.

The thickness of the intermediate layer is preferably in the range of 0.1 to 10 μm, more preferably in the range of 1 to 8 μm from the viewpoint of protecting the photosensitive film.

As the melamine and the melamine compound contained in the intermediate layer, known and commonly used compounds can be used. Further, in the present invention, the melamine compound also includes a mixture of the melamine compound and another substance. In the present invention, "melamine" refers to a resin cured by polycondensation of melamine (2,4,6-triamino-1,3,5-triazine) and formaldehyde, and the initial stage of such melamine and formaldehyde. The concept also includes methylol melamine, which is a reaction product, and alkylated methylol melamine, which is an alkylated product thereof. The melamine also includes modified melamines such as methylated methylol melamine, propylated methylol melamine, butylated methylol melamine, and isobutylized methylol melamine. It also includes melamine-modified products such as melamine (meth) acrylate.

The melamine compound is a mixture of the above-mentioned melamine and another resin 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, acrylic melamine and epoxy melamine are preferable, and acrylic melamine is more preferable, because more excellent impact resistance can be obtained. The acrylic melamine here is a mixture of an acrylic resin and a melamine resin, and refers to a type in which the acrylic resin is cured with the melamine resin. The epoxy melamine is a mixture of an epoxy resin and a melamine resin, and refers to a type in which the epoxy resin is cured with the melamine resin. Specific examples of melamine include Amidia J-820-60, L-109-65, L-117-60, L-127-60, 13-548, G-821-60, L-110- manufactured by DIC Corporation. Examples thereof include 60G, L-125-60, L-166-60B, L-105-60, Uban 20SE60, 20SB, 22R, 125, 132, 62, 60R and 169 manufactured by Mitsui Chemicals, Inc. Further, as the acrylic resin and the epoxy resin, known and commonly used ones can be used 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 Epomic R301 manufactured by Mitsui Chemicals, Inc. The content of the melamine resin is preferably 0.1 to 50% by mass, more preferably 1 to 40% by mass, based on the total amount of the acrylic resin or epoxy resin.

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

The intermediate layer may contain other resins as long as the effect is not impaired. In particular, it is preferable that the intermediate layer contains a silicone-based resin as a resin component. In the photosensitive film laminate according to the present invention, when the photosensitive film is cured to form a cured film, it is necessary to peel off the support film and the intermediate layer from the photosensitive film (cured film), but the intermediate layer is made of silicone. By containing the based resin, the support film and the intermediate layer can be easily peeled off from the photosensitive film, and the adhesion between the support film and the intermediate layer can be maintained. Further, when the above-mentioned melamine or melamine compound and the silicone-based resin are contained in the intermediate layer, it is possible to further suppress damage to the surface of the photosensitive film due to impact or pressing. The silicone-based resin can be used without particular limitation, and examples thereof include Cymac US-120, US-150, US-270, US-350, and Aron GS-30 manufactured by Toagosei Co., Ltd.

Further, the intermediate layer may appropriately contain a filler, a curing accelerator, an additive, an antistatic agent and the like as components other than the resin. As the filler, known fillers can be used without particular limitation, and examples thereof include silica and calcium carbonate. Among them, silica is preferable. The average particle size 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 even more preferably 2.0 to 3.0 μm. Further, as the antistatic agent, conventionally known power failure prevention agents can be used, and among them, a cationic surfactant containing a quaternary ammonium salt represented by the following general formula (I) as a main component is preferable. Can be used for. By including a cationic surfactant as represented by the following formula in the intermediate layer, it is possible to further suppress damage to the surface of the photosensitive film due to impact or pressing.

（式中、Ｒは炭素原子数８以上のアルキル基を表し、Ｒ_１は低級アルキル基を表し、Ｒ_２は低級アルキレン基を表す。）

(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.)

（式中、Ｒは炭素原子数８以上のアルキル基を表わす。） Among the cationic surfactants of the above formula (I), those represented by the following general formula (II) can be more preferably used.

(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 cured film provided on a circuit board. The cured film is preferably a solder resist layer. Such a photosensitive film is formed by using a photosensitive resin composition, and a conventionally known solder resist ink or the like can be used without limitation in the photosensitive resin composition, but the photosensitive film according to the present invention can be preferably used below. An example of the photosensitive resin composition will be described.

In the present invention, the photosensitive resin composition preferably contains a cross-linking component and a filler. Further, it is more preferable to include a photopolymerization initiator. The cross-linking component is preferably a carboxyl group-containing photosensitive resin or a photosensitive monomer, and when further heated, it preferably contains a component that is cross-linked by heat. Hereinafter, each component will be described.

[Crosslink component]
The cross-linking component is not particularly limited as long as it is a cross-linking component, and known and commonly used components can be used. In particular, a carboxyl group-containing photosensitive resin or a photosensitive monomer is preferable, and when further heated, it is preferable to contain a component that is crosslinked by heat (hereinafter, a thermally crosslinked component).

The carboxyl group-containing photosensitive resin is a component that is polymerized or crosslinked and cured by light irradiation, and can be made alkaline developable by containing a carboxyl group. Further, from the viewpoint of photocurability and development resistance, it is preferable to have an ethylenically unsaturated bond in the molecule in addition to the carboxyl group. The ethylenically unsaturated double bond is preferably derived from acrylic acid or methacrylic acid or a derivative thereof.

Further, as the carboxyl group-containing photosensitive resin, it is preferable to use a carboxyl group-containing photosensitive resin that does not use an epoxy resin as a starting material. The carboxyl group-containing photosensitive resin that does not use an epoxy resin as a starting material has a very low halide ion content and can suppress deterioration of insulation reliability. Specific examples of the carboxyl group-containing photosensitive resin include compounds (either oligomers or polymers) listed below.

(1) A bifunctional or higher polyfunctional (solid) epoxy resin is reacted with (meth) acrylic acid, and the hydroxyl groups present in the side chains are subjected to two bases such as phthalic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride. Carboxyl group-containing photosensitive resin with acid anhydride added,
(2) A (meth) acrylic acid is reacted with a polyfunctional epoxy resin obtained by epoxidizing a hydroxyl group of a bifunctional (solid) epoxy resin with epichlorohydrin, and a dibasic acid anhydride is added to the generated hydroxyl group. Carboxyl group-containing photosensitive resin,
(3) An epoxy compound having two or more epoxy groups in one molecule, a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule, and non-hydride such as (meth) acrylic acid. A multi-base such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipic acid, etc., with respect to the alcoholic hydroxyl group of the reaction product obtained by reacting with a saturated group-containing monocarboxylic acid. Carboxyl group-containing photosensitive resin obtained by reacting acid anhydride,
(4) Two or more in one molecule such as bisphenol A, bisphenol F, bisphenol S, novolak type phenol resin, poly-p-hydroxystyrene, condensate of naphthol and aldehydes, condensate of dihydroxynaphthalene and aldehydes, etc. A reaction obtained by reacting a reaction product obtained by reacting a compound having a phenolic hydroxyl group with an alkylene oxide such as ethylene oxide or propylene oxide with an unsaturated group-containing monocarboxylic acid such as (meth) acrylic acid. A carboxyl group-containing photosensitive resin obtained by reacting a product with a polybasic acid anhydride,
(5) An unsaturated group-containing monocarboxylic acid is reacted with a reaction product obtained by reacting a compound having two or more phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate. , A carboxyl group-containing photosensitive resin obtained by reacting the obtained reaction product with a polybasic acid anhydride,
(6) Aliphatic compounds such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates, and polycarbonate-based polyols, polyether-based polyols, polyester-based polyols, polyolefin-based polyols, acrylic-based polyols, and bisphenol A-based An alkylene oxide adduct diol, a terminal carboxyl group-containing urethane resin obtained by reacting an acid anhydride with the end of a urethane resin produced by a double addition reaction of a diol compound such as a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.
(7) Molecules such as hydroxyalkyl (meth) acrylate during the synthesis of a carboxyl group-containing urethane resin by a double addition reaction between a diisocyanate, a carboxyl group-containing dialcohol compound such as dimethylolpropionic acid and dimethylolbutyric acid, and a diol compound. A carboxyl group-containing urethane resin obtained by adding a compound having one hydroxyl group and one or more (meth) acryloyl groups to the terminal (meth) acrylic.
(8) During the synthesis of the carboxyl group-containing urethane resin by the double addition reaction of the diisocyanate, the carboxyl group-containing dialcohol compound, and the diol compound, 1 in the molecule, such as an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate. A carboxyl group-containing urethane resin that is terminally (meth) acrylicated by adding a compound having one isocyanate group and one or more (meth) acryloyl groups.
(9) Carboxyl group-containing photosensitive obtained by copolymerization of an unsaturated carboxylic acid such as (meth) acrylic acid with an unsaturated group-containing compound such as styrene, α-methylstyrene, lower alkyl (meth) acrylate, and isobutylene. resin,
(10) A carboxyl group obtained by reacting a polyfunctional oxetane resin as described later with a dicarboxylic acid such as adipic acid, phthalic acid, or hexahydrophthalic acid, and adding a dibasic acid anhydride to the generated primary hydroxyl group. A carboxyl group formed by adding a compound having one epoxy group and one or more (meth) acryloyl groups in one molecule such as glycidyl (meth) acrylate and α-methylglycidyl (meth) acrylate to the contained polyester resin. A compound having a cyclic ether group and a (meth) acryloyl group in one molecule was added to the containing photosensitive resin and (11) the carboxyl group-containing photosensitive resin according to any one of (1) to (10) described above. Examples thereof include a photosensitive resin containing a carboxyl group. Here, (meth) acrylate is a general term for acrylate, methacrylate and a mixture thereof, and the same applies to other similar expressions below.

Among the above-mentioned carboxyl group-containing photosensitive resins, as described above, a carboxyl group-containing photosensitive resin that does not use an epoxy resin as a starting material can be preferably used. Therefore, among the specific examples of the above-mentioned carboxyl group-containing photosensitive resin, one or more of the carboxyl group-containing photosensitive resins (4) to (8) can be particularly preferably used.

As described above, by not using the epoxy resin as a starting material, the amount of chlorine ion impurities can be suppressed to a very small value of 100 ppm or less, for example. The chlorine ion impurity content of the carboxyl group-containing photosensitive resin preferably used in the present invention is 0 to 100 ppm, more preferably 0 to 50 ppm, 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 resin having a reduced amount of hydroxyl groups) can be easily obtained. Generally, the presence of a hydroxyl group also has excellent characteristics such as improvement of adhesion due to hydrogen bonding, but it is known that the moisture resistance is significantly reduced, and a carboxyl group-containing photosensitive resin containing no hydroxyl group is used. This makes it possible to improve the moisture resistance.

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 having a chlorine ion impurity amount of 0 to 30 ppm is also preferably used. In such a urethane resin, a resin containing no hydroxyl group can be easily synthesized by matching the equivalents of the hydroxyl group and the isocyanate group.

Further, when synthesizing the urethane resin, an epoxy acrylate-modified raw material can also be used as the diol compound. Although chlorine ion impurities are included, it can be used from the viewpoint that the amount of chlorine ion impurities can be controlled.

From this point of view, for example, in order to obtain a photosensitive resin composition having more excellent PCT resistance, HAST resistance, and thermal shock resistance as a solder resist for a semiconductor package, the above-mentioned carboxyl group-containing photosensitive resin (4) to The carboxyl group-containing photosensitive resin of any one or more of (8) can be more preferably used.

Further, with respect to the carboxyl group-containing photosensitive resin (9) obtained by copolymerization with the unsaturated group-containing compound shown above, 3, 4 as a compound having a cyclic ether group and a (meth) acryloyl group in one molecule. -Since the carboxyl group-containing photosensitive resin reacted with the epoxycyclohexylmethylmethacrylate also uses the alicyclic epoxy, it has few chlorine ion impurities and can be preferably used.

Further, by using any one or more of the above-mentioned carboxyl group-containing photosensitive resins (4) to (8) in combination with the above-mentioned (9) carboxyl group-containing photosensitive resin, the adhesion to the molding material is further improved. ,preferable.

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

The acid value of the carboxyl group-containing photosensitive resin is preferably 40 to 150 mgKOH / g. When the acid value of the carboxyl group-containing photosensitive resin is 40 mgKOH / g or more, alkaline development becomes good. Further, by setting the acid value to 150 mgKOH / g or less, it is possible to easily draw a normal resist pattern. More preferably, it is 50 to 130 mgKOH / g.

The weight average molecular weight of the carboxyl group-containing photosensitive resin varies depending on the resin skeleton, but is generally preferably 2,000 to 150,000. By setting the weight average molecular weight to 2,000 or more, tack-free performance and resolution can be improved. Further, 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 carboxyl group-containing photosensitive resin is preferably 20 to 60% by mass in the total composition in terms of solid content. The coating film strength can be improved by setting the content to 20% by mass or more. Further, when the content is 60% by mass or less, the viscosity becomes appropriate and the workability is improved. More preferably, it is 30 to 50% by mass.

Examples of the compound used as the photosensitive monomer include commonly known polyester (meth) acrylate, polyether (meth) acrylate, urethane (meth) acrylate, carbonate (meth) acrylate, and epoxy (meth) acrylate. Specifically, hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol and propylene glycol; N, N-dimethylacrylamide. , N-methylol acrylamide, acrylamides such as N, N-dimethylaminopropyl acrylamide; aminoalkyl acrylates such as N, N-dimethylaminoethyl acrylate, N, N-dimethylaminopropyl acrylate; Polyhydric alcohols such as pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate or polyhydric acrylates such as their ethireoxyside adducts, propylene oxide adducts, or ε-caprolactone adducts; phenoxyacrylates, bisphenol A di. Acrylate, and polyvalent acrylates such as ethylene oxide adducts or propylene oxide adducts of these phenols; glycidyl ethers such as glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylolpropan triglycidyl ether, triglycidyl isocyanurate. Polyvalent acrylates; Not limited to the above, acrylates and melamine acrylates obtained by directly acrylated polyols such as polyether polyols, polycarbonate diols, hydroxyl group-terminated polybutadienes, and polyester polyols, or urethane acrylates via diisocyanates, and the acrylates. It can be appropriately selected and used from at least one of each methacrylate corresponding to the above.

An epoxy acrylate resin obtained by reacting a polyfunctional epoxy resin such as cresol novolac type epoxy resin with acrylic acid, and a hydroxy acrylate such as pentaerythritol triacrylate and a diisocyanate half urethane such as isophorone diisocyanate on the hydroxyl group of the epoxy acrylate resin. An epoxy urethane acrylate compound obtained by reacting the compound or the like may be used as the photosensitive monomer. Such an epoxy acrylate-based resin can improve the photocurability without lowering the dryness to the touch.

When the composition contains a carboxyl group-containing resin, the amount of the compound having an ethylenically unsaturated group in the molecule used as the photosensitive monomer is preferably 100 parts by mass of the carboxyl group-containing resin in terms of solid content. Is 5 to 100 parts by mass, more preferably 5 to 70 parts by mass. By setting the blending amount of the compound having an ethylenically unsaturated group to 5 parts by mass or more, the photocurability of the photocurable resin composition is improved. Further, the hardness of the coating film can be improved by setting the blending amount to 100 parts by mass or less. The carboxyl group-containing resin referred to here includes both a carboxyl group-containing photosensitive resin and a carboxyl group non-photosensitive resin. That is, when any one of them is blended alone in the composition, it means a single blend, and when both are blended, it means the total (the same applies in the following paragraphs).

When a carboxyl group-containing non-photosensitive resin having no ethylenically unsaturated double bond is used as the photosensitive monomer, one or more ethylenically unsaturated in the molecule is used to make the composition photocurable. It is effective because it is necessary to use a compound having a group (photosensitive monomer) in combination.

Examples of the heat-crosslinking component include thermosetting resins. Examples of the thermosetting resin include known and commonly used resins such as isocyanate compounds, blocked isocyanate compounds, amino resins, maleimide compounds, benzoxazine resins, carbodiimide resins, cyclocarbonate compounds, polyfunctional epoxy compounds, polyfunctional oxetane compounds, and episulfide resins. Can be used. Among these, a preferable heat-crosslinking component is a heat-crosslinking component having at least one of a plurality of cyclic ether groups and cyclic thioether groups (hereinafter, abbreviated as cyclic (thio) ether group) in one molecule. Many of these thermosetting components having a cyclic (thio) ether group are commercially available, and various properties can be imparted depending on the structure thereof.

A thermosetting component having a plurality of cyclic (thio) ether groups in a molecule has a plurality of one or two types of a 3, 4 or 5 membered cyclic ether group or a cyclic thio ether group in the molecule. A compound, for example, a compound having a plurality of epoxy groups in the molecule, that is, a polyfunctional epoxy compound, a compound having a plurality of oxetanyl groups in the molecule, that is, a polyfunctional oxetane compound, a compound having a plurality of thioether groups in the molecule. That is, an episulfide resin and the like can be mentioned.

Examples of the polyfunctional epoxy compound include jER828, jER834, jER1001, jER1004 manufactured by Mitsubishi Chemical Corporation, Epicron 840, Epicron 840-S manufactured by DIC Corporation, Epicron 850, Epicron 1050, Epicron 2055, and Epototo YD manufactured by Toto Kasei Co., Ltd. -011, YD-013, YD-127, YD-128, DIC manufactured by Dow Chemical Corporation. E. R. 317, D.I. E. R. 331, D.I. E. R. 661, D.I. E. R. 664, Sumitomo Chemical Co., Ltd. Sumi-Epoxy ESA-011, ESA-014, ELA-115, ELA-128, Asahi Kasei Kogyo Co., Ltd. E. R. 330, A. E. R. 331, A. E. R. 661, A. E. R. Bisphenol A type epoxy resin of 664 etc. (all trade names); jERYL903 manufactured by Mitsubishi Chemical Corporation, Epicron 152 and Epicron 165 manufactured by DIC, Epototo YDB-400, YDB-500 manufactured by Toto Kasei Co., Ltd., manufactured by Dow Chemical Corporation D. E. R. 542, Sumitomo Chemical Co., Ltd. Sumi-Epoxy ESB-400, ESB-700, Asahi Kasei Kogyo Co., Ltd. E. R. 711, A. E. R. Brominated epoxy resin of 714 etc. (both are trade names); jER152, jER154 manufactured by Mitsubishi Chemical Corporation, and D.C. E. N. 431, D.I. E. N. 438, Epicron N-730, Epicron N-770, Epicron N-865 manufactured by DIC, Epototo YDCN-701, YDCN-704 manufactured by Toto Kasei Co., Ltd., EPPN-201, EOCN-1025, EOCN manufactured by Nippon Kayaku Co., Ltd. -1020, EOCN-104S, RE-306, NC-3000H, Sumitomo Chemical Co., Ltd. Sumi-Epoxy ESCN-195X, ESCN-220, Asahi Kasei Kogyo Co., Ltd. E. R. Novolak type epoxy resins such as ECN-235 and ECN-299 (all trade names); Epicron 830 manufactured by DIC, jER807 manufactured by Mitsubishi Chemical Co., Ltd., Epototo YDF-170, YDF-175, YDF-2004 manufactured by Toto Kasei Co., Ltd. Etc. (trade names); hydrogenated bisphenol A type epoxy resins such as Epototo ST-2004, ST-2007, ST-3000 (trade name) manufactured by Toto Kasei Co., Ltd .; manufactured by Mitsubishi Chemical Co., Ltd. glycidylamine type epoxy resin such as jER604, Epototo YH-434 manufactured by Toto Kasei Co., Ltd., Sumi-epoxy ELM-120 manufactured by Sumitomo Chemical Co., Ltd .; ) Alicyclic epoxy resin; YL-933 manufactured by Mitsubishi Chemical Co., Ltd., T.K. E. N. , EPPN-501, EPPN-502, etc. (all trade names) trihydroxyphenylmethane type epoxy resins; Mitsubishi Chemical Co., Ltd. YL-6056, YX-4000, YL-6121 (all trade names), etc. Mold or biphenol type epoxy resin or a mixture thereof; Bisphenol S type epoxy resin such as EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by Asahi Denka Kogyo Co., Ltd., EXA-1514 (trade name) manufactured by DIC Co., Ltd .; Mitsubishi Chemical Bisphenol A novolac type epoxy resin such as jER157S (trade name) manufactured by Mitsubishi Chemical Co., Ltd .; Tetraphenylol ethane type epoxy resin such as jERYL-931 (trade name) manufactured by Mitsubishi Chemical Co., Ltd .; TEPIC etc. manufactured by Nissan Chemical Industry Co., Ltd. (trade name) ) Diglycidyl phthalate resin such as Blemmer DGT manufactured by Nippon Yushi Co., Ltd .; Tetraglycidyl xylenoyl ethane resin manufactured by Toto Kasei Co., Ltd. such as ZX-1063; ESN-190, ESN- Epoxy resin containing naphthalene group such as 360, HP-4032, EXA-4750, EXA-4700 manufactured by DIC; epoxy resin having a dicyclopentadiene skeleton such as HP-7200, HP-7200H manufactured by DIC, EXA-4816, EXA -4822, EXA-4850 series flexible tough epoxy resin; glycidyl methacrylate copolymerized epoxy resin such as CP-50S, CP-50M manufactured by Nippon Oil & Fats Co., Ltd .; and glycidyl methacrylate copolymerized epoxy resin of cyclohexyl maleimide and glycidyl methacrylate. However, it is not limited to these. 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, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, and 1,4-bis [(3-methyl-). 3-Oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3-oxetanyl) methyl acrylate, (3-ethyl-3-oxetanyl) In addition to polyfunctional oxetane such as methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate and their oligomers or copolymers, oxetane alcohol and novolak resin, poly (P-Hydroxystyrene), cardo-type bisphenols, calix arrayes, calix resorcinarenes, etherified compounds with a resin having a hydroxyl group such as silsesquioxane, and the like can be mentioned. In addition, a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate can also be mentioned.

Examples of the episulfide resin having a plurality of cyclic thioether groups in the molecule include YL7000 (bisphenol A type episulfide resin) manufactured by Mitsubishi Chemical Corporation. Further, using the same synthesis method, an episulfide resin in which the oxygen atom of the epoxy group of the novolak type epoxy resin is replaced with a sulfur atom can also be used.

The blending amount of the thermosetting component having a plurality of cyclic (thio) ether groups in the molecule is the solid content when the composition contains a thermosetting component having a plurality of cyclic (thio) ether groups in the molecule. In terms of conversion, it is preferably in the range of 0.3 to 2.5 equivalents, more preferably 0.5 to 2.0 equivalents, with respect to 1 equivalent of the carboxyl groups 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, no carboxyl group remains in the cured film, and heat resistance, alkali resistance, and electrical insulation are provided. Etc. are improved. Further, when the amount is 2.5 equivalents or less, low molecular weight cyclic (thio) ether groups do 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 the molecule is used, it is preferable to add a thermosetting catalyst. Examples of such a thermocuring catalyst include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole. , 1- (2-Cyanoethyl) -2-ethyl-4-methylimidazole and other imidazole derivatives; dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N Examples thereof include amine compounds such as -dimethylbenzylamine, 4-methyl-N, N-dimethylbenzylamine, hydrazine compounds such as adipate dihydrazide and sebacic acid dihydrazide; and phosphorus compounds such as triphenylphosphine. Commercially available products include, for example, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (both are trade names of imidazole compounds) manufactured by Shikoku Kasei Kogyo Co., Ltd., and U-CAT (registered) manufactured by San Apro Co., Ltd. Examples thereof include (trademarks) 3503N, U-CAT3502T (trade names of blocked isocyanate compounds of dimethylamine), DBU, DBN, U-CATSA102, U-CAT5002 (all of which are bicyclic amidine compounds and salts thereof). In particular, the present invention is not limited to these, as long as it is a thermosetting catalyst of an epoxy resin or an oxetane compound, or one that promotes the reaction of an epoxy group and / or an oxetaneyl group and a carboxyl group, and is used alone or in combination of two or more. You may use it. In addition, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino S-triazine derivatives such as -S-triazine-isocyanuric acid adduct and 2,4-diamino-6-methacryloyloxyethyl-S-triazine-isocyanulic acid adduct can also be used, preferably as these adhesion-imparting agents. A compound that also functions is used in combination with a thermosetting catalyst.

When the composition contains a thermosetting component having a plurality of cyclic (thio) ether groups in the molecule, the amount of the thermosetting catalyst blended is such that a plurality of cyclic (thio) ether groups in the molecule are contained in terms of solid content. It is preferably 0.1 to 20 parts by mass, and more preferably 0.5 to 15.0 parts by mass with respect to 100 parts by mass of the thermosetting component having.

Examples of the amino resin include amino resins such as melamine derivatives and benzoguanamine derivatives. For example, there are a methylol melamine compound, a methylol benzoguanamine compound, a methylol glycol uryl compound and a methylol urea compound. Further, the alkoxymethylated melamine compound, the alkoxymethylated benzoguanamine compound, the alkoxymethylated glycol uryl compound and the alkoxymethylated urea compound have the methylol groups of the methylol melamine compound, the methylol benzoguanamine compound, the methylol glycol uryl compound and the methylol urea compound, respectively. It is obtained by converting to an alkoxymethyl group. The type of the alkoxymethyl group is not particularly limited, and may be, for example, a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a butoxymethyl group, or the like. In particular, a melamine derivative having a formalin concentration of 0.2% or less, which is friendly to the human body and the environment, is preferable.

Examples of commercially available amino resins include Cymel 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202, and 1156. , 1158, 1123, 1170, 1174, UFR65, 300 (all manufactured by Mitsui Siana Mid), Nicarac Mx-750, Mx-032, Mx-270, Mx-280, Mx- 290, Mx-706, Mx-708, Mx-40, Mx-31, Ms-11, Mw-30, Mw-30HM, Mw-390, Mw-100LM, Mw- 750LM, (all manufactured by Sanwa Chemical Co., Ltd.) and the like can be mentioned.

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, aromatic polyisocyanate, aliphatic polyisocyanate or alicyclic polyisocyanate is used. Specific examples of the aromatic polyisocyanate include 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-xylylene diisocyanate, and m-. Examples include xylylene diisocyanate and 2,4-tolylen dimer. Specific examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-methylene bis (cyclohexyl isocyanate) and isophorone diisocyanate. Specific examples of the alicyclic polyisocyanate include bicycloheptane triisocyanate. In addition, the adduct form, the burette form and the isocyanurate form of the isocyanate compounds mentioned above can be mentioned.

The blocked isocyanate group contained in the blocked isocyanate compound is a group in which the isocyanate group is protected by the reaction with the blocking agent and temporarily inactivated. When heated to a predetermined temperature, the blocking agent dissociates to form an isocyanate group.

As the blocked isocyanate compound, an addition reaction product of the isocyanate compound and the isocyanate blocking agent is used. Examples of the isocyanate compound capable of reacting with the blocking agent include isocyanurate type, biuret type, adduct type and the like. Examples of the isocyanate compound used for synthesizing the blocked isocyanate compound include aromatic polyisocyanates, aliphatic polyisocyanates and alicyclic polyisocyanates. Specific examples of the aromatic polyisocyanate, the aliphatic polyisocyanate, and the alicyclic polyisocyanate include compounds as exemplified above.

Examples of the isocyanate blocking agent include phenolic blocking agents such as phenol, cresol, xylenol, chlorophenol and ethylphenol; lactam blocking agents such as ε-caprolactam, δ-parellolactam, γ-butyrolactam and β-propiolactam; Active methylene blocking agents such as ethyl acetoacetate and acetylacetone; methanol, ethanol, propanol, butanol, amyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, benzyl Alcohol-based blocking agents such as ether, methyl glycolate, butyl glycolate, diacetone alcohol, methyl lactate and ethyl lactate; oxime-based blocking agents such as formaldehyde oxime, acetoaldoxime, acetoxime, methyl ethyl ketoxim, diacetyl monooxime and cyclohexane oxime. Mercaptan-based blocking agents such as butyl mercaptan, hexyl mercaptan, t-butyl mercaptan, thiophenol, methyl thiophenol, ethyl thiophenol; acid amide-based blocking agents such as acetate amide and benzamide; imides such as succinate imide and maleate imide. Examples thereof include amine-based blocking agents such as xylidine, aniline, butylamine, and dibutylamine; imidazole-based blocking agents such as imidazole and 2-ethylimidazole; imine-based blocking agents such as methyleneimine and propyleneimine.

The blocked isocyanate compound may be commercially available, for example, Sumijour BL-3175, BL-4165, BL-1100, BL-1265, Death Module TPLS-2957, TPLS-2062, TPLS-2078, TPLS-2117. , Desmotherm 2170, Desmotherm 2265 (above, Sumitomo Bayer Urethane, trade name), Coronate 2512, Coronate 2513, Coronate 2520 (above, Nippon Polyurethane Industry Co., Ltd., trade name), B-830, B-815, B- 846, B-870, B-874, B-882 (above, Mitsui Takeda Chemicals, trade name), TPA-B80E, 17B-60PX, E402-B80T (above, Asahi Kasei Chemicals, trade name), etc. Can be mentioned. Sumijour BL-3175 and BL-4265 are obtained by using methyl ethyl oxime as a blocking agent.

The photosensitive resin composition may contain a urethanization catalyst in order to accelerate the curing reaction between the hydroxyl group or carboxyl group and the isocyanate group. As the urethanization catalyst, it is preferable to use a urethanization catalyst selected from at least one of a tin-based catalyst, a metal chloride, a metal acetylacetonate salt, a metal sulfate, an amine compound, and an amine salt.

Examples of the tin-based catalyst include organic tin compounds such as stanas octoate and dibutyltin dilaurate, and inorganic tin compounds. Further, the metal chloride is a chloride of a metal selected from the group consisting of Cr, Mn, Co, Ni, Fe, Cu and Al, for example, ferric chloride, nickel monochloride, ferric chloride and the like. Can be mentioned. The metal acetylacetonate salt is a metal acetylacetonate salt selected from the group consisting of Cr, Mn, Co, Ni, Fe, Cu and Al, and is, for example, cobalt acetylacetonate, nickel acetylacetonate, and iron. Examples include acetylacetonate. Further, the metal sulfate is a sulfate of a metal selected from the group consisting of Cr, Mn, Co, Ni, Fe, Cu and Al, and examples thereof include copper sulfate.

Examples of the amine compound include conventionally known triethylenediamine, N, N, N', N'-tetramethyl-1,6-hexanediamine, bis (2-dimethylaminoethyl) ether, N, N, N', N ", N" -pentamethyldiethylenetriamine, N-methylmorpholine, N-ethylmorpholine, N, N-dimethylethanolamine, dimorpholinodiethyl ether, N-methylimidazole, dimethylaminopyridine, triazine, N'-( 2-Hydroxyethyl) -N, N, N'-trimethyl-bis (2-aminoethyl) ether, N, N-dimethylhexanolamine, N, N-dimethylaminoethoxyethanol, N, N, N'-trimethyl-N' -(2-Hydroxyethyl) ethylenediamine, 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-dimethyl) Aminopropyl) amine, bis (N, N-dimethylaminopropyl) isopropanolamine, 2-aminoquinuclidine, 3-aminoquinuclidine, 4-aminoquinuclidine, 2-quinuclidiol, 3-quinuclidinol, 4 -Kinucridinol, 1- (2'-hydroxypropyl) imidazole, 1- (2'-hydroxypropyl) -2-methylimidazole, 1- (2'-hydroxyethyl) imidazole, 1- (2'-hydroxyethyl)- 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-dimethylaminoethyl-N', N' -At least one of bis (2-hydroxypropyl) amine, melamine and benzoguanamine and the like can be mentioned.

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

[Filler]
As the filler, known and commonly used inorganic or organic fillers can be used, but barium sulfate, spherical silica, titanium oxide, Neuburg diatomaceous earth particles, and talc are particularly preferably used. Further, aluminum hydroxide, magnesium hydroxide, boehmite and the like can also be used for the purpose of imparting flame retardancy. Further, NANOCRYL (trade name) XP 0396, XP 0596, XP 0733, XP 0746, XP 0765 manufactured by Hanse-Chemie, in which nanosilica is dispersed in a compound having one or more ethylenically unsaturated groups or the polyfunctional epoxy resin. , XP 0768, XP 0953, XP 0954, XP 1045 (all product grade names) and Hanse-Chemie NANOPOX (trade name) XP 0516, XP 0525, XP 0314 (all product grade names) can also be used. .. These can be used alone or in combination of two or more. By including the filler, the physical strength of the obtained cured product can be increased.

When the composition contains a carboxyl group-containing resin, the amount of the filler is preferably 500 parts by mass or less, more preferably 0.1 to 300 parts by mass, based on 100 parts by mass of the carboxyl group-containing resin in terms of solid content. Particularly preferably, it is 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 less likely to become brittle.

[Photopolymerization initiator]
In the present invention, known photopolymerization initiators can be used as the photopolymerization initiator used for photopolymerizing the above-mentioned carboxyl group-containing photosensitive resin, and among them, oxime ester-based light having an oxime ester group is used. A polymerization initiator, an α-aminoacetophenone-based photopolymerization initiator, and an acylphosphine oxide-based photopolymerization initiator are preferable. One type of photopolymerization initiator may be used alone, or two or more types may be used in combination.

Commercially available oxime ester-based photopolymerization initiators include BASF Japan's CGI-325, Irgacure (registered trademark) OXE01, Irgacure OXE02, ADEKA's N-1919, and ADEKA Arkuru's (registered trademark) NCI. -831 and the like can be mentioned.

（式中、Ｘ_１は、水素原子、炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、フェニル基、フェニル基（炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、アミノ基、炭素数１〜８のアルキル基を持つアルキルアミノ基またはジアルキルアミノ基により置換されている）、ナフチル基（炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、アミノ基、炭素数１〜８のアルキル基を持つアルキルアミノ基またはジアルキルアミノ基により置換されている）を表し、Ｙ_１、Ｚはそれぞれ、水素原子、炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、ハロゲン基、フェニル基、フェニル基（炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、アミノ基、炭素数１〜８のアルキル基を持つアルキルアミノ基またはジアルキルアミノ基により置換されている）、ナフチル基（炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、アミノ基、炭素数１〜８のアルキル基を持つアルキルアミノ基またはジアルキルアミノ基により置換されている）、アンスリル基、ピリジル基、ベンゾフリル基、ベンゾチエニル基を表し、Ａｒは、炭素数１〜１０のアルキレン、ビニレン、フェニレン、ビフェニレン、ピリジレン、ナフチレン、チオフェン、アントリレン、チエニレン、フリレン、２，５−ピロール−ジイル、４，４’−スチルベン−ジイル、４，２’−スチレン−ジイルを表し、ｎは０または１の整数である） Further, a photopolymerization initiator having two oxime ester groups in the molecule can also be preferably used, and specific examples thereof include an oxime ester compound having a carbazole structure represented by the following general formula (III). ..

(In the formula, X ₁ is 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 (alkyl groups having 1 to 17 carbon atoms, having 1 to 8 carbon atoms). Alkyl group, amino group, alkylamino group having 1 to 8 carbon atoms or dialkylamino group substituted), naphthyl group (alkyl group having 1 to 17 carbon atoms, alkoxy group having 1 to 8 carbon atoms) , amino group, a and are) substituted by an alkylamino group or a dialkylamino group having an alkyl group having 1 to 8 carbon atoms, Y _1, respectively _Z is a hydrogen atom, an alkyl group of 1 to 17 carbon atoms, carbon Alkyl amino having an alkoxy group of 1 to 8, a halogen group, a phenyl group, and a phenyl group (alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an amino group, and an alkyl group having 1 to 8 carbon atoms). Alkyl amino group having 1 to 17 carbon atoms, alkoxy group having 1 to 8 carbon atoms, amino group, alkyl group having 1 to 8 carbon atoms or a naphthyl group (substituted by a group or a dialkylamino group) (Substituted with a dialkylamino group), anthryl group, pyridyl group, benzofuryl group, benzothienyl group, Ar represents alkylene, vinylene, phenylene, biphenylene, pyridylene, naphthylene, thiophene, anthrylene, which have 1 to 10 carbon atoms. Represents thienylene, furylene, 2,5-pyrrole-diyl, 4,4'-stilben-diyl, 4,2'-styrene-diyl, where n is an integer of 0 or 1).

In particular, in the above formula, X ₁ and Y ₁ are methyl groups or ethyl groups, respectively, Z is methyl or phenyl, n is 0, and Ar is phenylene, naphthylene, thiophene or thienylene, respectively. Ester-based photopolymerization initiators are preferred.

As a preferable carbazole oxime ester compound, a compound represented by the following general formula (IV) can also be mentioned.

（式中、Ｒ_３は、炭素原子数１〜４のアルキル基、または、ニトロ基、ハロゲン原子もしくは炭素原子数１〜４のアルキル基で置換されていてもよいフェニル基を表す。
Ｒ_４は、炭素原子数１〜４のアルキル基、炭素原子数１〜４のアルコキシ基、または、炭素原子数１〜４のアルキル基もしくはアルコキシ基で置換されていてもよいフェニル基を表す。
Ｒ_５は、酸素原子または硫黄原子で連結されていてもよく、フェニル基で置換されていてもよい炭素原子数１〜２０のアルキル基、炭素原子数１〜４のアルコキシ基で置換されていてもよいベンジル基を表す。
Ｒ_６は、ニトロ基、または、Ｘ_２−Ｃ（＝Ｏ）−で表されるアシル基を表す。
Ｘ_２は、炭素原子数１〜４のアルキル基で置換されていてもよいアリール基、チエニル基、モルホリノ基、チオフェニル基、または、下記式（Ｖ）で示される構造を表す。）

(In the formula, R ₃ represents an alkyl group having 1 to 4 carbon atoms or a phenyl group which may be substituted with 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 alkoxy group having 1 to 4 carbon atoms, or a phenyl group which may be substituted with an alkyl group or an alkoxy group having 1 to 4 carbon atoms.
R ₅ may be linked with an oxygen atom or a sulfur atom, may be substituted with a phenyl group, and may be substituted with an alkyl group having 1 to 20 carbon atoms and an alkoxy group having 1 to 4 carbon atoms. Represents a good benzyl group.
R ₆ is a nitro group or _{a,, X 2 -C (= O} ) - represents an acyl group represented.
X ₂ represents an aryl group, a thienyl group, a morpholino group, a thiophenyl group, or a structure represented by the following formula (V), which may be substituted with an alkyl group having 1 to 4 carbon atoms. )

In addition, JP-A-2004-359639, JP-A-2005-097141, JP-A-2005-22097, JP-A-2006-160634, JP-A-2008-09470, JP-A-2008-50967, Examples thereof include carbazole oxime ester compounds described in JP-A-2009-040762 and JP-A-2011-80036.

When the oxime ester-based photopolymerization initiator is used, the blending amount is 0.01 to 5 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin in terms of solid content when the composition contains a carboxyl group-containing resin. Is preferable. By setting the amount to 0.01 parts by mass or more, the photocurability on copper becomes more reliable, and the coating film characteristics such as chemical resistance are improved. Further, when the amount is 5 parts by mass or less, light absorption on the surface of the coating film is suppressed, and the curability of the deep part tends to be improved. More preferably, it is 0.5 to 3 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin.

Specific examples of the α-aminoacetophenone-based photopolymerization initiator include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, 2-benzyl-2-dimethylamino-1. -(4-Molholinophenyl) -butane-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, Examples thereof include N, N-dimethylaminoacetophenone. Examples of commercially available products include Irgacure 907, Irgacure 369, and Irgacure 379 manufactured by BASF Japan Ltd.

Specific examples of the acylphosphine oxide-based photopolymerization initiator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and bis (2,6-dimethoxy). Benzoyl) -2,4,4-trimethyl-pentylphosphine oxide and the like can be mentioned. Examples of commercially available products include Irgacure TPO manufactured by BASF Japan Ltd. and Omnirad 819 (formerly Irgacure 819) manufactured by IGM Resins.

Further, as the photopolymerization initiator, Irgacure 389 and Irgacure 784 manufactured by BASF Japan Ltd. can also be preferably used.

When a photopolymerization initiator other than the oxime ester-based photopolymerization initiator is used, the blending amount is 0, when the composition contains a carboxyl group-containing resin, with respect to 100 parts by mass of the carboxyl group-containing resin in terms of solid content. It is preferably 01 to 15 parts by mass. By setting the amount to 0.01 parts by mass or more, the photocurability on copper becomes more reliable, and the coating film characteristics such as chemical resistance are improved. Further, by setting the amount to 15 parts by mass or less, a sufficient effect of reducing outgas can be obtained, light absorption on the surface of the cured film is suppressed, and the curability of the deep portion is also improved. More preferably, it is 0.5 to 10 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin.

A photoinitiator or sensitizer may be used in combination with the photopolymerization initiator described above. Examples of the photoinitiator aid or sensitizer include benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, benzophenone compounds, tertiary amine compounds, and xanthone compounds. Although these compounds may be used as a photopolymerization initiator, they are preferably used in combination with a photopolymerization initiator. In addition, one type of photoinitiator aid or sensitizer may be used alone, or two or more types may be used in combination.

Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and the like. Examples of the acetophenone compound include acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, and 1,1-dichloroacetophenone. Examples of the anthraquinone compound include 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butyl anthraquinone, and 1-chloroanthraquinone. Examples of the thioxanthone compound include 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and 2,4-diisopropylthioxanthone. Examples of the ketal compound include acetophenone dimethyl ketal and benzyl dimethyl ketal. Further, examples of the benzophenone compound include benzophenone, 4-benzoyldiphenyl sulfide, 4-benzoyl-4'-methyldiphenyl sulfide, 4-benzoyl-4'-ethyldiphenyl sulfide, 4-benzoyl-4'-propyldiphenyl sulfide and the like. Can be mentioned.

Examples of the tertiary amine compound include ethanolamine compounds and compounds having a dialkylaminobenzene structure. For example, commercially available products include 4,4'-dimethylaminobenzophenone (NissoCure (registered trademark) MABP manufactured by Nippon Soda Co., Ltd.), 4,4. Dialkylaminobenzophenone such as'-diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co., Ltd.), 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one (7- (diethylamino) -4-methylcoumarin), etc. Dialkylamino group-containing coumarin compound, ethyl 4-dimethylaminobenzoate (Kayacure (registered trademark) EPA manufactured by Nippon Kayaku Co., Ltd.), ethyl 2-dimethylaminobenzoate (Quantacure DMB manufactured by International Bio-Synthetics Co., Ltd.), 4-dimethyl Aminobenzoic acid (n-butoxy) ethyl (Quantacure BEA manufactured by International Bio-Synthetics), p-dimethylaminobenzoic acid isoamylethyl ester (Kayacure DMBI manufactured by Nippon Kayaku Co., Ltd.), 2-ethylhexyl 4-dimethylaminobenzoate (Esolol 507 manufactured by Van Dyk) and the like. As the tertiary amine compound, a compound having a dialkylaminobenzene structure is preferable, and among them, a dialkylaminobenzophenone compound, a dialkylamino group-containing coumarin compound having a maximum absorption wavelength of 350 to 450 nm, and ketocoumarins are particularly preferable.

As the dialkylaminobenzophenone compound, 4,4'-diethylaminobenzophenone is preferable because it has low toxicity. Since the dialkylamino group-containing coumarin compound has a maximum absorption wavelength of 350 to 410 nm in the ultraviolet region, it is less colored and uses a colorless and transparent photosensitive resin composition as well as a colored pigment to reflect the color of the colored pigment itself. It becomes possible to obtain a colored photosensitive film. In particular, 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one is preferable because it exhibits an excellent sensitizing effect on laser light having a wavelength of 400 to 410 nm.

Of these, thioxanthone compounds and tertiary amine compounds are preferred. In particular, the inclusion of the thioxanthone compound can improve the deep curability.

When the composition contains a carboxyl group-containing resin, the total amount of the photopolymerization initiator, photoinitiator aid, and sensitizer is 35 parts by mass or less with respect to 100 parts by mass of the carboxyl group-containing resin in terms of solid content. Is preferable. By setting the amount to 35 parts by mass or less, these light absorptions are suppressed and the curability of the deep part is also improved.

Since these photopolymerization initiators, photoinitiator aids, and sensitizers absorb specific wavelengths, their sensitivity may be lowered in some cases, and they may function as ultraviolet absorbers. However, these are not used solely for the purpose of improving the sensitivity of the composition. If necessary, it absorbs light of a specific wavelength to enhance the photoreactivity of the surface, change the line shape and opening of the resist into vertical, tapered, and reverse tapered shapes, and process accuracy of the line width and opening diameter. Can be improved.

The photosensitive resin composition used in the photosensitive film according to the present invention may contain other components such as block copolymers, colorants, elastomers, and thermoplastic resins in addition to the above-mentioned components. Hereinafter, these components will also be described.

A block copolymer can be suitably blended in the above-mentioned photosensitive resin composition. A block copolymer is a copolymer having a molecular structure in which two or more kinds of polymers having different properties are connected by a covalent bond to form a long chain. Those that are solid in the range of 20 ° C to 30 ° C are preferable. It may be a solid within this range, and may be a solid at a temperature outside this range. Since it is a solid in the above temperature range, it has excellent tackiness when it is used as a photosensitive film or when it is applied to a support film and temporarily dried.

As the block copolymer, XYX or XYX'type block copolymer is preferable. Of the XYX or XYX'type block copolymers, B in the center is a soft block and the glass transition point Tg is low, preferably less than 0 ° C., and both outer sides A to X'are hard blocks and have a high Tg. , Preferably those composed of polymer units at 0 ° C. or higher. The glass transition point Tg is measured by differential scanning calorimetry (DSC).

Further, among the XYX or XYX'type block copolymers, a block copolymer composed of a polymer unit in which the Tg of X to X'is 50 ° C. or higher and the Tg of Y is −20 ° C. or lower is further added. preferable. Further, among the XYX or XYX'type block copolymers, those in which X to X'are highly compatible with the carboxyl group-containing resin are preferable, and those in which Y is low in compatibility with the carboxyl group-containing resin are preferable. As described above, it is considered that by making the blocks at both ends compatible with the matrix and the central block a block copolymer incompatible with the matrix, it becomes easy to show a specific structure in the matrix.

The block copolymer can be used without particular limitation as long as it contains at least one hard block component and at least one soft block component as well as the XYX or XYX'type.

As the X to X'component, polymethylmethacrylate (PMMA), polystyrene (PS) and the like are preferable, and as the B component, polyn-butyl acrylate (PBA), polybutadiene (PB) and the like are preferable. Further, as a part of the X to X'components, a hydrophilic unit having excellent compatibility with the above-mentioned carboxyl group-containing resin represented by a styrene unit, a hydroxyl group-containing unit, a carboxyl group-containing unit, an epoxy-containing unit, an N-substituted acrylamide unit and the like is provided. It can be introduced and the compatibility can be further improved. The present inventors have particularly good compatibility with the above-mentioned carboxyl group-containing resin in the block copolymer thus obtained, and can surprisingly improve the thermal shock resistance. More surprisingly, it was found that the glass transition temperature (Tg) of the product to which the elastomer was added tends to decrease, whereas the Tg of the product to which the block copolymer was added tends to decrease.

Examples of the method for producing a 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 using living polymerization manufactured by Arkema. SBM type represented by polystyrene-polybutadiene-polymethyl methacrylate, MAM type represented by polymethyl methacrylate-polybutyl acrylate-polymethyl methacrylate, and MAM N type treated with carboxylic acid modification or hydrophilic group modification. And MAM A type. 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 examples of the MAM A type include SM4032XM10. Be done. Clarity manufactured by Kuraray Co., Ltd. is also a block copolymer derived from methyl methacrylate and butyl acrylate.

As the block copolymer, a block copolymer having three or more elements is preferable, and a block copolymer whose molecular structure is precisely controlled by the living polymerization method is more preferable for obtaining the effect of the present invention. It is considered that this is because the block copolymer synthesized by the living polymerization method has a narrow molecular weight distribution and the characteristics of each unit have been clarified. The molecular weight distribution of the block copolymer used is preferably 2.5 or less, more preferably 2.0 or less.

The weight average molecular weight of the block copolymer is generally in the range of 20,000 to 400,000, more preferably 30,000 to 300,000. If the weight average molecular weight is less than 20,000, the desired toughness and flexibility effects cannot be obtained, and the tackiness is also inferior. On the other hand, when the weight average molecular weight exceeds 400,000, the viscosity of the photocurable resin composition becomes high, and the printability and developability are remarkably deteriorated.

When the composition contains a carboxyl group-containing resin, the amount of the block copolymer is preferably 1 to 50 parts by mass, more preferably 5 to 35 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin in terms of solid content. It is a mass part. The effect can be expected at 1 part by mass or more, and the developability and coatability are good as a photocurable resin composition at 50 parts by mass or less.

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

Examples of red colorants include monoazo, disazo, azolake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridone. -Indexed (CI; issued by The Society of Dyersand Colorists).

Examples of monoazo 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 and the like can be mentioned. Examples of the disazo-based red colorant include Pigment Red 37, 38, 41 and the like. Further, as a monoazolake-based red colorant, Pigment Red 48: 1,48: 2,48: 3,48: 4,49: 1,49: 2,50: 1,52: 1,52: 2,53: Examples thereof include 1,53: 2,57: 1,58: 4,63: 1,63: 2,64: 1,68. Examples of the benzimidazolone-based red colorant include Pigment Red 171, 175, 176, 185, 208 and the like. Examples of the perylene-based red colorant include Solvent Red 135,179, Pigment Red 123, 149, 166, 178, 179, 190, 194, 224 and the like. Examples of the diketopyrrolopyrrole red colorant include Pigment Red 254, 255, 264, 270, 272 and the like. Examples of the condensed azo red colorant include Pigment Red 220, 144, 166, 214, 220, 221, 242 and the like. Examples of the anthraquinone-based red colorant include Pigment Red 168, 177, 216 and Solvent Red 149, 150, 52, 207. Examples of the quinacridone-based red colorant include Pigment Red 122, 202, 206, 207, 209 and the like.

Examples of the blue colorant include phthalocyanine-based and anthraquinone-based compounds, and pigment-based compounds include compounds classified as Pigment. 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 type, disazo type, condensed azo type, benzimidazolone type, isoindolinone type, anthraquinone type, and the like. For example, the anthraquinone type yellow colorant includes Solvent Yellow 163, Pigment Yellow 24, 108, 193, 147, 199, 202 and the like can be mentioned. Examples of the isoindolinone-based yellow colorant 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 the benzimidazolone-based yellow colorant include Pigment Yellow 120, 151, 154, 156, 175, 181 and the like. In addition, as a monoazo yellow colorant, 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 and the like can be mentioned. Examples of the disazo-based 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 the like. Can be mentioned.

In addition, colorants such as purple, orange, brown, black, and white may be added. 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, C.I. I. Pigment Orange 1,5,13,14,16,17,24,34,36,38,40,43,46,49,51,61,63,64,71,73, PigmentBrown 23,25, Titanium Oxide, Examples include carbon black.

The amount of the colorant to be blended is not particularly limited, but when the composition contains a carboxyl group-containing resin, it is preferably 10 parts by mass or less, more preferably 0 parts by mass, based on 100 parts by mass of the carboxyl group-containing resin in terms of solid content. .1 to 7 parts by mass. However, the blending amount of the white colorant such as titanium oxide is preferably 0.1 to 200 parts by mass, more preferably 1 to 100 parts by mass, more preferably 1 part by mass with respect to 100 parts by mass of the carboxyl group-containing resin in terms of solid content. Is 3 to 80 parts by mass.

In addition, an elastomer can be added to 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-based elastomers, polyurethane-based elastomers, polyester-urethane-based elastomers, polyamide-based elastomers, polyesteramide-based elastomers, acrylic-based elastomers, and olefin-based elastomers. Further, a resin obtained by modifying a part or all of the epoxy groups of the epoxy resin having various skeletons with both-terminal carboxylic acid-modified butadiene-acrylonitrile rubber can also be used. Further, epoxy-containing polybutadiene-based elastomers, acrylic-containing polybutadiene-based elastomers, hydroxyl group-containing polybutadiene-based elastomers, hydroxyl group-containing isoprene-based elastomers, and the like can also be used. The elastomer may be used alone or as a mixture of two or more.

Further, a commonly known binder polymer can be used for the purpose of improving the flexibility and the dryness to the touch of the obtained cured product. As the binder polymer, cellulose-based, polyester-based, and phenoxy resin-based polymers are preferable. Examples of the cellulose-based polymer include cellulose acetate butyrate (CAB) and cellulose acetate propionate (CAP) series manufactured by Eastman Co., Ltd., as the polyester-based polymer, the Byron series manufactured by Toyo Boseki Co., Ltd. Phenoxy resins of bisphenol F and their hydrogenated polymers are preferred.

When the composition contains a carboxyl group-containing resin, the amount of the binder polymer is preferably 50 parts by mass or less, more preferably 1 to 30 parts by mass, based on 100 parts by mass of the carboxyl group-containing resin in terms of solid content. Particularly preferably, it is 5 to 30 parts by mass. When the blending amount of the binder polymer is 50 parts by mass or less, the photosensitive resin composition is more excellent in alkali developability, and the developable pot life becomes longer.

Further, if necessary, the photosensitive resin composition may further contain components such as an adhesion accelerator, an antioxidant, and an ultraviolet absorber. As these, those known in the field of electronic materials can be used. In addition, at least one of known and commonly used thickeners such as fine silica, hydrotalcite, organic bentonite, and montmorillonite, antifoaming agents such as silicone-based, fluorine-based, and polymer-based and leveling agents, imidazole-based, and thiazole-based. At least one of known and commonly used additives such as a silane coupling agent such as a system or a triazole system, a rust preventive agent, and a fluorescent whitening agent can be blended.

The photosensitive film can be formed by applying the above-mentioned photosensitive resin composition to one surface of the support film and drying it. Considering the coatability of the photosensitive resin composition, the photosensitive resin composition is diluted with an organic solvent to adjust the viscosity to an appropriate level, and a comma coater, a blade coater, a lip coater, a rod coater, a squeeze coater, a reverse coater, etc. Apply to one surface of the support film with a transfer coater, gravure coater, spray coater, etc. to a uniform thickness, and usually dry at a temperature of 50 to 130 ° C. for 1 to 30 minutes to volatilize the organic solvent and tack. A free coating film can be obtained. The coating film thickness is not particularly limited, but in general, the film thickness after drying is appropriately selected in the range of 5 to 150 μm, preferably 10 to 60 μm.

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 solvents. be able to. More specifically, ketones such as methyl ethyl ketone (MEK) and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, Glycol ethers such as propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, propylene glycol Esters such as methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol butyl ether acetate; alcohols such as ethanol, propanol, ethylene glycol and propylene glycol; aliphatic hydrocarbons such as octane and decane; petroleum ether, petroleum naphtha, water Additives Petroleum-based solvents such as naphtha and solvent naphtha. Such an organic solvent may be used alone or as a mixture of two or more.

Volatile drying of organic solvents is supported by hot air circulation type drying furnaces, IR furnaces, hot plates, convection ovens, etc. It can be done by using the method of spraying on the body).

[Protective film]
The photosensitive film laminate according to the present invention has a protective film on the surface opposite to the intermediate layer of the photosensitive film for the purpose of preventing dust and the like from adhering to the surface of the photosensitive film and improving handleability. May be provided.

As the protective film, for example, a polyester film, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper or the like can be used, but the adhesive strength between the protective film and the photosensitive resin layer is different from that of the support film. It is preferable to select a material that has a smaller adhesive force with the photosensitive resin layer. Further, in order to facilitate the peeling of the protective film when the photosensitive film laminate is used, the surface of the protective film in contact with the photosensitive resin layer may be subjected to the above-mentioned mold release treatment.

The thickness of the protective film is not particularly limited, but is appropriately selected in the range of approximately 10 to 150 μm according to the application.

<Manufacturing method of cured product and printed wiring board>
A cured product is formed using the photosensitive film of the present invention or the photosensitive film laminate. A method of forming such a cured product and a method of manufacturing a printed wiring board having the cured product (cured film) on a substrate on which a circuit pattern is formed will be described. As an example, a method of manufacturing a printed wiring board using a photosensitive film laminate provided with a protective film will be described. First, i) the protective film is peeled off from the above-mentioned photosensitive film laminate to expose the photosensitive film, and ii) the photosensitive film of the photosensitive film laminate is formed on the substrate on which the circuit pattern is formed. Photosensitivity patterned on the substrate by laminating, iii) exposing from the support film of the photosensitive film laminate, and iv) peeling the support film from the photosensitive film laminate and developing. A printed wiring board is formed by forming a sex film and v) curing the patterned photosensitive film by light irradiation or heat to form a cured film. Needless to say, when a photosensitive film laminate without a protective film is used, the protective film peeling step (step i) is unnecessary. Hereinafter, each step will be described.

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 onto the substrate on which the circuit pattern is formed. As the substrate on which the circuit pattern is formed, in addition to the printed wiring board and the flexible printed wiring board in which the circuit is formed in advance, paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth / non-woven cloth epoxy, glass cloth / paper. All grades (FR-4, etc.) of copper-clad are made of materials such as copper-clad laminates for high-frequency circuits using epoxy, synthetic fiber epoxy, fluororesin / polyethylene / polyimideene ether, polyphenylene oxide / cyanate ester, etc. Laminated plates, other polyimide films, PET films, glass substrates, ceramic substrates, wafer plates and the like can be mentioned.

In order to bond the photosensitive film of the photosensitive film laminate onto the circuit board, it is preferable to bond the photosensitive film under pressure and heating using a vacuum laminator or the like. By using such a vacuum laminator, the photosensitive resin composition layer adheres to the circuit board, so that air bubbles are not mixed in and the hole filling property on the substrate surface is improved. The pressurizing condition is preferably about 0.1 to 2.0 MPa, and the heating condition is preferably 40 to 120 ° C.

Next, exposure (irradiation with active energy rays) is performed from the support film of the photosensitive film laminate. By this step, only the exposed photosensitive resin layer is cured. The exposure process is not particularly limited, and for example, it may be selectively exposed by active energy rays through a photomask having a desired pattern formed by a contact method (or a non-contact method), but it may be exposed by a direct drawing apparatus. The desired pattern may be exposed by active energy rays.

The exposure machine used for irradiating active energy rays may be a device equipped with a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, etc., and irradiates ultraviolet rays in the range of 350 to 450 nm. For example, a laser direct imaging apparatus that directly draws an image with a laser based on CAD data from a computer can also be used. As the laser light source of the direct drawing machine, either a gas laser or a solid-state laser may be used as long as a laser light having a maximum wavelength in the range of 350 to 410 nm is used. The amount of exposure for image formation varies depending on the film thickness and the like, but is generally 20 to 800 mJ / cm ² , preferably 20 to 600 mJ / cm ² .

After the exposure, the support film and the intermediate layer are peeled off from the photosensitive film laminate and developed to form a patterned photosensitive film on the substrate. When the support film and the intermediate layer are peeled off, the morphology of the surface of the intermediate layer is formed on the surface of the photosensitive film that has been exposed and cured.

The developing process is not particularly limited, and a dipping method, a shower method, a spray method, a brush method, or the like can be used. Further, as the developing solution, an alkaline aqueous solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia and 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 main curing or additional curing, which promotes the polymerization of unreacted monomers in the photosensitive film, and further heat-cures the carboxyl group-containing photosensitive resin and the epoxy resin to obtain the remaining carboxyl. The amount of groups can be reduced. The activation energy ray irradiation can be performed in the same manner as the above-mentioned exposure, but it is preferably performed under conditions stronger than the irradiation energy at the time of exposure. For example, it can be 500 to 3000 mJ / cm ^2. Further, the thermosetting can be performed at 100 to 200 ° C. under heating conditions of about 20 to 90 minutes. It is preferable that the main curing is performed by heat curing after photo-curing. By performing photocuring first, the flow of the resin may be suppressed even during heat curing, and the shaped surface may be maintained.

The photosensitive film laminate according to the present invention can be particularly suitably used for forming a solder resist layer for an IC package.

Next, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

<Preparation of Carboxyl Group-Containing Photosensitive Resin>
In an autoclave equipped with a thermometer, a nitrogen introduction device and an alkylene oxide introduction device, and a stirring device, 119.4 g of a novolak type cresol resin (Shonol CRG951 manufactured by Showa Denko Co., Ltd., OH equivalent: 119.4) and potassium hydroxide 1. 19 g and 119.4 g of toluene were charged, the inside of the system was replaced with nitrogen while stirring, and the temperature was raised by heating. Next, 63.8 g of propylene oxide was gradually added dropwise, and the mixture was reacted at ^{125 to 132 ° C. and 0 to 4.8 kg / cm 2 for 16 hours.} Then, the mixture was cooled to room temperature, and 1.56 g of 89% phosphoric acid was added to and mixed with this reaction solution to neutralize potassium hydroxide, and the non-volatile content was 62.1% and the hydroxyl value was 182.2 g / eq. A propylene oxide reaction solution of the novolak type cresol resin was obtained. The obtained novolak-type cresol resin had an average of 1.08 mol of alkylene oxide added per equivalent amount of phenolic hydroxyl groups.

293.0 g of the alkylene oxide reaction solution of the obtained novolak 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 mixed with a stirrer and a thermometer. And a reactor equipped with an air blowing tube was charged, air was blown at a rate of 10 ml / min, and the reaction was carried out at 110 ° C. for 12 hours with stirring. As for the water produced by the reaction, 12.6 g of water was distilled off as an azeotropic mixture with toluene. Then, the mixture was cooled to room temperature, the obtained reaction solution was neutralized with 35.35 g of a 15% aqueous sodium hydroxide solution, and then washed with water. Then, toluene was distilled off while substituting 118.1 g of diethylene glycol monoethyl ether acetate with an evaporator to obtain a novolak type acrylate resin solution. Next, 332.5 g of the obtained novolak-type acrylate resin solution and 1.22 g of triphenylphosphine were charged into a reactor equipped with a stirrer, a thermometer and an air blowing tube, and air was blown at a rate of 10 ml / min. While stirring, 62.3 g of tetrahydrophthalic anhydride was gradually added and reacted at 95 to 101 ° C. for 6 hours to obtain a carboxyl group-containing photosensitive resin varnish 1 having an acid value of 88 mgKOH / g and a non-volatile content of 71%. It was.

<Preparation of photosensitive resin composition>
The carboxyl group-containing photosensitive resin varnish 1 obtained as described above, dipentaerythritol hexaacrylate (KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd.), which is a photosensitive monomer as an acrylate compound, and an epoxy resin, which is a thermosetting component. As a bisphenol A type epoxy resin (EPICLON840-S manufactured by DIC) and a biphenol novolak type epoxy resin (NC-3000H manufactured by Nippon Kayaku Co., Ltd.), and as a photopolymerization initiator, IRGACURE TPO manufactured by BASF Japan or IRGACURE manufactured by BASF Japan. OXE02, barium sulfate (B-30 manufactured by Sakai Chemical Industry Co., Ltd.) and / or spherical silica (Admafine SO-E2 manufactured by Admatex Co., Ltd.) as a filler, melamine as a thermosetting catalyst, and Mitsubishi Chemical Co., Ltd. as a colorant. Carbon Black M-50, Dioxazine Violet C.I. I. Pigment Violet 23, C.I. I. Pigment Yellow 147, C.I. I. Pigment Blue 15: 3 and C.I. I. Each component selected from Pigment Red 177 and diethylene glycol monoethyl ether acetate as an organic solvent were mixed in the proportions (parts by mass) shown in Table 1 below, premixed with a stirrer, and then kneaded with a 3-roll mill. To prepare photosensitive resin compositions 1 and 2.

<Preparation of acrylic melamine resin 1>
Amidia G-821-60 (iso-butylated melamine resin, solid content 60%) manufactured by DIC Corporation and Acrydic A-405 (acrylic resin for melamine baking, solid content 50%) manufactured by DIC Corporation are solid in mass ratio. Acrylic melamine resin 1 was prepared by blending so that the ratio was 25:75 in terms of minutes, pre-stirring with a stirrer, and kneading with a three-roll mill.

<Preparation of epoxy melamine resin 2>
Uban 62 (iso-butylated melamine resin, solid content 60%) manufactured by Mitsui Chemicals Co., Ltd. and Epomic R301MIBK solution (bisphenol A type epoxy resin, solid content 60%) manufactured by Mitsui Chemicals Co., Ltd. have a mass ratio of 25 in terms of solid content. The epoxy melamine resin 2 was prepared by blending the mixture so as to have a ratio of 75, pre-stirring with a stirrer, and kneading with a three-roll mill.

<Preparation of support film 1 having intermediate layer 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. Methyl ethyl ketone is further added to this resin solution so as to have an appropriate solid content concentration according to the thickness of the coating film, and then a silicone resin (Cymac US-270 manufactured by Toa Synthetic Co., Ltd.) and silica are added to the acrylic melamine resin. 1 was added so that the mass ratio of each of the silicone resin and silica having an average particle diameter of 2.3 μm was 59.7: 0.3: 40, and the mixture was sufficiently stirred at room temperature to obtain a uniform coating liquid. .. This coating liquid is applied to one surface of a polyethylene terephthalate film (Lumirror T60 manufactured by Toray Industries, Inc.) which is a support film by a gravure roll method, dried at 130 ° C. for 20 seconds, and a support film 1 having an intermediate layer 1 (intermediate). A layer thickness of 3 μm, a support film thickness of 25 μm, and a total thickness of 28 μm) were prepared.

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

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

<Preparation of test board>
The circuit-formed FR-4 copper-clad laminate (100 mm x 150 mm x 0.8 mmt, double-sided copper foil, copper foil thickness is 18 μm on both sides) The surface is chemically polished with CZ8101 manufactured by MEC Co., Ltd. to form a substrate. The exposed surface of the photosensitive film exposed by peeling the polypropylene film from the photosensitive film laminate obtained as described above is attached to the chemically polished surface, and then a vacuum laminator (MVLP manufactured by Meiki Seisakusho) is attached. Test substrate 1 was prepared by heating and laminating under the conditions of pressurization degree: 0.8 Mpa, 70 ° C., 1 minute, vacuum degree: 133.3 Pa using −500) to bring the substrate and the photosensitive film into close contact with each other. ..

Example 2
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 in Example 1.

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

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

Comparative Example 1
In Example 1, a test substrate 5 was prepared in the same manner as in Example 1 except that a polyethylene terephthalate film having a thickness of 25 μm (Lumirror T60 manufactured by Toray Industries, Inc.) was used instead of the support film 1 having the intermediate layer 1. did.

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

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

Comparative Example 4
In Comparative Example 3, the 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.

<Weight drop resistance>
Each of the test substrates of Examples 1 to 4 and Comparative Examples 1 to 4 produced as described above was placed on concrete, and on the surface of the polyethylene terephthalate film of each of the test substrates, as a weight, a diameter of 30 mm and a weight of 120 g. The brass ball of No. 1 was dropped from a height of 30 cm in the direction perpendicular to the surface of the polyethylene terephthalate film. Next, using a parallel light exposure device equipped with a short arc type high-pressure mercury lamp, a solid exposure is performed on the polyethylene terephthalate film via an exposure mask, and then the polyethylene terephthalate film and the intermediate layer are peeled off to expose the photosensitive film. It was. The exposure amount was set to 7 steps when the polyethylene terephthalate film in contact with the photosensitive film was exposed using the 41 steps of Staffer. The dents on the surface of the exposed photosensitive film due to the dropped weights were visually evaluated. Ten weights were dropped for each of the test substrates of Examples 1 to 4 and Comparative Examples 1 to 4. The evaluation criteria were as follows. In addition, each test substrate was subjected to the main test and evaluation 5 minutes after the heat laminating in the above <Preparation of test substrate>. In addition, the main test and evaluation were carried out in a test environment of 23 ° C. and a relative humidity of 50%.
◯: No dents were confirmed on all the surfaces of 10 exposed photosensitive films ×: One or more dents were confirmed on the surface of 10 exposed photosensitive films The evaluation results are shown in Table 2 below. It was as shown in.

As a method for simply confirming the impact resistance of the surface of the photosensitive film, a weight drop resistance test was conducted and evaluated. As is clear from the examples, by using the photosensitive film laminate of the present invention, the photosensitive film laminate does not affect the photosensitive film surface even by a strong impact when the laminated substrates and the like are laminated. It turns out that can be realized. On the other hand, as is clear from the comparative example, it can be seen that the above effect cannot be realized even if a photosensitive film laminate that does not satisfy the requirements of the present invention is used.

Claims (5)

A photosensitive film laminate comprising a support film, an intermediate layer, and a photosensitive film formed of a photosensitive resin composition in that order.
The intermediate layer comprises at least one of melamine and a melamine compound and a silicone-based resin.
A photosensitive film laminate, wherein the photosensitive resin composition contains a heat-crosslinking component having at least one of a plurality of cyclic ether groups and cyclic thioether groups in one molecule. The photosensitive film laminate according to claim 1, wherein the support film has a thickness of 10 to 150 μm. The photosensitive film laminate according to claim 1 or 2, wherein the photosensitive resin composition further contains a filler. The photosensitive film laminate according to any one of claims 1 to 3, further comprising a protective film on the surface side of the photosensitive film opposite to the intermediate layer. A method for producing a cured product using the photosensitive film laminate according to any one of claims 1 to 4.
The photosensitive film of the photosensitive film laminate is exposed and
The support film and the intermediate layer are peeled off from the photosensitive film laminate.
The photosensitive resin composition constituting the photosensitive film is cured to form a cured product.
The method, including that .

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