TW201921105A - Photosensitive film laminate and cured product of same - Google Patents

Abstract

The present invention provides a photosensitive film laminate which doesn't degenerate a working environment in spite of including carbon black among a photosensitive resin composition forming a photosensitive film. In the photosensitive film laminate formed by laminating a support film and a photosensitive film made of the photosensitive resin composition, the photosensitive resin composition includes at least carbon black and a filler having a charge opposite to that of the carbon black.

Description

Photosensitive film laminate and its cured product

The present invention relates to a photosensitive film laminate and a cured product thereof.

Generally, in a printed wiring board used in an electronic device or the like, a solder resist layer is formed in an area excluding continuous holes on a substrate forming a circuit pattern in order to prevent solder from adhering to unnecessary portions when mounting electronic parts on the printed wiring board.

In recent years, electronic equipment has been accompanied by high precision and high density of printed wiring boards due to its thinness and shortness. At present, the solder resist layer is formed by coating a photosensitive resin composition on a substrate, and drying, exposing, and developing. Then, the so-called formed by a photoresist, which is hardened formally by heating or irradiating the pattern-forming resin, is the mainstream.

In addition, it is also proposed to form a solder resist layer using a so-called photosensitive film laminate including a photosensitive film instead of the liquid photosensitive resin composition as described above. These photosensitive film laminates are generally those in which a photosensitive film formed of a photosensitive resin composition is bonded to a support film, and a protective film is also bonded to the surface of the photosensitive film as needed. When these photosensitive film laminates are used, the protective film is peeled and laminated on the wiring substrate by heating and pressing. Before exposure or after exposure from the supporting film side, the supporting film is peeled for development, thereby forming a warp film. A patterned solder resist layer is formed. By using a photosensitive film laminate, in addition to the case of wet coating, in addition to the drying step after coating, the surface smoothness or surface hardness of the obtained solder resist layer is also excellent.

In addition, in recent years, from the viewpoint of workability, there has been a tendency to reduce the thickness of photosensitive films. Along with this, the concealment of the solder resist layer is reduced, and the discoloration of the lower layer, that is, the circuit is seen through the solder resist layer, causing problems related to the appearance defect. Therefore, in order to improve the concealment of the solder resist layer, it is required to be a black photosensitive film. From the viewpoint of design, a black photosensitive film is also required. The black photosensitive film as described above has conventionally used carbon black as a colorant (for example, Japanese Patent Application Laid-Open No. 2008-257045).

However, in a photosensitive film laminate using carbon black, when the support film is peeled off, a slight amount of carbon black may remain in the support film. In addition, although a protective film is also provided on the surface of the photosensitive film, when the photosensitive film is peeled off when the protective film is used, there is also a case where a slight amount of carbon black remains in the protective film. The trace amount of carbon black remaining in the supporting film or the protective film may be scattered or attached to the surroundings, which may deteriorate the working environment.

Therefore, an object of the present invention is to provide a photosensitive film laminate which does not deteriorate the working environment even if carbon black is contained in the photosensitive resin composition forming the photosensitive film. Still another object of the present invention is to provide a cured product formed using the photosensitive thin film laminate.

The present inventors have obtained the insight that when a photosensitive film containing carbon black has a positive or negative charge of the used carbon black, by using a filler having a negative or positive charge in combination with the carbon black, that is, having a The carbon black is used as a filler with an opposite charge and is used in a photosensitive film. The carbon black can effectively reside in the photosensitive film. As a result, the carbon black does not remain on the peeling support film or the protective film. The present invention has been completed based on this knowledge.

That is, the photosensitive film laminate system of the present invention is obtained by laminating a support film and a photosensitive film composed of a photosensitive resin composition, and is characterized in that in the photosensitive film laminate, the photosensitive resin The composition system includes at least carbon black and a filler, and the filler has a charge opposite to that of the carbon black.

In the aspect of the present invention, the amount of the carbon black blended in the photosensitive resin composition is preferably 0.3 to 5% by mass in terms of solid content.

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

In one aspect of the present invention, the support film is preferably a thermoplastic resin film.

In the aspect of the present invention, it is preferred that the thermoplastic resin film is selected from the group consisting of a polyester film, a polyimide film, a polyimide film, a polypropylene film, and a polystyrene film. At least one.

In an aspect of the present invention, the arithmetic mean surface roughness Ra of the support film is preferably 1000 nm or less.

In an aspect of the present invention, it is preferable to further include a protective film, and the protective film is laminated on a surface of the photosensitive film on a side opposite to the support film.

The hardened | cured material of another aspect of this invention is formed using the photosensitive thin film laminated body mentioned above.

According to the present invention, even if carbon black is contained in the photosensitive resin composition forming the photosensitive film, a photosensitive film laminate which does not deteriorate the working environment can be realized. According to another aspect of the present invention, a cured product formed by using the photosensitive thin film laminate can be realized.

The photosensitive film laminated body of this invention is demonstrated. The photosensitive film laminated system of the present invention is sequentially provided with a photosensitive film laminated body supporting a film and a photosensitive film. The photosensitive film laminate of the present invention may further include a protective film on the surface of the photosensitive film opposite to the support film. In addition, in this specification, a "photosensitive film" means the thing which made the photosensitive resin composition into the shape of a film, and did not laminate | stack other layers of a support film or a protective film. Hereinafter, each component which comprises the photosensitive film laminated body of this invention is demonstrated.

[Support film] The support film constituting the photosensitive film laminate of the present invention supports a photosensitive film described later (that is, a layer made of a photosensitive resin composition, hereinafter sometimes referred to simply as a "photosensitive resin layer") By.

The support film can be used without particular limitation as long as it is known, and for example, a film made of a thermoplastic resin can be preferably used. As the thermoplastic resin film, polyester films such as polyethylene terephthalate or polyethylene naphthalate, polyimide films, polyimide films, and polypropylene films can be preferably used. Film made of thermoplastic resin such as polystyrene film. In addition, when the thermoplastic resin film is used, a filler may be added to the resin when the film is formed (kneading treatment), a matte coating (coating treatment), or a spray treatment such as a sandblasting treatment may be performed on the surface of the film. , Or those who perform hairline processing or chemical etching. Among these, polyester films can be preferably used from the viewpoints of heat resistance, mechanical strength, handling properties, and the like.

The thermoplastic resin film as described above is preferably used for a film extending in a uniaxial direction or a biaxial direction for the purpose of improving strength.

Moreover, you may perform the mold release process on the surface of a support film. For example, a coating solution prepared by dissolving or dispersing a release agent such as a wax, a silicone wax, an alkyd resin, a urethane resin, a melamine resin, or a polysiloxane resin in an appropriate solvent. The coating film is coated on a supporting film and dried by a conventional coating method such as a roll coating method, a spray coating method, a gravure printing method, a screen printing method, or the like, and a mold release treatment is performed.

From the viewpoint of handleability, the thickness of the supporting film is preferably in the range of 10 to 150 μm, more preferably in the range of 10 to 100 μm, and even more preferably in the range of 10 to 50 μm. When the range is 10 to 150 μm, the resolution is further improved.

The arithmetic mean surface roughness Ra of the supporting film is preferably 1,000 nm or less, more preferably 750 nm or less, and even more preferably 500 nm or less. When the arithmetic mean surface roughness Ra of the supporting film is 1000 nm or less, the resolution is further improved. In addition, since the surface area is not too large, the risk of carbon black detachment can be reduced. Based on the above-mentioned effects, the arithmetic mean surface roughness Ra of the surface where the support film and the photosensitive film contact in the photosensitive film laminate is preferably 1000 nm or less. Furthermore, in the photosensitive film laminate of the present invention, when a protective film described later is laminated, even on the side of the support film that is opposite to the surface in contact with the photosensitive film, it is in contact with the photosensitive film when the laminate is wound. In this case, the arithmetic average surface roughness Ra on the side of the surface opposite to the surface in contact with the photosensitive film is preferably 1,000 nm or less. The arithmetic mean surface roughness Ra means a value measured by a measuring device in accordance with JIS B0601-1994.

In the present invention, since carbon black does not remain in the peeled support film or protective film, a small amount of carbon black can be prevented from scattering. In particular, the supporting film is formed by exposing the photosensitive film to a cured film, and then peeling the cured film from the cured film. It is not a normal manufacturing process to peel the supporting film before the photosensitive film is cured. It is considered that there is more residue before curing than after curing. Therefore, when the support film is peeled from the photosensitive film, if carbon black does not remain in the support film, it is considered that in the actual manufacturing step, even if the support film is peeled after the photosensitive film is cured to form a hardened film, the support film will not be removed. Residual carbon black.

[Photosensitive film] (1) The photosensitive film constituting the photosensitive film laminated body of the present invention refers to a film formed by using a photosensitive resin composition, and refers to a non-laminated support film or other layer of a protective film. The photosensitive film can be patterned by exposure and development to become a hardened film provided on a circuit board. The hardened film is preferably a solder resist layer. These photosensitive films are formed by using a photosensitive resin composition. The photosensitive resin composition may be conventionally used with conventionally known resist inks, but the following description can be suitably used for the photosensitive film of the present invention. An example of a photosensitive resin composition.

The photosensitive resin composition constituting the photosensitive film of the present invention contains at least fillers other than carbon black and carbon black. When carbon black has a positive or negative charge, the filler is one having a negative or positive charge. That is, in the present invention, a filler having a charge opposite to that of carbon black is used in combination with carbon black for a photosensitive resin composition. As a result of active research by the present inventors, it is found that since the photosensitive film contains carbon black, and further contains carbon black and a filler having a charge opposite to that of the carbon black, the carbon black does not remain in the peeled support film . The reason for this is not clear, but it is believed to be as follows. When the photosensitive film contains carbon black, the carbon black has a positive or negative charge potential. Therefore, when the support film or the protective film is peeled off, the support film or the protective film is believed to adhere to the carbon black due to electrostatic force. In the present invention, since the photosensitive film contains a filler having a charge opposite to that of carbon black, it is considered that the electrostatic force of the filler and the carbon black can suppress the release of the carbon black from the photosensitive film. As a result, it is estimated that carbon black will not cause migration to a support film or a protective film, but it is an estimated range after all, and it is not necessarily a limiter.

[Carbon Black] 若 If the carbon black used in the present invention is a carbon-based fine particle produced industrially by quality control, a conventional user can be used. The carbon black includes, for example, furnace black, thermal cracked carbon black, channel carbon black, acetylene black, and the like. Carbon black can also be surface-treated by a conventional method. In addition, carbon black may have either a positive charge or a negative charge. And the carbon black particle diameter is preferably 3 to 500 nm in diameter.

Carbon black has one of positive and negative charges that can be determined by determining the charge. The charge can be measured using a non-contact electrostatic detector. For example, SK-H050 manufactured by KYENCE Corporation can be used. Specifically, it can be measured in a charged potential measurement mode using an electrostatic measuring device. At this time, it is desirable that the electrostatic analyzer is grounded. Any mode can be selected for the measurement distance, measurement range, and measurement accuracy, but it is better to select the high-precision mode. It is preferable to make the electrostatic measuring device zero-adjusted to a grounded object. The zero point adjustment is preferably performed each time a sample is measured. Put the charged samples into the metal can. The type of metal can can be used without particular limitation as long as it can be conducted without surface treatment or the like. Metal cans are used on an insulating table. It is preferred that the metal can be placed on a stand and then removed from the battery, and no contact is made with the exception of the sample until the end of the measurement. Samples can be placed in metal cans using metal spoons. Any one of the capacity and sample volume of the metal can can be used, but it is preferably extended to the entire bottom surface of the metal can. From the viewpoint of handleability, it is preferable to use a metal can of 20 to 50 ml and measure it at a sample size of 3 to 10 g. The measurement is performed on the sample surface. The measurement is preferably performed for about 10 seconds. The measurement room at this time is preferably an environment with a temperature of 23 to 26 ° C and a humidity of 45 to 55%.

The blending amount of carbon black in the photosensitive resin composition is preferably 0.3 to 5% by mass, more preferably 0.5 to 3% by mass, and still more preferably 1 to 3% by mass in terms of solid content. When the blending amount of carbon black is 0.3% by mass or more, the concealment is improved. When the content is 5 mass% or less, the photosensitivity and resolution are better. In addition, carbon black is more likely to remain in the photosensitive film.

[Filler] In the present invention, as described above, a filler having a charge opposite to that of carbon black is included. Whether the filler is positively charged or negatively charged can be determined by measuring the charge in the same manner as described above. When carbon black has a positive charge, a filler having a negative charge is used. In contrast, when carbon black is negatively charged, a filler having a positive charge is used. In the present invention, if at least carbon black and one filler having a charge opposite to that of carbon black are included, other fillers may be further included.

As the filler, conventionally used inorganic or organic fillers can be used, and especially barium sulfate, spherical silica, titanium oxide, Neuberger silica particles, and talc are preferably used. In addition, if the filler contains at least one having a charge opposite to that of carbon black, the filler may be either positively or negatively charged. In addition, for the purpose of imparting flame resistance to a photosensitive film, aluminum hydroxide, magnesium hydroxide, boehmite, and the like can be used. Furthermore, NANOCRYL (trade name) XP 0396, XP 0596, XP manufactured by Hanse-Chemie Co., Ltd., which disperses nano-oxidizing system in the compound having one or more ethylenically unsaturated groups or the aforementioned multifunctional epoxy resin, can also be used. 0733, XP 0746, XP 0765, XP 0768, XP 0953, XP 0954, XP 1045 (all product brand names), or NANOPOX (trade name) made by Hanse-Chemie XP 0516, XP 0525, XP 0314 (all Product brand name). These can be used alone or in combination of two or more. By including a filler, the physical strength etc. of the hardened | cured material obtained can be improved.

The average particle diameter of the filler is preferably from 0.05 to 15 μm, more preferably from 0.1 to 5 μm. By falling within this range, carbon black can be more effectively and easily retained in the photosensitive film. Furthermore, the resolution and electrical characteristics are further improved.

The blending amount of the filler in the photosensitive resin composition is preferably 0.05 to 80% by mass, more preferably 0.1 to 75% by mass, and particularly preferably 1 to 70% by mass in terms of solid content. When the blending amount of the filler is 80% by mass or less, the viscosity of the photosensitive resin composition will not be too high, and the coating property when the photosensitive film is made will be good, and the cured product will not easily become brittle. When the blending amount of the filler is 0.05% by mass or more, carbon black is more likely to remain in the photosensitive film.

In the photosensitive resin composition, the blending ratio of carbon black and a filler having a charge opposite to that of carbon black is not particularly limited, but in terms of parts by mass, carbon black is preferred: a filler having a charge opposite to that of carbon black = 2: 98 ~ 98: 2 ratio. It is more preferably 3: 97 ~ 75: 25, and even more preferably 4: 96 ~ 50: 50. By blending at this ratio, carbon black is less likely to be detached.

In the present invention, the photosensitive resin composition preferably contains a crosslinking component in addition to the carbon black and the filler. Furthermore, it is more preferable to include a photopolymerization initiator. The cross-linking component is preferably a photosensitive resin or a photosensitive monomer containing a carboxyl group, and when further heated, it is preferable to include a component that is cross-linked by heat. Each component is explained below.

[Crosslinking component] (i) The crosslinkable component is not particularly limited as long as it is a component to be crosslinked, and a person skilled in the art can be used. Particularly, a carboxyl group-containing photosensitive resin or photosensitive monomer is preferred, and when further heated, a component including a crosslink by heat (hereinafter referred to as a thermal crosslink component) is improved in properties such as heat resistance and insulation reliability. And better.

A carboxyl group-containing photosensitive resin is a component that is polymerized or crosslinked and hardened by light irradiation, and alkali developability by containing a carboxyl group. From the viewpoint of photocurability and development resistance, it is preferable to have an ethylenically unsaturated bond in the molecule other than the carboxyl group. The ethylenically unsaturated double bond is preferably one derived from acrylic acid, methacrylic acid, or a derivative thereof.

As the carboxyl group-containing photosensitive resin, a carboxyl group-containing photosensitive resin obtained by synthesizing a carboxyl group-containing photosensitive resin or a resin other than an epoxy resin without using an epoxy resin as a starting material is preferably used. The carboxyl group-containing resin obtained by synthesizing a carboxyl group-containing photosensitive resin or a resin other than an epoxy resin without using an epoxy resin as a starting material has a very small halide ion content, and can suppress deterioration of insulation reliability. As a result, More excellent electrical characteristics. Specific examples of the carboxyl group-containing photosensitive resin include compounds (either oligomers or polymers) listed below.

(1) A bifunctional or more polyfunctional (solid) epoxy resin is reacted with (meth) acrylic acid, and hydroxyl groups present on the side chains are added to phthalic anhydride, tetra-light phthalic anhydride, and hexahydrogen. A carboxyl group-containing photosensitive resin obtained from a dibasic acid anhydride such as phthalic anhydride, (2) a polyfunctional epoxy resin obtained by epoxidizing the hydroxyl group of a bifunctional (solid) epoxy resin with epichlorohydrin and ( (Meth) acrylic acid reaction, the carboxyl group containing photosensitive resin obtained by adding a dibasic acid anhydride to a generated hydroxyl group, (3) For an epoxy compound having two or more epoxy groups in one molecule and at least one epoxy compound in one molecule An alcoholic hydroxyl group of a reaction product obtained by reacting an alcoholic hydroxyl group and a phenolic hydroxyl compound with an unsaturated monocarboxylic acid containing (meth) acrylic acid, etc., with maleic anhydride, tetrahydro o-benzene A carboxyl group-containing photosensitive resin obtained by reacting polycarboxylic anhydrides such as dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, and adipic acid. (4) bisphenol A, bisphenol F, bisphenol S, novolac type phenol resin , Poly-p-hydroxystyrene, naphthol and aldehyde condensation products, dihydroxynaphthalene and Condensates of aldehydes, etc. One compound having two or more phenolic hydroxyl groups in one molecule reacts with alkylene oxides such as ethylene oxide and propylene oxide to form reaction products containing (meth) acrylic acid and the like A carboxyl group-containing photosensitive resin obtained by reacting an unsaturated monocarboxylic acid with a polybasic acid anhydride. (5) A compound having two or more phenolic hydroxyl groups in one molecule and ethyl carbonate A reaction product obtained by reacting a cyclic carbonate compound such as propylene carbonate, a reaction product obtained by reacting with a monocarboxylic acid containing an unsaturated group, and a carboxyl group-containing photosensitive resin obtained by reacting with a polybasic acid anhydride, (6) Synthesis of a carboxyl group-containing urethane resin by the polyaddition reaction of a carboxyl group-containing diol compound and a diol compound, such as dimethylolpropionic acid, dimethylolbutyric acid, and the like. Add a compound with one hydroxyl group and one or more (meth) acrylfluorenyl groups in the molecule such as hydroxyalkyl (meth) acrylate, etc., and make the terminal (meth) acrylated carboxyl group-containing urethane Resin, rhenium (7) with diisocyanate In the synthesis of a carboxyl group-containing urethane resin containing a carboxyl group-containing diol compound and a polyaddition reaction of a diol compound, molecules such as isophorone diisocyanate and pentaerythritol triacrylate are added to the molecule. A compound containing one isocyanate group and one or more (meth) acrylfluorene groups, and a terminal (meth) acrylated carboxyl group-containing urethane resin, and (8) a polyfunctional oxetane resin It reacts with dicarboxylic acids such as adipic acid, phthalic acid, hexahydrophthalic acid, etc., and adds carboxylic acid-containing polyester resin to the generated primary hydroxyl group by adding dibasic acid anhydride, and further adds Carboxyl group-containing photosensitivity obtained from a compound having one epoxy group and one or more (meth) acrylfluorenyl groups in one molecule, such as glycidyl acrylate, α-methyl glycidyl (meth) acrylate, etc. And (9) a carboxyl group obtained by adding a compound having a cyclic ether group and a (meth) acryl group in one molecule to a photosensitive resin containing a carboxyl group in any of (1) to (8) above. Photosensitive resin. (10) By copolymerizing an unsaturated carboxylic acid such as (meth) acrylic acid and an unsaturated group-containing compound such as styrene, α-methylstyrene, lower alkyl (meth) acrylate, isobutylene, and the like, Carboxyl-containing resin obtained by reacting with a compound having a cyclic ether group and a (meth) acrylfluorenyl group in a molecule such as 3,4-epoxycyclohexyl methacrylate Resin, etc. The term “(meth) acrylate” used herein is a generic term for acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions.

Among the above-mentioned carboxyl group-containing photosensitive resins, as described above, a carboxyl group-containing resin obtained by synthesizing a carboxyl group-containing photosensitive resin or a resin other than an epoxy resin without using an epoxy resin as a starting material can be preferably used. Photosensitive resin. Therefore, in the specific examples of the carboxyl group-containing photosensitive resin, any one or more of the carboxyl group-containing photosensitive resins (4) to (7) can be particularly preferably used. It can have the characteristics required for semiconductor package solder resist, namely PCT resistance, HAST resistance, cold and heat resistance.

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

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

In addition, a carboxyl group-containing urethane resin having a chlorine ion impurity amount of 0 to 30 ppm synthesized from an isocyanate compound that does not use phosgene as a starting material and a raw material that does not use epihalohydrin can also be preferably used. Among these urethane resins, a resin having no hydroxyl group can be easily synthesized by blending the equivalents of a hydroxyl group and an isocyanate group.

When synthesizing a urethane resin, an epoxy acrylate modified raw material may be used as the diol compound. Although chloride ion impurities are incorporated, they can also be used based on the controllable aspects of chloride ion impurities. In addition, the carboxyl group-containing photosensitive resin of the above (10) has a small amount of chloride ion impurities and can be preferably used.

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

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

The weight average molecular weight of the carboxyl group-containing photosensitive resin varies depending on the resin skeleton, but is generally preferably 2,000 to 150,000. When the weight-average molecular weight is 2,000 or more, the non-sticky performance or resolution when the photosensitive film is formed can be improved. In addition, by setting the weight average molecular weight to 150,000 or less, it is possible to improve developability and storage stability. More preferably 5,000 ~ 100,000.

The blending amount of the carboxyl group-containing photosensitive resin is preferably 20 to 60% by mass in terms of solid content in the photosensitive resin composition. By setting it as 20 mass% or more, the coating film strength at the time of making a photosensitive film can be improved. In addition, by setting the content to 60% by mass or less, the viscosity can be appropriately increased and the workability can be improved. More preferably, it is 30 to 50% by mass.

Examples of the compound used as the photosensitive monomer include conventionally known polyester (meth) acrylate, polyether (meth) acrylate, urethane (meth) acrylate, and carbonate (meth) Acrylate, epoxy (meth) acrylate, and the like. Specifically, it is hydroxyalkyl acrylates of 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol. Class; N, N-dimethyl acrylamide, N-methyl methacrylamide, N, N-dimethylaminopropyl acrylamide and other acrylamides; N, N-dimethyl acrylic acid Amine alkyl acrylates such as aminoamino ethyl ester, N, N-dimethylaminopropyl acrylate; hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tri-hydroxyethyl isocyanuric acid Polyols such as esters or polyacrylates such as ethylene oxide adducts, propylene oxide adducts or ε-caprolactone adducts; phenoxy acrylates, bisphenol A diacrylic acid Esters and polyacrylic acid esters of ethylene oxide adducts or propylene oxide adducts of these phenols; glycerol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, Polyglycidyl ethers of glycidyl ethers such as triglycidyl isocyanurate, etc .; not limited to the foregoing, and at least the following can be appropriately selected and used One type: Polyacrylate polyols, polycarbonate diols, hydroxyl-terminated polybutadiene, polyester polyols, and the like are directly acrylated, or urethane acrylates are acrylated via diisocyanates. And melamine acrylate, and each methacrylate corresponding to the aforementioned acrylate.

A polyfunctional epoxy resin such as a cresol novolac epoxy resin is reacted with an epoxy acrylate resin obtained by acrylic acid, or a hydroxyl group of the epoxy acrylate resin is further reacted with a hydroxy acrylate such as pentaerythritol triacrylate and isophor An epoxy urethane acrylate compound or the like obtained by reacting a bis-urethane compound of a diisocyanate such as ketone diisocyanate can also be used as a photosensitive monomer. These epoxy acrylate-based resins do not reduce touch dryness and can improve photocurability.

The compounding amount of the compound having an ethylenically unsaturated group in the molecule used as the photosensitive monomer is preferably 0.2 to 60% by mass and more preferably 0.2 to 50% by mass in terms of solid content in the photosensitive resin composition. %. When the compounding amount of the compound having an ethylenically unsaturated group is 0.2% by mass or more, the photocurability of the photocurable resin composition is improved. In addition, by setting the blending amount to 60% by mass or less, the hardness of the coating film can be increased.

In particular, when a non-photosensitive resin containing a carboxyl group having no ethylenically unsaturated double bond is used as the photosensitive monomer, in order to make the composition photocurable, a compound having one or more ethylenically unsaturated groups must be used in combination ( Photosensitive monomer), so it is effective.

Examples of the thermal crosslinking component include a thermosetting resin. As the thermosetting resin, an isocyanate compound, a blocked isocyanate compound, an amine resin, a maleimide resin, a benzoxazine resin, a carbodiimide resin, a cyclic carbonate compound, a polyfunctional epoxy compound, Multifunctional oxetane compounds, episulfide resins and the like are commonly used. Among these, a preferable thermal cross-linking component is a thermal cross-linking component having at least any one of a cyclic ether group and a cyclic thioether group (hereinafter referred to as a cyclic (thio) ether group) in one molecule. These thermosetting components having a cyclic (thio) ether group are commercially available in various types, and various properties can be imparted according to their structures.

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

Examples of the polyfunctional epoxy compound include, for example, jER828, jER834, jER1001, jER1004 manufactured by Mitsubishi Chemical Corporation, Epiclon 840, Epiclon 840-S, Epiclon 850, Epiclon 1050, Epiclon 2055, and Nippon Steel Corporation manufactured by DIC Corporation. EPOTOT YD-011, YD-013, YD-127, YD-128 manufactured by Sumitomo Chemical Co., Ltd., DER317, DER331, DER661, DER664 manufactured by Dow Chemical Co., Ltd., and manufactured by Sumitomo Chemical Co., Ltd. Sumi-epoxy ESA-011, ESA-014, ELA-115, ELA-128, bisphenol A ring of AER330, AER331, AER661, AER664, etc. (all trade names) manufactured by Asahi Kasei Industrial Co., Ltd. Oxygen resin; jERYL 903 manufactured by Mitsubishi Chemical Corporation, Epiclon 152, Epiclon 165 manufactured by DIC Corporation, EPOTOT YDB-400, YDB-500 manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., manufactured by Dow Chemical Co., Ltd. DER542, Sumi-epoxy ESB-400, ESB-700 manufactured by Sumitomo Chemical Co., Ltd., AER711, AER714, etc. (all trade names) brominated epoxy resins manufactured by Asahi Kasei Industrial Co., Ltd .; Mitsubishi JER 152, jER 154 made by Japan Chemical Corporation, DEN431, DEN438 made by Dow Chemical Co., Ltd., Epiclon N-730, Epiclon N-770, Epiclon N-865 made by DIC Corporation, Nippon Steel & Sumikin EPOTOT YDCN-701, YDCN-704 made by Chemical Co., Ltd., EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, NC-3000H made by Nippon Kayaku Co., Ltd., Sumitomo Chemical Co., Ltd. Co., Ltd. Sumi-epoxy ESCN-195X, ESCN-220, AER ECN-235, ECN-299, etc. (all trade names) manufactured by Asahi Kasei Industrial Co., Ltd. (Novolac type epoxy resin); manufactured by DIC Corporation Epiclon 830, jER 807 manufactured by Mitsubishi Chemical Corporation, EPOTOT YDF-170, YDF-175, YDF-2004, etc. (all trade names) of bisphenol F-type epoxy resin manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd. Resin; EPOTOT ST-2004, ST-2007, ST-3000 (trade name) and other hydrogenated bisphenol A epoxy resins manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd .; jER 604 manufactured by Mitsubishi Chemical Co., Ltd., new EPOTOT YH-434 manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., Sumitomo Chemical Glycidylamine type epoxy resins such as Sumi-epoxy ELM-120 (all trade names) manufactured by Industrial Co., Ltd .; Alicyclic epoxy resins such as Celloxide 2021 (trade name) manufactured by Dicel Corporation; Mitsubishi YL-933 manufactured by Chemical Co., Ltd., and TEN, EPPN-501, EPPN-502, etc. (all trade names) by the Dow Chemical Company; trihydroxyphenylmethane type epoxy resin; manufactured by Mitsubishi Chemical Co., Ltd. YL-6056, YX-4000, YL-6121 (all are trade names), bisxylenol-type or biphenol-type epoxy resins or mixtures thereof; EBPS-200 manufactured by Nippon Kayaku Co., Ltd., Bisphenol S-type epoxy resins such as EPX-30 manufactured by Asahi Chemical Industry Co., Ltd. and EXA-1514 (trade name) manufactured by DIC Corporation; and jER 157S (trade name) manufactured by Mitsubishi Chemical Corporation. Phenol A novolac epoxy resin; jERYL-931 and other (trade names) tetrahydroxyphenylethane type epoxy resins manufactured by Mitsubishi Chemical Corporation; TEPIC and others (trade names) manufactured by Nissan Chemical Industry Co., Ltd. Heterocyclic epoxy resin; Blem manufactured by Japan Oil & Fat Co., Ltd. er DGT and other diglycidyl phthalate resins; Nippon Steel and Sumitomo Chemical Co., Ltd. and other tetraglycidyl xylyl fluorenyl ethane resins; Nippon Steel and Sumitomo Chemical Co., Ltd. ESN-190 and ESN-360 made by DIC, HP-4032, EXA-4750, EXA-4700 and other naphthalene-based epoxy resins made by DIC Corporation; HP-7200 and HP-7200H made by DIC Corporation Other epoxy resins with a dicyclopentadiene skeleton, EXA-4816, EXA-4822, EXA-4850 series of soft and strong epoxy resins; shrinkage of CP-50S, CP-50M, etc. made by Japan Oil Co., Ltd. Glyceryl methacrylate copolymer-based epoxy resin; furthermore, there are, but are not limited to, copolymerized epoxy resins of cyclohexyl maleimide and glycidyl methacrylate. These epoxy resins can be used individually or in combination of 2 or more types.

Examples of polyfunctional oxetane compounds include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether and bis [(3-ethyl-3-oxetanylmethoxy) Methyl] ether, 1,4-bis [(3-methyl-3-oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) (Meth) methyl] benzene, (3-methyl-3-oxetanyl) methyl acrylate, (3-ethyl-3-oxetanyl) methyl acrylate, (3-methyl methacrylate) Polyfunctional oxetanyl 3-oxetanyl) methyl ester, (3-ethyl-3-oxetanyl) methacrylate, or oligomers or copolymers thereof Alkanes, in addition, examples include oxetanol and novolac resins, poly (p-hydroxystyrene), Cardo type bisphenols, calixarenes, resorcinarene (calix resorcinarene) ), Or etherates of resins having a hydroxyl group such as silsesquioxane. In addition, a copolymer of an unsaturated monomer having an oxetan ring and an alkyl (meth) acrylate is also exemplified.

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

The compounding amount of the thermosetting component having a plurality of cyclic (thio) ether groups in the molecule, and when the composition includes a thermosetting component having a plurality of cyclic (thio) ether groups in the molecule, the conversion is based on the solid content. With respect to 1 equivalent of the carboxyl group of the carboxyl group-containing resin, it is preferably 0.3 equivalent or more, and more preferably in the range of 0.5 to 3.0 equivalents. By setting the compounding amount of the thermosetting component having a plurality of cyclic (thio) ether groups in the molecule to be 0.3 equivalent or more, the carboxyl group is not left in the cured film, and the heat resistance, alkali resistance, and electrical insulation properties are further improved. . In addition, when the carboxyl group-containing resin is not included in the photosensitive resin composition, the blending amount of the thermosetting component having a plurality of cyclic (thio) ether groups in the molecule is converted into a solid content in the photosensitive resin composition. It is preferably 20 to 60% by mass. By setting it as 20 mass% or more, the coating film strength at the time of making a photosensitive film can be improved. In addition, by setting the content to 60% by mass or less, the viscosity is improved and the workability is improved. More preferably, it is 30 to 50% by mass.

When a thermosetting component having a plurality of cyclic (thio) ether groups in a molecule is used, it is preferable to mix a thermosetting catalyst. Examples of such thermosetting catalysts are, for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanide Imidazole derivatives such as ethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4- ( (Dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl-N, N-dimethylbenzylamine, etc. Amine compounds, hydrazine adipate, hydrazine adipate, dihydrazine sebacate, etc .; phosphorus compounds such as triphenylphosphine, and the like. Examples of commercially available products include, for example, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (all are trade names of imidazole compounds) manufactured by Shikoku Chemical Industry Co., Ltd., and SAN-APRO Co., Ltd. Made of U-CAT (registered trademark) 3503N, U-CAT3502T (both are the trade names of blocked isocyanate compounds of dimethylamine), DBU, DBN, U-CATSA102, U-CAT5002 (all are bicyclic fluorene compounds And its salts) and so on. It is not particularly limited to these, as long as it is a thermosetting catalyst for epoxy resin or oxetane compound or one that can promote the reaction between at least one of epoxy group and oxetanyl group with carboxyl group, may be Use alone or in combination of two or more. Also, guanamine, acetoguanamine, 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-methacryloxyethyl-S-triazine. S-triazine derivatives such as isocyanuric acid adducts are preferably used in combination with a compound that can also function as an adhesion-imparting agent and a thermosetting catalyst.

When the blending amount of the thermosetting catalyst contains a thermosetting component having a plurality of cyclic (thio) ether groups in the molecule in the composition, the solid content is converted to a number of cyclic (thio) ethers in the molecule in terms of solid content. The base thermosetting component is 100 parts by mass, preferably 0.1 to 20 parts by mass, and more preferably 0.5 to 15.0 parts by mass.

Examples of the amine-based resin include amine-based resins such as melamine derivatives and benzoguanamine derivatives. For example, a methylol melamine compound, a methylol benzoguanamine compound, a methylol glycol urea compound, and a methylol urea compound are mentioned. In addition, alkoxymethylated melamine compounds, alkoxymethylated benzoguanamine compounds, alkoxymethylated glycoluril compounds, and alkoxymethylated urea compounds can be obtained by using A melamine compound, a methylol benzoguanamine compound, a methylol glycol urea compound, and a methylol urea compound are converted into an alkoxymethyl group. The type of these alkoxymethyl groups is not particularly limited, and examples thereof include methoxymethyl, ethoxyethyl, propoxymethyl, and butoxymethyl. Particularly preferred is a melamine derivative having a formaldehyde concentration of 0.2% or less that is excellent for humans or the environment.

Examples of commercially available amine resins include CYMEL 300, CYMEL 301, CYMEL 303, CYMEL 370, CYMEL 325, CYMEL 327, CYMEL 701, CYMEL 266, CYMEL 267, CYMEL 238, CYMEL 1141, CYMEL 202 , CYMEL 1156, CYMEL 1158, CYMEL 1123, CYMEL 1170, CYMEL 1174, CYMEL UFR65, CYMEL 300 (the above is made by Mitsui CYANMIDE Co., Ltd.), NIKALAC Mx-750, NIKALAC Mx-032, NIKALAC Mx-270, NIKALAC Mx-270 280, NIKALAC Mx-290, NIKALAC Mx-706, NIKALAC Mx-708, NIKALAC Mx-40, NIKALAC Mx-31, NIKALAC Ms-11, NIKALAC Mw-30, NIKALAC Mw-30HM, NIKALAC Mw-390, NIKALAC Mw- 100LM, NIKALAC Mw-750LM (the above is made by Sanwa Chemical Co., Ltd.), etc.

As the isocyanate compound, a polyisocyanate compound having a plurality of isocyanate groups in the molecule can be used. As the polyisocyanate compound, for example, an aromatic polyisocyanate, an aliphatic polyisocyanate, or an alicyclic polyisocyanate is used. Specific examples of the aromatic polyisocyanate include 4,4'-diphenylmethane diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, naphthalene-1,5-diisocyanate, and o-di Toluene diisocyanate, m-xylene diisocyanate and 2,4-toluene dimer. Specific examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, and 4,4-methylenebis (cyclo Hexyl isocyanate) and isophorone diisocyanate. A specific example of the alicyclic polyisocyanate is dicycloheptane triisocyanate. As well as the adducts, biuret and isocyanurate of the isocyanate compounds previously exemplified.

The blocked isocyanate group-containing isocyanate group contained in the blocked isocyanate compound is a group that is protected and temporarily inertized by reacting with a blocking agent. When heated to a specific temperature, the blocking agent dissociates to form an isocyanate group.

As the blocked isocyanate compound, an addition reaction product of an isocyanate compound and an isocyanate blocking agent can be used. Examples of the isocyanate compound that can react with the blocking agent include isocyanurate type, biuret type, and adduct type. Examples of the isocyanate compound used in the synthesis of the blocked isocyanate compound are, for example, aromatic polyisocyanate, aliphatic polyisocyanate, or alicyclic polyisocyanate. Specific examples of the aromatic polyisocyanate, the aliphatic polyisocyanate, or the alicyclic polyisocyanate are compounds exemplified previously.

Examples of the isocyanate blocking agent include phenol-based blocking agents such as phenol, cresol, xylenol, chlorophenol, and ethylphenol; ε-caprolactam, δ-valprolactam, and γ-butyrolactam And β-propiolactam-type end-capping agents; active methylene-based capping agents such as ethyl acetate and ethyl acetone; methanol, ethanol, propanol, butanol, pentanol, Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, benzyl ether, methyl glycolate, butyl glycolate, diacetone alcohol , Methyl lactate, ethyl lactate and other alcohol-based end-capping agents; formaldehyde oxime, acetaldehyde oxime, acetoxime, methyl ethyl ketone oxime, diethylfluorenyl monooxime, cyclohexane oxime and other oxime-based capping agents ; Thiol-based end-capping agents such as butyl mercaptan, hexyl mercaptan, third butyl mercaptan, thiophenol, methyl mercaptan, ethyl mercaptan; and other amines such as acetamide and benzamide End-capping agent; stilbene imine and maleimide, etc .; imine-based end-capping agent; dimethylaniline, aniline, butylamine, dibutylamine, etc. Ethyl imidazole Agent; methylene imine and propylene imine imine extending capping agent.

The blocked isocyanate compound may be a commercially available one, and examples thereof include Sumidur BL-3175, BL-4165, BL-1100, BL-1265, Desmodur TPLS-2957, TPLS-2062, TPLS-2078, TPLS-2117, Desmosome 2170, Desmosome 2265 (above are manufactured by Sumitomo Bayer Urethane Co., Ltd., trade names), Coronate 2512, Coronate 2513, Coronate 2520 (above are manufactured by TOSOH Co., Ltd., trade names), B-830, B-815, B-846, B-870, B-874, B-882 (above are manufactured by Mitsui Chemicals Co., Ltd., trade names), TPA-B80E, 17B-60PX, E402-B80T (above are manufactured by Asahi Kasei Corporation, products First name) and so on. In addition, Sumidur BL-3175 and BL-4265 can be used as a capping agent.

In the photosensitive resin composition, in order to accelerate the curing reaction of the hydroxyl group or the carboxyl group with the isocyanate group, a urethane-forming catalyst may be blended. As the urethane catalyst, a urethane selected from at least one of a tin-based catalyst, a metal chloride, a metal acetamylpyruvate, a metal sulfate, an amine compound, and an amine salt is preferably used.化 catalyst.

[Photopolymerization initiator]] In the present invention, as the photopolymerization initiator used for photopolymerizing the photosensitive resin composition, a conventional one can be used, but an oxime ester having an oxime ester group is preferred among them. Based photopolymerization initiator, α-aminoacetophenone based photopolymerization initiator, and fluorenylphosphine oxide based photopolymerization initiator. The photopolymerization initiator may be used singly or in combination of two or more kinds.

As the oxime ester photopolymerization initiator, as a commercially available product, CGI-325, IRGACURE (registered trademark) OXE01, IRGACURE OXE02, ADEKA N-1919, ADEKA ARKLS (registered trademark) manufactured by BASF Japan Co., Ltd. are examples. ) NCI-831, TR-PBG-304 manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd., etc.

In addition, a photopolymerization initiator having two oxime ester groups in the molecule can be preferably used, and specifically, an oxime ester compound having a carbazole structure represented by the following general formula (I) is exemplified. (In the formula, X ₁ represents a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group, and a phenyl group. 8 alkoxy, amine, alkylamino or dialkylamino with alkyl having 1 to 8 carbon atoms), naphthyl (can be substituted by alkyl with 1 to 17 carbon atoms, 1 to 8 carbon atoms) 8 alkoxy group, amine group, alkylamino group or dialkylamino group having an alkyl group having 1 to 8 carbon atoms), Y ₁ and Z each represent a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, Alkoxy, halo, phenyl, phenyl with 1 to 8 carbons (can pass through 1 to 17 carbons, alkoxy, 1 to 8 carbons, amines, 1 to 8 carbons Substituted by alkylamino or dialkylamino of alkyl group), naphthyl (may be substituted by alkyl group having 1 to 17 carbon atoms, alkoxy group having 1 to 8 carbon atoms, amine group, having 1 to 8 carbon atoms Alkylamino or dialkylamino substituted with alkyl), anthracenyl, pyridyl, benzofuranyl, benzothienyl, Ar represents alkylene, vinylene, or benzene having 1 to 10 carbon atoms Phenylene, phenylene, phenylene, naphthyl, thienyl, anthracene, thiophene, furanyl, 2,5-pyrrolediyl, 4,4'-stilbene diyl, 4,2 '-Qijiji, n is 0 or 1 Integer)

Particularly preferably, in the above, X ₁ and Y ₁ are methyl or ethyl, Z is methyl or phenyl, n is 0, and Ar is phenylene, naphthyl, thienyl, or thienyl. Oxime ester-based photopolymerization initiator.

As a preferred carbazoxime ester compound, a compound represented by the following general formula (II) can also be exemplified.

(In the formula, R ₃ represents an alkyl group having 1 to 4 carbon atoms, or a phenyl group which may be substituted by a nitro group, a halogen atom or an alkyl group having 1 to 4 carbon atoms, and R ₄ represents an alkyl group having 1 to 4 carbon atoms. Alkyl group, alkoxy group having 1 to 4 carbon atoms or phenyl group which can be substituted by alkyl group or alkoxy group having 1 to 4 carbon atoms, R ₅ represents a phenyl group which can be connected by an oxygen atom or a sulfur atom A substituted alkyl group having 1 to 20 carbon atoms, a benzyl group which may be substituted with an alkoxy group having 1 to 4 carbon atoms, R ₆ represents a nitro group, or a fluorenyl group represented by X ₂ -C (= O)- X ₂ represents an aryl group, thienyl group, morpholinyl group, thiophenyl group, or a structure represented by the following formula (III) which may be substituted by an alkyl group having 1 to 4 carbon atoms.

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

The blending amount when using an oxime ester-based photopolymerization initiator is preferably 0.01 to 10% by mass in terms of solid content in the photosensitive resin composition. By setting it as 0.01 mass% or more, the photo-hardening property on copper can be made more reliable, and coating film characteristics such as chemical resistance can be improved. When it is 10% by mass or less, halo and the like are less likely to occur, and the resolvability is also improved. More preferably, it is 0.05 to 5 mass%.

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

Specific examples of the fluorenylphosphine oxide-based photopolymerization initiator include 2,4,6-trimethylbenzylfluorenyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzylfluorenyl) ) -Phenylphosphine oxide, bis (2,6-dimethoxybenzylidene) -2,4,4-trimethyl-pentylphosphine oxide, and the like. Examples of commercially available products include Omnirad TPO and Omnirad 819 manufactured by IGM Resin.

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

When using a photopolymerization initiator other than the oxime ester-based photopolymerization initiator, the blending amount is preferably 0.01 to 10% by mass in terms of solid content in the photosensitive resin composition. By setting it as 0.01 mass% or more, the photo-hardening property on copper can be made more reliable, and coating film characteristics such as chemical resistance can be improved. In addition, by setting the content to 10% by mass or less, the effect of reducing outgassing can be sufficiently obtained, and further, light absorption on the surface of the cured film is suppressed, and deep hardenability is also improved. More preferably, it is 0.05 to 8% by mass.

A photoinitiator or a sensitizer may be used in combination with the photopolymerization initiator. Examples of the photoinitiator or sensitizer include benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, benzophenone compounds, tertiary amine compounds, and xanthone Compounds etc. These compounds may be used as a photopolymerization initiator, but they are preferably used in combination with a photopolymerization initiator. The photoinitiator or sensitizer may be used alone or in combination of two or more.

In addition, since these photopolymerization initiators, photostarters, and sensitizers absorb specific wavelengths, they may have low sensitivity depending on the situation, and they may function as ultraviolet absorbers. However, these are not used only for the purpose of improving the sensitivity of the composition. It can absorb light of specific wavelength according to need, improve surface light reactivity, make the line shape and opening of the resist perpendicular, change into cone shape, inverted cone shape, and improve the processing accuracy of line width or opening diameter.

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

The photosensitive resin composition may contain a colorant. As the colorant, conventional coloring agents such as red, blue, green, and yellow may be used, and any of pigments, dyes, and pigments may be used. However, from the viewpoint of reducing the environmental load and the impact on the human body, halogen-free is preferred.

In the photosensitive resin composition, an elastomer may be blended for the purpose of imparting flexibility to the obtained cured product and improving the brittleness of the cured product. The elastomer may be used singly or as a mixture of two or more kinds.

Moreover, conventionally well-known adhesive polymers can also be used for the purpose of improving the flexibility and touch-drying property of the hardened | cured material obtained.

Moreover, in a photosensitive resin composition, components, such as an adhesion promoter, an antioxidant, an ultraviolet absorber, can be mix | blended as needed. These are known in the art of electronic materials. In addition, at least one of silicone-based, fluorine-based, polymer-based defoamers and leveling agents can be blended, such as imidazole-based, thiazole-based, triazole-based silane coupling agents, rust inhibitors, and fluorescent agents. At least any one of conventional additives such as whitening agents.

The photosensitive film can be formed by coating the photosensitive resin composition on one surface of the supporting film and drying it. Considering the applicability of the photosensitive resin composition, the photosensitive resin composition is diluted with an organic solvent to adjust the viscosity to a suitable viscosity. The notch wheel applicator, doctor blade applicator, lip mold applicator, rod applicator, A rubber roll coater, a reverse roll coater, a transfer roll coater, a gravure coater, a spray coater, etc., apply a uniform thickness on one side of the supporting film, usually, dried at a temperature of 50 to 130 ° C. The organic solvent is volatilized within 1 to 30 minutes to obtain a non-touch coating film. The coating film thickness is not particularly limited, but the film thickness after drying is generally selected from 5 to 150 μm, preferably 10 to 60 μm.

The usable organic solvent is not particularly limited, and examples thereof include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, and petroleum-based solvents. . These organic solvents may be used alone or as a mixture of two or more.

Volatile drying of organic solvents can use hot-air circulation drying furnaces, IR furnaces, heating plates, convection ovens, etc. (using a heat source with air heating method using steam to make convection contact of hot air in the dryer and using nozzle blowing support System method).

[Protective film] 感光 The photosensitive film laminate of the present invention may be provided with a protective film on the opposite side of the photosensitive film from the support film for the purpose of preventing dust and the like from adhering to the surface of the photosensitive film and improving handling properties. As described later, a photosensitive film laminate having a protective film is peeled off when the photosensitive film laminate is used. However, since the protective film is peeled in a state where the photosensitive film is not cured, the photosensitive film is hardened into a cured film in general When the support film is peeled off later, carbon black is more likely to remain on the protective film. In the present invention, as described above, the photosensitive film includes a filler having a charge opposite to that of the carbon black together with the carbon black. When the protective film is peeled off, the carbon black can be effectively left in the photosensitive film.

As the protective film, for example, a polyester film, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, or a surface-treated paper can be used. However, the adhesion between the protective film and the photosensitive film is preferably smaller than that of the photosensitive film. Then force the material. Moreover, when using a photosensitive film laminated body, in order to peel a protective film easily, you may perform the mold release process as mentioned above on the surface of a protective film which contacts a photosensitive film.

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

In the protective film, the arithmetic average surface roughness Ra of the side in contact with the photosensitive film is preferably 1000 nm or less, more preferably 750 nm or less, and even more preferably 500 nm or less. By setting it to 1000 nm or less, the surface area does not become too large, so the risk of carbon black detachment is reduced. The arithmetic mean roughness Ra means a value measured by a measuring device in accordance with JIS B0601-1994.

<The manufacturing method of a hardened | cured material and a printed wiring board> 硬化 A hardened | cured material is formed using the photosensitive film laminated body of this invention. A method of forming the cured product and a method of manufacturing a printed wiring board including the cured product (cured film) on a substrate on which a circuit pattern is formed will be described. As an example, a method for manufacturing a printed wiring board using a photosensitive film laminate including a protective film will be described. First, (i) peel off the protective film from the above-mentioned photosensitive film laminate to expose the photosensitive film, (ii) attach the photosensitive film of the photosensitive film laminate on the substrate on which the circuit pattern is formed, and (iii) ) Exposing from the support film of the photosensitive film laminate, (iv) peeling the support film from the photosensitive film laminate to develop, thereby forming a patterned photosensitive film on the substrate, (v ) The patterned photosensitive film is cured by light irradiation or heat to form a cured film, thereby forming a printed wiring board. When a photosensitive film laminate without a protective film is used, the peeling step (i step) of the protective film is of course not necessary. Each step is described below.

First, the protective film is peeled from the photosensitive film laminate to expose the photosensitive film, and the photosensitive film of the photosensitive film laminate is bonded to a substrate on which a circuit pattern is formed. Examples of the substrate on which the circuit pattern is formed include printed wiring boards or flexible printed wiring boards in which circuits are formed in advance. Phenolic paper, epoxy paper, epoxy glass cloth, glass polyimide, and glass cloth / epoxy can be used. Non-woven cloth, glass cloth / epoxy paper, synthetic fiber epoxy resin, fluorine resin. Polyethylene. Polyphenylene oxide, polyphenylene oxide. For those materials such as cyanate ester, copper-clad laminates for high-frequency circuits, all grades (FR-4, etc.) copper-clad laminates, and polyimide films, PET films, glass substrates, ceramic substrates, wafers Board, etc.

It is preferable to use a vacuum laminator or the like for laminating the photosensitive film of the photosensitive film laminate on a circuit board, and laminating it under pressure and heating. By using such a vacuum laminator, since the photosensitive film is closely adhered to the circuit substrate, air bubbles are not mixed, and the hole embedding property to the substrate surface can be improved. The pressing conditions are preferably about 0.1 to 2.0 MPa, and the heating conditions are preferably 40 to 120 ° C.

Next, exposure is performed from the support film of the photosensitive film laminate (irradiation of active energy rays). With this step, only the exposed photosensitive resin layer is hardened. The exposure step is not particularly limited, and may be, for example, a contact (or non-contact), selective exposure by active energy rays through a mask formed with a desired pattern, but it may also be activated by a direct drawing device. Expected pattern of energy line exposure.

As an exposure machine for active energy ray irradiation, any device that irradiates ultraviolet rays in the range of 350 to 450 nm equipped with a high-pressure mercury lamp, an ultra-high pressure mercury lamp, or a metal halide lamp may be used, and a direct drawing device (for example The CAD data of the computer directly uses the laser direct imaging device to draw images. As the laser light source of the direct drawing machine, if a laser light having a maximum wavelength in the range of 350 to 410 nm is used, it may be either a gas laser or a solid laser. The amount of exposure used for image formation varies depending on the film thickness, etc., but is generally in the range of 20 to 800 mJ / cm ² and preferably in the range of 20 to 600 mJ / cm ² .

After the exposure, the support film was peeled from the photosensitive film laminate. In this step, a supporting film for confirming the presence or absence of carbon black is obtained. The method for peeling the supporting film is not particularly limited, and there are methods such as using an adhesive tape or an automatic peeler such as an automatic hair dryer to peel off by hand.

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

Next, the patterned photosensitive film is hardened by (light) irradiating active energy rays or heat to form a cured material (cured film). This step can be called formal hardening or additional hardening, which can promote the polymerization of unreacted monomers in the photosensitive film, and then thermally harden the carboxyl-containing photosensitive resin and epoxy resin, which can reduce the amount of remaining carboxyl groups. The irradiation of active energy rays can be performed in the same manner as the above-mentioned exposure, but it is preferably performed under conditions that are stronger than the irradiation energy during exposure. For example, it can be set to 500 to 3000 mJ / cm ² . The heat curing can be performed at 100 to 200 ° C. under heating conditions of about 20 to 90 minutes.

The photosensitive film laminate of the present invention can be suitably used as a printed wiring board insulating material, a semiconductor insulating material, or a semiconductor sealing material, and can be better used as a solder resist layer or an interlayer insulating layer. Good for forming solder resist layer. [Example]

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

<Checking the state of charge> First, ground the ground connection terminal of the static tester (SK-H050, manufactured by KYENCE Co., Ltd.) in Type D. Start the static meter connected to ground, and select "Static Meter" from "MODE". Next, in the "RANGE" key, select "Near" in the high-precision mode. The measurement response time was 0.8 seconds, and the measurement area was set to ϕ60 mm. Next, press the "START" key to set the measurement state. Press the "ZERO" key to the grounded object of the static analyzer. Confirm that the potential is zero, and press the "STOP" key to adjust the zero point. Next, confirm that continuity was obtained, place a 30-ml metal can without surface treatment, etc. on an insulating table, and use a blower-type ionizer (SJ-F030, manufactured by KYENCE Co., Ltd.) to charge the metal can for 10 seconds. Using a metal spoon, put 5 g of carbon black into the entire metal can. At this time, do not touch the metal can except the sample. Then, use the laser pointer of the electrostatic measuring device to measure the distance of the carbon black surface. Press the "START" button to measure the surface charge potential. After 10 seconds, press the "STOP" button to end the measurement. The measurement is performed under the conditions of a temperature of 25 ° C and a humidity of 50%, and a zero adjustment is performed for each measurement. Determine the maximum, minimum, and absolute values of the charged potential obtained each time. The measurement was performed three times for each sample, and the positive and negative values were determined based on a value obtained by averaging the absolute values of the three times. In the case of measuring the filler, the same operation was performed to determine whether it was positive or negative.

<Confirmation of the state of charge of carbon black> Prepare carbon black A with an average particle size of 24 nm and carbon black B with an average particle size of 38 nm, and confirm the charged state of the carbon black by the method described above (both carbon black A and carbon black B are in powder form) . As a result, it was confirmed that carbon black A was positively charged and carbon black B was negatively charged.

<Confirmation of the charged state of the filler> 确认 Confirm the charged state of the filler described later (the filler is powdered) by the method described above. It was confirmed that spherical silica having an average particle diameter of 0.55 μm was negatively charged, titanium oxide A having an average particle diameter of 0.28 μm was positively charged, and titanium oxide B having an average particle diameter of 0.25 μm was negatively charged.

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

293.0 g of the propylene oxide reaction solution of the obtained novolac cresol resin, 43.2 g of acrylic acid, 11.53 g of methanesulfonic acid, 0.18 g of methylhydroquinone, and 252.9 g of toluene were fed into a reaction equipped with a stirrer, a thermometer, and an air blowing pipe Air was blown into the device at a rate of 10 ml / minute, and the reaction was carried out at 110 ° C. for 12 hours while stirring. The water produced by the reaction was used as an azeotropic mixture with toluene, and 12.6 g of water was distilled off. After cooling to room temperature, the obtained reaction solution was neutralized with 35.35 g of a 15% aqueous sodium hydroxide solution, followed by washing with water. Subsequently, toluene was replaced with 118.1 g of diethylene glycol monoethyl ether acetate in an evaporator and distilled off to obtain a novolac type acrylate resin solution. Next, 332.5 g of the obtained novolac acrylate resin solution and 1.22 g of triphenylphosphine were fed into a reactor equipped with a stirrer, a thermometer, and an air blowing tube, and air was blown in at a rate of 10 ml / minute, and slowly added while stirring. 62.3 g of tetrahydrophthalic anhydride was reacted at 95 to 101 ° C. for 6 hours to obtain a carboxyl-containing photosensitive resin varnish 1 having a nonvolatile content of 71% and an acid value of 88 mgKOH / g.

<Preparation of Photosensitive Resin Compositions 1 to 10> The carboxyl group-containing photosensitive resin varnish 1 obtained as described above is used as a photosensitive monomer of an acrylate compound. DPHA), bisphenol A type epoxy resin (EPICLON840-S manufactured by DIC Corporation) as a thermosetting component, biphenol novolac type epoxy resin (NC-3000H manufactured by Nippon Kayaku Co., Ltd.) ), IRGACURE OXE02 manufactured by BASF Japan Co., Ltd. as a photopolymerization initiator, melamine as a thermosetting catalyst, carbon black A or carbon black B, and self-spherical silica, titanium oxide A, titanium oxide as fillers Each component selected in B was prepared in the proportion (parts by mass) shown in Table 1 below, and preliminarily mixed with a blender and kneaded with a 3-roll mill to prepare photosensitive resin compositions 1 to 10.

[Example 1] <Preparation of photosensitive film laminated body> 300 g of methyl ethyl ketone was added to the photosensitive resin composition 1 obtained as described above, diluted, and stirred with a stirrer for 15 minutes to obtain a coating solution. The coating solution was applied to a polyethylene terephthalate film (LUMIRROR T60, manufactured by Toray Corporation, Ra = 0.03 μm) having a thickness of 25 μm as a supporting film, and dried at 80 ° C. for 15 minutes to form A photosensitive film having a thickness of 20 μm. Next, a 15 μm-thick polypropylene film (ARUFAN MA-411, manufactured by OJI F-TEX Co., Ltd., Ra = 0.4 μm) was laminated on the photosensitive film to produce a photosensitive film laminate.

[Example 2] In Example 1, a photosensitive film laminate 2 was produced in the same manner as in Example 1 except that the photosensitive resin composition 2 was used instead of the photosensitive resin composition 1.

[Example 3] In Example 1, a photosensitive film laminate 3 was produced in the same manner as in Example 1, except that the photosensitive resin composition 3 was used instead of the photosensitive resin composition 1.

[Example 4] In Example 1, except that the photosensitive resin composition 4 was used instead of the photosensitive resin composition 1, a photosensitive film laminate 4 was produced in the same manner as in Example 1.

[Example 5] In Example 1, a photosensitive film laminate 5 was produced in the same manner as in Example 1 except that the photosensitive resin composition 5 was used instead of the photosensitive resin composition 1.

[Example 6] In Example 1, a photosensitive film laminate 6 was produced in the same manner as in Example 1, except that the photosensitive resin composition 6 was used instead of the photosensitive resin composition 1.

[Example 7] In Example 1, a photosensitive film laminate 7 was produced in the same manner as in Example 1 except that the photosensitive resin composition 7 was used instead of the photosensitive resin composition 1.

[Comparative Example 1] In Example 1, a photosensitive film laminate 8 was produced in the same manner as in Example 1, except that the photosensitive resin composition 8 was used instead of the photosensitive resin composition 1.

[Comparative Example 2] In Example 1, a photosensitive film laminate 9 was produced in the same manner as in Example 1 except that the photosensitive resin composition 9 was used instead of the photosensitive resin composition 1.

[Comparative Example 3] In Example 1, a photosensitive film laminate 10 was produced in the same manner as in Example 1 except that the photosensitive resin composition 10 was used instead of the photosensitive resin composition 1.

＜ Production of the test substrate ＞ CZ8101 chemically polished FR-4 copper-clad laminated board (100mm × 150mm × 0.8mmt, both sides of copper foil, copper foil thickness 18μm) manufactured by MERCK Co., Ltd. The chemically polished surface was bonded to the exposed surface of the photosensitive film by peeling off the protective film from each of the photosensitive film laminates obtained as described above, and then using a vacuum laminator (MVLP-500, manufactured by Meiki Seisakusho Co., Ltd.) at a pressure of : 0.8 MPa, 70 ° C., 1 minute, and vacuum: 133.3 Pa. The test laminate was obtained by heating and laminating the substrate and the photosensitive film in close contact.

<Evaluation of the presence or absence of carbon black> From the test substrate produced as described above, the support film was peeled off by hand for about 1 second, and the peeled support film and the peeled protective film in the above-mentioned <Preparation of the test substrate> were cut to about 1 ×, respectively. 1 cm square, Pt is vapor-deposited on the surface of the supporting film and the protective film which is in contact with the photosensitive resin. The surface of the vapor-deposited Pt was observed with a SEM (scanning electron microscope, JSM-7600 manufactured by Japan Electronics Co., Ltd.), and it was confirmed whether carbon black remained on the supporting film and the protective film. For each film, an arbitrary part was observed at an acceleration voltage of 10 kV and a measurement magnification of 50,000 times, and evaluated based on the following criteria. ○: measurement area of 1 m ² is not detected in the carbon black particles ×: area of 1 m ² assay detected results of the evaluation as carbon black particles or more in Table 2 below.

<Resolution Evaluation> The resolutions were further evaluated for Examples 1 to 7 in which carbon black did not remain on the support film and the protective film. After the lamination in the above-mentioned <Manufacture of test substrates>, a parallel light exposure device equipped with a short-arc high-pressure mercury lamp was used, and through the exposure mask, the polyethylene terephthalate film side of the self-supporting film was designed to be SRO. (Solder resist opening) After the negative pattern of 200 μm is exposed separately, the support film is peeled off by hand for about 1 second to expose the photosensitive film. The exposure amount is set to a 7-segment exposure when a support film that is in contact with the photosensitive film is exposed using Stouffer 41-segment exposure. Subsequently, the exposed surface of the exposed photosensitive film was developed using a 1% by weight Na ₂ CO ₃ aqueous solution at 30 ° C. and a spray pressure of 2 kg / cm ² for 60 seconds to be patterned. Next, the patterned photosensitive film was irradiated with a UV conveying furnace equipped with a high-pressure mercury lamp at an exposure of 1 J / cm ² , and then heated at 160 ° C. for 60 minutes for additional hardening to form a hardened film, which was formed on a substrate. Test substrate for hardened film. The openings having an opening diameter of 200 μm of each of the produced test substrates of Examples 1 to 7 were observed by SEM and evaluated by the following criteria. ○: Halo and undercut did not occur, and a good opening shape was obtained. X: Halo and undercut did not occur, and a good opening shape could not be obtained. The evaluation results are shown in Table 2 below.

<Electrical Characteristics Evaluation> The electrical characteristics were further evaluated for Examples 1 to 7 in which carbon black did not remain on the supporting film and the protective film. A test substrate was produced in the same manner as the resolution evaluation except that a comb-shaped electrode pattern with a line / space = 100/100 μm was used, and the electrical characteristics were evaluated. The evaluation was carried out in a high-temperature and high-humidity tank under an environment of a temperature of 130 ° C and a humidity of 85%, and a voltage of 5.5 V was applied to perform a HAST test in the tank. The insulation resistance value in the tank was measured after a specific time elapsed to evaluate the HAST resistance. The judgment criteria are as follows. ○: For more than 100 hours, the insulation resistance value in the tank did not reach 10 ⁶ Ω or a short circuit occurred. ×: In less than 100 hours, the insulation resistance value in the tank did not reach 10 ⁶ Ω or a short circuit occurred. The evaluation results are shown in Table 2 below.

As can be understood from the above results, the photosensitive film contains at least carbon black, and further includes a photosensitive film laminate composed of a filler having a charge opposite to that of carbon black. From the evaluation results of the presence or absence of carbon black, it can be seen that carbon black effectively resides As a result, in the photosensitive film, in addition to the absence of carbon black remaining in the peeled support film and protective film, the workability does not deteriorate, and from other evaluation results, it is understood that the resolution and electrical characteristics are also good.

Claims (8)

A photosensitive film laminate is obtained by laminating a support film and a photosensitive film composed of a photosensitive resin composition, and is characterized in that: in the photosensitive film laminate, the photosensitive resin composition It is made of at least carbon black and a filler, and the filler has a charge opposite to that of the carbon black. For example, the photosensitive film laminate according to the first patent application range, wherein in the photosensitive resin composition, the blending amount of the carbon black is 0.3 to 5% by mass in terms of solid content. For example, the photosensitive film laminate of the first or second patent application range, wherein the thickness of the aforementioned support film is 10 to 150 μm. For example, the photosensitive film laminate according to the first or second patent application range, wherein the aforementioned support film is a thermoplastic resin film. For example, the photosensitive film laminate according to item 4 of the application, wherein the thermoplastic resin film is selected from the group consisting of polyester film, polyimide film, polyimide film, polypropylene film, and polystyrene film. At least one of the groups. For example, if the photosensitive thin film laminate of the first or second scope of the patent application is applied, the arithmetic mean surface roughness Ra of the aforementioned support film is 1000 nm or less. For example, the photosensitive film laminate according to the first or second patent application scope further includes a protective film, and the protective film is laminated on the surface of the photosensitive film on the side opposite to the support film. A hardened product, which is formed by using a photosensitive thin film laminate as described in the first or second patent application.