TWI697404B - Laminated film - Google Patents

Abstract

Provide a laminated film that is less likely to cause wrinkles on the resin layer and the film is less likely to remain on the resin layer.

A film with (A) resin layer and (B) a 5% elongation load per unit width at 80°C exceeding 90g/mm and less than 500g/mm, the melt viscosity of the aforementioned (A) resin layer at 80°C is 10 ~10000dPa. s is a characteristic laminated film, etc.

Description

Laminated film

The present invention relates to laminated films.

In the past, as one of the methods for forming protective films or insulating layers such as resists or interlayer insulating layers used in printed wiring boards used in electronic equipment, laminated films (dry films) were used (for example, Patent Documents 1 and 2) With the thinning of substrates and the miniaturization of circuits in recent years, the demand for laminated films for forming protective films or insulating layers such as resists has increased. The laminated film has a resin layer obtained by coating a resin composition with desired characteristics on a support film and then drying, generally in a state in which a protective film that protects the side opposite to the support film is further laminated on the market. After the resin layer of the laminated film is pasted on the substrate (hereinafter also referred to as "laminating"), the above-mentioned protective film or insulating layer can be formed on the printed wiring board by patterning or curing treatment.

When forming a laminate film on a wiring board on which a fine patterned circuit is formed, like a laminate film for the formation of adhesive resists, it is generally performed under heating conditions because of the requirement for circuit compliance. Under vacuum lamination or hot pressing of SUS board, etc., a more flat film is obtained.

[Prior technical literature] 〔Patent Literature〕

[Patent Document 1] Japanese Patent Application Publication No. 7-15119

[Patent Document 2] JP 2002-162736 A

It is known that wrinkles are generated in the resin layer of the laminated film after a series of bonding steps of the laminated film. The presence of such wrinkles not only causes poor appearance, but it is known that the groove portion of the wrinkles becomes thinner than the designed film thickness, and there is a problem that desired characteristics such as solder heat resistance are lowered.

Moreover, after a series of laminating film sticking steps, when the supporting film (or protective film) of the laminating film is peeled from the resin layer using mechanical means, such as an automatic exposure machine, it is known that the film is torn and remains in the resin layer The situation above. The film remains on the resin layer, and it is also known that there is a problem of residual development during development.

The object of the present invention is to provide a laminated film in which wrinkles are not easily generated in the resin layer, and the film is not likely to remain on the resin layer.

The inventors of the present invention conducted the above-mentioned diligent review results and found that by using a film with a 5% elongation load per unit width at 80°C exceeding 90g/mm and less than 500g/mm, and using 80°C melting as the resin layer The viscosity is 10~10000dPa. s can solve the aforementioned problems and complete the present invention.

That is, the laminated film of the present invention is characterized by having (A) a resin layer and (B) a film with a 5% elongation load per unit width at 80°C exceeding 90 g/mm and 500 g/mm or less.

The laminated film of the present invention preferably has the aforementioned (A) resin layer as photosensitive.

The laminated film of the present invention preferably has the aforementioned (A) resin layer containing an alkali-soluble resin, a photopolymerization initiator, and a thermosetting resin.

The laminated film of the present invention is preferably used by sticking to the surface of the wiring substrate.

The laminated film of the present invention is preferably adhered to the surface of the wiring substrate using a vacuum laminator.

The laminated film of the present invention is preferably adhered to the surface of the wiring substrate by the laminating process using a vacuum laminator and the subsequent flattening process of hot pressing.

The laminated film of the present invention is preferably used for the formation of a permanent film on a wiring board.

According to the present invention, it is possible to provide a laminated film in which wrinkles are less likely to occur in the resin layer and the film is less likely to remain on the resin layer.

A‧‧‧Resin layer

B‧‧‧5% elongation load per unit width at 80℃ exceeds 90g/mm and is Film below 500g/mm

C‧‧‧Film

[Fig. 1] A schematic cross-sectional view schematically showing an embodiment of the laminated structure of the present invention.

[Fig. 2] A schematic cross-sectional view schematically showing another embodiment of the laminated structure of the present invention.

<Laminated Film>

The laminated film of the present invention is a film containing (A) resin layer and (B) at 80°C per unit width of 5% elongation load exceeding 90g/mm and less than 500g/mm (hereinafter also referred to as "(B) Film”), and the melt viscosity of the aforementioned (A) resin layer at 80°C is 10~10000dPa. s is the characteristic. It is believed that the main cause of the wrinkles of the above-mentioned resin layer is the wrinkles generated in the unpeeled film during vacuum lamination under heating conditions or during subsequent hot pressing. That is, after the laminate film is laminated in such a way that the resin layer is in contact with the wiring substrate, the support film is usually vacuum laminated under heating conditions before peeling the support film from the resin layer. However, it is considered that if the support film is wrinkled in this step, This transfer to the resin layer also produces wrinkles in the resin layer. When using a film whose 5% elongation load per unit width at 80°C exceeds 90g/mm and is 500g/mm or less, the film is not prone to wrinkles even under the temperature conditions of heat lamination. As a result, it is believed that the resin layer is also difficult to wrinkle.

Also, (B) the maximum value of the 5% elongation load per unit width at 80°C.

The laminated film of the present invention has a structure in which (A) a resin layer and (B) a film are laminated (Figure 1). Other resin layers may be provided between the (B) film and (A) resin layer without impairing the effect of the present invention. The laminated film of the present invention can be laminated with (A) the resin layer on the side of the wiring board, and (B) the film on the surface side, that is, the resin layer (A) is located on the opposite side of the wiring board. Wiring board to use. Thereby, even if vacuum lamination is performed under heating conditions, the (A) resin layer is less likely to be wrinkled.

In the laminate film of the present invention, in order to protect the surface of the (A) resin layer, it is preferable to laminate the (C) film on the side opposite to the (B) film (Figure 2). The (C) film laminated in this way may be peeled when the (A) resin layer is laminated on the wiring board. If necessary, other resin layers can be provided between (A) resin layer and (C) film.

The laminated film of the present invention, when the aforementioned 5% elongation load of the film (B) exceeds 90g/mm, not only is it less prone to wrinkles when vacuum lamination is carried out under the above-mentioned heating conditions, but even if the mechanical means like an automatic exposure machine ( B) Film peeling is not easy to produce film residue. In addition, when the aforementioned 5% elongation load of the (B) film exceeds 90g/mm, like the laminated film shown in Figure 2, on the opposite side of the (B) film, even with the (C) film, roll the laminated film Wrinkles are not easy to produce due to the tension balance of (B) film and (C) film when rolling.

In addition, the laminated film of the present invention, by making the aforementioned elongation load less than 500g/mm, like the laminated film shown in Fig. 2, on the opposite side of the (B) film, even if it has the (C) film, the laminated film When rolling, because The tension between (B) film and (C) film is balanced, and wrinkles generated on the surface of (A) resin layer on the side of (C) film are less likely to occur. In addition, the circuit compliance of (A) resin layer becomes better. Resin becomes easy to enter between narrow pitches.

The aforementioned elongation load is preferably more than 90 g/mm and 400 g/mm or less, more preferably more than 90 g/mm and 300 g/mm or less.

The laminated film of the present invention is (A) The resin layer has a melt viscosity of 10~10000dPa at 80°C. s. The above melt viscosity is 10dPa. When s is above, during vacuum lamination under heating conditions, the fluidity of the resin layer during thermal lamination will not become too high, and wrinkles will become less likely to occur. The above melt viscosity is 10000dPa. When s or less, the fluidity of the resin layer during vacuum lamination under heating conditions is good and the circuit compliance becomes better, so the resin is easy to enter even in a narrow pitch. The above melt viscosity is 50~5000dPa. s is better, 100~4000dPa. s is better, 200~2500dPa. s is better.

Each component is described in detail below.

[(A) Resin layer]

The resin layer of the laminated film of the present invention can be obtained through a drying step after coating the resin composition on the support film. The aforementioned resin composition is not particularly limited, and conventionally known resists, interlayer insulating layers, cover films, and other resin compositions used for the formation of protective layers or insulating layers provided on printed wiring boards can be used. The film thickness of the resin layer is not particularly limited, and the film thickness after drying is preferably 1 to 200 μm. In the case of a photosensitive curable resin layer, when the thickness is 200 μm or less, a decrease in deep curability can be suppressed. The resin layer contains curable resin and filler Based on the total amount of the resin layer of the dry film from which the solvent has been removed, the amount of filler is preferably 10% by mass or more. Specific examples of the following resin composition include, for example, a photocurable resin composition containing a photopolymerization initiator, a photocurable thermosetting resin composition, a photocurable resin composition containing a photobase generator, and Photocurable resin composition of photoacid generator, negative type photocurable resin composition, positive type photocurable resin composition, alkali development type photocurable resin composition, solvent development type photocurable resin composition, etc. The photosensitive resin composition, thermosetting resin composition, swelling and peeling resin composition, and dissolving and peeling resin composition, but not limited to these. Among them, a photosensitive resin composition is preferable, and a photosensitive resin composition containing an alkali-soluble resin, a photopolymerization initiator, a compound having an ethylenically unsaturated bond, and a thermosetting resin is more preferable.

(Photocurable thermosetting resin composition)

An example of the photocurable thermosetting resin composition is a resin composition containing an alkali-soluble resin, a photopolymerization initiator, a compound having an ethylenically unsaturated bond, and a thermosetting resin, as described below.

Alkali-soluble resins are resins that contain one or more functional groups among phenolic hydroxyl groups, thiol groups, and carboxyl groups, and are soluble in alkaline solutions, and preferably include compounds having two or more phenolic hydroxyl groups, and carboxyl-containing resins. Resin, compound having phenolic hydroxyl group and carboxyl group, compound having two or more thiol groups. As the alkali-soluble resin, although carboxyl group-containing resins or phenolic hydroxyl group-containing resins can be used, carboxyl group-containing resins are preferred.

The carboxyl-containing resin is polymerized and crosslinked by light irradiation. The hardening component can be alkali developable by containing a carboxyl group. In addition, from the viewpoint of photocurability or development resistance, in addition to the carboxyl group, it is preferable to have an ethylenically unsaturated bond in the molecule, but it is also possible to use only a carboxyl group-containing resin that does not have an ethylenically unsaturated double bond. In terms of ethylenic unsaturated bonds, those derived from acrylic acid or methacrylic acid or their derivatives are preferred. Among the carboxyl group-containing resins, a carboxyl group-containing resin with a copolymerization structure, a carboxyl group-containing resin with a urethane structure, a carboxyl group-containing resin with an epoxy resin as a starting material, and a phenol compound as a starting material The carboxyl-containing resin is better. Specific examples of the carboxyl group-containing resin include the compounds listed below (either oligomer or polymer may be used).

(1) The reaction of a bifunctional or higher multifunctional epoxy resin with (meth)acrylic acid adds anhydrous phthalic acid, tetrahydroanhydrous phthalic acid, hexahydroanhydrous phthalic acid, etc. to the hydroxyl groups present in the side chain The carboxyl-containing photosensitive resin of dibasic acid anhydride. Here, the solid form of a bifunctional or higher multifunctional epoxy resin is preferable.

(2) A polyfunctional epoxy resin in which the hydroxyl group of the bifunctional epoxy resin is further epoxidized with epichlorohydrin is reacted with (meth)acrylic acid, and a dibasic acid anhydride carboxyl group-containing photosensitive resin is added to the generated hydroxyl group. Here, the bifunctional epoxy resin is preferably in a solid form.

(3) Epoxy compounds having two or more epoxy groups in one molecule, compounds having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule, and unsaturated groups containing (meth)acrylic acid, etc. The reaction of monocarboxylic acid, the alcoholic hydroxyl group of the reaction product obtained with anhydrous maleic acid, tetrahydro anhydrous phthalic acid, anhydrous trimellitic acid, pyromellitic dianhydride, hexamethylene A carboxyl group-containing photosensitive resin obtained by reacting polybasic acid anhydrides such as acids.

(4) Bisphenol A, Bisphenol F, Bisphenol S, novolac type phenol resin, poly-p-hydroxystyrene, condensate of naphthol and aldehydes, condensate of dihydroxy naphthalene and aldehydes, etc. The reaction product obtained by reacting a compound having two or more phenolic hydroxyl groups in the molecule with an alkylene oxide such as ethylene oxide and propylene oxide reacts with an unsaturated group-containing monocarboxylic acid such as (meth)acrylic acid , A carboxyl group-containing photosensitive resin obtained by reacting the obtained reaction product with a polybasic acid anhydride.

(5) The reaction product obtained by reacting a compound having two or more phenolic hydroxyl groups in a molecule with a cyclic carbonate compound such as ethylene carbonate and propylene carbonate is reacted with an unsaturated group-containing monocarboxylic acid to obtain A carboxyl group-containing photosensitive resin obtained by reacting the reaction product of with polybasic acid anhydride.

(6) Diisocyanate compounds such as aliphatic diisocyanate, branched aliphatic diisocyanate, alicyclic diisocyanate, aromatic diisocyanate, etc. and polycarbonate polyol, polyether polyol, polyester polyol, Polyolefin polyols, acrylic polyols, bisphenol A alkylene oxide adduct diols, compounds having phenolic hydroxyl groups and alcoholic hydroxyl groups and other diol compounds by the polyaddition reaction of urethane A terminal carboxyl group-containing urethane resin formed by the reaction of the end of the resin with an acid anhydride.

(7) In the synthesis of diisocyanate, carboxyl-containing diol compounds such as dimethylolpropionic acid and dimethylolbutyric acid, and carboxyl-containing urethane resins that have been polymerized and reacted with diol compounds , Add hydroxyalkyl (meth)acrylate and other molecules with 1 hydroxyl and more than 1 (Meth)acrylic compound and terminal (meth)acrylated carboxyl group-containing urethane resin.

(8) In the synthesis of diisocyanate, carboxyl-containing diol compound, and carboxyl-containing urethane resin by polyaddition reaction with diol compound, one of isophorone diisocyanate and pentaerythritol triacrylate is added A carboxyl group-containing urethane resin that is a compound having one isocyanate group and one or more (meth)acrylic acid groups in the molecule, such as a molar reactant, and the terminal (meth)acrylation.

(9) Copolymerization of unsaturated carboxylic acids such as (meth)acrylic acid with unsaturated group-containing compounds such as styrene, α-methylstyrene, lower alkyl (meth)acrylate, isobutylene, etc. The carboxyl-containing photosensitive resin.

(10) The polyfunctional oxetane resin described later reacts with dicarboxylic acids such as adipic acid, phthalic acid, and hexahydrophthalic acid to form a carboxyl-containing polyester containing a primary hydroxyl group and a dibasic acid anhydride The resin is further added with glycidyl (meth)acrylate, α-methylglycidyl (meth)acrylate, etc., having one epoxy group and one or more (meth)acryloyl groups in one molecule A carboxyl group-containing photosensitive resin made of the compound.

(11) Addition of the carboxyl group-containing resin in any one of the above (1) to (10), a carboxyl group-containing photosensitive resin having a compound of a cyclic ether group and a (meth)acryloyl group in one molecule.

In addition, (meth)acrylate here refers to the general term of acrylate, methacrylate and their mixture, and other similar expressions are also the same below.

The acid value of the carboxyl-containing resin is preferably 40~150mgKOH/g. When the acid value of the carboxyl group-containing resin is 40 mgKOH/g or more, alkali development becomes good. In addition, since the acid value is below 150 mgKOH/g, the normal resist pattern can be easily drawn. More preferably, it is 50~130mgKOH/g.

The blending amount of the alkali-soluble resin is based on the total amount of the resin layer removed from the solvent, for example, 15-60% by mass, preferably 20-60% by mass. By being 15% by mass or more, preferably 20% by mass or more, the strength of the coating film can be improved. At 60% by mass or less, the viscosity becomes appropriate and the workability is improved. More preferably, it is 30-50% by mass.

For the photopolymerization initiator used for photopolymerization of the alkali-soluble resin, conventional ones can be used. Among them, an oxime ester-based photopolymerization initiator having an oxime ester group and an α-aminoacetophenone-based photopolymerization initiator can be used. A photopolymerization initiator, an phosphine oxide-based photopolymerization initiator, and a titanocene-based photopolymerization initiator are preferred. The photopolymerization initiator may be used alone or in combination of two or more kinds.

The matching amount of the photopolymerization initiator is preferably 0.01-20 parts by mass relative to 100 parts by mass of the alkali-soluble resin. In this range, the photocurability on copper is sufficient, the curability of the coating film becomes good, the coating film characteristics such as chemical resistance are improved, and the deep curability is also improved. More preferably, it is 0.5-15 mass parts with respect to 100 mass parts of alkali-soluble resins.

When the oxime ester-based photopolymerization initiator is used, the blending amount is preferably 0.01 to 5 parts by mass relative to 100 parts by mass of the alkali-soluble resin. By using 0.01 parts by mass or more, the photocuring property on copper becomes more reliable and the coating film properties such as chemical resistance are improved. In addition, when it is 5 parts by mass or less, the light absorption on the surface of the coating film is suppressed, and the curability in the deep part tends to be improved. more Preferably, it is 0.1 to 3 parts by mass relative to 100 parts by mass of the alkali-soluble resin.

When using the α-aminoacetophenone-based photopolymerization initiator or the phosphine oxide-based photopolymerization initiator, the respective blending amount is preferably 0.01-15 parts by mass relative to 100 parts by mass of the alkali-soluble resin. By using 0.01 parts by mass or more, the photocuring property on copper becomes more reliable and the coating film properties such as chemical resistance are improved. In addition, by 15 parts by mass or less, a sufficient exhaust gas reduction effect can be obtained, and light absorption on the surface of the cured film is suppressed, and the curability of the deep part is also improved. More preferably, it is 0.5-10 mass parts with respect to 100 mass parts of alkali-soluble resins.

In combination with the above-mentioned photopolymerization initiator, a photoinitiator or sensitizer can also be used. In terms of photo-initiating aids or sensitizers, for example, benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, benzophenone compounds, tertiary amine compounds, and xanthones Compound etc. Although these compounds can be used as photopolymerization initiators, they are preferably used in combination with photopolymerization initiators. In addition, a photo-initiator or sensitizer may be used alone or in combination of two or more kinds.

The photocurable thermosetting resin composition may contain a thermosetting resin for the purpose of improving characteristics such as heat resistance and insulation reliability. For thermosetting resins, isocyanate compounds, blocked isocyanate compounds, amino resins, maleimide compounds, benzoxazine resins, carbodiimide resins, cyclic carbonate compounds, and polyfunctional epoxy compounds can be used , Polyfunctional oxetane compounds, episulfide resins and other conventional thermosetting resins. Among these, the preferable thermosetting resin is one having plural cyclic ether groups and cyclic sulfide groups (hereinafter referred to as cyclic (Thio group) ether group) at least any thermosetting resin. These thermosetting resins having a cyclic (thio) ether group are commercially available in many types and can be given various characteristics due to their structure. These thermosetting resins preferably contain a softening point or have a melting point of 100°C or less. When an epoxy resin with a softening point or melting point of 100°C or less is used, the time required for the viscosity of the resin layer to decrease due to heating during lamination is shortened, the circuit compliance of the resin layer is improved, and the resin layer is easily flattened, so it is heat resistant Sexual improvement is better. These thermosetting resins can be used alone or in combination with thermosetting resins having a softening point or melting point exceeding 100°C.

The amount of thermosetting resin having plural cyclic (thio) ether groups in the molecule is in the range of 1 equivalent relative to the alkali soluble group of the alkali soluble resin, preferably 0.3 to 2.5 equivalents, more preferably 0.5 to 2.0 equivalents . By making the blending amount of the thermosetting resin having plural cyclic (thio) ether groups in the molecule more than 0.3 equivalents, no alkali-soluble groups remain in the cured film, and the heat resistance, alkali resistance, electrical insulation, etc. are improved. In addition, by being 2.5 equivalents or less, the low molecular weight cyclic (thio) ether group does not remain in the dry coating film, and the strength of the cured coating film is improved.

When using a thermosetting resin having a plurality of cyclic (thio) ether groups in the molecule, it is preferable to contain a thermosetting catalyst. Such thermal hardening catalysts include, for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanide Dicyandiamide, benzyldimethylamine, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole and other imidazole derivatives; dicyandiamide, benzyldimethylamine, 4- (Dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl -Amine compounds such as N,N-dimethylbenzylamine, hydrazine compounds such as dihydrazine adipate and dihydrazine sebacate; phosphorus compounds such as triphenylphosphine, etc. In addition, guanamine, betaguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloxyethyl-S-triazine, 2-vinyl-2, 4-Diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine. Isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine. S-triazine derivatives such as isocyanuric acid adducts are preferably used in combination with a thermosetting catalyst and a compound that can also serve as an adhesion imparting agent.

The blending amount of the thermosetting catalyst is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15 parts by mass relative to 100 parts by mass of the thermosetting resin having plural cyclic (thio) ether groups in the molecule.

In the photocurable thermosetting resin composition, in addition to the above-mentioned alkali-soluble resin, photopolymerization initiator, and thermosetting resin, a compound having one or more ethylenically unsaturated bonds in the molecule may be contained as a photosensitive monomer. body. The photosensitive monomer is one that assists the photohardening of the alkali-soluble resin irradiated with active energy rays.

Compounds that can be used as compounds having ethylenically unsaturated bonds include, for example, conventionally used polyester (meth)acrylates, polyether (meth)acrylates, urethane (meth)acrylates, and carbonates ( Meth) acrylate, epoxy (meth) acrylate, etc. Specifically, hydroxyalkyl acrylates appropriately selected from 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, etc.; ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, propylene glycol, etc. Diacrylates of diols; N,N-dimethylacrylamide, N-methylolacrylamide, N,N-dimethylaminopropyl Acrylic amides such as acrylamide; Amino alkyl acrylates such as N,N-dimethylaminoethyl acrylate and N,N-dimethylaminopropyl acrylate; Hexanediol , Trimethylolpropane, pentaerythritol, dipentaerythritol, ginseng-hydroxyethyl isocyanurate and other polyols or these ethylene oxide adducts, propylene oxide adducts, or ε-hexanone Polyvalent acrylates such as ester adducts; phenoxy acrylates, bisphenol A diacrylates, and polyvalent ethylene oxide adducts or propylene oxide adducts of these phenols Acrylic esters; polyvalent acrylic esters of glycidyl ether such as glycerol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, triglycidyl isocyanurate, etc. ; Not limited to the foregoing, polyols such as polyether polyols, polycarbonate diols, hydroxyl-terminated polybutadiene, polyester polyols, etc. are directly acrylated, or, through diisocyanate and urethane acrylate At least one of the modified acrylates and melamine acrylates, and each methacrylate corresponding to the aforementioned acrylates.

It is also possible to use epoxy acrylate resins in which multifunctional epoxy resins such as cresol novolac type epoxy resins react with acrylic acid, or hydroxy acrylates such as the hydroxyl groups of the epoxy acrylate resins and pentaerythritol triacrylate. The epoxy urethane acrylate compound etc. obtained by reacting the half urethane compound of the diisocyanate, such as isophorone diisocyanate, are used as a photosensitive monomer. Such an epoxy acrylate-based resin does not reduce the dryness to the touch, and can improve the photocurability.

The compounding amount of the compound having an ethylenically unsaturated bond is preferably a ratio of 5-100 parts by mass relative to 100 parts by mass of the alkali-soluble resin, and more preferably 5-70 parts by mass. By the compound with ethylenic unsaturated bond When the blending amount of the substance is 5 parts by mass or more, the photocurability of the photocurable thermosetting resin composition is improved. In addition, when the blending amount is 100 parts by mass or less, the hardness of the coating film can be improved.

In addition to the above-mentioned components, the photocurable thermosetting resin composition may contain other components such as fillers, colorants, elastomers, and thermoplastic resins. These ingredients are explained below.

In the photocurable thermosetting resin composition, fillers are preferably used in order to improve the physical strength of the cured product or to adjust the viscosity. In terms of fillers, conventionally used inorganic or organic fillers can be used, and barium sulfate, spherical silica, titanium oxide, Neuburg silica particles, and talc are particularly suitable. In addition, aluminum hydroxide, magnesium hydroxide, gibbsite, etc. may also be used for the purpose of imparting flame retardancy. These can be used alone or in combination of two or more.

The average particle diameter (D50) of the inorganic filler is preferably 25 μm or less, more preferably 10 μm or less, and still more preferably 3 μm or less. Here, D50 refers to the particle size in 50% of the cumulative volume obtained by the laser diffraction scattering particle size distribution measurement method based on Mie scattering theory. More specifically, by using a laser diffraction scattering type particle size distribution measuring device, the particle size distribution of the fine particles can be created on a volume basis, and the median diameter can be used as the average particle size for measurement. It is advisable to use a sample that has fine particles dispersed in water by ultrasonic waves. For the laser diffraction particle size distribution measuring device, LA-500 manufactured by Horiba Manufacturing Co., Ltd. can be used.

The shape of the filler includes, for example, a spherical shape, a needle shape, a plate shape, a scale shape, a hollow shape, an amorphous shape, a hexagonal shape, a cubic shape, and a flake shape.

The amount of filler added is relative to 100 mass of alkali-soluble resin Parts, preferably 500 parts by mass or less, more preferably 0.1 to 350 parts by mass. When the added amount of the filler is 500 parts by mass or less, the viscosity of the photocurable thermosetting resin composition will not become too high, the printability will be good, and the cured product will not easily become brittle.

The photocurable thermosetting resin composition may contain a coloring agent. As for the coloring agent, conventional coloring agents such as red, blue, green, yellow, black, and white can be used, and they can be any of pigments, dyes, and pigments. However, from the viewpoint of environmental load reduction and human body impact, halogen-free is preferred.

Although the addition amount of the coloring agent is not particularly limited, it is sufficient to be 10 parts by mass or less, particularly preferably 0.1-7 parts by mass relative to 100 parts by mass of the alkali-soluble resin.

In addition, in the photocurable thermosetting resin composition, an elastomer can be used for the purpose of imparting flexibility to the obtained cured product and improving the brittleness of the cured product. Elastomers, for example, polyester elastomers, polyurethane elastomers, polyester urethane elastomers, polyamide elastomers, polyester amide elastomers, acrylic Elastomers, olefin-based elastomers, etc. In addition, a resin in which a part or all of the epoxy groups of an epoxy resin having various skeletons is modified with a carboxylic acid-modified butadiene-acrylonitrile rubber at both ends can also be used. Furthermore, epoxy-containing polybutadiene-based elastomers, acrylic-containing polybutadiene-based elastomers, hydroxyl-containing polybutadiene-based elastomers, hydroxyl-containing isoprene-based elastomers, etc. can also be used . The elastomer can be used alone or in a mixture of two or more types.

The amount of elastomer added relative to 100 parts by mass of the alkali-soluble resin is preferably 50 parts by mass or less, more preferably 1-30 parts by mass, particularly preferably 5-30 parts by mass. When the addition amount of the elastomer is 50 parts by mass or less, the alkali developability of the photocurable thermosetting resin composition becomes good, and the developing pot life is unlikely to be shortened.

In addition, in the photocurable thermosetting resin composition, components such as block copolymers, adhesion promoters, antioxidants, and ultraviolet absorbers can be further blended as necessary. These are known in the field where electronic materials can be used. In addition, it can be combined with conventionally used thickeners such as micronized silica, magnesia, organic bentonite, and montmorillonite, as well as defoamers and leveling agents of silicone, fluorine, and polymer systems. At least one of the conventionally used additives such as imidazole-based, thiazole-based, triazole-based silane coupling agents, rust inhibitors, and fluorescent whitening agents.

The usable organic solvents are not particularly limited, but are ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum solvents, and the like. More specifically, ketones such as methyl ethyl ketone, cyclohexanone, methyl butyl ketone, methyl isobutyl ketone, methyl ethyl ketone, etc.; among toluene, xylene, tetramethylbenzene, etc. Aromatic hydrocarbons; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether , Ethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether and other glycol ethers; ethyl acetate, butyl acetate Base ester, isobutyl acetate, ethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol butyl ether ethyl Esters such as acid esters; ethanol, propanol, 2-methoxypropanol, n-butanol, isobutyl alcohol, isoamyl alcohol, ethyl Alcohols such as diol and propylene glycol; aliphatic hydrocarbons such as octane and decane; petroleum ether, naphtha, hydrogenated naphtha, and petroleum solvents such as coal soluble petroleum spirit, etc., for example, N , N-dimethylformamide (DMF), tetrachloroethylene, turpentine, etc. In addition, SWASOL 1000 and SWASOL 1500 manufactured by Nine Sun Petrochemical Co., Ltd., Solvesso 100 and Solvesso 150 manufactured by Standard Petroleum Osaka Sales Office, Solvent #100 and Solvent #150 manufactured by Sankyo Chemical Co., Ltd., Shellzoru A100 and Shellzoru A150 manufactured by Shell Chemical Japan Co., Ltd. , Idemitsu Kosan Co.'s Ipzole No. 100, Ipzole No. 150 and other organic solvents. Such an organic solvent can be used alone or in a mixture of two or more.

As for the manufacturing method of the printed wiring board using the laminated film which has the resin layer which consists of a photocurable thermosetting resin composition, the conventionally known method may be used. For example, when the (A) resin layer is used as shown in FIG. 2 to sandwich a laminate film of the (B) film and the (C) film, a printed wiring board can be manufactured in the following manner. The (C) film is peeled from the laminated film to expose the (A) resin layer, and the (A) resin layer of the aforementioned laminated film is heated on the substrate on which the circuit pattern is formed, using a vacuum laminator, etc. Vacuum lamination, pattern exposure on the resin layer (A).

(B) The film may be peeled off either after lamination or after exposure. After that, by performing alkali development, a patterned resin layer is formed on the substrate, and the patterned resin layer is cured by light irradiation or heat to form a cured film, and a printed wiring board can be manufactured.

(Thermosetting resin composition)

A resin composition containing a thermosetting resin as an example of a thermosetting resin composition is described below.

The thermosetting resin is a resin having a functional group that can undergo a curing reaction when heated. The thermosetting resin is not particularly limited, and epoxy compounds, polyfunctional oxetane compounds, compounds having two or more thioether groups in the molecule, that is, episulfide resins, etc. can be used.

The above-mentioned epoxy compound is a compound having an epoxy group, and any conventionally known one may also be used. For example, a bifunctional epoxy compound having two epoxy groups in the molecule, a polyfunctional epoxy compound having a plurality of epoxy groups in the molecule, and the like can be mentioned. In addition, it may be a hydrogenated bifunctional epoxy compound.

As the epoxy compound, for example, bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol A epoxy resin, brominated bisphenol A epoxy resin, bisphenol S epoxy resin, Phenolic novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin, biphenyl type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, two Cyclopentadiene type epoxy resin, triphenylmethane type epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin, phosphorus-containing epoxy resin, anthracene type epoxy resin, norbornene type ring Oxygen resin, adamantane type epoxy resin, sulphur type epoxy resin, aminophenol type epoxy resin, aminocresol type epoxy resin, alkylphenol type epoxy resin, etc. These epoxy resins can be used alone or in combination of two or more types.

The epoxy compound may be any one of solid epoxy resin, semi-solid epoxy resin, and liquid epoxy resin. In this manual, solid epoxy resin refers to epoxy resin that is solid at 40°C, and semi-solid epoxy resin refers to An epoxy resin that is solid at 20°C and liquid at 40°C. Liquid epoxy resin refers to an epoxy resin that is liquid at 20°C. The determination of the liquid state is based on the "Method of Confirming Liquid State" in Annex No. 2 of the provincial ordinance related to the test and characteristics of the dangerous substance (the first year of the Heisei Provincial Government Order No. 1).

The thermosetting resin may be used alone or in combination of two or more kinds. The blending amount of the thermosetting resin is based on the total amount of the resin layer removed from the solvent, and is preferably 10-50% by mass, preferably 10-40% by mass, and more preferably 10-35% by mass. In addition, the mixing amount of liquid epoxy resin when mixing liquid epoxy resin is to make the glass transition temperature (Tg) and crack resistance of the cured product better, and the total mass of thermosetting resin is 0~45 The mass% is good, 0-30 mass% is preferable, and 0-5 mass% is particularly preferable.

In the thermosetting resin composition, in order to improve the physical strength of the resulting cured product, fillers can be used as necessary. The filler is not particularly limited, and examples thereof include those exemplified in the aforementioned photocurable thermosetting resin composition. The filler can be used alone or in a mixture of two or more.

The usable organic solvent is not particularly limited, and examples thereof include the organic solvents exemplified in the aforementioned photocurable thermosetting resin composition. The organic solvent can be used alone or in a mixture of two or more.

The thermosetting resin composition may contain a curing agent. Examples of the curing agent include phenol resins, polycarboxylic acids and anhydrides thereof, cyanate ester resins, active ester resins, maleimide compounds, and alicyclic olefin polymers. The hardener can be used alone or in combination of two or more kinds.

The ratio of the above-mentioned curing agent, the epoxy group of the thermosetting resin, etc., which can undergo a thermosetting reaction and the ratio of the functional group in the curing agent that reacts with the functional group, is based on the functional group of the curing agent/the thermosetting reaction can be carried out The ratio of functional groups (equivalent ratio)=0.2~2 is better. When the functional group of the hardener/the functional group capable of thermal hardening reaction (equivalent ratio) is within the above range, the roughening of the film surface in the desmearing step can be prevented. More preferably, the functional group of the hardening agent/the functional group capable of thermal hardening reaction (equivalent ratio)=0.2~1.5, and more preferably the functional group of the hardener/the functional group capable of thermal hardening reaction (the equivalent ratio)=0.3~ 1.2.

The thermosetting resin composition may further contain a thermoplastic resin in order to increase the mechanical strength of the resulting cured film. The thermoplastic resin is preferably soluble in a solvent. When it is soluble in solvents, the softness of the dry film is improved, and the generation of cracks or powder falling can be prevented. In terms of thermoplastic resins, for example, phenoxy resins of thermoplastic polyhydroxypolyether resins or condensates of epichlorohydrin and various bifunctional phenol compounds, or various acid anhydrides or chlorinated hydroxy groups in the hydroxy ether portion of the skeleton. And esterified phenoxy resin, polyvinyl acetal resin, polyamide resin, polyimide imine resin, block copolymer and so on. Thermoplastic resin can be used individually by 1 type or in combination of 2 or more types.

The blending amount of the thermoplastic resin is 0.5-20% by mass, preferably 0.5-10% by mass based on the total amount of the resin layer removed from the solvent. If the blending amount of the thermoplastic resin is outside the above range, it becomes difficult to obtain a uniform roughened surface state.

Furthermore, the thermosetting resin composition may contain rubber-like particles as necessary. For such rubber-like particles, for example, polybutylene Diene rubber, polyisopropylene rubber, urethane modified polybutadiene rubber, epoxy modified polybutadiene rubber, acrylonitrile modified polybutadiene rubber, carboxyl modified polybutadiene Rubber, acrylonitrile butadiene rubber modified with carboxyl or hydroxyl groups, and their crosslinked rubber particles, core-shell rubber particles, etc., can be used alone or in combination of two or more. These rubber-like particles are added in order to improve the flexibility of the resulting cured film, increase the crack resistance, allow surface roughening treatment with an oxidizing agent, and increase the adhesion strength with copper foil.

The average particle diameter of the rubber-like particles is preferably in the range of 0.005 to 1 μm, more preferably in the range of 0.2 to 1 μm. The average particle diameter of the rubber-like particles in the present invention can be measured using a dynamic light scattering method. For example, the rubber-like particles can be uniformly dispersed in an appropriate organic solvent by ultrasonic waves, etc., using FPRA-1000 (manufactured by Otsuka Electronics Co., Ltd.), and the particle size distribution of the rubber-like particles can be produced on a mass basis, and the median diameter is used as the average particle size. Determination.

The mixing amount of rubber-like particles is based on the total amount of the resin layer removed from the solvent, preferably 0.5-10% by mass, and more preferably 1-5% by mass. At 0.5% by mass or more, crack resistance can be obtained, and adhesion strength with conductor patterns can be improved. At 10% by mass or less, the coefficient of thermal expansion (CTE) decreases, the glass transition temperature (Tg) increases, and the hardening characteristics improve.

The thermosetting resin composition may contain a curing accelerator. The hardening accelerator is one that promotes the thermal hardening reaction and is used to further improve the characteristics of adhesion, chemical resistance, and heat resistance. Specific examples of such hardening accelerators include imidazole and its derivatives; guanamines such as betaguanamine and benzoguanamine; diaminodiphenylmethane, m-phenylenediamine, and m-xylene two Polyamines such as amines, diaminodiphenyl sulfides, dicyandiamide, urea, urea derivatives, melamine, polyhydrazine, etc.; these organic acid salts and/or epoxy adducts; 3. Amine complexes of boron fluoride; ethyldiamino-S-triazine, 2,4-diamino-S-triazine, 2,4-diamino-6-xylyl-S-triazine Triazine derivatives such as oxazine; trimethylamine, triethanolamine, N,N-dimethyloctylamine, N-benzyldimethylamine, pyridine, N-methylmorpholine, hexa(N- Methyl)melamine, 2,4,6-ginseng (dimethylaminophenol), tetramethylguanidine, m-aminophenol and other amines; polyvinylphenol, polyvinylphenol bromide, phenol series Polyphenols such as novolacs and alkylphenol novolacs; organic phosphines such as tributylphosphine, triphenylphosphine, and ginseng-2-cyanoethylphosphine; tri-n-butyl(2,5 -Dihydroxyphenyl) phosphonium bromide, hexadecyltributylphosphonium chloride and other phosphonium salts; benzyltrimethylammonium chloride, phenyltributylammonium chloride and other quaternary ammonium salts; The aforementioned polybasic acid anhydrides; diphenyliodonium tetrafluoroborate, triphenyl alumium hexafluoroantimonate, 2,4,6-triphenyl-ylthiopyrylium hexafluorophosphate, etc. Medium; Styrene-anhydrous maleic acid resin; Equal molar reactant of phenyl isocyanate and dimethylamine or organic polyisocyanate such as toluene diisocyanate, isophorone diisocyanate and dimethylamine Conventional hardening accelerators such as reactants and metal catalysts. Among the hardening accelerators, phosphonium salts are preferred because of the BHAST resistance.

The hardening accelerator can be used alone or in combination of two or more kinds. Although the use of a hardening accelerator is not essential, it can be used in the range of 0.01 to 5 parts by mass, particularly when it is desired to accelerate hardening, relative to 100 parts by mass of the thermosetting resin. In the case of a metal catalyst, relative to 100 parts by mass of the thermosetting resin, the metal conversion is preferably 10 to 550 ppm, and 25 to 200 ppm good.

Thermosetting resin composition, and if necessary, phthalocyanine can be used. Blue, phthalocyanine. Green, iodine green, bis-azo yellow, crystal violet, titanium oxide, carbon black, naphthalene black and other conventional coloring agents, asbestos, Orben, Benton, micronized silica, etc. conventional tackifiers, silicone series , Fluorine-based, polymer-based defoamers and/or leveling agents, thiazole-based, triazole-based, silane coupling agents, etc. Adhesion imparting agents, flame retardants, titanate-based, aluminum-based conventional Know the additives.

As for the manufacturing method of the printed wiring board using the laminated film which has the resin layer which consists of a thermosetting resin composition, the conventionally known method may be used. For example, as shown in FIG. 2, when the (A) resin layer is used to sandwich a laminate film of the (B) film and the (C) film, a printed wiring board can be manufactured in the following manner. The (C) film is peeled off from the laminated film, and the circuit board on which the circuit pattern is formed is laminated under heating conditions using a vacuum laminator, and then thermally cured. Thermal hardening can be hardened in an oven or hardened by pressing on a hot plate. When laminating the circuit-formed wiring board and the laminate film of the present invention or hot plate pressing, copper foil or the circuit-formed wiring board may be simultaneously laminated. At the position corresponding to the designated position on the substrate on which the circuit pattern is formed, a pattern or via hole is formed by laser irradiation or a drill to expose the circuit wiring, and a printed wiring board can be manufactured. At this time, when there are residual components (drilling stains) that cannot be completely removed on the circuit wiring in the pattern or vias, the desmearing treatment is performed. (B) The film can be peeled off after lamination, thermal hardening, laser processing or desmearing treatment.

(Composition containing photobase generator)

An example of a composition containing a photobase generator is a composition containing an alkali developable resin, a heat-reactive component, and a photobase generator, and is described below.

Alkali developable resins are resins that contain one or more functional groups among phenolic hydroxyl groups, thiol groups, and carboxyl groups, and can be developed in an alkaline solution. For example, compounds having two or more phenolic hydroxyl groups and carboxyl groups are preferred. The resin, compounds with phenolic hydroxyl and carboxyl groups, and compounds with more than two thiol groups.

Regarding resins containing carboxyl groups, resins containing conventional carboxyl groups can be used. Due to the presence of carboxyl groups, the resin composition can be made alkali developable. In addition to the carboxyl group, a compound having an ethylenically unsaturated bond in the molecule can be used, but in the present invention, the carboxyl group-containing resin is preferably only a carboxyl group-containing resin that does not have an ethylenically unsaturated double bond.

Specific examples of the aforementioned carboxyl group-containing resin include, for example, the carboxyl group-containing resin contained in the aforementioned photocurable thermosetting resin composition, other than (1) to (11), and examples of the following compounds (oligomers) And polymers can be any).

(12) Diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, etc., and carboxyl-containing compounds such as dimethylol propionic acid and dimethylol butanoic acid Diol compound and polycarbonate polyol, polyether polyol, polyester polyol, polyolefin polyol, acrylic polyol, bisphenol A alkylene oxide adduct diol, phenolic Among hydroxyl and alcoholic hydroxyl compounds, etc. A carboxyl group-containing urethane resin obtained by the polyaddition reaction of a diol compound.

(13) Diisocyanate, bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisxylenol epoxy resin, double A carboxyl-containing amine group obtained by the polyaddition reaction of (meth)acrylates of bifunctional epoxy resins such as phenolic epoxy resins or partial acid anhydride modified products, carboxyl-containing diol compounds and diol compounds Formate resin.

(14) In the synthesis of the resin of (12) or (13) above, a compound having one hydroxyl group and one or more (meth)acryloyl groups in the molecule such as hydroxyalkyl (meth)acrylate is added. Terminal (meth)acrylated carboxyl-containing urethane resin.

(15) In the synthesis of the resin of (12) or (13) above, a molar reactant such as isophorone diisocyanate and pentaerythritol triacrylate is added, and the molecule has one isocyanate group and one or more ( (Meth)acrylic compound and terminal (meth)acrylated carboxyl-containing urethane resin.

(16) Polyfunctional epoxy resin reacts with saturated monocarboxylic acid, and is obtained by adding dibasic acid anhydrides such as anhydrous phthalic acid, tetrahydroanhydrous phthalic acid, and hexahydroanhydrous phthalic acid to the hydroxyl group present in the side chain Resins containing carboxyl groups. Here, the multifunctional epoxy resin is preferably in a solid form.

(17) A carboxyl group-containing polyester resin obtained by reacting a polyfunctional oxetane resin with a dicarboxylic acid and adding a dibasic acid anhydride to the generated primary hydroxyl group.

(18) A carboxyl group-containing resin obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with an alkylene oxide such as ethylene oxide and propylene oxide and a polybasic acid anhydride.

(19) The reaction product obtained by reacting a compound having plural phenolic hydroxyl groups in one molecule with alkylene oxide such as ethylene oxide and propylene oxide reacts with saturated monocarboxylic acid, and the obtained reaction product reacts with polybasic acid anhydride The carboxyl-containing resin obtained by the reaction.

(20) The reaction product obtained by reacting a compound having plural phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethylene carbonate and propylene carbonate reacts with saturated monocarboxylic acid, and the obtained reaction product reacts with a multi-component A carboxyl group-containing resin obtained by the reaction of acid anhydride.

(21) A carboxyl group-containing resin obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethylene carbonate and propylene carbonate and a polybasic acid anhydride.

(22) An epoxy compound having plural epoxy groups in one molecule and a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule such as p-hydroxyphenethyl alcohol react with saturated monocarboxylic acid to obtain A carboxyl group-containing resin obtained by reacting the alcoholic hydroxyl group of the reaction product with anhydrous maleic acid, tetrahydroanhydrous phthalic acid, anhydrous trimellitic acid, pyromellitic dianhydride, adipic acid and other polybasic acid anhydrides .

(23) The reaction product of an epoxy compound having plural epoxy groups in one molecule and a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule, such as p-hydroxyphenethyl alcohol Alcoholic hydroxyl A carboxyl group-containing resin obtained by reacting anhydrous maleic acid, tetrahydroanhydrous phthalic acid, anhydrous trimellitic acid, pyromellitic dianhydride, adipic acid and other polybasic acid anhydrides.

(24) The resin of any one of the above (12) to (23) is further added with glycidyl (meth)acrylate, α-methylglycidyl (meth)acrylate, etc., having one ring in the molecule A carboxyl group-containing resin derived from a compound of an oxy group and one or more (meth)acrylic groups.

The above-mentioned alkali developable resin is linear. Since the side chain of the polymer has many carboxyl groups or hydroxyl groups, etc., it becomes possible to develop an alkaline aqueous solution.

In addition, the hydroxyl equivalent or the carboxyl equivalent of the alkali developable resin is preferably 80 to 900 g/eq., more preferably 100 to 700 g/eq. When the hydroxyl equivalent or the carboxyl equivalent is 900 g/eq. or less, the adhesion of the pattern layer can be obtained and alkali development becomes easy. On the other hand, when the hydroxyl equivalent or carboxyl equivalent is 80 g/eq. or more, the dissolution of the light-irradiated part due to the developer is suppressed, and the unnecessary line becomes narrower, making it easy to draw the normal resist pattern. And good. In addition, when the carboxyl group equivalent or the phenol group equivalent is large, it is preferable that it can be developed even if the content of the alkali developable resin is small.

The acid value of the alkali developable resin is preferably 40~150mgKOH/g. When the acid value of the alkali developable resin is 40 mgKOH/g or more, alkali development becomes good. In addition, since the acid value is below 150 mgKOH/g, the normal resist pattern can be easily drawn. More preferably, it is 50~130mgKOH/g.

The blending amount of the alkali developable resin is preferably 20-60% by mass based on the total amount of the resin layer of the dry film without solvent. By being above 20% by mass, the strength of the coating film can be improved. Is below 60% by mass, then The viscosity becomes appropriate and the coatability improves. More preferably, it is 30-50% by mass.

The thermoreactive compound is a resin having a functional group that can undergo a hardening reaction when heated. For example, epoxy resin, polyfunctional oxetane compound, etc. are mentioned.

The above-mentioned epoxy resin is a resin having an epoxy group, and conventional ones can be used. For example, a bifunctional epoxy resin having two epoxy groups in the molecule, a multifunctional epoxy resin having a plurality of epoxy groups in the molecule, and the like can be mentioned. In addition, it may be a hydrogenated bifunctional epoxy compound.

For epoxy resin, the epoxy equivalent is preferably 90 or more. When the epoxy equivalent is 90 or more, the curving of the cured film is suppressed, and the developability is excellent even when left under high humidity for a long time.

Regarding the combination amount of the above-mentioned heat-reactive compound, the equivalent ratio with the alkali-developable resin (heat-reactive group: alkali-developable group) is preferably 1:0.1 to 1:10, and more preferably 1:0.2 to 1:8. When the ratio is within such a range, the development becomes good.

The photobase generator is a compound that changes its molecular structure upon irradiation with light such as ultraviolet light or visible light, or generates one or more basic substances that can act as catalysts for the addition reaction of the thermoreactive compound due to molecular cracking. Examples of basic substances include secondary amines and tertiary amines.

Photobase generators, such as α-aminoacetophenone compounds, oxime ester compounds, or imino groups having an acyloxy group, N-formation aromatic amine group, N-acylation aromatic amine group, nitrobenzyl Compounds with substituents such as carbamic acid ester group and alkoxybenzylcarbamate group.

The above photobase generators can be used alone or two or more Used in combination. The matching amount of the photobase generator in the composition containing the photobase generator is preferably 100 parts by mass of the relative thermally reactive compound, 1-50 parts by mass, more preferably 1-40 parts by mass. When it is 1 part by mass or more, development becomes easy, which is preferable.

In the composition containing the photobase generator, fillers can be used in order to improve the physical strength of the resulting hardened product. The filler is not particularly limited, and examples thereof include those exemplified in the aforementioned photocurable thermosetting resin composition. The filler can be used alone or in a mixture of two or more.

The usable organic solvent is not particularly limited, and examples thereof include the organic solvents exemplified in the aforementioned photocurable thermosetting resin composition. The organic solvent can be used alone or in a mixture of two or more.

In the composition containing the photobase generator, if necessary, components such as mercapto compounds, adhesion promoters, antioxidants, and ultraviolet absorbers can be further combined. These are known in the field where electronic materials can be used.

In addition, the above-mentioned photobase generator-containing composition can be combined with conventionally used tackifiers, silicone-based, fluorine-based, etc., such as micronized silica, magnesia, organic bentonite, and montmorillonite. Commonly used additives such as defoaming agent and/or leveling agent, silane coupling agent, rust inhibitor, etc. of polymer series.

As for the manufacturing method of the printed wiring board using the laminated film which has the resin layer which consists of a composition containing a photobase generator, the conventionally known method may be used. For example, as shown in Figure 2, when the (A) resin layer is used to sandwich a laminate film of (B) film and (C) film, the following is possible General method to manufacture printed wiring boards. The (C) film is peeled from the laminated film to expose the (A) resin layer, and the (A) resin layer of the laminated film is vacuumed under heating conditions on the substrate on which the circuit pattern is formed, using a vacuum laminator, etc. Laminated. After that, the photobase generator contained in the resin composition containing the photobase generator is activated by light irradiation in a negative pattern to harden the light-irradiated part, and the unirradiated part is removed by alkali development to form Negative pattern layer. (B) The film may be peeled at any point after lamination or after exposure. In addition, it is preferable to heat the (A) resin layer after light irradiation and before development. By this, the (A) resin layer is sufficiently cured, and a patterned layer with excellent curing characteristics can be obtained. In addition, the heating after light irradiation and before development is preferably a temperature at which the non-irradiated part is not thermally cured. Furthermore, it is preferable to perform thermal curing (post-curing) after development. After image development, it is irradiated with ultraviolet rays to activate the photoalkali generator that is not activated during light irradiation, and then perform thermal curing (post-curing).

(Positive photosensitive thermosetting resin composition)

An example of a positive photosensitive thermosetting resin composition, a resin composition containing a compound that generates a carboxyl group upon light irradiation, is described below.

Among the compounds that generate a carboxyl group upon light irradiation, a naphthoquinonediazide compound is preferably used. Compared with the past, naphthoquinone diazide compounds can be used in systems that form complexes with carboxyl groups or phenolic hydroxyl groups to suppress alkali solubility of carboxyl groups, etc., and the complexes are dissociated by subsequent light irradiation to exhibit alkali solubility. . At this time, the naphthoquinone diazide compound remains in the film, and the complex compound may be dissociated due to light irradiation, and may become soluble. Therefore, in the semiconductor field, the remaining The existing naphthoquinone diazide compounds are finally removed by high temperature dissipation. However, such a high temperature cannot be applied in the field of printed wiring boards, because from the viewpoint of stability, it cannot be used as a permanent film, so naphthoquinonediazide compounds are not actually used. In the present invention, when a naphthoquinone diazide compound is used as a compound that generates a carboxyl group upon light irradiation, the naphthoquinone diazide compound remaining in the unexposed area is taken into the cross-linked structure during the thermosetting reaction and stabilized. Therefore, the problem of conventional removal does not occur, and the film strength and toughness, that is, the bending resistance or electrical properties can be improved. In particular, by using the naphthoquinonediazide compound as a compound that generates a carboxyl group upon light irradiation together with a polyamide imide resin and a thermosetting component, it is possible to ensure good developability or developability while effectively improving flexibility. , And good.

As for the naphthoquinone diazide compound, specifically, the naphthoquinone diazide adduct of ginseng (4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene (for example, manufactured by Sambo Chemical Research Co., Ltd. TS533, TS567, TS583, TS593) or naphthoquinone diazide adducts of tetrahydroxybenzophenone (for example, BS550, BS570, BS599 manufactured by Sanbao Chemical Research Institute).

In the positive photosensitive thermosetting resin composition, fillers can be used in order to improve the physical strength of the cured product. The filler is not particularly limited, and examples thereof include those exemplified in the aforementioned photocurable thermosetting resin composition. The filler can be used alone or in a mixture of two or more.

Specific examples of the alkali developable resin contained in the positive photosensitive thermosetting resin composition include the aforementioned photocurable thermosetting resin The carboxyl group-containing resin exemplified in the lipid composition, and the alkali developable resin exemplified in the aforementioned photobase generator-containing composition.

The positive photosensitive thermosetting resin composition may contain a thermosetting component for the purpose of improving characteristics such as heat resistance and insulation reliability. For thermosetting components, isocyanate compounds, blocked isocyanate compounds, amino resins, maleimide compounds, benzoxazine resins, carbodiimide resins, cyclic carbonate compounds, and polyfunctional epoxy compounds can be used , Polyfunctional oxetane compounds, episulfide resins and other conventional thermosetting resins. Among these, a preferable thermosetting component is a thermosetting component having plural cyclic ether groups and/or cyclic sulfide groups (hereinafter referred to as cyclic (thio) ether groups) in one molecule. These thermosetting components having a cyclic (thio) ether group are commercially available in many types and can be given various characteristics due to their structure.

The amount of the thermosetting component having plural cyclic (thio) ether groups in the molecule is preferably 0.3 to 2.5 equivalents, more preferably 0.5 to 2.0 equivalents relative to 1 equivalent of the carboxyl group of the photosensitive resin containing carboxyl groups range. When the blending amount of the thermosetting component having plural cyclic (thio) ether groups in the molecule is 0.3 equivalent or more, no carboxyl groups remain in the cured film, and heat resistance, alkali resistance, electrical insulation, etc. are improved. In addition, by being 2.5 equivalents or less, the low molecular weight cyclic (thio) ether group does not remain in the dried coating film, and the strength of the cured coating film is improved.

The usable organic solvent is not particularly limited, and examples thereof include the organic solvents exemplified in the aforementioned photocurable thermosetting resin composition. Organic solvents can be used alone or in a mixture of two or more use.

In addition to the above-mentioned components, the positive photosensitive thermosetting resin composition may also contain other components such as block copolymers, fillers, colorants, elastomers, and thermoplastic resins. In addition, in the positive photosensitive thermosetting resin composition, components such as adhesion promoters, antioxidants, and ultraviolet absorbers can be further blended as necessary. These are known in the field where electronic materials can be used. In addition, it can be combined with conventionally used thickeners such as micronized silica, magnesia, organic bentonite, and montmorillonite, as well as defoamers and leveling agents of silicone, fluorine, and polymer systems. At least one of the conventionally used additives such as imidazole-based, thiazole-based, triazole-based silane coupling agents, rust inhibitors, and fluorescent whitening agents.

As for the manufacturing method of the printed wiring board using the laminated film which has the resin layer which consists of a positive photosensitive thermosetting resin composition, the conventionally known method may be used. For example, when the (A) resin layer is sandwiched between the (B) film and the (C) film as shown in FIG. The (C) film is peeled from the laminated film to expose the (A) resin layer, and the (A) resin layer of the laminated film is heated on the substrate on which the circuit pattern is formed, using a vacuum laminator, etc. Vacuum lamination. After that, the (A) resin layer is irradiated with light in a positive pattern, and the resin layer is alkali-developed to remove the light irradiated portion, thereby forming a positive pattern layer. (B) The film may be peeled at any point after lamination or after exposure. In addition, after the development, the resin layer is heated and cured (post-curing) to cure the non-irradiated portion to produce a printed wiring board. In the positive photosensitive thermosetting resin composition, it is caused by light irradiation The acid becomes a composition that is soluble in the alkali developer, so it can be developed by the alkali to form a positive pattern.

[(B) Film]

In the laminated film of the present invention, the (B) film has an elongation load per unit width of 5% at 80°C exceeding 90 g/mm and 500 g/mm or less. When laminating a laminate film having a resin layer sandwiched between a support film and a protective film, it is often laminated so that the surface of the resin layer on the side contacting the protective film is in contact with the wiring board after the protective film is peeled off. However, after peeling the support film, there are cases in which it is laminated so that the surface of the resin layer on the side contacting the support film is in contact with the wiring board. In the present invention, since the surface of the resin layer (A) on the opposite side of the film (B) is in contact with the wiring board, it is sufficient to laminate on the wiring board, so the film (B) stretches at 5% per unit width at 80°C The film with a load of more than 90g/mm and less than 500g/mm can be either a support film or a protective film. The (B) film is preferably a support film.

The supporting film refers to a person who plays the role of supporting the resin layer of the laminated film. When the resin layer is formed, it is a film coated with a resin composition. Supporting film, such as polyester film such as polyethylene terephthalate or polyethylene naphthalate, polyimide film, polyimide film, polyethylene film, polytetrafluoroethylene Films composed of thermoplastic resins such as vinyl film, polypropylene film, polystyrene film, etc., and paper with surface treatment. Among these, from the viewpoints of heat resistance, mechanical strength, handleability, etc., a polyester film is preferably used. Although the thickness of the support film is not particularly limited, it is appropriately selected in the range of about 10 to 150 μm depending on the application. In the setting support film The surface of the resin layer can be demolded. In addition, sputtering or ultra-thin copper foil can be formed on the surface where the resin layer of the support film is provided.

The protective film can be installed on the side opposite to the support film of the resin layer for the purpose of preventing dust and the like from adhering to the surface of the resin layer of the laminated film and improving the workability. As the protective film, for example, a film composed of a thermoplastic resin exemplified in the above-mentioned support film, a surface-treated paper, etc. can be used, but among these, a polyester film, a polyethylene film, and a polypropylene film are preferred. Although the thickness of the protective film is not particularly limited, it is appropriately selected in the range of about 10 to 150 μm depending on the application. The surface of the resin layer on which the protective film is set can be subjected to mold release treatment.

(B) For films, commercially available films with an elongation load of 5% per unit width at 80°C exceeding 90 g/mm and 500 g/mm or less can be used. For example, Diafoil R310 manufactured by Mitsubishi Plastics Corporation, Lumilar T6AM manufactured by Toray Corporation, Toyobo Ester Film E5041 manufactured by Toyobo Corporation, Emblet PTHA manufactured by Unitika Ltd., and the like.

((C) Film)

(C) Film, for example, polyethylene film, polytetrafluoroethylene film, polypropylene film, polyethylene naphthalate (PEN) film, etc. can be used. Considering that when the (A) resin layer is laminated on the substrate, the (C) film is peeled off, and the adhesive force between (A) resin layer and (C) film is smaller than that between (A) resin layer and (B) film good. In addition, the films exemplified in the examples of (B) films can also be used as (C) films. (C) The film is preferably a protective film.

The laminated film of the present invention is preferably used in the formation of a permanent protective film of a printed wiring board, and more preferably used in the formation of a resist layer, an interlayer insulating layer, and a cover film of a flexible printed wiring board. In addition, the laminated film of the present invention may form a wiring board by bonding wiring. It can also be used as a sealing resin for semiconductor wafers.

The laminated film of the present invention, as a bonding method of the laminated film, even under heating conditions, such as the vacuum lamination at 40~160℃, the resin layer is not prone to wrinkles, so it is suitable for use. The aforementioned heating conditions are preferably 50 to 150°C, more preferably 50 to 130°C. In addition, from the viewpoint of circuit compliance, it can be applied to the formation of a printed wiring board with a fine patterned circuit that is vacuum laminated under heating conditions. The laminated film of the present invention is preferably laminated on a wiring substrate and then subjected to a flattening treatment by hot pressing. Hot pressing is performed at, for example, 40 to 160°C, preferably 50 to 150°C, and more preferably 50 to 130°C.

[Example]

Hereinafter, the present invention will be described in detail with examples, comparative examples and test examples of the present invention, but the present invention is not limited to those limited by the following examples. In addition, the following "parts" and "%" are all based on quality unless otherwise specified.

(Synthesis of carboxyl-containing resin A-1)

To an autoclave equipped with a thermometer, a nitrogen introduction device, an alkylene oxide introduction device, and a stirring device, 119.4 g of novolak type cresol resin (Shonol CRG951 manufactured by Showa Denko Corporation, OH equivalent: 119.4), potassium hydroxide 1.19 g, With 119.4 g of toluene, the system was replaced with nitrogen while stirring, and the temperature was increased by heating. Next, 63.8 g of propylene oxide was slowly dropped, and the reaction was performed at 125 to 132°C and 0 to 4.8 kg/cm ² for 16 hours. After cooling to room temperature, 1.56 g of 89% phosphoric acid was added and mixed in the reaction solution, and then neutralized with potassium hydroxide to obtain a novolac type cresol with a non-volatile content of 62.1% and a hydroxyl value of 182.2 g/eq. Resin's propylene oxide reaction solution. The obtained novolak-type cresol resin had an average addition of 1.08 moles of alkylene oxide per equivalent of phenolic hydroxyl groups.

293.0g of the obtained novolak-type cresol resin alkylene oxide reaction solution, 43.2g of acrylic acid, 11.53g of methanesulfonic acid, 0.18g of methylhydroquinone, and 252.9g of toluene were added to the equipment equipped with a mixer, thermometer and air blowing Into the tube reactor, air was blown in at a rate of 10 ml/min, and the reaction was carried out at 110°C for 12 hours while stirring. The water produced by the reaction was used as an azeotropic mixture with toluene, and 12.6 g of water was distilled out. After that, it was cooled to room temperature, and the obtained reaction solution was neutralized with 35.35 g of a 15% sodium hydroxide aqueous solution, followed by washing with water. After that, the toluene was distilled off with an evaporator while substituting 118.1 g of diethylene glycol monoethyl ether acetate to obtain a novolak type acrylate resin solution. Next, 332.5 g of the obtained novolac-type acrylate resin solution and 1.22 g of triphenylphosphine were added to a reactor equipped with a stirrer, a thermometer, and an air blowing tube, and the air was blown in at a rate of 10 ml/min, while stirring slowly. Slowly add 62.3g of tetrahydrophthalic anhydride, and react at 95~101℃ for 6 hours to obtain a carboxyl-containing photosensitive resin resin with a solid content of 88mgKOH/g solid content and 71% solid content. Solution. Hereinafter, this will be referred to as paint A-1.

(Synthesis of carboxyl-containing resin A-2)

To 600 g of diethylene glycol monoethyl ether acetate, o-cresol novolac epoxy resin (manufactured by DIC, EPICLON N-695, softening point 95°C, epoxy equivalent 214, average number of functional groups 7.6 ) 1070 g (glycidyl number (total number of aromatic rings): 5.0 mol), 360 g (5.0 mol) of acrylic acid, and 1.5 g of hydroquinone, heated and stirred at 100°C to uniformly dissolve. Next, 4.3 g of triphenylphosphine was added, heated at 110°C, and reacted for 2 hours, then the temperature was raised to 120°C and the reaction was continued for 12 hours. To the obtained reaction liquid, 415 g of aromatic hydrocarbons (Solvesso 150) and 456.0 g (3.0 mol) of tetrahydroanhydrous phthalic acid were added, and the reaction was carried out at 110°C for 4 hours, followed by cooling. In this way, a resin solution with a solid content of 89 mgKOH/g and a solid content of 65% was obtained. Hereinafter, this will be referred to as paint A-2.

(Adjustment of photosensitive resin composition)

According to the combination shown in the following table, mix the ingredients and prepare the mixture with a mixer, then disperse and knead with 3 roller mills to prepare the first and second liquids. The obtained first liquid and the second liquid were combined to prepare photosensitive resin compositions I to V. The matching amount in the table is parts by mass.

A-1: The carboxyl-containing resin paint obtained above A-1

A-2: The carboxyl-containing resin paint obtained above A-2

*1: C.I.Pigment Blue 15: 3

*2: C.I.Pigment Yellow147

*3: IRGANOX1010: made by BASF JAPAN

*4: 2-Mercaptobenzothiazole (Accel M: manufactured by Kawaguchi Chemical Industry Co., Ltd.)

*5: Silicon dioxide

*6: Barium sulfate (B-30: manufactured by Sakai Chemical Co., Ltd.)

*7: Talc (SG-2000: manufactured by Nippon Talc)

*8: Bischofite (DHT-4A: manufactured by Kyowa Chemical Industry Co., Ltd.)

*9: 1-Methoxypropyl-2-acetate

*10: Dipentaerythritol hexaacrylate

*11: Biphenyl novolac type epoxy resin (NC3000HCA75: manufactured by Nippon Kayaku Co., Ltd.: softening point 70°C)

*12: Bisxylenol type epoxy resin (YX-4000: manufactured by Mitsubishi Chemical Corporation: melting point 105°C)

*13: Phenolic novolac type epoxy resin (RE306CA90: manufactured by Nippon Kayaku Co., Ltd.: softening point 50°C)

*14: 2-Methyl-1-(4-methyl-thiophenyl)-2-morpholinopropan-1-one (IRGACURE907: manufactured by BASF JAPAN)

*15: 2,4-Diethylthioxanthone (KAYACURE DETX-S: manufactured by Nippon Kayaku Co., Ltd.)

*16: 2,4,6-trimethylbenzyl-diphenyl-phosphine oxide (LucirinTPO: manufactured by BASF JAPAN)

*17: Ethyl ketone, 1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-, 1-(0-acetyloxime) (IRGACURE OXE02: made by BASF JAPAN)

*18: Diethylene glycol monoethyl ether acetate

(Measurement of melt viscosity of resin layer material)

The photosensitive resin compositions I to V obtained above were each diluted with methyl ethyl ketone and applied to a polyethylene terephthalate film with a thickness of 25 μm using a 90 μm coater. , Perform 15 at 80℃ It dried in minutes to obtain a resin layer 1~V. The film was peeled off from the obtained resin layers I to V, and a sample with a thickness of 300 μm was obtained by stacking. Using this sample, under the conditions of Rheo Stress RS-6000 (manufactured by HAAKE), oscillation mode, stress control method, heating rate 5°C/min, controlled stress 3Pa, gap 260μm, and frequency 1Hz, the melting at 80°C was measured Viscosity. The results are shown in Table 2.

(Measurement of 5% elongation load (EL80 value) per unit width at 80℃)

The (B) film described in Table 3 below was cut into strips with a length of 50 mm and a width of 3 mm, and mounted at room temperature between 30 mm between RSA-G2 chucks manufactured by TA Company. After raising the temperature and maintaining 80°C, the drawing speed was 30 mm/min. Perform a tensile test, and divide the load when the sample shows 5% extension by the width of the sample as the EL80 value (g/mm). The test is carried out 5 times in the length direction and width direction of the film, and the second value from the largest is the largest value, and the second value from the smallest is the smallest value.

(Production of laminated film)

On the (B) film described in Table 3 below, the photosensitive resin composition obtained above was diluted with methyl ethyl ketone and dried It was coated with a thickness of 20 μm, and dried with warm air at 80°C for 15 minutes to obtain a photosensitive (A) resin layer. Next, as the (C) film, a 15 μm-thick biaxially stretched polypropylene film (manufactured by Oji Alfa Co., MA) was laminated on the resin layer (A) to produce a laminated film. The obtained laminated film was wound up with the (C) film as the outer side, and the laminated film of Examples 1-8 and Comparative Example 1 was produced.

(Production of evaluation board a for adhesive performance evaluation)

A circuit pattern substrate with a copper thickness of 25 μm and a minimum circuit-to-circuit width of 100 μm was subjected to a copper surface roughening treatment using MEC Etch Bond CZ-8101 manufactured by MEC, and then washed with water and dried. On the obtained dry substrate, the laminated films of Examples 1 to 8 and Comparative Example 1 were used in a vacuum laminator (CVP-300: manufactured by Nichigo Morton Co., Ltd.) in the first chamber at a temperature of 80°C and a vacuum pressure of 3hPa, Under the condition of vacuum time of 30 seconds, after lamination under vacuum, pressing was carried out under conditions of pressing pressure of 0.5 MPa and pressing time of 30 seconds to produce an evaluation substrate a for evaluation of adhesion performance.

(Production of evaluation substrate b for adhesive performance evaluation)

The evaluation substrate a for evaluation of the adhesion performance produced above was pressed in the second chamber at a temperature of 80°C with a pressing pressure of 8kgf/m ² using a stainless steel petri dish for 60 seconds to perform a flattening process. Evaluation board b for bonding performance evaluation.

(Assessment of wrinkles after vacuum lamination under heating conditions)

The presence or absence of wrinkles on the surface of the evaluation substrate a for evaluating the adhesion performance prepared above was visually confirmed, and the evaluation was performed using the following criteria. The evaluation is carried out 5 times. The results are shown in Table 2.

○: No wrinkles occurred on all evaluation substrates

×: Wrinkles with a length of 1cm or more are generated on more than one evaluation substrate

(Evaluation of wrinkles after flattening by hot pressing)

Whether or not wrinkles are generated on the surface of the evaluation substrate b for evaluating the adhesion performance prepared above in the (B) film was visually confirmed, and the evaluation was performed using the following criteria. The evaluation is carried out 5 times. The results are shown in Table 2.

○: No wrinkles occurred on all evaluation substrates

×: There are wrinkles over 1cm in length

(Production of evaluation board c for adhesive performance evaluation)

Instead of using a solid copper substrate with a thickness of 0.8 mm, a substrate produced in the same manner as the evaluation substrate b was exposed using an exposure device equipped with a high-pressure mercury lamp to produce an evaluation substrate c.

(Automatic exposure machine test)

Using the evaluation substrate c, the film peeling device for printed circuit boards manufactured by Hitachi Industrial Equipment Machinery Co., Ltd., under the conditions of roll pressure 0.4MPa, peeling tape pressing pressure 0.4MPa, and peeling speed 15m/min, peel off the (B) film, and use the following conditions to evaluate. The evaluation is carried out 5 times.

○: The film can be peeled off from the resin layer on all evaluation substrates (B)

×: (B) The film is cracked and remains in the (A) resin layer after exposure

(Production of evaluation substrate d for evaluation of hardened properties)

The evaluation substrate b for the adhesion performance evaluation produced above was exposed through Step Tablet (Kodak No. 2) using an exposure device equipped with a high-pressure mercury lamp. Development (30°C, 0.2MPa, 1% by mass sodium carbonate aqueous solution) for 90 seconds, the exposure amount when the pattern of the remaining stepped board is 7 segments is the optimal exposure amount, and the optimal exposure amount is used to form a patterned hardened product . After the substrate to UV belt furnace, a cumulative exposure amount of 1000mJ / cm ² ultraviolet irradiation conditions, heated for 90 minutes at 150 ℃ hardened to produce a characteristic diagram formed cured shape was evaluated by hardening of Evaluation substrate d.

(Developability)

Except for replacing the circuit pattern substrate with a copper thickness of 25 μm and a minimum circuit width of 100 μm, an overall copper laminate substrate is used, and an evaluation substrate b'is produced in the same manner as the evaluation substrate b for evaluation of adhesion performance. For the evaluation substrate b'prepared in this manner, except that an opening pattern of 150 µm was used as the opening formation pattern, an evaluation substrate e for evaluation of the properties of the cured product was produced in the same manner as the evaluation substrate d for evaluation of the properties of the cured product. The opening shape of the produced evaluation substrate e for evaluating the properties of the cured product was observed with SEM (Scanning Electron Microscope), and evaluated with the following criteria. The evaluation is carried out 5 times. The results are shown in Table 2.

○: There is no vignetting and undercut, and a stable opening shape can be obtained

×: A stable opening shape cannot be obtained due to vignetting or undercutting

(Soldering heat resistance)

After applying the rosin-based flux to the evaluation substrate d for evaluating the properties of the cured product prepared above, it was immersed in a solder tank set at 260°C in advance. Next, after the flux was washed with modified alcohol, the swelling and peeling of the resist layer was visually observed, and the evaluation was performed with the following criteria. The results are shown in Table 2.

◎: Even if the immersion is repeated 4 times or more for 10 seconds, no peeling is confirmed in the resist layer

○: Even if the immersion is repeated twice for 10 seconds, no peeling is confirmed in the resist layer

×: Within 1 time of immersion for 10 seconds, there is swelling and peeling of the resist layer

*19: Diafoil R310 (polyethylene terephthalate film) manufactured by Mitsubishi Plastics Corporation

*20: Lumilar T6AM (polyethylene terephthalate film) manufactured by Toray

*21: Toyobo ester film E5041 (polyethylene terephthalate film) manufactured by Toyobo Co., Ltd.

*22: Emblet PTHA (polyethylene terephthalate film) manufactured by Unitika Ltd.

*23: Lumilar 12F68 (polyethylene terephthalate film) manufactured by Toray

From the results shown in Table 3 above, it can be seen that in the laminated film of the example, wrinkles are less likely to occur even after vacuum lamination under heating conditions, and even if the film is peeled off with an automatic exposure machine, the film is less likely to remain in the resin layer on. On the other hand, it can be seen that when a film with a 5% elongation load per unit width exceeding 90 g/mm and 500 g/mm or less, which does not meet 80°C, is used, wrinkles are generated after vacuum lamination under heating conditions. The reduction in developability and soldering heat resistance due to the reduction in the film thickness of the wrinkles can be seen. Furthermore, when the film is peeled off with an automatic exposure machine, the film remains on the resin layer.

A‧‧‧Resin layer

B‧‧‧5% elongation load per unit width at 80℃ exceeds 90g/mm and For film below 500g/mm

Claims (5)

A laminated film characterized by (A) a resin layer with a thickness of 1 to 200 μm and a thickness of (B) with a thickness of 10 to 150 μm (B) at 80°C per 5% elongation per unit width. The load exceeds 90 g/mm and is 500 g/mm or less The aforementioned (A) resin layer contains an alkali-soluble resin, a photopolymerization initiator, a thermosetting resin, and a filler. The amount of the aforementioned filler is 10% by mass based on the total amount of the resin layer of the dry film without solvent Above, and 500 parts by mass or less relative to 100 parts by mass of the alkali-soluble resin, the filler includes at least one selected from silica, barium sulfate, and talc having an average particle diameter (D50) of 25 μm or less, and the (A) resin The melt viscosity of the layer at 80℃ is 200~2500dPa. s. The aforementioned 5% elongation load per unit width at 80°C is 10~150μm in thickness (B) The film is cut into strips with a length of 50mm and a width of 3mm. After the temperature is maintained at 80°C, the tensile speed is 30mm. /min to carry out the tensile test, and divide the value of the load when the aforementioned sample shows 5% extension by the width of the sample. The laminated film as described in claim 1, which is used for pasting on the surface of a wiring board. The laminated film described in claim 2 is pasted on the surface of the wiring board using a vacuum laminator. Such as the laminated film described in claim 3, which is made by using vacuum The laminating process of the laminating machine and the subsequent flattening process of hot pressing are adhered to the surface of the wiring substrate. The laminated film described in any one of claims 1 to 4 is used to form a permanent film for a wiring board.

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