JP2023168087A - Method for manufacturing dry film - Google Patents

Abstract

To provide a method for manufacturing a dry film in which a photosensitive resin layer with excellent leveling property can be formed even in the case of forming the photosensitive resin layer on a rough-surfaced first film (support film).SOLUTION: A method for manufacturing a dry film comprising a first film and a photosensitive resin layer provided on one face of the first film includes: a process of preparing a first film which has a first principal plane and a second principal plane, in which the arithmetic average roughness Ra of a first surface is 0.1 to 1 μm; and a process of coating photosensitive resin composition on the surface of the first principal plane of the first film to form a photosensitive resin layer, and further includes a process of removing static electricity before coating the photosensitive resin composition such that the amount of static electricity of the first principal plane of the first film becomes 0.7kV or less.SELECTED DRAWING: None

Description

The present invention relates to a method for manufacturing a dry film, and more particularly, to a method for manufacturing a dry film that is suitably used for forming an insulating film or the like provided on the surface of a printed wiring board or the like.

An insulating film, also called a solder resist film, is formed on the surface of printed wiring boards to protect conductor circuits and prevent solder from adhering to areas other than those where soldering is required. There is. As a method for forming an insulating film, there is a method in which a photosensitive resin composition is applied onto a circuit substrate, dried, exposed to light, and developed to form an insulating film only on a desired portion of the circuit board surface. The mainstream method is to bond a film with a photosensitive resin layer called a dry film to a circuit board, and then form an insulating film only on a desired portion of the circuit board surface by exposure and development.

In the above circuit board, it is known that by roughening the surface of the insulating film, the solder adhesion resistance and wiring concealment property during solder flow can be improved. Moreover, since the glossiness of the roughened insulating film is moderately suppressed, good design properties can be obtained. Furthermore, since scratches are harder to see on a roughened surface than on a glossy surface, quality control is also better. In recent years, in IC package substrates and the like, insulating films have been roughened in order to improve die attach adhesion. For example, Patent Document 1 proposes providing a predetermined number of depressions per unit on the surface of a photosensitive resin layer. Further, Patent Document 2 proposes that if the photosensitive resin layer has a surface having a specific average interval between protrusions and recesses, pattern edge collapse is less likely to occur, and the yield of visual inspection can also be improved.

As a dry film in which the surface of the photosensitive resin layer as described above is roughened, for example, Patent Document 3 describes that by using a support film whose surface in contact with the photosensitive resin layer has a predetermined surface roughness, It has been proposed that the solder resist layer can be roughened.

Japanese Patent Application Publication No. 2018-124452 JP2018-116255A International Publication No. 2015-163455 pamphlet

When trying to form a photosensitive resin layer by coating a photosensitive resin composition on the surface of a support film with an uneven surface as in Patent Document 3, the results are compared with the case where a support film with a smooth surface is used. Therefore, poor leveling of the coating film of the photosensitive resin composition is likely to occur. Furthermore, compared to a film with a smooth surface, a film with a roughened surface is more likely to generate static electricity due to friction with a conveyance roller when conveyed to a coating device. Therefore, there are problems in that foreign matter tends to adhere to the coated surface of the support film, foreign matter gets mixed into the photosensitive resin layer, and it is difficult to form a photosensitive resin layer with good leveling properties. Furthermore, if the photosensitive resin composition is applied to the support film in a state where the amount of static electricity on the surface is high, coating defects such as uneven coating, streaks, and missing spots are likely to occur.

Therefore, an object of the present invention is to form a photosensitive resin layer with good leveling properties even when the photosensitive resin layer is formed on a roughened first film (supporting film). It is an object of the present invention to provide a method for producing a dry film that can be produced.

The present inventors have found that when removing electricity from a charged film, it is more difficult to remove electricity from a film having an uneven surface than from a film having a smooth surface. Even if the film has a roughened surface, if the amount of static electricity on the surface is below a certain value, a photosensitive resin layer with good leveling properties can be formed when a photosensitive resin composition is applied to the surface. We obtained the knowledge that it is possible to do this. The present invention is based on this knowledge. That is, the gist of the present invention is as follows.

[1] A method for producing a dry film comprising a first film and a photosensitive resin layer provided on one surface of the first film, the method comprising:
a step of preparing a first film having a first principal surface and a second principal surface, the first surface having an arithmetic mean roughness Ra of 0.1 to 1 μm; and a first principal surface of the first film. a step of applying a photosensitive resin composition to the surface of the photosensitive resin layer to form a photosensitive resin layer;
including;
Before applying the photosensitive resin composition, the method further includes the step of removing static electricity so that the amount of static electricity on the first main surface of the first film is 0.7 kV or less.
Method of manufacturing dry film.
[2] The method according to [1], wherein the amount of static electricity on the first main surface of the first film before static electricity removal is 4 kV or more.
[3] The method according to [1], wherein the photosensitive resin composition is applied so that the film thickness after drying is 1 μm or more.
[4] The method according to [1], wherein the photosensitive resin composition has a surface tension of 20 to 50 mN/m.
[5] The method according to [1], wherein the first film has a thickness of 10 to 150 μm.
[6] The method according to [1], wherein the first film is a polyester film.
[7] The method according to [1], wherein the dry film is used to form an insulating film for electronic components.

According to the present invention, before applying the photosensitive resin composition, the first film is neutralized to reduce the amount of static electricity to a predetermined value or less, so that the photosensitive resin is coated on the roughened first film. Even when forming a layer, a photosensitive resin layer with good leveling properties can be formed.

The method for producing a dry film according to the present invention is a method for producing a dry film including a first film and a photosensitive resin layer provided on one surface of the first film. Note that the "dry film" in the present invention refers to a film that includes at least a first film and a photosensitive resin layer, and does not exclude a film that includes other layers. For example, an intermediate layer or the like may be provided between the first film and the resin layer to prevent dust from adhering to the surface of the photosensitive resin layer and to take into account the ease of handling of the dry film. In addition, a second film may be further provided on the surface of the photosensitive resin layer opposite to the surface in contact with the first film. Each step in the dry film manufacturing method of the present invention will be described in detail below.

<First film preparation process>
The first film in the present invention refers to a film that is integrally laminated onto a base material such as a substrate by heating or the like so that the layer (photosensitive resin layer) made of a photosensitive resin composition formed on a dry film is in contact with the base material. It refers to something that is adhered to at least the photosensitive resin layer during molding.

The first film used for the dry film has a first main surface and a second main surface, and the arithmetic mean roughness Ra of the first surface is 0.1 to 1 μm. The first film supports the photosensitive resin layer, which will be described later, and also plays a role in shaping the photosensitive resin layer by the uneven form of the first main surface of the first film during exposure and development of the photosensitive resin layer. have The Ra of the first principal surface can be adjusted appropriately within the above range according to the requirements of the cured product obtained using a dry film, but it is preferably 0.15 to 0.50 μm, and 0. More preferably, the thickness is from .15 to 0.30 μm. In this specification, the arithmetic surface roughness Ra means the arithmetic mean surface roughness measured with a measuring device compliant with JIS B0601-2001.

The first film whose first principal surface has the above-mentioned arithmetic surface roughness can be obtained by, for example, adding a filler to the resin (kneading treatment) when forming the film used for the first film. The film may be subjected to matte coating (coating treatment), blast treatment such as sandblasting, hairline treatment, chemical etching, or other treatment. Among these, those that have been coated can be preferably used. For example, a first film with an intermediate layer containing particles on the first film can be used. The intermediate layer containing particles is not limited to a single layer, and may be laminated as two or more layers.

As the support film constituting the first film, any known and commonly used film can be used without particular limitation, such as polyester films such as polyethylene terephthalate and polyethylene naphthalate, polyimide films, polyamideimide films, polypropylene films, and polystyrene films. Films made of thermoplastic resin such as films can be preferably used, and among these, polyester films can be preferably used from the viewpoints of heat resistance, mechanical strength, handleability, and the like.

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

Examples of the particles contained in the intermediate layer include inorganic particles and organic particles, and known and commonly used particles can be used. Examples of inorganic particles include zinc oxide, nickel oxide, silicon oxide, barium sulfate, talc, kaolin, chromium oxide, cadmium sulfide, goethite, and alumina, and examples of organic particles include acetylcellulose, polyethylene, polypropylene, Examples include thermoplastic resins such as polystyrene, thermoplastic polyester, polyamide, polyacrylonitrile, and polyacetal resin powder, and thermosetting resins such as phenol resins, urea resins, triazine resins, epoxy resins, furan resins, and acrolein resins. These particles can be used alone or in combination of two or more.

The average primary particle size of the particles is preferably 0.1 to 10 μm. By setting it within the above range, it is possible to suppress the visibility of scratches and improve resolution at an even higher level. Further, it is preferable that the maximum particle size has an upper limit equal to the thickness of the intermediate layer. In this specification, the average primary particle size refers to the average primary particle size obtained from a scanning electron microscope image after the particles contained in the intermediate layer are dispersed in a solvent using ultrasonic waves, deagglomerated, dried to remove the solvent. , the particle diameters of 10 randomly selected particles are measured and the value is the arithmetic average value.

It is preferable that the intermediate layer containing the particles described above contains at least one of melamine and melamine compounds. By using a dry film obtained by coating and drying a photosensitive resin composition on a first film containing at least one of melamine and melamine compounds in the intermediate layer, a substrate etc. on which the dry film is laminated can be used. This is preferable in that it is possible to suppress the influence on the surface of the dry film even by strong impact or pressure when stacked. Further, it is preferable that a large amount of melamine and melamine compound contained in the intermediate layer of the first film be contained on the side in contact with the coating film (ie, photosensitive resin layer) of the photosensitive resin composition.

As the melamine and melamine compound, known and commonly used ones can be used. In the present invention, melamine compounds also include mixtures of melamine compounds and other substances. In the present invention, "melamine" refers to a resin cured by addition condensation of melamine (2,4,6-triamino-1,3,5-triazine) and formaldehyde. The concept also includes methylolmelamine, which is a reactant, and alkylated methylolmelamine, which is an alkylated product thereof. Melamines also include modified melamines such as methylated methylolmelamine, propylated methylolmelamine, butylated methylolmelamine, and isobutylated methylolmelamine. Also included are melamine modified products such as melamine (meth)acrylate.

The melamine compound is a mixture of the above-described melamine and other resins such as acrylic resin, epoxy resin, and alkyd resin, and includes, for example, acrylic melamine, alkyd melamine, polyester melamine, and epoxy melamine. Among these, acrylic melamine and epoxy melamine are preferred, and acrylic melamine is more preferred since they provide better impact resistance. Note that acrylic melamine here is a mixture of acrylic resin and melamine resin, and refers to a type in which acrylic resin is cured with melamine resin. Specific examples of acrylic melamine include Acridic 54-172-60, A-322, A-405, and A-452 manufactured by DIC Corporation.

The intermediate layer containing particles can be formed by dissolving the above-mentioned melamine and melamine compound in a suitable solvent, blending the particles to form a coating liquid, applying the coating liquid onto a support film, and drying. The blending amount of the particles is preferably 10 to 200 parts by weight, more preferably 20 to 190 parts by weight, based on 100 parts by weight of melamine and melamine compound.

The surface of the first film to which the photosensitive resin composition is applied may be subjected to a mold release treatment. For example, a coating solution prepared by dissolving or dispersing a mold release agent such as wax, silicone wax, or silicone resin in an appropriate solvent can be coated using coating methods such as roll coating, spray coating, gravure printing, or screen printing. The release treatment can be performed by coating the surface of the first film and drying it by a known means such as a printing method. Moreover, these mold release agents may be included in the intermediate layer containing the above particles.

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

<First film static elimination process>
A film with surface irregularities such as the Ra of the first principal surface of 0.1 to 1 μm as described above generates static electricity due to contact with the conveyance roller during conveyance, compared to a film with a smooth surface. It is known to be easy. Further, a film having surface irregularities has a property that it is difficult to eliminate static electricity. Therefore, in the present invention, before applying the photosensitive resin composition of the first film, static electricity is removed so that the amount of static electricity on the applied surface (ie, the first principal surface) becomes 0.7 kV or less. By removing static electricity until the amount of static electricity charged on the first principal surface becomes 0.7 kV or less, good leveling properties can be achieved even when forming a photosensitive resin layer on a roughened first film. A photosensitive resin layer can be formed. A preferable amount of static electricity is 0.5 kV or less.

For static elimination, a known static eliminator such as an ion supply type static eliminator, a roller type static eliminator, a static eliminator brush device, and a static eliminator cloth device can be used. Among these, it is preferable to use an ion supply type static eliminator. The ion supply type static eliminator is not particularly limited, but examples thereof include a corona discharge type static eliminator, a soft X-ray type static eliminator, a static eliminator equipped with a static eliminator that generates ions by applying a voltage, and the like. .

When static electricity is removed from the first main surface of the first film using the static eliminator as described above, the static electricity may be removed sequentially, but considering dry film production efficiency, it is necessary to apply the first film It is preferable to eliminate static electricity from the running first film when it is continuously conveyed to the device. The running first film is usually in contact with conveyance rollers and the like, so it is easily charged with static electricity, and the amount of static electricity on the first main surface of the first film is usually 4 kV or more. In this case, a pair of static elimination electrodes having surfaces extending in a direction perpendicular to the running direction (width direction of the first film) are arranged to face each other with the first film in between. AC high voltage is generated from the power unit and supplied to the static elimination electrode from the high voltage cable. An unequal electric field is generated around the sharp tip of the discharge electrode to which a high voltage is applied, causing a corona discharge, and air molecules (actually oxygen, nitrogen, water vapor, etc.) near the electrode tip mix positive ions and negative ions. (hereinafter also referred to as "ionization of air molecules" for short). Charges of opposite polarity attract each other, and the charge on a charged object attracts ions of opposite polarity until the charge is neutralized. In this way, the amount of static electricity charged on the first main surface side of the first film during running can be reduced to 0.7 kV or less. Note that the static eliminator (static electricity eliminator) as described above generally includes a static eliminator including a discharge electrode and a ground electrode, a high voltage cable, and a power unit.

The first film is preferably neutralized in an environment with a relative humidity of 45 to 65% in order to easily reduce the amount of static electricity.

<Formation process of photosensitive resin layer>
After removing the static electricity on the first main surface side of the first film to 0.7 kV or less as described above, a photosensitive resin composition is applied to the surface of the first main surface to make it photosensitive. Form a resin layer. The photosensitive resin layer is patterned by exposure and development when the dry film is used, and becomes an insulating film (solder resist layer) provided on an electronic member such as a circuit board. For the formation of such a photosensitive resin layer, for example, conventionally known solder resist inks can be used without limitation, but below, photosensitive resins that can be preferably used for forming the photosensitive resin set layer of the dry film according to the present invention will be described. An example of the composition will be explained.

The alkali-soluble resin may be any resin as long as it is alkali-soluble, and known and commonly used resins may be used. The alkali-soluble resins can be used alone or in combination of two or more. Examples include carboxyl group-containing resins and water-soluble resins such as phenolic hydroxyl group-containing resins. Among these, carboxyl group-containing resins and phenolic hydroxyl group-containing resins are preferred, and carboxyl group-containing resins are more preferred because they have excellent developability. When the alkali-soluble resin contains a carboxyl group, it can be made alkali developable. In addition, from the viewpoint of photosensitivity, it is preferable to have ethylenically unsaturated double bonds in the molecule in addition to carboxyl groups, but only carboxyl group-containing resins that do not have ethylenically unsaturated double bonds are used. It's okay. Preferably, the ethylenically unsaturated double bond is derived from acrylic acid or methacrylic acid or derivatives thereof. When using only a carboxyl group-containing resin that does not have ethylenically unsaturated double bonds, in order to make the composition photocurable, it is necessary to use a compound having a plurality of ethylenically unsaturated groups in the molecule, which will be described later. It is necessary to use a polymerizable monomer together. Specific examples of carboxyl group-containing resins include the following compounds (which may be oligomers or polymers). In this specification, (meth)acrylate is a term that collectively refers to acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions.

(1) A carboxyl group-containing resin obtained by copolymerizing an unsaturated carboxylic acid such as (meth)acrylic acid with an unsaturated group-containing compound such as styrene, α-methylstyrene, lower alkyl (meth)acrylate, or isobutylene.

(2) Diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, carboxyl group-containing dialcohol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid, polycarbonate polyols, and polyethers. A carboxyl group-containing urethane resin produced by polyaddition reaction of diol compounds such as polyols, polyester polyols, polyolefin polyols, acrylic polyols, bisphenol A-based alkylene oxide adduct diols, and compounds having phenolic hydroxyl groups and alcoholic hydroxyl groups.

(3) Diisocyanate and bifunctional epoxy resins such as bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bixylenol epoxy resin, and biphenol epoxy resin ( Carboxyl group-containing photosensitivity resulting from polyaddition reaction of partially acid anhydride-modified products of reactants with monocarboxylic acid compounds having ethylenically unsaturated double bonds such as meth)acrylic acid, carboxyl group-containing dialcohol compounds, and diol compounds. Urethane resin.

(4) During the synthesis of the resin in (2) or (3) above, a compound having one hydroxyl group and one or more (meth)acryloyl groups in the molecule, such as hydroxyalkyl (meth)acrylate, is added, and the terminal ( meth)acrylated carboxyl group-containing photosensitive urethane resin.

(5) During the synthesis of the resin of (2) or (3) above, one isocyanate group and one or more (meth)acryloyl groups are added in the molecule, such as an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate. A carboxyl group-containing photosensitive urethane resin that is terminally (meth)acrylated by adding a compound that has a carboxyl group.

(6) A carboxyl group-containing photosensitive resin obtained by reacting (meth)acrylic acid with a bifunctional or higher polyfunctional (solid) epoxy resin and adding a dibasic acid anhydride to the hydroxyl group present in the side chain.

(7) A carboxyl product obtained by reacting (meth)acrylic acid with a polyfunctional epoxy resin in which the hydroxyl groups of a bifunctional (solid) epoxy resin are further epoxidized with epichlorohydrin, and adding a dibasic acid anhydride to the resulting hydroxyl groups. Group-containing photosensitive resin.

(8) Difunctional oxetane resin is reacted with a dicarboxylic acid such as adipic acid, phthalic acid, hexahydrophthalic acid, etc., and the resulting primary hydroxyl group is converted into a dibase such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, etc. Carboxyl group-containing polyester resin with acid anhydride added.

(9) An epoxy compound having multiple epoxy groups in one molecule, a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule, such as p-hydroxyphenethyl alcohol, and (meth) Maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipine are reacted with an unsaturated group-containing monocarboxylic acid such as acrylic acid, and the alcoholic hydroxyl group of the resulting reaction product is A carboxyl group-containing photosensitive resin obtained by reacting polybasic acid anhydrides such as acids.

(10) Reaction obtained by reacting a reaction product obtained by reacting a compound having multiple phenolic hydroxyl groups in one molecule with an alkylene oxide such as ethylene oxide or propylene oxide with an unsaturated group-containing monocarboxylic acid. A carboxyl group-containing photosensitive resin obtained by reacting a product with a polybasic acid anhydride.

(11) Obtained by reacting a reaction product obtained by reacting a compound having multiple phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate with an unsaturated group-containing monocarboxylic acid. A carboxyl group-containing photosensitive resin obtained by reacting a reaction product with a polybasic acid anhydride.

(12) A carboxyl group-containing photosensitive resin obtained by adding a compound having one epoxy group and one or more (meth)acryloyl groups in one molecule to the resins (1) to (11) above.

The alkali-soluble resins that can be used in the present invention are not limited to those listed above. Also. The alkali-soluble resins listed above may be used alone or in combination.

The weight average molecular weight of the alkali-soluble resin varies depending on the resin skeleton, but is generally in the range of 2,000 to 150,000, preferably in the range of 5,000 to 100,000. By using an alkali-soluble resin having a weight average molecular weight of 2,000 or more, resolution and tack-free performance can be improved. Further, by using an alkali-soluble resin having a weight average molecular weight of 150,000 or less, developability and storage stability can be improved.

The blending amount of the alkali-soluble resin in the photosensitive resin composition is preferably 20 to 60% by mass, more preferably 25 to 50% by mass based on the entire photosensitive resin composition, in terms of solid content. be. By setting the content to 20% by mass or more, the strength of the coating film can be improved. Further, by setting the content to 60% by mass or less, the viscosity becomes appropriate and workability is improved.

The photopolymerizable monomer contained in the photosensitive resin composition is a monomer having an ethylenically unsaturated double bond. Examples of such photopolymerizable monomers 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; glycol diacrylates such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol; N,N-dimethylacrylamide , N-methylol acrylamide, N,N-dimethylaminopropylacrylamide, and other acrylamides; N,N-dimethylaminoethyl acrylate, N,N-dimethylaminopropyl acrylate, and other aminoalkyl acrylates; hexanediol, trimethylolpropane, Polyhydric alcohols such as pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate, or polyhydric acrylates such as their ethylene oxide adducts, propylene oxide adducts, or ε-caprolactone adducts; phenoxy acrylate, bisphenol A di Acrylates and polyhydric acrylates such as ethylene oxide adducts or propylene oxide adducts of these phenols; Polyhydric acrylates; not limited to the above, acrylates and melamine acrylates obtained by directly acrylating polyols such as polyether polyols, polycarbonate diols, hydroxyl-terminated polybutadienes, and polyester polyols, or converting them into urethane acrylates via diisocyanates, and the above-mentioned acrylates. At least one of the methacrylates corresponding to the above can be appropriately selected and used. Such photopolymerizable monomers can also be used as reactive diluents.

Epoxy acrylate resins are made by reacting acrylic acid with multifunctional epoxy resins such as cresol novolac type epoxy resins, and half urethanes are made of hydroxy acrylates such as pentaerythritol triacrylate and diisocyanates such as isophorone diisocyanate. An epoxy urethane acrylate compound or the like obtained by reacting a compound may be used as the photopolymerizable monomer. Such an epoxy acrylate resin can improve photocurability without reducing dryness to the touch.

The amount of the photopolymerizable monomer is preferably 0.2 to 60 parts by weight, more preferably 0.5 to 50 parts by weight, based on 100 parts by weight of the alkali-soluble resin, in terms of solid content. When the amount of the photopolymerizable monomer is 0.2 parts by mass or more, the photocurability of the photosensitive resin composition is improved. Moreover, by setting the blending amount to 60 parts by mass or less, the hardness of the cured coating film can be improved.

The photopolymerization initiator contained in the photosensitive resin composition is for causing the above-described alkali-soluble resin and photopolymerizable monomer to react upon exposure to light. As the photopolymerization initiator, any known ones can be used. The photopolymerization initiators may be used alone or in combination of two or more.

Specific examples of the photopolymerization initiator include bis-(2,6-dichlorobenzoyl)phenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-2,5-dimethylphenylphosphine oxide, and bis-(2,6-dichlorobenzoyl)-2,5-dimethylphenylphosphine oxide. -(2,6-dichlorobenzoyl)-4-propylphenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-1-naphthylphosphine oxide, bis-(2,6-dimethoxybenzoyl)phenylphosphine oxide , bis-(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis-(2,6-dimethoxybenzoyl)-2,5-dimethylphenylphosphine oxide, bis-(2, Bisacylphosphine oxides such as 4,6-trimethylbenzoyl)-phenylphosphine oxide; 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,4,6-trimethyl Monoacylphosphine oxides such as benzoylphenylphosphinic acid methyl ester, 2-methylbenzoyldiphenylphosphine oxide, pivaloylphenylphosphinic acid isopropyl ester, 2,4,6-trimethylbenzoyldiphenylphosphine oxide; phenyl ( Ethyl 2,4,6-trimethylbenzoyl)phosphinate, 1-hydroxy-cyclohexylphenylketone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propane-1- one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one, 2-hydroxy-2-methyl-1 -Hydroxyacetophenones such as phenylpropan-1-one; benzoins such as benzoin, benzyl, benzoin methyl ether, benzoin ethyl ether, benzoin n-propyl ether, benzoin isopropyl ether, benzoin n-butyl ether; benzoin alkyl ethers; benzophenone , p-methylbenzophenone, Michler's ketone, methylbenzophenone, 4,4'-dichlorobenzophenone, 4,4'-bisdiethylaminobenzophenone and other benzophenones; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy -2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexylphenylketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-1-propanone, 2-benzyl-2-dimethyl Amino-1-(4-morpholinophenyl)-butanone-1,2-(dimethylamino)-2-[(4-methylphenyl)methyl)-1-[4-(4-morpholinyl)phenyl]-1- Acetophenones such as butanone, N,N-dimethylaminoacetophenone; thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropyl Thioxanthone such as thioxanthone; Anthraquinone such as anthraquinone, chloroanthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, 2-aminoanthraquinone; acetophenone dimethyl ketal , ketals such as benzyl dimethyl ketal; benzoic acid esters such as ethyl-4-dimethylaminobenzoate, 2-(dimethylamino)ethylbenzoate, p-dimethylbenzoic acid ethyl ester; 1,2-octanedione, 1-[ 4-(phenylthio)phenyl]-,2-(O-benzoyloxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-( Oxime esters such as O-acetyloxime); bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, Titanocenes such as bis(cyclopentadienyl)-bis[2,6-difluoro-3-(2-(1-pyl-1-yl)ethyl)phenyl]titanium; phenyl disulfide 2-nitrofluorene, butyroin, aniso Examples include inethyl ether, azobisisobutyronitrile, and tetramethylthiuram disulfide.

Commercially available α-aminoacetophenone photopolymerization initiators include Omnirad 907, 369, 369E, and 379 manufactured by IGM Resins. Further, as a commercially available acylphosphine oxide photopolymerization initiator, Omnirad 819 manufactured by IGM Resins, etc. may be mentioned. Commercially available oxime ester photopolymerization initiators include Irgacure OXE01 and OXE02 manufactured by BASF Japan Co., Ltd., N-1919 manufactured by ADEKA Co., Ltd., NCI-831 and NCI-831E manufactured by ADEKA Co., Ltd., and Irgacure NCI-831 and NCI-831E manufactured by Changzhou Strong Electronics New Materials Co., Ltd. Examples include TR-PBG-304.

In addition, JP 2004-359639, JP 2005-097141, JP 2005-220097, JP 2006-160634, JP 2008-094770, JP 2008-509967, Examples include carbazole oxime ester compounds described in Japanese Patent Application Publication No. 2009-040762 and JP-A No. 2011-80036.

The amount of the photopolymerization initiator is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 18 parts by mass, based on 100 parts by mass of the alkali-soluble resin in terms of solid content. , more preferably 1 to 15 parts by mass. If the amount is 0.01 part by mass or more, the photocurability of the photosensitive resin composition will be good, and the film properties such as chemical resistance will also be good. Further, when the amount is 20 parts by mass or less, light absorption on the surface of the resist film (cured film) becomes good, and deep curability is less likely to deteriorate.

A photoinitiation aid or sensitizer may be used in combination with the photopolymerization initiator described above. Examples of the photoinitiation aid or sensitizer include benzoin compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, benzophenone compounds, tertiary amine compounds, and xanthone compounds. In particular, it is preferable to use thioxanthone compounds such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, and 4-isopropylthioxanthone. By including the thioxanthone compound, deep curability can be improved. Although these compounds can be used as a photopolymerization initiator in some cases, it is preferable to use them in combination with a photopolymerization initiator. Moreover, one type of photoinitiation aid or sensitizer may be used alone, or two or more types may be used in combination.

Note that these photopolymerization initiators, photoinitiation aids, and sensitizers absorb specific wavelengths, and therefore may have low sensitivity and function as ultraviolet absorbers in some cases. However, these are not used solely for the purpose of improving the sensitivity of the photosensitive resin composition. If necessary, it absorbs light of a specific wavelength to increase the photoreactivity of the surface, change the line shape and aperture of the resist pattern to vertical, tapered, or reverse tapered, and improve the accuracy of line width and aperture diameter. can be improved.

In the present invention, the photosensitive resin composition may contain a thermosetting component in addition to the above-mentioned components. By including a thermosetting component in the photosensitive resin composition, the heat resistance of the cured film can be improved. Examples of thermosetting components include amino resins such as melamine resins, benzoguanamine resins, melamine derivatives, and benzoguanamine derivatives, isocyanate compounds, blocked isocyanate compounds, cyclocarbonate compounds, epoxy compounds, oxetane compounds, episulfide resins, bismaleimides, and carbodiimide resins. Known thermosetting components such as can be used. Particularly preferred are thermosetting components having a plurality of cyclic ether groups or cyclic thioether groups (hereinafter abbreviated as cyclic (thio)ether groups) in the molecule. The thermosetting components can be used alone or in combination of two or more.

The above-mentioned thermosetting component having multiple cyclic (thio)ether groups in the molecule is a compound having multiple 3-, 4-, or 5-membered cyclic (thio)ether groups in the molecule, for example, Examples include compounds having multiple epoxy groups, ie, polyfunctional epoxy compounds, compounds having multiple oxetanyl groups in the molecule, ie, polyfunctional oxetane compounds, and compounds having multiple thioether groups in the molecule, ie, episulfide resins.

Examples of such epoxy resins include bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol A epoxy resin, brominated bisphenol A epoxy resin, bisphenol S epoxy resin, phenol novolak epoxy resin, Cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, triphenylmethane type epoxy resin and the like.

Commercially available epoxy resins include, for example, jER 828, 806, 807, YX8000, YX8034, 834 manufactured by Mitsubishi Chemical Corporation, YD-128, YDF-170, ZX-1059 manufactured by Nippon Steel Chemical & Materials Corporation, ST-3000, EPICLON 830, 835, 840, 850, N-730A, N-695 manufactured by DIC Corporation, and RE-306 manufactured by Nippon Kayaku Corporation.

Examples of polyfunctional oxetane compounds 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- In addition to polyfunctional oxetanes such as (oxetanyl) methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate, and their oligomers or copolymers, oxetane alcohol and novolac resins , poly(p-hydroxystyrene), cardo-type bisphenols, calixarenes, calixresorcinarenes, and etherification products with resins having hydroxyl groups such as silsesquioxane. Other examples include copolymers of unsaturated monomers having an oxetane ring and alkyl (meth)acrylates.

Examples of the compound having a plurality of cyclic thioether groups in the molecule include bisphenol A episulfide resin. Furthermore, an episulfide resin in which the oxygen atom of the epoxy group of a novolac type epoxy resin is replaced with a sulfur atom can also be used using a similar synthesis method.

Examples of amino resins such as melamine derivatives and benzoguanamine derivatives include methylolmelamine compounds, methylolbenzoguanamine compounds, methylolglycoluril compounds, and methylolurea compounds.

As the isocyanate compound, a polyisocyanate compound can be blended. Examples of the polyisocyanate compound include 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-xylylene diisocyanate, m-xylylene diisocyanate, and Aromatic polyisocyanates such as 2,4-tolylene dimer; aliphatic polyisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-methylene bis(cyclohexyl isocyanate) and isophorone diisocyanate; bicyclo Examples include alicyclic polyisocyanates such as heptane triisocyanate; and adducts, biurets, and isocyanurates of the above-mentioned isocyanate compounds.

As the blocked isocyanate compound, an addition reaction product of an isocyanate compound and an isocyanate blocking agent can be used. Examples of the isocyanate compound that can react with the isocyanate blocking agent include the above-mentioned polyisocyanate compounds. Isocyanate blocking agents include, for example, phenolic blocking agents; lactam blocking agents; active methylene blocking agents; alcohol blocking agents; oxime blocking agents; mercaptan blocking agents; acid amide blocking agents; imide blocking agents; Examples include amine blocking agents, imidazole blocking agents, and imine blocking agents.

The blending amount of the thermosetting component is preferably 0.5 to 2.5 mol, more preferably the number of functional groups of the thermosetting component reacting per 1 mol of carboxyl group contained in the alkali-soluble resin in terms of solid content. is 0.8 to 2.0 mol.

Moreover, in addition to the above-mentioned thermosetting components, a thermosetting catalyst can be blended into the photosensitive resin composition. Examples of the thermosetting catalyst include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- Imidazole derivatives such as (2-cyanoethyl)-2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzyl Examples include amines, amine compounds such as 4-methyl-N,N-dimethylbenzylamine, hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; and phosphorus compounds such as triphenylphosphine. In addition, commercially available products include, for example, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, and 2P4MHZ (all brand names of imidazole compounds) manufactured by Shikoku Kasei Kogyo Co., Ltd., and U-CAT manufactured by San-Apro Co., Ltd. Examples include 3513N (trade name of dimethylamine compound), DBU, DBN, U-CAT SA 102 (all bicyclic amidine compounds and salts thereof). In particular, it is not limited to these, and any catalyst that promotes the reaction of a carboxyl group with a thermosetting catalyst for an epoxy resin or an oxetane compound, or at least one of an epoxy group and an oxetanyl group may be used, either alone or in combination. You may use a mixture of more than one species.

Furthermore, guanamine, acetoguanamine, benzoguanamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S - S-triazine derivatives such as triazine/isocyanuric acid adduct and 2,4-diamino-6-methacryloyloxyethyl-S-triazine/isocyanuric acid adduct can also be used, and preferably these also function as adhesion imparting agents. The compound is used in combination with a thermosetting catalyst. One type of thermosetting catalyst may be used alone, or two or more types may be used in combination.

The thermosetting catalyst may further contain substances other than those mentioned above, such as phenol resins, polycarboxylic acids and their acid anhydrides, cyanate ester resins, active ester resins, and the like.

Phenol resins include phenol novolac resin, alkylphenol volac resin, bisphenol A novolac resin, dicyclopentadiene type phenol resin, Xylok type phenol resin, terpene-modified phenol resin, cresol/naphthol resin, polyvinylphenols, phenol/naphthol resin, Conventionally known resins such as α-naphthol skeleton-containing phenol resins and triazine-containing cresol novolac resins can be used singly or in combination of two or more.

Polycarboxylic acids and their acid anhydrides are compounds having two or more carboxyl groups in one molecule and their acid anhydrides, such as (meth)acrylic acid copolymers and maleic anhydride copolymers. , condensates of dibasic acids, and resins having carboxylic acid terminals such as carboxylic acid terminal imide resins.

Cyanate ester resin is a compound having two or more cyanate ester groups (-OCN) in one molecule. Any conventionally known cyanate ester resin can be used. Examples of the cyanate ester resin include phenol novolac type cyanate ester resin, alkylphenol novolac type cyanate ester resin, dicyclopentadiene type cyanate ester resin, bisphenol A type cyanate ester resin, bisphenol F type cyanate ester resin, and bisphenol S type cyanate ester resin. can be mentioned. Moreover, a prepolymer partially triazine-ized may also be used.

Active ester resin is a resin having two or more active ester groups in one molecule. Active ester resins can generally be obtained by a condensation reaction between a carboxylic acid compound and a hydroxy compound. Among these, active ester compounds obtained using a phenol compound or a naphthol compound as the hydroxy compound are preferred. Examples of phenolic compounds or naphthol compounds include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol , dicyclopentadienyl diphenol, phenol novolak, and the like.

Furthermore, an alicyclic olefin polymer may be used as the thermosetting catalyst. As a specific example of the method for producing an alicyclic olefin polymer, (1) an alicyclic olefin having at least one of a carboxyl group and a carboxylic acid anhydride group (hereinafter referred to as "carboxyl group, etc.") (2) Aromatic (co)polymer obtained by polymerizing an aromatic olefin having a carboxyl group, etc., with other monomers as necessary. (3) A method of copolymerizing an alicyclic olefin that does not have a carboxyl group, etc. and a monomer that has a carboxyl group, (4) Aromatic olefin that does not have a carboxyl group, etc. (5) A method of hydrogenating the aromatic ring portion of a copolymer obtained by copolymerizing a monomer having a carboxyl group, etc. with a monomer having a carboxyl group, etc.; or (6) introducing the carboxylic acid ester group of the alicyclic olefin polymer having the carboxylic acid ester group obtained as in (1) to (5) above by a modification reaction. Examples include a method of converting into a carboxyl group by hydrolysis or the like.

Among thermosetting catalysts, phenol resins, active ester resins, and cyanate ester resins are preferred.

The above thermosetting catalyst has a ratio of a functional group capable of a thermosetting reaction such as an epoxy group of the thermosetting resin to a functional group in the thermosetting catalyst that reacts with the functional group, in terms of solid content. It is preferable to blend the catalyst functional groups/functional groups capable of thermosetting reaction (equivalence ratio) in a ratio of 0.2 to 2.0. By setting the functional group of the thermosetting catalyst/functional group capable of thermosetting reaction (equivalence ratio) within the above range, roughening of the surface of the cured film in the desmear step can be prevented. More preferably, the functional group of the thermosetting catalyst/functional group capable of thermosetting reaction (equivalent ratio) is 0.3 to 1.0.

The blending amount of the thermosetting catalyst is preferably 0.1 to 25 parts by weight, more preferably 0.1 to 20 parts by weight, based on 100 parts by weight of the alkali-soluble resin, in terms of solid content. When the amount is 0.1 part by mass or more, heat resistance can be further improved. When the amount is 25 parts by mass or less, stability over time is further improved.

In the present invention, from the viewpoint of improving the physical strength of the cured resin film formed using a dry film and adjusting the matte feel of the surface, fillers may be added to the photosensitive resin composition as necessary. I can do it. As the filler, any known inorganic or organic filler can be used, and barium sulfate, spherical silica, hydrotalcite, and talc are particularly preferably used. Further, in order to obtain flame retardancy, metal oxides and metal hydroxides such as aluminum hydroxide can be used as extender pigment fillers.

The amount of the filler is not particularly limited, but from the viewpoint of viscosity, applicability, moldability, etc., it is preferably 400 parts by mass or less based on 100 parts by mass of the alkali-soluble resin in terms of solid content. More preferably 50 to 300 parts by mass.

Further, the filler described above may be surface-treated to improve dispersibility in the photosensitive resin composition. By using a filler that has been surface treated, aggregation can be suppressed. The surface treatment method is not particularly limited and any known and commonly used method may be used, but the surface of the inorganic filler may be treated with a surface treatment agent having a curable reactive group, such as a coupling agent having a curable reactive group as an organic group. Preferably.

As the coupling agent, silane-based, titanate-based, aluminate-based, and zircoaluminate-based coupling agents can be used. Among these, silane coupling agents are preferred. Examples of such silane coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, N-(2-aminomethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-amino Propyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-anilinopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxy Examples include cyclohexyl)ethyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane, and these can be used alone or in combination. These silane coupling agents are preferably immobilized on the surface of the filler in advance by adsorption or reaction. Here, the amount of the coupling agent to be treated with respect to 100 parts by mass of spherical silica is preferably 0.5 to 10 parts by mass.

The photosensitive resin composition may contain a colorant as necessary. As the coloring agent, known coloring agents such as red, blue, green, and yellow can be used.Pigments, dyes, and dyes may be used, but from the viewpoint of reducing environmental burden and having less impact on the human body, halogens are preferred. It is preferable that the colorant does not contain.

Red coloring agents include monoazo, disazo, azo lake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridone.Specifically, the following colors are used. - Index (C.I.; published by The Society of Dyers and Colorists) numbered.

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

Blue colorants include phthalocyanine and anthraquinone, and pigments include compounds classified as pigments, such as 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, etc. can be used. In addition to the above, metal-substituted or unsubstituted phthalocyanine compounds can also be used.

Examples of yellow colorants include monoazo, disazo, condensed azo, benzimidazolone, isoindolinone, and anthraquinone. For example, anthraquinone yellow colorants include Solvent Yellow 163, Pigment Yellow 24, 108, 193, 147, 199, 202 and the like. Examples of the isoindolinone yellow colorant include Pigment Yellow 110, 109, 139, 179, 185, and the like. As the condensed azo yellow colorant, Pigment Yellow
93, 94, 95, 128, 155, 166, 180 and the like. Examples of the benzimidazolone yellow colorant include Pigment Yellow 120, 151, 154, 156, 175, 181, and the like. In addition, as the 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. In addition, examples of the disazo yellow colorant include Pigment Yellow 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152, 170, 172, 174, 176, 188, 198, etc. can be mentioned.

In addition, coloring agents 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. Pigment Orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63, 64, 71, 73, Pigment Brown 23, 25, carbon black, Examples include titanium oxide.

Although the amount of the colorant in the photosensitive resin composition is not particularly limited, it is preferably 0.1 to 5% by mass based on the entire photosensitive resin composition in terms of solid content.

An organic solvent may be added to the photosensitive resin composition from the viewpoint of ease of preparation and coatability when forming a photosensitive resin layer. Examples of organic solvents include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, and propylene glycol monomethyl ether. Glycol ethers such as , dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, diethylene glycol monomethyl ether acetate, tripropylene glycol monomethyl ether; ethyl acetate, butyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbyl Esters such as tall acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, and propylene carbonate; aliphatic hydrocarbons such as octane and decane; petroleum solvents such as petroleum ether, petroleum naphtha, and solvent naphtha; Conventional organic solvents can be used. These organic solvents can be used alone or in combination of two or more.

The photosensitive resin composition further contains an elastomer, a mercapto compound, a urethanization catalyst, a thixoating agent, an adhesion promoter, a block copolymer, a chain transfer agent, a polymerization inhibitor, a copper inhibitor, and an antioxidant, as necessary. antifoaming agents, rust inhibitors, thickeners such as organic bentonite and montmorillonite, at least one of silicone-based, fluorine-based, polymer-based antifoaming agents and leveling agents, phosphinates, phosphate ester derivatives, phosphazene compounds Components such as flame retardants such as phosphorus compounds such as As these materials, those known in the field of electronic materials can be used.

The photosensitive resin composition preferably has a surface tension of 20 to 50 mN/m, more preferably 30 to 40 mN/m. By applying a photosensitive resin composition having a surface tension within the above range to the first main surface of the first film that has been neutralized so that the amount of static electricity is 0.7 kV or less, the leveling property is further improved. . Note that the surface tension can be measured using a dynometer in accordance with JIS K6768. The surface tension of the photosensitive resin composition can be adjusted by the above-mentioned components, their blending ratios, and the addition of leveling agents.

The photosensitive resin layer is prepared by diluting the above-mentioned photosensitive resin composition with an organic solvent to adjust the viscosity to an appropriate level, and coating the surface of the first film with a comma coater, a blade coater, a lip coater, a rod coater, a squeeze coater, or the like. A film can be obtained by applying it to a uniform thickness on the first film using a reverse coater, transfer roll coater, gravure coater, spray coater, etc., and drying it for 1 to 30 minutes, usually at a temperature of 50 to 130°C. . There are no particular restrictions on the coating film thickness, but it is generally selected as appropriate within the range of 1 to 250 μm, preferably 3 to 200 μm after drying. If the coating amount of the photosensitive resin composition is too small, leveling properties may deteriorate.

In addition, the photosensitive resin composition to be applied preferably has a viscosity of 50 to 10,000 mPa·s at 25°C, and the photosensitive resin composition to be applied may be adjusted depending on the thickness of the photosensitive resin layer to be formed. You can also adjust the viscosity of the product. For example, when the thickness of the photosensitive resin layer is small (about 5 μm), the viscosity of the photosensitive resin composition at 25°C is preferably in the range of 30 to 400 mPa·s, more preferably It is 50 to 300 mPa·s. Furthermore, when the thickness of the photosensitive resin layer is large (approximately 200 μm), the viscosity of the photosensitive resin composition at 25°C is preferably 1000 to 10000 mPa·s, more preferably 4000 to 10000 mPa·s. It is 8000mPa・s.

When the photosensitive resin composition contains an organic solvent, it is preferable to perform evaporation drying after applying the photosensitive resin composition to the first main surface of the first film. Volatilization drying is carried out using a hot air circulation drying oven, IR oven, hot plate, convection oven, etc. (equipped with an air heating heat source using steam) and a method in which the hot air in the dryer is brought into countercurrent contact, and the first method is to use a nozzle. This can be done using a spraying method on a film).

The drying time is not particularly limited, and is preferably carried out until the residual amount of the solvent in the resin layer is 5% or less, and the drying time is preferably carried out until the residual amount of the solvent in the resin layer is 5% or less. It can be adjusted as appropriate by considering the drying temperature and the like. Considering productivity etc., the time is approximately 10 seconds to 20 minutes, preferably about 10 seconds to 2 minutes.

<Second film lamination process>
As mentioned above, in order to prevent dust etc. from adhering to the surface of the photosensitive resin layer, and in consideration of the handling of the dry film, the surface of the photosensitive resin layer opposite to the surface in contact with the first film is A second film may also be provided on the side. Note that the second film in this specification refers to a film that is peeled off from the resin layer before lamination when a dry film is laminated to an adherend such as a circuit substrate and integrally molded.

As the second film, for example, polyester film, polyethylene film, polytetrafluoroethylene film, polypropylene film, surface-treated paper, etc. can be used, but the adhesive strength between the second film and the photosensitive resin layer It is preferable to select a material whose adhesive force is smaller than that between the first film and the photosensitive resin layer. Moreover, in order to make it easier to peel off the second film when using the dry film, the surface of the second film that comes into contact with the photosensitive resin layer may be subjected to a release treatment as described above.

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

[Uses of dry film]
An insulating film for electronic components can be formed using the above dry film. A method for forming an insulating film for electronic components and a method for manufacturing an electronic component including the cured product (insulating film for electronic components) on a substrate on which a circuit pattern is formed will be described. As an example of use when the dry film is photosensitive, a method of manufacturing an electronic member using a dry film provided with a second film will be described.

i) First, peel off the second film from the dry film described above to expose the photosensitive resin layer,
ii) Next, laminating the photosensitive resin layer of the dry film on the electronic member on which the circuit pattern is formed,
iii) performing exposure from above the first film of the dry film,
iv) forming a patterned photosensitive resin layer on the substrate by peeling off the first film from the dry film and performing development;
v) curing the patterned photosensitive resin layer with light irradiation or heat to form an insulating film;
By this, an electronic component including an insulating film can be manufactured. It goes without saying that when a dry film without a second film is used, the step of peeling off the second film (step i) is not necessary. Each step will be explained below.

First, the second film is peeled off from the dry film to expose the photosensitive resin layer, and the photosensitive resin layer of the dry film is bonded to the electronic component. Examples of the electronic member include a substrate on which a circuit pattern is formed. Substrates with circuit patterns include printed wiring boards and flexible printed wiring boards on which circuits have been formed in advance, as well as paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth/nonwoven epoxy, and glass cloth/paper. Copper clad of all grades (FR-4 etc.) using materials such as copper clad laminates for high frequency circuits using epoxy, synthetic fiber epoxy, fluororesin, polyethylene, polyphenylene ether, polyphenylene oxide, cyanate ester, etc. Examples include laminate plates, polyimide films, PET films, glass substrates, ceramic substrates, wafer plates, and the like.

In order to bond the photosensitive resin layer of the dry film onto the electronic component, it is preferable to bond under pressure and heat using a vacuum laminator or the like. By using such a vacuum laminator, the photosensitive resin layer is brought into close contact with the electronic component, so that no air bubbles are mixed in, and the ability to fill holes on the surface of the electronic component 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 above the first film of the dry film. Through 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 to active energy rays through a photomask on which a desired pattern is formed using a contact method (or a non-contact method); A desired pattern may be exposed to active energy rays.

The exposure machine used for active energy ray irradiation may be any device that is equipped with a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, an LED, etc., and irradiates ultraviolet rays in the range of 350 to 450 nm. A device (eg, a laser direct imaging device that draws an image directly with a laser using CAD data from a computer) can also be used. The laser light source for the direct drawing machine may be either a gas laser or a solid laser, as long as it uses laser light with a maximum wavelength in the range of 350 to 410 nm. The exposure amount for image formation varies depending on the film thickness, etc., but can generally be in the range of 20 to 800 mJ/cm ² , preferably 20 to 600 mJ/cm ² . Further, the exposure may be performed using scattered light or parallel light.

After exposure, the first film is peeled off from the photosensitive resin layer and developed, thereby forming a patterned photosensitive resin layer on the electronic member. In the non-patterned portions of the photosensitive resin layer, the surface of the photosensitive resin layer is formed into an uneven shape by exposure through the first film. Note that, as long as the characteristics are not impaired, exposure may be performed after the first film is peeled from the photosensitive resin layer after bonding onto the electronic member.

Note that a photomask, which will be explained later in the method for forming an insulating film using a photosensitive resin composition, may be used. In such a case, it is preferable to use a first film that does not have the above-mentioned pattern, and the first film may be peeled off from the dry film before exposure to the extent that the characteristics are not impaired. Exposure and development may also be performed.

The developing process is not particularly limited, and a dipping method, a shower method, a spray method, a brush method, etc. can be used. Further, as the developer, an alkaline aqueous solution of potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines, tetramethylammonium hydroxide, etc. can be used.

Next, the patterned photosensitive resin layer can be cured by irradiation with active energy rays (light) or heat to form an insulating film for electronic components. This process is called main curing or additional curing, and it promotes the polymerization of unreacted monomers in the exposed photosensitive resin layer, and further heat-cures the carboxyl group-containing photosensitive resin and the epoxy resin. , the amount of remaining carboxyl groups can be reduced. Active energy ray irradiation can be performed in the same manner as the above-described exposure, but it is preferably performed under conditions stronger than the irradiation energy during exposure. For example, it can be 500 to 3000 mJ/cm ² . Further, thermal curing can be performed under heating conditions of 100 to 200° C. for about 20 to 90 minutes. In addition, in the main curing, it is preferable to carry out thermal curing after photocuring. By performing photocuring first, the flow of the resin is suppressed even during heat curing, and the shaped surface may be maintained.

The method for manufacturing an insulating film for electronic components described above uses a dry film formed from a photocurable and thermosetting resin composition as a photosensitive resin composition. A method for manufacturing an insulating film for electronic components using each dry film formed from a photocurable resin composition or a thermosetting resin composition will also be described below.

When forming an insulating film only by photocuring, for example, after laminating the photosensitive resin layer of the dry film on the electronic component, the photosensitive resin layer is irradiated with active energy rays (for example, 1,000 to 2,000 mJ). /cm ² ) to form an insulating film for electronic components.
In addition, when forming an insulating film only by thermosetting, for example, after laminating the photosensitive resin layer of the dry film on the electronic component, the photosensitive resin layer is heated (for example, at a temperature of 100 to 220°C for 30 to An insulating film for electronic components may be formed by curing the insulating film for 90 minutes).

The first film is peeled off either before or after curing, but it is preferably peeled off after the photosensitive resin composition is cured. In addition to the methods described above, it is also possible to form a specific shape on the surface of a dried coating film of a photosensitive resin composition using a transfer roller or the like so that it has a predetermined surface morphology, or to This can be done by applying a photosensitive resin composition to a first film that has been previously processed into a specific shape and using a dry film, but the method is not limited thereto.

[Electronic components]
Examples of electronic components to be provided with the insulating film according to the present invention include printed wiring boards and flexible printed wiring boards on which circuits are previously formed using copper, etc., as well as paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth/nonwoven epoxy. All grades (FR-4 etc.), as well as wafer substrates, metal substrates, polyimide films, polyethylene terephthalate films, polyethylene naphthalate (PEN) films, glass substrates, ceramic substrates, wafer plates, and the like. Among these, copper-clad laminates are particularly preferred.

The insulating film for electronic components according to the present invention is useful as a permanent coating for printed wiring boards such as solder resists, coverlays, and interlayer insulation layers, and is particularly useful as a cured coating for solder resists. In particular, it can be suitably used in applications requiring a matte-like insulating film. Moreover, it can be used not only for applications that require a patterned insulating film, but also for applications that do not require patterning, such as mold applications (sealing applications). It can also be suitably used to form a solder resist layer for IC packages.

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

<Preparation of first films 1 to 4>
[First film 1]
iso-butylated melamine resin (Amidia L-125-60, solid content 60%, manufactured by DIC Corporation) and acrylic resin for melamine baking (Acridic A-405, solid content 50%, manufactured by DIC Corporation), They were blended so that the blending ratio was 25:75 (in terms of solid content) on a mass basis, and pre-stirred with a stirrer to obtain an acrylic melamine resin.
Next, the obtained acrylic melamine resin was diluted with methyl ethyl ketone to prepare a resin solution having a solid content concentration of 35% by mass. After adding methyl ethyl ketone to this resin solution to obtain an appropriate solid content concentration depending on the thickness of the coating film, a silicone resin (Cymac US-270, manufactured by Toagosei Co., Ltd.) with a maximum particle size of 2 μm was added. The blending ratio of acrylic melamine resin, silicone resin, and filler was 59.7:0.3:108 on a mass basis. (in terms of solid content) and stirred sufficiently at room temperature to obtain a uniform coating solution.
The obtained coating liquid was applied to a 38 μm thick polyethylene terephthalate film (Lumirror T60, manufactured by Toray Industries, Inc.) and dried at 130° C. for 20 seconds to produce the first film 1 including an intermediate layer. . The total thickness of the first film 1 was 40 μm. In addition, the arithmetic surface roughness Ra of the side provided with the intermediate layer was specifically measured in shape measurement mode using a laser microscope (VX-100, manufactured by Keyence Corporation) in accordance with JIS B 0601:2001. In the shape measurement mode of the laser microscope, start the observation application (VK-H1XV), place the sample to be measured on the XY stage, and use the 50x objective lens to autofocus in the shape measurement mode. I focused. The Z-axis was controlled as necessary to adjust the focus to the optimal position. Observation images were captured in automatic measurement mode or manual measurement mode. Next, the analysis application (VK-H1XA) was launched and measurement of Ra was started. As a result of the measurement, the arithmetic surface roughness Ra of the surface of the first film 1 on which the intermediate layer was provided (ie, the first principal surface) was 0.180 μm.

[First film 2]
The filler was changed to spherical silica (SO-C2, manufactured by Admatex Co., Ltd.), and the blending ratio of acrylic melamine resin, silicone resin, and filler was 59.7:0.3:12.0 (solid A first film 2 including an intermediate layer was produced in the same manner as the first film 1 except that the film was changed to (in terms of minutes). The total thickness of the first film 2 was 43 μm. Further, the arithmetic surface roughness Ra of the surface on the side where the intermediate layer was provided (ie, the first principal surface) was 0.196 μm.

[First film 3]
An intermediate film was prepared in the same manner as the first film 2, except that the blending ratio of acrylic melamine resin, silicone resin, and filler was changed to 59.7:0.3:21.0 (in terms of solid content) on a mass basis. A first film 3 containing layers was produced. The total thickness of the first film 3 was 43 μm. Further, the arithmetic surface roughness Ra of the surface on which the intermediate layer was provided (ie, the first principal surface) was 0.248 μm.

[First film 4]
The blending ratio of acrylic melamine resin, silicone resin, and filler was 59.7:0. A first film 4 including an intermediate layer was produced in the same manner as the first film 2 except that the ratio was changed to 3:48.0. The total thickness of the first film 4 was 43 μm. Further, the arithmetic surface roughness Ra of the surface on which the intermediate layer was provided (ie, the first principal surface) was 0.412 μm.

[Preparation of photosensitive resin composition]
220 g of a cresol novolac type epoxy resin (manufactured by DIC Corporation, EPICLON N-695, epoxy equivalent: 220) was placed in a four-necked flask equipped with a stirrer and a reflux condenser, and 214 g of carbitol acetate was added and dissolved by heating. Next, 0.1 g of hydroquinone as a polymerization inhibitor and 2.0 g of dimethylbenzylamine as a reaction catalyst were added. This mixture was heated to 95 to 105°C, 72 g of acrylic acid was gradually added dropwise, and the mixture was reacted for 16 hours. This reaction product was cooled to 80 to 90°C, 106 g of tetrahydrophthalic anhydride was added thereto, and the reaction product was allowed to react for 8 hours. After cooling, it was taken out. The alkali-soluble resin resin varnish thus obtained had a solid content of 65%, an acid value of solid content of 100 mgKOH/g, and a weight average molecular weight Mw of about 3,500.

100 parts by mass (solid content equivalent) of the alkali-soluble resin varnish obtained as above, 30 parts by mass of dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., DPHA) as a photopolymerizable monomer, and photopolymerization was started. As an agent, 10 parts by mass of 2-[4-(methylthio)benzoyl]-2-(4-morpholinyl)propane (manufactured by IGM Resins Co., Ltd., Omnirad 907), ethanone, 1-[9-ethyl-6-(2-methyl) 0.5 parts by mass of benzoyl)-9H-carbazol-3-yl]-,1-(0-acetyloxime) (manufactured by BASF Japan Ltd., Irgacure OXE02), and 2,4-diethylthioxanthone (Japan) as a sensitizer. 0.5 parts by mass of KAYACURE DETX-S (manufactured by Kayaku Co., Ltd.), 20 parts by mass of bisphenol A type epoxy resin (manufactured by DIC Corporation, EPICLON 840-S) as a thermosetting component, 1,3,5- 10 mass of tris(2,3-epoxypropyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (high melting point type, manufactured by Nissan Chemical Co., Ltd., TEPIC-HP) 90 parts by mass of barium sulfate (manufactured by Sakai Chemical Industry Co., Ltd., B-30) as a filler, and 0.8 parts by mass of a blue colorant (CI.Pigment Blue 15:3) as a colorant, yellow coloring. After blending 0.3 parts by mass of a pigment (C.I. Pigment Yellow 147) and 1.2 parts by mass of a red coloring agent (Paliogen Red K3580, manufactured by BASF Japan Co., Ltd.) and premixing with a stirrer, A photosensitive resin composition was prepared by kneading in a three-roll mill.

The photosensitive resin composition obtained as described above was diluted by adding 300 g of methyl ethyl ketone, and stirred for 15 minutes with a stirrer to obtain coating liquid 1. The viscosity of this coating liquid at 25° C. (5 rpm) was measured using a cone plate viscometer (manufactured by Toki Sangyo Co., Ltd., TVH-33) and found to be 250 mPa·s. Further, the surface tension of the coating liquid 1 was measured using a dynometer (manufactured by BYK-GARDNER) in accordance with JIS K6768, and was found to be 32 mN/m.
Further, 200 g of methyl ethyl ketone was added to the photosensitive resin composition obtained as described above to dilute it, and the mixture was stirred for 15 minutes with a stirrer to obtain a coating liquid 2. The viscosity of this coating liquid at 25° C. (5 rpm) was measured using a cone plate viscometer (manufactured by Toki Sangyo Co., Ltd., TVH-33) and found to be 6000 mPa·s. Further, the surface tension of the coating liquid 2 was measured using a dynometer (manufactured by BYK-GARDNER) in accordance with JIS K6768, and was found to be 34 mN/m.

<Formation of photosensitive resin layer>
Before applying the coating liquid to the surface on which the intermediate layer is provided (first principal surface) of each first film obtained as described above, the film is transported on a transport roller at a transport speed of 5 m/min. While running the first film, a static eliminating bar (Blue Bar R50, manufactured by Simco Japan Co., Ltd.) was installed in a direction perpendicular to the running direction to eliminate static electricity. In addition, in the running direction, the amount of static electricity on the first main surface side of the first film before and after the position where the static elimination bar was provided was measured using a static electricity meter (static meter FMX-003, manufactured by Simco Japan Co., Ltd.). . Note that the amount of static electricity was measured five times at arbitrary locations, and the average value was taken as the average value. The amount of static electricity before and after static electricity removal was as shown in Table 1 below.

After removing static electricity as described above, coating liquid 1 is applied to the first main surface of each first film and dried at a temperature of 90°C for 15 minutes to form a photosensitive resin layer with a thickness of 25 μm after drying. did. Regarding the first film 2, three types of photosensitive resin layers having different thicknesses after drying of 25 μm, 5 μm, and 3 μm were formed by changing the coating amount. Furthermore, for the first film 2, a photosensitive resin layer having a thickness of 200 μm after drying was formed using coating liquid 2 instead of coating liquid 1.

After forming the photosensitive resin layer as described above, a polypropylene film (manufactured by Futamura Co., Ltd., OPP-FOA) with a thickness of 18 μm is laminated as a second film on the photosensitive resin layer, and each dry film is Created.

<Evaluation of leveling properties of photosensitive resin layer>
An arbitrary area of 100 mm x 100 mm on the surface of the photosensitive resin layer of each dry film was visually observed to check for uneven coating, streaks, missing spots, and adhesion of foreign matter. The evaluation criteria for leveling properties were as follows.
○: 0 coating unevenness, streaks, missing spots, and foreign matter adhesion △: 1 to 5 coating unevenness, streaks, missing spots, and foreign matter adhesion ×: Coating unevenness, streaks, missing spots, and foreign matter adhesion 6 or more The evaluation results are as shown in Table 1.

<Surface condition of cured product obtained using dry film>
The surface of a copper-clad laminate board (95 mm x 150 mm x 1.6 mm) was chemically polished, the second film was peeled off from the dry film obtained as described above to expose the photosensitive resin layer, and the surface of the board was polished. A photosensitive resin layer of dry film was attached to the polished side, and then a vacuum laminator (MVLP-500, Japan Steel Works, Ltd.) was used to apply pressure: 0.8 Mpa, 70°C, 1 minute. The substrate and the photosensitive resin layer were brought into close contact with each other by heating and laminating at a vacuum degree of 133.3 Pa. Subsequently, the photosensitive resin layer was completely cured by heating at 150° C. for 60 minutes to form an insulating film (cured product).
The insulating film obtained as described above was illuminated with a fluorescent lamp, and the state of the fluorescent lamp reflected on the surface of the insulating film was visually observed, and the matt feel of the insulating layer was evaluated based on the following evaluation criteria.
○: The image of the fluorescent lamp is blurred. ×: The image of the fluorescent lamp is clearly visible. The evaluation results are as shown in Table 1.

As is clear from the evaluation results in Table 1, the dry films (Examples 1 to 7) in which static electricity was removed from the first principal surface (coated surface) of the first film before applying the photosensitive resin composition were It can be seen that the leveling property of the formed photosensitive resin layer is better than that of the dry film (Comparative Example 1) in which the photosensitive resin layer was applied without static elimination.

Claims (7)

A method for producing a dry film comprising a first film and a photosensitive resin layer provided on one surface of the first film, the method comprising:
a step of preparing a first film having a first principal surface and a second principal surface, the first surface having an arithmetic mean roughness Ra of 0.1 to 1 μm; and a first principal surface of the first film. a step of applying a photosensitive resin composition to the surface of the photosensitive resin layer to form a photosensitive resin layer;
including;
Before applying the photosensitive resin composition, the method further includes the step of removing static electricity so that the amount of static electricity on the first main surface of the first film is 0.7 kV or less.
Method of manufacturing dry film. The method according to claim 1, wherein the amount of static electricity on the first main surface of the first film before static electricity removal is 4 kV or more. The method according to claim 1, wherein the photosensitive resin composition is applied so that the film thickness after drying is 1 μm or more. The method according to claim 1, wherein the photosensitive resin composition has a surface tension of 20 to 50 mN/m. The method according to claim 1, wherein the first film has a thickness of 10 to 150 μm. 2. The method of claim 1, wherein the first film comprises a polyester film. The method according to claim 1, wherein the dry film is used to form an insulating film for electronic components.