TWI787305B - Photosensitive resin composition, dry film, cured product and printed wiring board - Google Patents

Abstract

The object of the present invention is to provide a photosensitive resin composition that satisfies the high resolution of the coating film after the full-scale hardening, and can also suppress the contamination of the developer in the developing step or the clogging of the developing device due to sediment. , dry film and hardened products. The present invention uses a photosensitive resin composition as a means, which is a photosensitive resin composition containing an alkali-soluble resin, and is characterized in that the coating film formed by coating the photosensitive resin composition is carried out at 80°C for 40 minutes. The contact angle of water on the dry coating film after drying is A (°), and the contact angle of water on the dry coating film after drying the coating film formed by coating the photosensitive resin composition at 80°C for 70 minutes When the contact angle is B(°), A is 75.0° or more, and the rate of change R ₈₀ represented by R ₈₀ (%)=|(BA)/A|×100 is 3.0 or less.

Description

Photosensitive resin composition, dry film, cured product and printed wiring board

The present invention relates to a photosensitive resin composition, and more specifically, to an alkali-developable photosensitive resin composition containing an alkali-soluble resin, a dry film, a cured product, and a printed wiring board.

In recent years, the requirements for miniaturization, high density, and high precision have been increased in mobile phones, personal computers, or touch panel displays, etc. Solder resist or coating layer of printed wiring boards formed in these Refinement of insulating layers such as interlayer insulation or conductive circuits or electrodes has become more necessary than ever.

In order to meet such requirements, in order to apply the optical etching method that can be highly finely patterned compared to the pattern printing method, an insulating layer or a conductive circuit is formed using an insulating paste or a conductive paste made of a photosensitive resin composition ( For example, refer to Patent Documents 1 to 6). In consideration of environmental issues, alkali-developing insulating pastes or conductive pastes that use dilute alkaline aqueous solutions as the developer during development have also become mainstream. [Prior Art Document] [Patent Document]

[Patent Document 1] Japanese Patent Application Publication No. 2014-101412 [Patent Document 2] Japanese Patent Application Publication No. 2013-137511 [Patent Document 3] Japanese Patent Application Publication No. 2013-136727 [Patent Document 4] Japanese International Publication No. 2010/ Handbook No. 113287 [Patent Document 5] Japanese Patent Application Laid-Open No. 2014-167090 [Patent Document 6] Japanese Patent Application Laid-Open No. 2015-026013

[Problems to be Solved by the Invention]

However, the alkali-developing type photosensitive resin composition used in the insulating paste or the conductive paste is in the developing step, and the components of the photosensitive resin composition dissolved in the developing solution are deposited at the bottom of the developing solution. , and there is a problem that the developer is contaminated. If the contamination of the developing solution worsens, the developing device will also be contaminated, resulting in a decrease in developing capability. In addition, the components precipitated in the developer solution become residues, causing the problem of clogging of the developing device. Therefore, in order not to lower the developing ability, it is necessary to increase the exchange frequency of the developer and to wash the developing device in a short time, so there is also a problem of poor processability.

Therefore, the object of the present invention is to provide a photosensitive resin composition that satisfies the high resolution of the coating film after formal hardening, and can also suppress the contamination of the developer in the developing step or the clogging of the mesh of the developing device caused by sediment. objects, dry film and hardened objects. [Means to solve the problem]

When developing the dry coating film of the photosensitive resin composition, a development management sheet (hereinafter, also referred to as a development life.) is provided. The development management width refers to the width of the drying time when drying the coating film formed by coating. If the development management width of the dried coating film is wide, the drying time can be prolonged when the coating film formed by coating is dried, so that the residual solvent in the photosensitive resin composition can be fully volatilized, and the photohardening or Coating film characteristics such as dryness to touch become favorable. Therefore, in the management of the steps, more than a certain development management width is required. The inventors of the present invention have found that the cause of the contamination of the developing solution in the developing step or the clogging of the developing device due to sediment is due to the heat history when drying the coating film formed using the photosensitive resin composition. The development management width. That is, it was found that if the development management width is narrow, the development state will be worse than that of the development management width, and since the state of the dry coating film to be developed is also different, deposits are also easy to form, and the developer It is polluted and further produces the clogging of the developing device's mesh.

In addition, as a result of active research by the present inventors, they focused on the contact angle of water on the dry coating film of the photosensitive resin composition. If the contact angle of water shows a specific value and satisfies a specific formula, it can be The above-mentioned problems can be solved by imparting a developing life of more than a certain level to the photosensitive resin composition. The present invention is based on this knowledge.

That is, the photosensitive resin composition of the present invention is a photosensitive resin composition containing an alkali-soluble resin, and is characterized in that the coating film formed by coating the photosensitive resin composition is carried out at 80° C. for 40 minutes. The contact angle of water on the dry coating film after drying is A (°), and the contact angle of water on the dry coating film after drying the coating film formed by coating the photosensitive resin composition at 80°C for 70 minutes When the contact angle is B(°), A is 75.0° or more, and the rate of change R ₈₀ represented by R ₈₀ (%)=|(BA)/A|×100 is 3.0 or less.

Also, the photosensitive resin composition of the present invention is a photosensitive resin composition containing an alkali-soluble resin, wherein the coating film formed by coating the photosensitive resin composition is dried at 90°C for 20 minutes The contact angle of water on the subsequent dried coating film is C (°), and the contact angle of water on the dried coating film after drying the coating film formed by coating the photosensitive resin composition at 90°C for 35 minutes When the angle is D (°), C is 75.0° or more, and the rate of change R ₉₀ represented by R ₉₀ (%)=|(DC)/C|×100 is 3.0 or less.

Moreover, the dry film according to another aspect of the present invention is characterized in that it has a resin layer obtained by coating and drying the above-mentioned photosensitive resin composition on a film.

Moreover, the cured product according to another aspect of the present invention is characterized in that it is obtained by curing the above-mentioned photosensitive resin composition, or the resin layer of the above-mentioned dry film.

Furthermore, a printed wiring board according to another aspect of the present invention is characterized in that it has the above-mentioned cured product. [Effect of the invention]

According to the present invention, it is possible to provide a photosensitive resin composition that satisfies the high resolution of the coating film after the full-scale hardening, and can also suppress the contamination of the developer in the developing step or the clogging of the mesh of the developing device caused by sediment, Dry film and cured product.

The photosensitive resin composition according to the first embodiment of the present invention contains an alkali-soluble resin and has a specific relationship as a contact angle of water when drying a coating film. That is, the photosensitive resin composition of the present invention is characterized in that the contact angle of water on the dried coating film after drying the coating film formed by coating the photosensitive resin composition at 80° C. for 40 minutes is defined as A (°), when the contact angle of water on the dry coating film after drying the coating film formed by coating the photosensitive resin composition at 80°C for 70 minutes is B (°), A is 75.0 ° or more, and the rate of change R ₈₀ represented by R ₈₀ (%)=|(BA)/A|×100 is 3.0 or less.

Also, the photosensitive resin composition according to the second embodiment of the present invention is one containing an alkali-soluble resin, wherein the coating film formed by coating the photosensitive resin composition is dried at 90° C. for 20 minutes The contact angle of water on the subsequent dried coating film is C (°), and the contact angle of water on the dried coating film after drying the coating film formed by coating the photosensitive resin composition at 90°C for 35 minutes When the angle is D (°), C is 75.0° or more, and the rate of change R ₉₀ represented by R ₉₀ (%)=|(DC)/C|×100 is 3.0 or less.

As a result of active research, the present inventors have found that by making the contact angle of water on the dried coating film of the photosensitive resin composition satisfy the above-mentioned relationship, it is possible to provide a development life of more than a certain level, and to prevent the developer from developing. Pollution or blockage of the developing device caused by sediment. The reason for this is not clear, but it is considered as follows. Generally speaking, the smaller the contact angle with water, the more hydrophilic it is. However, in the case of a dried coating film, if the hydrophilicity is strong, an alkali developing solution becomes easy to dissolve in the dried coating film, and there is a problem that development becomes difficult on the contrary. In the present invention, since the contact angle of water on the dry coating film of the photosensitive resin composition is 75.0° or more, the alkali developer and the dry coating film of the composition are in a moderately compatible state, and development becomes easy. Furthermore, it is inferred that even if the drying conditions for forming a dried coating film are changed, this state is maintained, and therefore a moderately developed state is also maintained. Contamination of the liquid or clogging of the mesh of the developing device will not occur. However, the above-mentioned mechanism is only the conjecture of the present inventors, and the present invention is not bound by this theory.

Here, the contact angle is defined in JIS R3257:1999, and in the present invention, the contact angle is defined by the contact angle of water. In addition, the so-called water in the present invention refers to ion-exchanged water. Specifically, ion exchange water with a water quality of 1 μS/cm or less is used. Exchange water. As an example of the measurement method, the following method can be mentioned. The contact angle system of water can be measured and analyzed by the true circle fitting method under the following conditions using DropMaster DM300 as a contact angle meter and FAMS (both manufactured by Kyowa Interface Science Co., Ltd.) as an interface measurement and analysis integration system. <Measurement conditions and measurement methods> ・First, start the interface measurement analysis integrated system, and turn on the CA/PD controller. In this case, select "Standard" for "Field of View" on the screen of the controller. Next, ion-exchanged water was put into a plastic syringe, a stainless steel needle (size 22) was attached to the tip, and then it was dripped on the surface of the test piece (dry coating film surface). When dropping, check whether the focus of the camera attached to the contact angle meter is correct. Immediately after dropping, press the "measurement" button on the controller screen.・Water used in the measurement: Ion-exchanged water with a water quality of 1 μS/cm or less prepared by a device (PureLite PRO-0250-003 manufactured by Olucano Co., Ltd.) ・Amount of water dropped: 2 μL ・Measurement temperature : 20°C ・Viewing range of the lens: Standard Next, the contact angle after water drop is measured at any 5 positions on the horizontally placed test piece, and the average value of the measured results is taken as the water contact angle . Here, the values of the contact angles at five arbitrary positions are the values automatically calculated by pressing the "Measurement" button respectively. The present invention is characterized in that A or C is 75.0° or more. A preferable value of A or C is 80.0° or more. Also, the upper limit of A or C is preferably 120.0° or less, more preferably 110.0° or less. Also, in the present invention, the change rate R ₈₀ or R ₉₀ of the contact angle calculated by the above formula is 3.0% or less, preferably 2.5% or less.

The photosensitive resin composition of the present invention is characterized in that it contains an alkali-soluble resin. Moreover, the photosensitive resin composition of this invention may contain arbitrary components as components other than alkali-soluble resin. For example, when the photosensitive resin composition is used as an insulating resin composition like a solder resist, it may contain a photopolymerization initiator, a filler, a reactive diluent, a thermosetting component, and the like. Moreover, when using a photosensitive resin composition as a conductive resin composition, each component, such as a photoinitiator, a filler, a reactive diluent, a thermosetting component, and an organic acid, may be contained.

On the other hand, the contact angle A of water on the dry coating film after drying the coating film formed by coating the photosensitive resin composition at 80°C for 40 minutes or the coating film formed by coating is The contact angle C of water on the dried coating film after drying at 90° C. for 20 minutes is 75.0° or more, and it is necessary to adjust the composition of the photosensitive resin composition. The method of adjustment is not particularly limited, but as the adjustment of organic components, for example, those having a methyl or fennel skeleton are used, and organic acids, higher fatty acid-based, styrene-acrylic, styrene-maleic acid are used Additives such as polyacrylamide, alkyl ketene dimer, alkenyl succinic anhydride, petroleum or silicone defoamers are preferred, but not limited thereto.

Also, even if the drying conditions for forming a dry coating film of the photosensitive resin composition are changed, the contact angle can be maintained within a certain range by adjusting the composition of the photosensitive resin composition, that is, _R80 Or R ₉₀ is 3.0% or less. The adjustment method is not particularly limited, but in the photosensitive resin composition, for example, selection of a photosensitive component or hardening component that is not easily thermally decomposed, or selection of an organic solvent with an appropriate boiling point can be mentioned. It is presumed that this is due to the possibility that the surface state of the dried coating film may change due to the hardening reaction and volatilization of the solvent by the drying conditions, but it is only a speculative range anyway, so it is not limited to this. In addition, the method of adjustment is not subject to these restrictions.

Next, each component of the photosensitive resin composition of this invention which satisfies the above-mentioned relationship with respect to the water contact angle system of a dry coating film is demonstrated in detail. In addition, in the patent specification of the present invention, the so-called (meth)acrylate is a term that collectively refers to acrylate, methacrylate and their mixtures, and other similar expressions are also the same.

[Alkali-soluble resin] The photosensitive resin composition of the present invention contains an alkali-soluble resin. Alkali-soluble resins can be any alkali-soluble resins, and known and conventional ones can be used. Alkali-soluble resins can be used alone or in combination of two or more. Examples include water-soluble resins such as carboxyl group-containing resins or phenolic hydroxyl group-containing resins. Among these, carboxyl group-containing resins or phenolic hydroxyl group-containing resins are preferable because of excellent developability, and carboxyl group-containing resins are more preferable. The carboxyl group-containing resin can be developed by alkali due to the carboxyl group contained therein. Also, from the viewpoint of photosensitivity, it is preferable to have an ethylenically unsaturated bond in the molecule other than a carboxyl group, but only a carboxyl-containing resin that does not have an ethylenically unsaturated double bond may be used. When the carboxyl group-containing resin does not have an ethylenically unsaturated bond, a reactive diluent must be used together in order to make the composition exhibit photocurability. The ethylenically unsaturated double bond is preferably derived from acrylic acid or methacrylic acid or derivatives thereof.

Specific examples of the carboxyl group-containing resin include compounds listed below (which may be oligomers or polymers).

(1) A carboxyl group-containing resin having an aromatic ring obtained by copolymerization of an unsaturated carboxylic acid such as (meth)acrylic acid with an unsaturated group-containing compound such as styrene or α-methylstyrene . In this case, at least one of the unsaturated group-containing compound and the unsaturated carboxylic acid may contain an aromatic ring.

(2) Diisocyanates such as aliphatic diisocyanate, branched aliphatic diisocyanate, alicyclic diisocyanate, aromatic diisocyanate, etc., and carboxyl group-containing diisocyanate such as dimethylol propionic acid, dimethylol butyric acid, etc. Polyol compounds and polycarbonate-based polyols, polyether-based polyols, polyester-based polyols, polyolefin-based polyols, acrylic-based polyols, bisphenol A-based alkylene oxide adduct diols, phenolic hydroxyl groups Carboxyl group-containing urethane resin obtained by addition polymerization of diol compounds such as compounds with alcoholic hydroxyl groups. When this carboxyl group-containing urethane resin has an aromatic ring, at least one of diisocyanate, carboxyl group-containing diol compound, and diol compound should just contain an aromatic ring.

(3) Diisocyanate compounds such as aliphatic diisocyanate, branched aliphatic diisocyanate, alicyclic diisocyanate, aromatic diisocyanate, etc., and polycarbonate polyol, polyether polyol, polyester polyol Addition polymerization of diol compounds such as alcohols, polyolefin polyols, acrylic polyols, bisphenol A-based alkylene oxide adduct diols, phenolic hydroxyl groups, and compounds with alcoholic hydroxyl groups. The terminal carboxyl group-containing urethane resin is formed by reacting acid anhydride at the end of the formate resin. When this carboxyl group-containing urethane resin has an aromatic ring, at least one of a diisocyanate compound, a diol compound, and an acid anhydride may contain an aromatic ring.

(4) By diisocyanate, bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenol type epoxy resin The photosensitive carboxyl group-containing epoxy resin obtained from the addition polymerization reaction of (meth)acrylate of bifunctional epoxy resin such as biphenol type epoxy resin or its partial anhydride modification, carboxyl group-containing dihydric alcohol compound and diol compound Urethane resin. When the photosensitive carboxyl group-containing urethane resin has an aromatic ring, diisocyanate, (meth)acrylate of bifunctional epoxy resin or its partial anhydride modification, carboxyl group-containing diol compound and diol compound It is sufficient that at least one of them contains an aromatic ring.

(5) In bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, bixylenol type Diol compounds are added to bifunctional epoxy resins such as epoxy resins and biphenolic epoxy resins, and glycidyl groups are further added to urethane epoxy resins obtained by adding diisocyanate compounds. The (meth)acrylate reaction is a carboxyl-terminal-containing urethane resin obtained by reacting an acid anhydride at the end of the urethane epoxy (meth)acrylate resin obtained by this reaction. When the terminal carboxyl group-containing urethane resin has an aromatic ring, at least one of bifunctional epoxy resin, diol compound, diol compound, diisocyanate compound, and acid anhydride may contain an aromatic ring.

(6) In bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, bixylenol type For bifunctional epoxy resins such as epoxy resins and biphenol-type epoxy resins, react monocarboxylic acids having ethylenically unsaturated groups, and add diisocyanate compounds to the obtained epoxy carboxylate compounds A carboxyl group-containing urethane resin obtained from a carboxyl group-containing diol compound such as 2,2-bis(dimethylol)-propionic acid. When this carboxyl group-containing urethane resin has an aromatic ring, at least one of a bifunctional epoxy resin, a monocarboxylic acid and a diisocyanate compound, and a carboxyl group-containing diol compound may contain an aromatic ring.

(7) Carboxyl group-containing urethane resin whose terminal is oxidized by (meth)propylene, which is used in the synthesis of the above-mentioned resin (2) or (4), in hydroxyalkyl (meth)acrylate, etc. A compound having one hydroxyl group and one or more (meth)acryloyl groups is added to the molecule. When the photosensitive carboxyl group-containing urethane resin has an aromatic ring, the compound having one hydroxyl group and one or more (meth)acryl groups in the molecule may contain an aromatic ring.

(8) A carboxyl-containing urethane resin whose terminal is oxidized by (meth)propylene, which is prepared by adding isophorone diisocyanate and pentaerythritol triacrylic acid during the synthesis of the above resin (2) or (4). Compounds having one isocyanate group and one or more (meth)acryloyl groups in the molecule, such as equimolar reactants of esters. When the photosensitive carboxyl group-containing urethane resin has an aromatic ring, the compound having one isocyanate group and one or more (meth)acryl groups in the molecule may contain an aromatic ring.

(9) React (meth)acrylic acid with a multifunctional epoxy resin, and add dihydrophthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, etc. to the hydroxyl groups present in the side chain. Photosensitive carboxyl-containing resin of acid anhydride. When the photosensitive carboxyl group-containing resin has an aromatic ring, at least one of the polyfunctional epoxy resin and the dibasic acid anhydride may contain an aromatic ring.

(10) The hydroxyl group of the bifunctional epoxy resin is reacted with (meth)acrylic acid in a multifunctional epoxy resin epoxidized with epichlorohydrin in only one step, and the photosensitive carboxyl group of dibasic acid anhydride is added to the generated hydroxyl group of resin. When the photosensitive carboxyl group-containing resin has an aromatic ring, at least one of the bifunctional epoxy resin and the dibasic acid anhydride may contain an aromatic ring.

(11) A polyfunctional oxetane resin is reacted with a dicarboxylic acid, and the carboxyl group of the dibasic acid anhydride is added to the generated primary hydroxyl group to a polyester resin containing a dibasic acid. When the photosensitive carboxyl group-containing polyester resin has an aromatic ring, at least one of the polyfunctional oxetane resin, dicarboxylic acid, and dibasic acid anhydride may contain an aromatic ring.

(12) The reaction product obtained by reacting a compound having multiple phenolic hydroxyl groups in one molecule with alkylene oxides such as ethylene oxide and propylene oxide is reacted with an unsaturated group-containing monocarboxylic acid, and obtained The reaction product is a carboxyl group-containing photosensitive resin obtained by reacting polybasic acid anhydride.

(13) 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 is reacted with an unsaturated group-containing monocarboxylic acid, and A carboxyl group-containing photosensitive resin is obtained by reacting polybasic acid anhydride with the obtained reaction product.

(14) Epoxy compounds having multiple epoxy groups in one molecule, compounds having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule such as p-hydroxyphenethyl alcohol, and (meth)acrylic acid For the reaction of monocarboxylic acids containing unsaturated groups such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, adipic acid, etc. Carboxyl group-containing photosensitive resin obtained by the reaction of polybasic anhydrides. The photosensitive carboxyl group contains the case where the polyester resin has an aromatic ring, among epoxy compounds, compounds having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule, unsaturated group-containing monocarboxylic acids and polybasic acid anhydrides At least one of them has only to contain an aromatic ring.

(15) In any one of the above (1)~(12) resins, glycidyl (meth)acrylate, α-methylglycidyl (meth)acrylate, etc. are further added to the molecule A photosensitive carboxyl-containing resin composed of a compound having one epoxy group and one or more (meth)acryl groups. When the photosensitive carboxyl-containing urethane resin has an aromatic ring, a compound having one epoxy group and one or more (meth)acryl groups in the molecule may have an aromatic ring.

(16) A photosensitive carboxyl group-containing resin obtained by reacting a compound having an oxirane ring and an ethylenically unsaturated group in one molecule of a carboxyl group-containing (meth)acrylic copolymer resin .

(17) A compound having one epoxy group and an unsaturated double bond in each molecule, and a copolymer of the unsaturated double bonds of each compound having an unsaturated double bond, the unsaturated monocarboxylic acid The reaction is to react saturated or unsaturated polybasic acid anhydride on the generated second-stage hydroxyl group to obtain a photosensitive carboxyl-containing resin.

(18) After reacting a saturated or unsaturated polybasic acid anhydride in a hydroxyl-containing polymer, react a compound having an epoxy group and an unsaturated double bond in each molecule of the resulting carboxylic acid to obtain a compound containing Photosensitive hydroxyl and carboxyl resins.

As the carboxyl group-containing resin mentioned above has multiple carboxyl groups in the main chain and side chain of the polymer, it can be developed by an aqueous alkali solution.

Also, among the above-mentioned resins, among the resins exemplified in (1) or the resins exemplified in (2) to (10), it is preferable to use a carboxyl group-containing resin having an aromatic ring. Among these resins, the resins exemplified in (2)~(8) and (10) are more preferable, and the resins exemplified in (2)~(8) are more preferable.

The phenolic hydroxyl group-containing resin is not particularly limited as long as it has a phenolic hydroxyl group in the main chain or a side chain, that is, has a hydroxyl group bonded to a benzene ring. It is preferably a resin containing two or more phenolic hydroxyl groups in one molecule. Examples of resins containing two or more phenolic hydroxyl groups in one molecule include catechol, resorcinol, hydroquinone, dihydroxytoluene, naphthalenediol, t-butyrocatechol, and t-butylhydroquinone , pyrogallol, phloroglucinol, bisphenol A, bisphenol F, bisphenol S, bisphenol, bis-xylenol, novolac type phenol resin, novolak type alkylphenol resin, bisphenol A novolac Varnish resins, dicyclopentadiene-type phenolic resins, new phenolic (Xylok)-type phenolic resins, terpene-modified phenolic resins, polyvinylphenols, condensates of phenols and aromatic aldehydes with phenolic hydroxyl groups, 1 -Naphthol or condensates of 2-naphthol and aromatic aldehydes, etc., but not limited thereto.

In addition, the acid dissociation constant (pKa) of the alkali-soluble resin in the ethylene glycol butyl ether solution at 25°C is less than 9.5 because it can have a higher resolution of the coating film after formal hardening It is preferable from the viewpoint of contamination of the developing solution in the developing step. In addition, when the alkali-soluble resin is a mixture of two or more alkali-soluble resins combined, the pKa of the mixture (all the alkali-soluble resins) is less than 9.5. The value of pKa is preferably 7.5-9.4, more preferably 8.2-9.0.

The alkali-soluble resin may or may not have an aromatic ring in its structure, but is preferably an alkali-soluble resin having an aromatic ring. Especially preferred is an alkali-soluble resin with a bisphenol structure.

Also, the alkali-soluble resin having a urethane bond is preferable from the viewpoint of further suppressing the contamination of the developing solution in the developing step and the clogging of the developing device due to deposits. That is, in the case of imparting developability, for example, in the case of an alkali-soluble resin having a urethane bond, even if an alkaline developer is used for development, the generation of development residue is suppressed regardless of the concentration of Na ₂ CO ₃ , The resolution is also good. Regarding the suppression of development residue, the urethane bond system has high wettability with other components, and as a result, it is considered that deposits are difficult to form even if the drying conditions are changed. On the other hand, since the development is carried out by a dilute alkaline aqueous solution, it is possible to form an image with less damage to the exposed area. In addition, in the exposed area and the unexposed area, the dissolution of the alkaline developer is compared. As a result of the improvement, it is presumed that the analysis property becomes good. However, this is purely speculative and the invention is not bound by this theory.

The acid value of the above-mentioned alkali-soluble resin is desirably in the range of 20-200 mgKOH/g, more preferably in the range of 40-180 mgKOH/g, still more preferably in the range of 50-160 mgKOH/g. If it is in the range of 20~200mgKOH/g, the adhesion of the coating film after the main hardening is obtained, the alkali development system becomes easy, the dissolution of the exposed part caused by the developer is suppressed, and the line system is maintained more than required Since drawing of a normal resist pattern becomes easy without becoming too thin, it is preferable. Moreover, since the contrast between the development resistance of an exposed part and the developability of an unexposed part can be maintained, and resolution is good, it is preferable.

Also, the weight average molecular weight of the alkali-soluble resin used in the present invention is preferably in the range of 2,000 to 150,000, although it varies depending on the resin skeleton. If it is within this range, the non-adhesive property is good, the moisture resistance of the coating film after exposure is good, and film reduction hardly occurs during image development. Moreover, if it exists in the range of the said weight average molecular weight, resolution improves, developability becomes favorable, and storage stability also becomes favorable. More preferably, it is 5,000~100,000. In addition, the weight average molecular weight can be calculated|required by the gel permeation chromatography (GPC) method (polystyrene standard). Also, when the photosensitive resin composition contains two or more alkali-soluble resins, it is preferable that each resin is within the above-mentioned range, but the measurement is performed in a state where the respective resins are mixed, and it is also preferably within the above-mentioned range.

The glass transition temperature of the alkali-soluble resin is preferably in the range of -10 to 60°C. When the temperature is above -10℃, no stickiness is better. When the temperature is lower than 60°C, the crack resistance becomes better. More preferably, it is 0-40°C. In addition, the glass transition temperature of the alkali-soluble resin can be obtained by measuring the differential scanning calorimeter (DSC) of the photosensitive component. In addition, when two or more alkali-soluble resins are contained in the photosensitive resin composition, it is preferable that each resin is within the above-mentioned range, but the measurement is performed in a state where the respective resins are mixed, and it is preferably within the above-mentioned range. When the measurement is performed in a state in which the resins are mixed, it is preferable to measure in a state in which the resins are uniformly stirred in a paint state.

The appropriate blending amount of such an alkali-soluble resin can be appropriately adjusted depending on the application of the photosensitive resin composition. For example, when used as an insulating resin composition like a solder resist, the blending amount of the alkali-soluble resin is 10 to 60% by mass, preferably 15 to 50% by mass, in terms of solid content in the entire composition. On the other hand, when used as a conductive resin composition, the blending amount of the alkali-soluble resin is 5 to 50% by mass, preferably 5 to 40% by mass, of the entire composition in terms of solid content. When the blending amount of the alkali-soluble resin is within the above-mentioned range, the strength of the coating film after main curing will not be lowered, and the thickening of the composition and the decrease in coating properties can be suppressed.

The photosensitive resin composition of the present invention may contain arbitrary components as components other than the alkali-soluble resin. Hereinafter, arbitrary components will be described in detail.

[Photopolymerization initiator] The photosensitive resin composition of the present invention may contain a photopolymerization initiator. The photopolymerization initiator is not particularly limited, and examples thereof include bis-(2,6-dichlorobenzoyl)phenylphosphine oxide, bis-(2,6-dichlorobenzoyl) -2,5-Dimethylphenylphosphine oxide, bis-(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-(2,4,6-tri Bisacylphosphine oxides such as methylbenzoyl)-phenylphosphine oxide; 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide Phenylphosphine oxide, methyl 2,4,6-trimethylbenzoylphenylphosphonate, 2-methylbenzoyldiphenylphosphine oxide, isopropyl pivalylphenylphosphonate Monoacyl phosphine oxides such as base esters, 2,4,6-trimethylbenzoyldiphenylphosphine oxide; 1-hydroxy-cyclohexyl phenyl ketone, 1-[4-(2-hydroxyethyl Oxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl )-benzyl]phenyl}-2-methyl-propane-1-one, 2-hydroxy-2-methyl-1-phenylpropane-1-one and other hydroxyacetophenones; benzoin, benzyl Benzoin esters, benzoin methyl ether, benzoin ethyl ether, benzoin n-propyl ether, benzoin isopropyl ether, benzoin n-butyl ether, etc.; benzoin alkyl ethers; benzophenone, p-methyl ether Benzophenones such as methylbenzophenone, Michler's ketone, methylbenzophenone, 4,4'-dichlorobenzophenone, 4,4'-bisdiethylaminobenzophenone, etc. class; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-Hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinyl-1-propanone, 2-benzyl-2-dimethylamine -1-(4-morpholinophenyl)-butanone-1,2-(dimethylamine)-2-[(4-methylphenyl)methyl)-1-[4-(4- Acetophenones such as morphoyl)phenyl]-1-butanone, N,N-dimethylaminoacetophenone, etc.; thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthene Thioxanthones such as ketones, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone, etc.; anthracene Quinone, chloroanthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, 2-aminoanthraquinone, etc. Anthraquinones; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; ethyl-4-dimethylamine benzoate, 2-(dimethylamine) ethyl Benzoic acid esters, benzoic acid esters such as ethyl p-dimethylbenzoate; 1,2-octanedione, 1-[4-(phenylthio)- , 2-(O-benzoyl oxime ester)], ethyl ketone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, Oxime esters such as 1-(O-acetyl oxime ester); bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrole -1-yl)phenyl)titanium, bis(cyclopentadienyl)-bis[2,6-difluoro-3-(2-(1-pyrrol-1-yl)ethyl)phenyl]titanium, etc. Titanocenes; Phenyl disulfide 2-Nitrofen, Buterin, Anisoin ethyl ether, Azobisisobutyronitrile, Tetramethylthiuram disulfide, etc. All of the above photopolymerization initiators may be used alone or in combination of two or more.

As commercially available products, examples of commercially available photopolymerization initiators of phosphine oxides such as bisacyl phosphine oxides and monoacyl phosphine oxides include IRGACURE TPO manufactured by BASF JAPAN, and IRGACURE TPO manufactured by IGM Resins. Omnirad 819 et al. Moreover, as a commercial item of the photoinitiator of acetophenone series, BASF JAPAN company make IRGACURE 369, IRGACURE 379EG, IGM Resins company make Omnirad 907, etc. are mentioned. In addition, examples of commercially available photopolymerization initiators of oxime esters include CGI-325, IRGACURE OXE01, IRGACURE OXE02 manufactured by BASF JAPAN, N-1919 manufactured by ADEKA, NCI-831, Nippon Chemical Industry Co., Ltd. TOE-004 made by the company, TR-PBG-304 made by Changzhou Qiangli Electronic New Material Co., Ltd., etc.

The blending amount of the photopolymerization initiator is not particularly limited, but the blending amount in the case of using an oxime ester-based photopolymerization initiator is preferably in terms of solid content relative to 100 parts by mass of the alkali-soluble resin. It is 0.01-10 mass parts, More preferably, it is the range of 0.1-5 mass parts. By setting this at 0.01 parts by mass or more, it is preferable from the viewpoint that the photocurability on copper becomes more reliable, and the coating film characteristics after main curing such as chemical resistance improve. Moreover, by setting it as 5 mass parts or less, it is preferable from a viewpoint that the light absorption by the surface of a coating film after exposure can be suppressed, and the curability of a deep part improves.

On the other hand, the content of photopolymerization initiators other than oxime ester-based photopolymerization initiators is, in terms of solid content, preferably 0.1 to 30 parts by mass, more preferably 0.5 parts by mass, based on 100 parts by mass of the alkali-soluble resin. ~25 parts by mass, more preferably in the range of 1-15 parts by mass. It is preferable from viewpoints, such as photocurability and chemical resistance, as it is 0.1 mass part or more. On the other hand, if it is 30 mass parts or less, it is preferable from the viewpoint that the light absorption of the coating film surface after full hardening by a photoinitiator can be controlled, and the curability of a deep part also improves.

[Filler] The photosensitive resin composition of the present invention may contain a filler. The filler system is not particularly limited, and known and commonly used inorganic or organic fillers can be used. The purpose of blending the filler is not particularly limited, and may be for improving the physical strength of the coating film after main hardening. When imparting conductivity, it is preferable to use a conductive filler, and when the photosensitive resin composition of the present invention is used for the formation of an insulating layer, it is preferable to use an insulating filler.

As the material of the conductive filler, any filler that imparts conductivity to the photosensitive resin composition of the present invention can be used. Examples of such conductive fillers include Ag, Au, Pt, Pd, Ni, Cu, Al, Sn, Pb, Zn, Fe, Ir, Os, Rh, W, Mo, Ru, and the like. Ag is preferred. These conductive fillers can be used in the form of the above components alone, but can also be used in the form of alloys or oxides. In addition, tin oxide (SnO ₂ ), indium oxide (In ₂ O ₃ ), ITO (Indium Tin Oxide), and the like can also be used. In addition, carbon powder such as carbon black, graphite, and carbon nanotubes may be used as the conductive filler. However, caution is required because the light transmittance decreases.

Although the shape of the conductive filler is not particularly limited, it is preferably in the form of flakes, especially in the form of needles or spheres. Thereby, the light transmittance is improved, and a conductive circuit or an electrode with excellent resolution can be formed.

The conductive filler is for forming fine wires, so the maximum particle diameter is preferably 30 μm or less. By making the maximum particle size 30 μm or less, the resolution of the conductive circuit or the electrode is improved.

In addition, the particle size of the conductive filler is the average particle size of 10 random conductive fillers observed at 10,000 times using an electron microscope (SEM), and the range is preferably 0.1-10 μm. The average particle diameter is preferably 0.1 μm or more from the viewpoint of conductivity. On the other hand, an average particle diameter of 10 μm or less is preferable from the viewpoint of preventing clogging of screen meshes. In addition, among the average particle diameters measured by Microtrac, it is preferable to use those with a size of 0.5 to 3.5 μm. The intrinsic volume resistivity (JIS K 6911) of the conductive filler is preferably 10 ^-3 Ω·cm or less.

The insulating filler preferably has insulating properties with a specific volume resistivity (JIS K 6911) of 10 ¹⁰ Ω·cm or more. Examples of insulating fillers include silicon dioxide such as amorphous silica, fused silica, and spherical silica, barium sulfate, hydrotalcite, talc, clay, magnesium carbonate, calcium carbonate, oxide Aluminum, titanium oxide, aluminum hydroxide, silicon nitride, aluminum nitride, boron nitride, Neuburg silica particles, etc.

The fillers can be used alone or in combination of two or more.

The appropriate blending amount of the filler can be appropriately adjusted according to the application of the photosensitive resin composition. For example, when used as an insulating resin composition like a solder resist, the blending amount of the insulating filler is based on solid content conversion, and is preferably 50 to 500 parts by mass, more preferably 100~300 parts by mass. It is preferable from the viewpoint of printability that the compounding quantity of an insulating filler is 50 mass parts or more. Moreover, it is preferable that the compounding quantity of an insulating filler is 500 mass parts or less from a viewpoint of printability and light transmittance. On the other hand, when used as a conductive resin composition, the blending amount of the conductive filler is preferably 700 to 1300 parts by mass in terms of solid content relative to 100 parts by mass of the alkali-soluble resin. It is preferable that the compounding quantity of a conductive filler is 700 mass parts or more from a viewpoint of conductivity. Moreover, it is preferable that the compounding quantity of a conductive filler is 1300 mass parts or less from a viewpoint of printability and light transmittance.

(Reactive diluent) The photosensitive resin composition of the present invention can effectively cross-link with light, so it may also contain a reactive diluent. As reactive diluents, (meth)acrylate compounds are preferably used. Also, the reactive diluent is preferably bifunctional or more, that is, preferably polyfunctional. The reason why it is preferable to be polyfunctional is that the photoreactivity is improved and the resolution is excellent compared to the case where the number of functional groups is one. In addition, in the patent specification of the present invention, the so-called (meth)acrylate is a term collectively referring to acrylate and methacrylate, and other similar expressions are also the same.

Examples of (meth)acrylate compounds include polyfunctional (meth)acrylate monomers or oligomers (difunctional or more functional (meth)acrylate monomers or oligomers), and specifically, for example, Commonly known polyester (meth)acrylate, polyether (meth)acrylate, urethane (meth)acrylate, carbonate (meth)acrylate, epoxy (meth)acrylate, etc. ) acrylate, etc. Specifically, hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; diols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol Acrylic esters; Acrylamides such as N,N-dimethylacrylamide, N-methylolacrylamide, N,N-dimethylaminopropylacrylamide, etc.; N,N-dimethylacrylamide Aminoalkyl acrylates such as N,N-dimethylaminopropyl acrylamide and N,N-dimethylaminopropyl acrylamide; hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tri-hydroxyethyliso Polyvalent alcohols such as cyanurate or polyvalent acrylates such as ethylene oxide adducts, propylene oxide adducts, or ε-caprolactone adducts; phenoxyacrylic acid esters, bisphenol A diacrylate, and polyvalent acrylates such as ethylene oxide adducts or propylene oxide adducts of these phenols; propylene glycol diglycidyl ester, propylene glycol triglycidyl Polyvalent acrylates of glycidyl esters such as trimethylolpropane triglycidyl ester, triglycidyl isocyanurate, etc.; not limited to the foregoing, but also polyether Direct acrylated polyols such as polyols, polycarbonate diols, hydroxyl-terminated polybutadiene, polyester polyols, or acrylated urethane acrylated by diisocyanate and Melamine acrylate, at least one of methacrylates corresponding to the aforementioned acrylates, and the like.

In addition, it is also possible to use polyfunctional epoxy resins such as cresol novolak type epoxy resins, epoxy acrylate resins that react acrylic acid, or further use epoxy acrylate resins such as pentaerythritol triacrylate on the hydroxyl groups of the epoxy acrylate resins. Epoxyurethane acrylate compound in which hydroxyacrylate is reacted with hemiurethane compound of diisocyanate such as isophorone diisocyanate, and each methacrylate resin or compound corresponding to the aforementioned acrylate, etc. Used as a reactive diluent. Such an epoxy acrylate resin system can improve photocurability without reducing dryness to touch.

Among them, it is preferable to use a multi-functional (meth)acrylate monomer system, especially a tetrafunctional (meth)acrylate monomer system. Examples of tetrafunctional (meth)acrylate monomers include pentaerythritol tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, and urethane (meth)acrylate, among which , For the same reason as the alkali-soluble resin, one having a urethane bond, that is, a urethane (meth)acrylate type is preferable. As the urethane (meth)acrylate, any one having a urethane bond may be used, for example, one represented by the following formula (I) may be mentioned.

In the above formula (I), Z ¹ represents an alkylene group, R ¹ represents a hydrogen atom, R ² represents a methyl group, R ³ and R ⁴ represent a hydrogen atom or a methyl group independently, but R ³ and R At least one of ⁴ represents a methyl group.

As the above-mentioned tetrafunctional urethane (meth)acrylate, urethane (meth)acrylate or ester (meth)acrylate in which acrylic acid and methacrylic acid are 1:1 is preferable.

Urethane (meth)acrylate or ester (meth)acrylate as such a four-functional group is, for example, added acrylic acid to glycidyl methacrylate, and the hydroxyl group produced at this time is combined with two Those reacting with isocyanate or dicarboxylic acid are preferred.

The reactive diluents can be used alone or in combination of two or more.

The appropriate blending amount of the reactive diluent can be appropriately adjusted according to the application of the photosensitive resin composition. For example, when it is used as an insulating resin composition like a solder resist, the blending amount of the reactive diluent is based on the solid content, and is preferably 1 to 30 parts by mass, more preferably 100 parts by mass of the alkali-soluble resin. 2~20 parts by mass. In the case of 1 part by mass or more, photocurability is good, and in alkali image development after active energy ray irradiation, it is easy to form lines of a pattern. Moreover, when it is 30 mass parts or less, the solubility with respect to an aqueous alkali solution is favorable, and a pattern film system is hard to become fragile. On the other hand, when used as a conductive resin composition, the blending amount of the reactive diluent is based on solid content, and is preferably 1 to 40 parts by mass, more preferably 5 parts by mass, relative to 100 parts by mass of the alkali-soluble resin. ~40 parts by mass. In the case of 1 part by mass or more, photocurability is good, and in alkali image development after active energy ray irradiation, it is easy to form lines of a pattern. When it is 40 parts by mass or less, the solubility to an aqueous alkali solution is good, and the patterned film is less likely to become fragile.

(Thermosetting Components) The photosensitive resin composition of the present invention may further contain a thermosetting component because the crack resistance is further improved. As the thermosetting component used in the present invention, amine resins such as melamine resins and benzoguanamine resins, blocked isocyanate compounds, cyclocarbonate compounds, polyfunctional epoxy compounds, polyfunctional oxetane compounds, Known and commonly used thermosetting resins such as episulfide resins and melamine derivatives. A thermosetting component can be used individually by 1 type or in combination of 2 or more types. In the present invention, a thermosetting component having at least one selected from two or more cyclic ether groups and cyclic thioether groups (hereinafter, simply referred to as cyclic (thio)ether groups) in the molecule, or , A thermosetting component having two or more isocyanate groups or blocked isocyanate groups in one molecule is preferred.

Thermosetting components with more than 2 cyclic (thio) ether groups in the molecule are cyclic ether groups with 3, 4 or 5-membered rings in the molecule, or any one or two of cyclic thioether groups Compounds of the above two types of groups, for example, compounds having at least 2 or more epoxy groups in the molecule, that is, polyfunctional epoxy compounds, compounds having at least 2 or more oxetanyl groups in the molecule , that is, polyfunctional oxetane compounds, compounds with more than two sulfide groups in the molecule, that is, episulfide resins, etc.

Examples of polyfunctional epoxy compounds include jER828, jER834, jER1001, jER1004 manufactured by Mitsubishi Chemical Corporation, EPICLON 840, EPICLON 850, EPICLON 1050, EPICLON 2055 manufactured by DIC Corporation, Nippon Steel & Sumitomo Metal Co., Ltd. EPOTOHTO YD-011, YD-013, YD-127, YD-128 manufactured by the company, D.E.R.317, D.E.R.331, D.E.R.661, D.E.R.664 manufactured by The Dow Chemical Company, Sumi-Epoxy ESA- manufactured by Sumitomo Chemical Co., Ltd. 011, ESA-014, ELA-115, ELA-128, bisphenol A epoxy resins such as A.E.R.330, A.E.R.331, A.E.R.661, A.E.R.664 manufactured by Asahi Kasei Industries, Ltd.; jERYL903, DIC manufactured by Mitsubishi Chemical Corporation EPICLON 152, EPICLON 165 manufactured by a joint-stock company, EPOTOHTO YDB-400, YDB-500 manufactured by Nippon Steel & Sumitomo Metal Co., Ltd., D.E.R.542 manufactured by Dow Chemical Company, Sumi-Epoxy ESB-400 manufactured by Sumitomo Chemical Industries, Ltd., Brominated epoxy resins such as ESB-700, A.E.R.711 and A.E.R.714 manufactured by Asahi Kasei Industries Co., Ltd.; jER152 and jER154 manufactured by Mitsubishi Chemical Co., Ltd.; D.E.N.431 and D.E.N.438 manufactured by Dow Chemical Co., Ltd.; EPICLON N-730, EPICLON N-770, EPICLON N-865, EPOTOHTO YDCN-701, YDCN-704 manufactured by Nippon Steel & Sumitomo Metal Corporation, EPPN-201 manufactured by Nippon Kayaku Co., Ltd., EOCN-1025, EOCN-1020 , EOCN-104S, RE-306, Sumi-Epoxy ESCN-195X, ESCN-220 manufactured by Sumitomo Chemical Industries, Ltd., A.E.R.ECN-235, ECN-299 manufactured by Asahi Kasei Industries, Ltd., etc. Novolac-type epoxy resins; Epiclon 830 manufactured by DIC Co., Ltd., jER807 manufactured by Mitsubishi Chemical Co., Ltd., EPOTOHTO YDF-170, YDF-175, YDF-2004 manufactured by Nippon Steel & Sumitomo Metal Co., Ltd. and other bisphenol F epoxy resins; Hydrogenated bisphenol A type epoxy resins such as EPOTOHTO ST-2004, ST-2007, ST-3000 manufactured by a joint-stock company; jER604 manufactured by Mitsubishi Chemical Co., Ltd., EPOTOHTO YH-434 manufactured by Nippon Steel & Sumitomo Metal Co., Ltd., Sumitomo Chemical Industrial AG Glycidylamine-type epoxy resins such as Sumi-Epoxy ELM-120 manufactured by the company; hydantoin-type epoxy resins; alicyclic epoxy resins such as CELLOXIDE 2021P manufactured by Daicel Co., Ltd.; Mitsubishi Chemical Corporation YL-933 manufactured by Dow Chemical Co., Ltd., T.E.N., EPPN-501, EPPN-502, etc. Trishydroxyphenylmethane-type epoxy resins; YL-6056, YX-4000, YL-6121 manufactured by Mitsubishi Chemical Co., Ltd. Bixylenol-type or biphenol-type epoxy resins or mixtures thereof; EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by ADEKA Co., Ltd., EXA-1514 manufactured by DIC Co., Ltd., etc. Bisphenol S-type epoxy resins; bisphenol A novolak-type epoxy resins such as jER157S manufactured by Mitsubishi Chemical Corporation; tetraphenol ethane-type epoxy resins such as jERYL-931 manufactured by Mitsubishi Chemical Corporation; Nissan Chemical Co., Ltd. Heterocyclic epoxy resins such as TEPIC manufactured by Industrial Co., Ltd.; Diglycidyl phthalate resins such as BLENMER DGT manufactured by NOF Co., Ltd.; ZX-1063 manufactured by Nippon Steel & Sumitomo Metal Co., Ltd., etc. Tetraglycidyl xylenyl ethane resin; ESN-190, ESN-360 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., HP-4032, EXA-4750, EXA-4700 manufactured by DIC Co., Ltd., etc. Naphthyl epoxy resins; epoxy resins having a dicyclopentadiene skeleton such as HP-7200 and HP-7200H manufactured by DIC Co., Ltd.; glycidyl epoxy resins such as CP-50S and CP-50M manufactured by NOF Corporation Methacrylate copolymerized epoxy resin; further copolymerized epoxy resin of cyclohexylmaleimide and epoxypropyl methacrylate; epoxy modified polybutadiene rubber derivatives (such as Daicel EPL PB-3600 manufactured by a joint-stock company), CTBN modified epoxy resin (such as YR-102, YR-450 manufactured by Nippon Steel Sumitomo Metal Chemical Co., Ltd.), etc., but not subject to these restrictions. These epoxy resins can be used individually by 1 type or in combination of 2 or more types. Among these, novolak-type epoxy resins, heterocyclic epoxy resins, bisphenol A-type epoxy resins, or mixtures thereof are preferred.

Furthermore, it may have a methyl group or a fennel skeleton from the viewpoint of making it easy to adjust the value of the contact angle of the dried coating film to a constant value. As the epoxy resin having a methyl group, any one having a methyl group may be used, for example, one represented by the following formula (II) may be mentioned. In the following formula (II), the number of n is preferably 5-10.

On the other hand, any epoxy resin having a fennel skeleton may be used, for example, those represented by the following formula (III) may be mentioned.

Examples of polyfunctional oxetane compounds include bis[(3-methyl-3-oxetanemethoxy)methyl]ether, bis[(3-ethyl-3-oxetane Cyclobutanemethoxy)methyl]ether, 1,4-bis[(3-methyl-3-oxetanemethoxy)methyl]benzene, 1,4-bis[(3-ethane Base-3-oxetanemethoxy)methyl]benzene, (3-methyl-3-oxetane)methacrylate, (3-ethyl-3-oxetane ) methacrylate, (3-methyl-3-oxetane) methyl methacrylate, (3-ethyl-3-oxetane) methyl methacrylate or the like In addition to polyfunctional oxetanes such as oligomers or copolymers, oxetanol, and novolac resins, poly(p-hydroxystyrene), cardo-type bisphenols, calixarene Etherification of resins with hydroxyl groups such as calix resorcinol aromatic hydrocarbons, silsesquioxane, etc. Other examples include copolymers of unsaturated monomers having an oxetane ring and alkyl (meth)acrylates, and the like.

Examples of episulfide resins having two or more cyclic thioether groups in the molecule include bisphenol A episulfide resin YL7000 manufactured by Mitsubishi Chemical Corporation. In addition, using the same synthesis method, an episulfide resin in which an oxygen atom of an epoxy group of a novolak-type epoxy resin is substituted by a sulfur atom can also be used.

Also, in the photosensitive resin composition of the present invention, in order to improve the curability of the photosensitive resin composition and the toughness of the obtained cured film, it is preferable to add an isocyanate group having two or more isocyanate groups in one molecule, or a blocked isocyanate base compound. Such compounds having two or more isocyanate groups or blocked isocyanate groups in one molecule include compounds having two or more isocyanate groups in one molecule, that is, polyisocyanate compounds, or compounds having two or more isocyanate groups in one molecule. The above compounds with blocked isocyanate groups, that is, blocked isocyanate compounds and the like.

As the polyisocyanate compound, for example, aromatic polyisocyanate, aliphatic polyisocyanate or alicyclic polyisocyanate can be used. Specific examples of aromatic polyisocyanates include 4,4'-diphenylmethane diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, naphthyl-1,5-diisocyanate, o-stubble diisocyanate, m-stubble diisocyanate and 2,4-toluene dimer. Specific examples of aliphatic polyisocyanates include tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-methylene bis (cyclohexyl isocyanate) and isophorone diisocyanate. As a specific example of alicyclic polyisocyanate, dicycloheptane triisocyanate is mentioned. And the adduct body, diurea body, and isocyanurate body of the isocyanate compound mentioned above are mentioned.

The blocked isocyanate group contained in the blocked isocyanate compound is protected by the reaction of the isocyanate group with a blocking agent, and temporarily becomes an inert group. When heated to the set temperature, the blocking agent dissociates to generate isocyanate groups.

As the blocked isocyanate compound, an addition reaction product of an isocyanate compound and an isocyanate blocking agent can be used. Isocyanurate type, diurea type, addition type, etc. are mentioned as an isocyanate compound which can react with a blocking agent. As this isocyanate compound, for example, the same aromatic polyisocyanate, aliphatic polyisocyanate, or alicyclic polyisocyanate as described above can be used.

As the isocyanate blocking agent, for example, phenolic blocking agents such as phenol, cresol, xylenol, chlorophenol, and ethylphenol; ε-caprolactam, δ-valerolactamide, γ - Lactamide-based blocking agents such as butyrolactam and β-propiolactamide; active methylene-based blocking agents such as acetylacetate and acetylacetone; methanol, ethanol, propanol, butyl Alcohol, Amyl Alcohol, Ethylene Glycol Monomethyl Ether, Ethylene Glycol Monoethyl Ether, Ethylene Glycol Monobutyl Ether, Diethylene Glycol Monomethyl Ether, Propylene Glycol Monomethyl Ether, Benzyl Ether, Glycol Alcohol-based blocking agents such as methyl ester, butyl glycolate, diacetone alcohol, methyl lactate and ethyl lactate; formaldehyde oxime, acetaldoxime, acetoxime, formaldehyde Oxime ester blockers such as ethyl ethyl ketone oxime, diacetyl monoxime ester, cyclohexane oxime, etc.; butyl mercaptan, hexyl mercaptan, t-butyl mercaptan, thiophenol, methyl thio Thiol-based blocking agents such as phenol and ethylthiophenol; acid amide-based blocking agents such as acetate amide and benzamide; imide-based blocking agents such as succinic imide and maleic imide Blocking agent; amine-based blocking agents such as stubble amine, aniline, butylamine, dibutylamine, etc.; imidazole-based blocking agents such as imidazole, 2-ethylimidazole, etc.; methyleneimine and propyleneimine, etc. imine blocking agent, etc.

Blocked isocyanate compounds may also be commercially available, for example, 7950, 7951, 7960, 7961, 7982, 7990, 7991, 7992 (above, manufactured by Baxenden) Sumidur BL-3175, BL-4165, BL-1100 , BL-1265, Desmodur TPLS-2957, TPLS-2062, TPLS-2078, TPLS-2117, Desmotherm 2170, Desmotherm 2265 (above, manufactured by Sumitomo Bayer Urethane AG), Coronate 2512, Coronate 2513, Coronate 2520 (above, manufactured by Tosoh Co., Ltd.), B-830, B-815, B-846, B-870, B-874, B-882 (made by Mitsui Takeda Chemicals Co., Ltd.), DURANATE TPA-B80E, 17B -60PX, E402-B80T, MF-B60B, MF-K60B, SBN-70D (manufactured by Asahi Kasei Chemicals Co., Ltd.), CURRANTS MOI-BM (manufactured by Showa Denko Co., Ltd.), etc. In addition, Sumidur BL-3175 and BL-4265 are obtained by using methyl ethyl oxime ester as a blocking agent.

The compounds having two or more isocyanate groups or blocked isocyanate groups in one molecule can be used alone or in combination of two or more.

The blending amount of such a compound having two or more isocyanate groups or blocked isocyanate groups in one molecule is based on solid content, preferably 1 to 100 parts by mass, more preferably 1 to 100 parts by mass, based on 100 parts by mass of the alkali-soluble resin It is 2 to 70 parts by mass. If it is 1 part by mass or more, it is preferable from the viewpoint of the toughness of the coating film after full-scale hardening. On the other hand, it is preferable from the viewpoint of storage stability that it is 100 parts by mass or less.

(Organic acid) The photosensitive resin composition of the present invention may also contain an organic acid. For organic acids, its function as a developing aid is also effectively realized. And because it is easy to adjust the contact angle of the dry coating film to a certain value, the components contained in the dissolved photosensitive resin composition will not settle at the bottom of the developer solution, and as a result, the development step can be suppressed. The point of view of liquid pollution or clogging of the screen of the developing device caused by sediment is valid. Among them, if dicarboxylic acid is contained, the above-mentioned remarkable effect can be exhibited, so it is preferable to contain dicarboxylic acid. In particular, it is more preferable to use a photosensitive resin composition as a conductive resin composition because the resistance is low, that is, the conductivity is further improved. Moreover, as an organic acid, the organic acid which does not have an aromatic ring is preferable. By blending an organic acid that does not have an aromatic ring, the light absorption of the organic acid itself is suppressed, and the photoreactivity of the photosensitive component is relatively improved, so that excellent resolution can be obtained.

Specific examples of organic acids include 2,2'-thiodiacetic acid, adipic acid, isobutyric acid, formic acid, citric acid, glutaric acid, acetic acid, oxalic acid, tartaric acid, lactic acid, pyruvic acid, and malonic acid. , butyric acid, malic acid, salicylic acid, benzoic acid, phenylacetic acid, acrylic acid, maleic acid, fumaric acid, crotonic acid and other carboxylic acids; dibutyl phosphite, butyl phosphite, dimethyl phosphite , methyl phosphite, dipropyl phosphite, propyl phosphite, diphenyl phosphite, phenyl phosphite, diisopropyl phosphite, isopropyl phosphite, phosphite-n-methyl-2 - Mono- or diesters of phosphorous acid such as ethylhexyl ester; dibutyl phosphate, butyl phosphate, dimethyl phosphate, methyl phosphate, dipropyl phosphate, propyl phosphate, diphenyl phosphate, phenyl phosphate Mono- or diesters of phosphoric acid such as diisopropyl phosphate, isopropyl phosphate, n-butyl-2-ethylhexyl phosphate, etc. Among them, especially in terms of the contamination of the developer in the developing step or the suppression of the clogging of the developing device caused by sediment, the conductivity and the resolution can produce more excellent effects, preferably 2, 2'-thiodiacetic acid.

The blending amount of the organic acid is preferably in the range of 1 to 10 parts by mass, more preferably 1 to 5 parts by mass, in terms of solid content, based on 100 parts by mass of the alkali-soluble resin. When it is 1 mass part or more, it becomes easy to exhibit the effect as a developing aid, and on the other hand, when it is 10 mass parts or less, resolution becomes better.

(Dispersant) The photosensitive resin composition of the present invention may also contain a dispersant. By blending a dispersant, the dispersibility and sedimentation properties of the photosensitive resin composition can be improved. As a dispersant, DISPERBYK-191 (made by BYK Japan company) is mentioned, for example.

(Photopolymerization inhibitor) The photosensitive resin composition of the present invention may also contain a photopolymerization inhibitor. By adding a photopolymerization inhibitor, it is possible to suppress radical polymerization that occurs inside the photosensitive resin composition due to exposure, and a certain amount of free radical polymerization corresponds to the type of polymerization inhibitor and the amount added.

(Thermosetting catalyst) When the photosensitive resin composition of the present invention contains a thermosetting component having two or more cyclic (thio)ether groups in the molecule, it may also contain a thermosetting catalyst. Examples of such thermosetting catalysts include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, Imidazoles such as 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, etc. Derivatives; dicyandiamide, benzyldimethylamine, 4-(dimethylamine)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine , amine compounds such as 4-methyl-N,N-dimethylbenzylamine, hydrazine compounds such as dihydrazide adipate and dihydrazide sebacate, phosphorus compounds such as triphenylphosphine, etc. In addition, commercially available products include, for example, curezol 2MZ-A, curezol 2P4MHZ, and curezol 2PHZ-PW (all of which are trade names of imidazole-based compounds) manufactured by Shikoku Chemical Industry Co., Ltd. -CAT3503N, U-CAT3502T (all are trade names of blocked isocyanate compounds of dimethylamine), DBU, DBN, U-CATSA102, U-CAT5002 (all are bicyclic amidine compounds and their salts), etc. In particular, without being limited thereto, a thermosetting catalyst for an epoxy resin or an oxetane compound, or one that promotes a reaction between an epoxy group and an oxetane group and a carboxyl group is Yes, they can be used alone or in combination of two or more. In addition, guanamine, acetylguanamine, 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-methylpropene For S-triazine derivatives such as acyloxyethyl-S-triazine and isocyanuric acid adducts, it is preferable to combine these compounds that also function as adhesion imparting agents with the aforementioned thermosetting catalyst Use in combination.

The blending amount of these thermosetting catalysts may be a general amount ratio. For example, in terms of solid content, it is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, based on 100 parts by mass of the alkali-soluble resin. parts by mass.

(Thermal polymerization inhibitor) The photosensitive resin composition of the present invention may also contain a thermal polymerization inhibitor. The thermal polymerization inhibitor can be used to prevent thermal polymerization or time-dependent polymerization of the photosensitive resin composition of the present invention.

(Chain transfer agent) In order to increase the sensitivity, the photosensitive resin composition of the present invention may contain known N-phenylglycine acids, phenoxyacetic acids, thiophenoxyacetic acids, mercaptothiazoles, etc. as chain transfer agents. .

(Organic solvent) The photosensitive resin composition of the present invention may contain an organic solvent in order to obtain a good coating state. As the organic solvent, known and commonly used solvents can be used. As organic solvents, ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; cellosolve (ethylene glycol monoethyl ether), methyl solvent Cellulose agent, butyl cellosolve, carbitol (carbitol), methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether (DPGME), dipropylene glycol dimethyl ether, three Glycol ethers such as propylene glycol monomethyl ether; ethyl acetate, butyl acetate, butyl lactate, cellosolve acetate (ethylene glycol monoethyl ether acetate), butyl cellosolve acetate, Carbitol acetate (diethylene glycol monoethyl ether acetate; EDGAC), butyl carbitol acetate, propylene glycol monomethyl ether acetate (PMA), dipropylene glycol monomethyl ether ethyl esters such as acid esters and propylene carbonate; aliphatic hydrocarbons such as octane and decane; petroleum-based solvents such as petroleum ether, naphtha, hydrogenated naphtha, aromatic petroleum-based solvents, etc. solvent. These solvents can be used alone or in combination of two or more.

(Other Added Components) In the photosensitive resin composition of the present invention, in addition to the above-mentioned components, of course, it is also possible to appropriately mix well-known and commonly used components, such as tackifiers, such as higher fatty acid systems, styrene-acrylic systems, etc. , styrene-maleic acid-based, polyacrylamide-based, alkyl ketene dimerization system, alkenyl succinic anhydride-based, petroleum-based, silicone-based defoamers, leveling agents, coupling agents, oxidation inhibitors , antirust agent, coloring agent, etc.

The kneading and dispersing of the above-mentioned essential components and optional components in the photosensitive resin composition of the present invention can use machines such as a three-roller or a blender. The photosensitive resin composition in which the components are dispersed in this way is applied to the substrate by an appropriate coating method such as screen printing, bar coater, or knife coater.

After coating, in order to obtain dryness to touch, it is preferable to dry the coating film formed by coating. The drying condition of the photosensitive resin composition of the present invention is to obtain a good dry coating film or developability thereafter, so it is characterized in that it is dried at 40 to 70°C at 80°C. The drying method is not particularly limited, but as an example, a hot air circulation drying furnace is mentioned. Specifically, samples such as substrates to be dried are placed in the center of the furnace by using a tray or the like. Department, by air circulation or pipeline adjustment, the temperature inside the device is kept constant within the range of 80°C and 90°C±1°C. Examples of the device name include DF610 manufactured by Yamato Science Co., Ltd., and the like. In addition, it has the same effect as above, that is, if the temperature in the device can be kept constant within the range of 80°C and 90°C±1°C, a far-infrared drying oven or the like can also be used. The film thickness after drying, that is, the dry film thickness is not particularly limited, but from the viewpoint of easier development and better printability, insulating resin compositions such as solder resist coatings are preferable It is 10-150 μm, more preferably 20-60 μm. On the other hand, the conductive resin composition such as conductive paste is more preferably 1 to 20 μm, more preferably 1 to 10 μm.

Next, contact exposure or non-contact exposure is performed using a negative image mask having a specific exposure pattern. As the exposure light source, a halogen lamp, a high pressure mercury lamp, a laser light, a metal halide lamp, a lamp black, an electrodeless lamp, etc. are used. As the exposure amount, a low light amount such that the integrated light amount is 200 mJ/cm ² or less may be used. In addition, it is also possible to form a pattern on the dry coating film by using a laser direct imaging device without using a mask.

Next, the coating film after exposure is made into a pattern form by image development, such as a spray method and a dipping method. As a developer for a dry coating film formed using the photosensitive resin composition of the present invention, an aqueous alkali solution such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and sodium silicate can be used. In particular, although a dilute alkali aqueous solution with a concentration of about 1.5% by mass or less is suitable for use, as long as the carboxyl groups in the photosensitive resin composition are saponified and the unhardened portion (unexposed portion) is removed, it is not necessary. Subject to the same restrictions as the developer mentioned above.

According to the photosensitive resin composition of the present invention, by using a dilute alkali aqueous solution as a developing solution, an exposed coating film with less damage to the exposed coating film and excellent resolution can be obtained.

Therefore, in one aspect of the present invention, the developer used in the method of forming the coated film after exposure is used in the pattern formation after development, preferably a dilute solution with a Na ₂ CO ₃ concentration of 0.1 to 2.0% by mass. alkaline aqueous solution. In particular, it is more preferable that the insulating resin composition such as solder resist paint is a dilute alkaline aqueous solution with a Na ₂ CO ₃ concentration of 0.2 to 2.0% by mass. On the other hand, the conductive resin composition such as conductive paste is more preferably a dilute alkaline aqueous solution with a Na ₂ CO ₃ concentration of 0.1 to 1.0% by mass.

After image development, in order to remove unnecessary developing solution, it is preferable to perform water washing or acid neutralization.

Next, the obtained exposed coating film is fully cured by heat or ultraviolet irradiation. Thereby, it is possible to form a cured product having excellent printability, a cured film having excellent adhesion and crack resistance. In the case of thermosetting, the thermosetting temperature is preferably at most 180°C, more preferably at most 150°C, even more preferably at most 140°C, particularly preferably at most 130°C. On the other hand, when hardened by ultraviolet irradiation, it is preferably 500-3000 mJ/cm ² , more preferably 500-2000 mJ/cm ² .

The photosensitive resin composition of the present invention can be used as a dry film or as a liquid. When using in liquid form, it is also possible to use 1-component or 2-component or more. In the case of dry film formation, the photosensitive resin composition of the present invention is coated on a carrier film, and the formed resin layer is obtained after drying. An example of the case where the photosensitive resin composition of the present invention is used as a dry film is shown below.

The dry film has a structure in which a carrier film, a resin layer, and a peelable protective film are laminated in sequence. The resin layer is a layer formed by coating and drying the photosensitive resin composition of the present invention on a carrier film or a protective film. After the resin layer is formed on the carrier film, a protective film is laminated thereon, or a resin layer is formed on the protective film, and the laminate is laminated on the carrier film to obtain a dry film.

As the carrier film, for example, a thermoplastic film such as a polyester film of polyethylene terephthalate or polyethylene naphthalate having a thickness of 2 to 150 μm can be used.

Resin layer system The photosensitive resin composition can be uniformly coated on a carrier film or a protective film, for example, with a thickness of 10-150 μm by a knife coater, a die lip coater, a chip coater, a film coater, etc. formed by drying.

As the protective film, for example, a polyethylene film, a polypropylene film, etc. can be used, but those having a smaller adhesive force with the resin layer than the carrier film are preferable.

Use a dry film to form a hardened film on a substrate, for example, peel off the protective film, overlap the resin layer with the substrate on which the circuit is formed, and use a laminating machine to bond the substrate to form a resin on the substrate on which the circuit is formed. Floor. The formed resin layer is subjected to the same exposure, development, and full-scale curing as described above to form a cured product of a cured film. The carrier film may be peeled off before exposure or after exposure.

In these steps, as a base material, in addition to a printed wiring board or a flexible printed wiring board on which a circuit is formed with copper or the like in advance, paper phenol resin, paper epoxy resin, glass cloth epoxy resin, glass polystyrene resin, etc. can be used. Adhesives for high-frequency circuits such as imide, glass cloth/non-woven epoxy resin, glass cloth/paper epoxy resin, synthetic fiber epoxy resin, fluororesin・polyethylene・polyphenylene ether, polyphenylene ether・cyanate, etc. Copper-clad laminates of all grades (FR-4, etc.) of materials such as copper laminates, others such as metal substrates, polyimide films, polyethylene terephthalate (PET) films, polyethylene naphthalene Ethylene diformate (PEN) film, glass substrate, ceramic substrate, wafer plate, etc.

In addition, in the present invention, a resin-made substrate having no heat resistance may be used in addition to the above-mentioned substrate. Specifically, examples of the base material made of resin include polyimide, polyester resin, polyether resin (PES), polystyrene (PS), polymethyl methacrylate (PMMA) , polycarbonate (PC), polyamide (PA), polypropylene (PP), polyoxyxylene (PPO) and the like, polyester-based resins can be suitably used.

The photosensitive resin composition or dry film of the present invention is suitable for manufacturing printed wiring boards, more preferably for forming permanent coatings. At this time, a cured product is formed by the above-mentioned production method or the like using the photosensitive resin composition or dry film of the present invention. When the resin layer of the photosensitive resin composition or dry film of the present invention has insulating properties, it is suitably used to form a solder resist, a cover layer, or an interlayer insulating layer. In addition, the photosensitive resin composition of the present invention can also be used to form tin banks. On the other hand, when the resin layer of the photosensitive resin composition or dry film of the present invention is conductive, it is suitable for use in conductive circuits, electrodes, electromagnetic wave shielding, conductive adhesives, and the like. [Example]

Next, examples will be given to further describe the present invention in detail, but the present invention is not limited by these examples.

[Preparation of Photosensitive Resin Composition] The components listed in the following Tables 1 and 2 were blended and stirred, and three steps were performed using a three-roll mill. Thereafter, carbitol acetate as a solvent was added so that the slurry viscosity became 250 dPa·s±20 Pa·s, and each photosensitive resin composition described in the same table was obtained.

上述一般式(IV)中X為C(CH₃ )₂ ，將平均聚合度n為3.3之雙酚A型環氧樹脂(環氧當量650g/eq、軟化點80℃)371份與環氧氯丙烷925份溶解於二甲亞碸462.5份後，於攪拌下在70℃以100分鐘添加98.5%NaOH52.8份。添加後進一步在70℃下進行3小時之反應。反應結束後，添加水250份進行水洗。油水分離後，由油層將二甲亞碸之大部分及過量的未反應環氧氯丙烷在減壓下蒸餾回收、使含有殘留的副生成鹽與二甲亞碸之反應生成物溶解於甲基異丁基酮750份，再添加30%NaOH 10份，在70℃進行1小時反應。反應結束後，以水200份進行2次水洗。油水分離後，由油層將甲基異丁基酮蒸餾回收，得到環氧當量287g/eq、軟化點65℃的環氧樹脂(a)。獲得的環氧樹脂(a)由環氧基當量計算，為前述起始物質雙酚A型環氧樹脂中之醇性羥基3.3個中約3.1個被環氧化者。將該環氧樹脂(a)310份及卡必醇乙酸酯282份置入燒瓶，在90℃進行加熱・攪拌，進行溶解。得到的溶液一旦冷卻至60℃，加入丙烯酸72份(1莫耳)、甲基對苯二酚0.5份、三苯基膦2份，加熱至100℃，進行約60小時反應，得到酸價為0.2mgKOH/g之反應物。於其中加入四氫苯二甲酐140份(0.92莫耳)，加熱至90℃，進行反應，得到鹼可溶性樹脂1的樹脂溶液。生成物的固體成分濃度為64質量%，固體成分酸價為100mgKOH/g。(Synthesis of Alkali-Soluble Resin 1)

In the general formula (IV) above, X is C(CH ₃ ) ₂ , and 371 parts of bisphenol A epoxy resin (epoxy equivalent 650g/eq, softening point 80°C) with an average degree of polymerization n of 3.3 and epoxy chloride After dissolving 925 parts of propane in 462.5 parts of dimethylsulfoxide, 52.8 parts of 98.5% NaOH were added at 70° C. for 100 minutes with stirring. After the addition, a reaction was further performed at 70° C. for 3 hours. After completion of the reaction, 250 parts of water were added and washed with water. After the oil and water are separated, most of the dimethyloxide and excess unreacted epichlorohydrin are distilled and recovered from the oil layer under reduced pressure, and the reaction product containing the residual by-product salt and dimethyloxide is dissolved in the methyl 750 parts of isobutyl ketone was added, and 10 parts of 30% NaOH was added, and it reacted at 70 degreeC for 1 hour. After completion of the reaction, washing with water was performed twice with 200 parts of water. After oil-water separation, methyl isobutyl ketone was distilled and recovered from the oil layer to obtain an epoxy resin (a) having an epoxy equivalent of 287 g/eq and a softening point of 65°C. The obtained epoxy resin (a) is calculated from the equivalent weight of epoxy groups, and is about 3.1 of the 3.3 alcoholic hydroxyl groups in the aforementioned starting material bisphenol A type epoxy resin that have been epoxidized. 310 parts of this epoxy resin (a) and 282 parts of carbitol acetate were put into a flask, and it heated and stirred at 90 degreeC, and melt|dissolved. Once the obtained solution was cooled to 60°C, 72 parts (1 mole) of acrylic acid, 0.5 parts of methyl hydroquinone, and 2 parts of triphenylphosphine were added, heated to 100°C, and reacted for about 60 hours to obtain an acid value of 0.2mgKOH/g reactant. 140 parts (0.92 mol) of tetrahydrophthalic anhydride was added there, and it heated at 90 degreeC, and it reacted, and the resin solution of alkali-soluble resin 1 was obtained. The solid content concentration of the product was 64% by mass, and the solid content acid value was 100 mgKOH/g.

(Synthesis of Alkali-Soluble Resin 2) In a 2L flask equipped with a stirring device and a return pipe, EP-4300E (2 Functional bisphenol A epoxy resin, epoxy equivalent: 185.0g/equivalent) 370.0g, acrylic acid (molecular weight: 72.06) 144.1g as the monocarboxylate compound (b) having an ethylenically unsaturated group in the molecule, as heat 1.10g of hydroquinone monomethyl ether as a polymerization inhibitor and 1.61g of triphenylphosphine as a reaction catalyst are reacted at a temperature of 98°C until the acid value of the reaction solution becomes below 0.5mg・KOH/g. An epoxy carboxylate compound (theoretical molecular weight: 548.2) was obtained. Next, 627.6 g of methyl ethyl ketone as a reaction solvent, 3.59 g of hydroquinone monomethyl ether as a thermal polymerization inhibitor, and 2,2 - 222.9 g of bis(dimethylol)-propionic acid (molecular weight: 134.1), and the temperature was raised to 45°C. 394.4 g of isophorone diisocyanate (molecular weight: 222.3) which is a diisocyanate compound was dripped gradually in this solution so that reaction temperature may not exceed 65 degreeC. After the dropping, the temperature was raised to 80° C., and reacted by infrared absorption spectrometry for 6 hours until the absorption around 2250 cm ⁻¹ disappeared, to obtain a resin solution of alkali-soluble resin 2 . The solid content was 65% by mass, and the solid content acid value was 80 mgKOH/g.

(Measurement method of acid dissociation constant (pKa) of alkali-soluble resin) In a 100ml beaker, the prepared or prepared resin solutions of alkali-soluble resins 1 to 3 were accurately weighed to 0.5g, and then dissolved in ethyl alcohol Diol butyl ether solution in 50ml. This solution was titrated with 0.1 mol/L ethanolic potassium hydrate solution. As a titration device, an automatic titration device (COM-1500) manufactured by Hiranuma Sangyo Co., Ltd. (half titration method) was used. The acid dissociation constant (pKa) is defined as the half equivalence point (half of the titrated amount at the equivalence point). The pKa's of the alkali-soluble resins 1 to 3 are shown in Table 1 below, respectively.

(Measurement of Contact Angle) A base material of a full-surface copper foil having a copper thickness of 35 μm was ground with a buff roll, washed with water, and dried. On this substrate, the compositions of Examples 1-9 and Comparative Examples 1-5 were coated on the entire surface by screen printing method. After that, for each composition of Examples 1-7 and Comparative Examples 1-3, the drying time was changed to 40, 50, 60, and 70 minutes in a hot air circulation drying oven (DF610 manufactured by Yamato Science Co., Ltd.) at 80°C. For each composition of Examples 8-9 and Comparative Examples 4-5, the drying time was changed to 20, 25, 30, and 35 minutes with a hot air circulation drying oven (DF610 manufactured by YAMATO Science Co., Ltd.) at 90°C, Each was dried to obtain a dried coating film of 95 mm×75 mm. The substrates to be dried are placed in the center of the furnace by using trays, and the temperature in the device is adjusted at 80°C and 90°C by air circulation or pipeline adjustment. within 1°C. The contact angle of water uses DropMaster DM300 as a contact angle meter and FAMAS (both manufactured by Kyowa Interface Science Co., Ltd.) as an integrated system for interface measurement and analysis, and is measured and analyzed by the true circle fitting method under the following conditions and methods .・Start the integrated system of interface measurement and analysis, and start the CA/PD controller. In this case, select "Standard" for "Field of View" on the screen of the controller. Next, water was put into a plastic syringe, a stainless steel needle (size 22) was attached to the tip, and dripped on the evaluation surface. When dropping, check whether the focus of the camera attached to the contact angle meter is correct. Immediately after dropping, press the "Measurement" button on the controller screen.・Water used in the measurement: Ion-exchanged water with a water quality of 0.7 μS/cm or less prepared by a device (PureLite PRO-0250-003 manufactured by Olucano Co., Ltd.) ・Amount of water dropped: 2 μL ・Measurement temperature: 20°C ・Viewing range of the lens: standard Next, measure the contact angle immediately after the water drop on the above-mentioned dry coating film placed horizontally at any 5 positions, and define the average value as the water contact angle . Here, the values of the contact angles at five arbitrary positions are values automatically calculated by pressing the "Measurement" button respectively. In addition, for each composition of Examples 1 to 7 and Comparative Examples 1 to 3, the contact angle of water on the dried coating film after drying at 80° C. for 40 minutes was obtained as A (°), and expressed as After drying at 80°C for 70 minutes, the contact angle of water on the dry coating film is taken as B (°): The change rate R represented by R ₈₀ (%)=｜(BA)/A｜×100 ₈₀ (%). In addition, for each composition of Examples 8 to 9 and Comparative Examples 4 to 5, the contact angle of water on the dried coating film after drying at 90°C for 20 minutes was obtained as C (°), and was expressed as The following formula for the contact angle of water on the dry coating film after drying at 90°C for 35 minutes is D (°): R ₉₀ (%)=｜(DC)/C｜×100 The rate of change R ₉₀ (%). The water contact angle and rate of change are shown in Table 1.

(Development Management Width) The base material of the entire surface copper foil with a copper thickness of 35 μm was ground with a polishing roll, washed with water, and dried. On this substrate, each composition of Examples 1-9 and Comparative Examples 1-5 was coated on the entire surface by screen printing method. After that, for each composition of Examples 1-7 and Comparative Examples 1-3, the drying time was changed to 40, 50, 60, and 70 minutes in a hot air circulation drying oven (DF610 manufactured by Yamato Science Co., Ltd.) at 80°C. , for each composition of Examples 8~9 and Comparative Examples 4~5, the drying time was changed to 20, 25, 30, and 35 minutes respectively in a hot air circulation drying oven (DF610 manufactured by YAMATO Science Co., Ltd.) at 90°C. Drying is performed to obtain a dry coating film. The obtained dried coating films were respectively used in Examples 1~4, 8 and Comparative Examples 1~2, 4 using 30°C 1% by mass Na ₂ CO ₃ aqueous solution, in Examples 5~7, 9 and Comparative Example 3 5. Use 0.2% by mass Na ₂ CO ₃ aqueous solution at 30°C to develop for 60 seconds under the condition of spray pressure of 0.2 MPa, and check whether the dried coating film obtained by the respective drying time can be developed, and test to make it When drying, there will be no poor development time caused by thermal fogging. Visually inspecting the copper, if the components of the curable resin composition do not remain as residues, it is defined as developable, and the drying time defined as developable is used as an evaluation standard. This definition means that the longest drying time that can be developed is called the development management width. The longer the time is, the wider the width caused by drying is, and the manufacturing management through the substrate manufacturing step becomes easier. The evaluation criteria are as follows. The obtained results are shown in Table 1. ○: Over 60 minutes at 80°C or over 30 minutes at 90°C ×: Less than 60 minutes at 80°C or less than 30 minutes at 90°C

(Preparation method of test piece for analytical performance 1 evaluation) A substrate having a circuit pattern of 30 μm/40 μm lines and spaces (L/S) with a copper thickness of 35 μm was ground with a polishing roll, washed with water, and dried. On this substrate, each composition of Examples 1~4, 8 and Comparative Examples 1~2, 4 among the photosensitive resin compositions recorded in the following Tables 1 and 2 was used for 200 Mesh polyester screen full surface coating. Then, it dried with the 80 degreeC hot-air circulation type drying oven (Yamato Science Co., Ltd. product DF610) for 30 minutes of drying time, and obtained the dry coating film whose film thickness after drying was 20 micrometers. After that, the obtained dried coating film was subjected to an exposure device equipped with a metal halide lamp as a light source (HMW-680-GW20 manufactured by ORC MANUFACTURING CO., LTD.), with a line and a space of 30 μm/40 μm (L /S) negative image mask to expose the pattern at the optimum exposure. Here, the optimum exposure dose is defined as exposing the dry coating film obtained above using an exposure device equipped with a metal halide lamp, and using a trapezoidal plate with a sensitivity of 21 steps, and using 1% by mass of a liquid temperature of 30°C When Na ₂ CO ₃ aqueous solution is developed for 60 seconds under the condition of spray pressure of 0.2 MPa, the remaining pattern of the trapezoidal plate becomes the exposure amount of 6 stages. Next, development and water washing were performed using a 1% by mass Na ₂ CO ₃ aqueous solution at a liquid temperature of 30°C. Finally, it was made to harden at 150 degreeC x 60 minutes, and the test piece for analytical 1 evaluation was produced.

(Resolution 1) The resolubility was evaluated in the line and space (L/S) of 30μm/40μm in the test piece. ○: There is no thread defect and no undercut. × : The thread is missing or undercut.

(Preparation method of test piece for analysis 2 evaluation) On a PET film (LUMIRROR T60 thickness 125 μm manufactured by Toray Co., Ltd.), among the photosensitive resin compositions described in the following Tables 1 and 2, Examples 5 to 7 were mixed , 9, and Comparative Examples 3 and 5, each conductive resin composition for evaluation was coated on the entire surface using a 380-mesh polyester screen so that the film thickness after drying became 5 μm, and then, For each composition of Examples 5 to 7 and Comparative Example 3, use a hot air circulation drying oven (DF610 manufactured by YAMATO Science Co., Ltd.) at 80° C. for 30 minutes, and for each composition of Example 9 and Comparative Example 5, use 90 Each was dried in a hot air circulating drying oven (DF610 manufactured by Yamato Science Co., Ltd.) at °C for 15 minutes to form a dry coating film with good dryness to the touch. After that, the obtained dried coating film was subjected to an exposure device equipped with a metal halide lamp as a light source (HMW-680-GW20 manufactured by ORC MANUFACTURING CO., LTD.), with a line and a space of 30 μm/40 μm (L /S) negative image mask to expose the pattern at the optimum exposure. Here, the optimum exposure dose is defined as using an exposure device equipped with a metal halide lamp for the dry coating film obtained above, a trapezoidal plate with a separation sensitivity of 21, and using 0.2% by mass Na ₂ at a liquid temperature of 30°C. When CO ₃ aqueous solution is developed for 60 seconds under the condition of a spray pressure of 0.2 MPa, the remaining pattern of the trapezoidal plate becomes the exposure amount of 6 stages. Next, development and water washing were performed using an aqueous solution of Na ₂ CO ₃ having a liquid temperature of 30° C. and a concentration of 0.2% by mass. Finally, it was made to harden at 150 degreeC x 60 minutes, and the test piece for analytical evaluation was produced.

(Resolution 2) The resolubility was evaluated in the 30μm/40μm line and space (L/S) of the test piece. ○: There is no thread defect and no undercut. × : The thread is missing or undercut.

(Contamination evaluation of developing solution) After each composition of Examples 1-9 and Comparative Examples 1-5 was precisely weighed to 4g in a 100ml threaded tube, 80% was used for Examples 1-7 and Comparative Examples 1-3 ℃ for 70 minutes in a hot air circulation drying oven (DF610 manufactured by Yamato Scientific Co., Ltd.), and for Examples 8 to 9 and Comparative Examples 4 to 5, use a hot air circulation drying oven (DF610 manufactured by Yamato Scientific Co., Ltd.) at 90 °C for 35 minutes , each dried to obtain a dry coating film. Put into the threaded tube of dry coating film, for embodiment 1～4, 8 and comparative example 1～ ₂ , 4 system with 1 mass % _Na2CO3 aqueous solution, for embodiment 5～7, 9 and comparative example 3, In the 5 series, 30 g of 0.2% by mass Na ₂ CO ₃ aqueous solution was added, the lid was closed and stirred for 8 minutes, and then left to stand at 20° C. for 40 minutes. After that, it was checked visually whether solid matter adhered to the liquid surface of the threaded tube. The evaluation criteria are as follows. The results obtained are shown in the above table. ◎: There is no solid substance at all, and the liquid in the threaded tube is transparent. ○: Although there is no solid substance, the liquid in the threaded tube is not transparent. △: There is only a small amount of solid matter, and the liquid in the threaded tube is not transparent. × : There is a large amount of solid matter, and the liquid in the threaded tube is not transparent.

(Clogging of the developing device's mesh) The threaded tube evaluated in "Contamination of the developer" was further left to stand at 20°C for 40 minutes. Afterwards, through a filter with a pore size of 10 μm, the clogging status of the solid components in the filter was visually evaluated. ◎: There is no clogging of solid components in the filter. ○: There is only a small amount of solid clogging in the filter. ×: The filter is blocked by a large amount of solid components.

The test results are summarized in Table 1. In addition, about the numerical value which does not indicate the unit among each component in Table 1, it represents a mass part.

＊11：由下述結構式所表示之環氧樹脂(環氧當量：300~330g/eq)

＊12：熱硬化性成分，共榮社化學股份公司製Epolight 40E，乙二醇二環氧丙酯 　　＊13：熱硬化性成分，旭化成化學品股份公司製DURANATE MF-B60B，嵌段異氰酸酯 　　＊14：2-苯基-4,5-二羥基甲基咪唑，四國化成工業股份公司製curezol 2PHZ-PW 　　＊15：C.I.Pigment Blue 15：3 　　＊16：C.I.Pigment Yellow 147 　　＊17：矽氧系消泡劑，信越化學工業股份公司製KS-66 　　＊18：分散劑，BYK・JAPAN公司製DISPERBYK-191 　　＊19：有機酸，關東化學股份公司製2,2'-硫代二乙酸 　　＊20：填充劑，堺化學工業股份公司製Baryace B-30、硫酸鋇 　　＊21：填充劑，Admatechs股份公司製SO-E2，球狀二氧化矽 　　＊22：填充劑，日本滑石股份公司製SG-2000，滑石 　　＊23：填充劑，球狀銀粉末(最大粒徑30μm以下、平均粒徑2μm，此外，平均粒徑係藉由使用電子顯微鏡(SEM)10,000倍觀察之隨機的10個粒子的平均粒徑。) 　　＊24：溶劑、出光興產股份公司製Ipzole 150，石油系溶劑In addition, *1~*24 in Table 1 represent the following components. In addition, the description of "-" in Table 1 means that it has not been evaluated. *1: Carboxyl-containing bisphenol A type epoxy acrylate resin, solid content 64% by mass, solid content acid value 100mgKOH/g, referring to the synthesis of alkali-soluble resin 1, the blending amount in the table is the blending amount of the resin solution Quantity*2: Carboxyl group-containing bisphenol A urethane epoxy acrylate resin, solid content 51% by mass, solid content acid value 85mgKOH/g, refer to the synthesis of alkali-soluble resin 2, the blending amount in the table is the blending amount of the resin solution *3: CYCLOMER P (ACA) Z230AA, carboxyl group-containing photosensitive copolymer resin solution manufactured by DAICEL-ALLNEX Co., Ltd., solid content 53.0% by mass, solid content acid value 40mgKOH/g, in the table The blending amount is the blending amount of the resin solution *4: Reactive diluent, Nippon Kayaku Co., Ltd. KAYARAD DPHA, a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate *5: Reactive diluent, Japan KAYARAD DPCA-60 manufactured by Kayaku Co., Ltd., caprolactone-modified substance of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate *6: reactive diluent, NK OLIGO U-4HA manufactured by Shin-Nakamura Chemical Industry Co., Ltd., Tetrafunctional urethane (meth)acrylate obtained by reacting hexamethylene diisocyanate with 2-hydroxy-3-acryloxypropyl methacrylate*7: Bisacylphosphine oxide-based photopolymerization Initiator, Omnirad 819 manufactured by IGM Resins *8: Oxime ester-based photopolymerization initiator, IRGACURE OXE02 manufactured by BASF JAPAN Corporation *9: Thermosetting component, jER828 manufactured by Mitsubishi Chemical Corporation, bisphenol A type epoxy resin *10: Epoxy resin represented by the following structural formula (epoxy equivalent: 300~330g/eq)

*11: Epoxy resin represented by the following structural formula (epoxy equivalent: 300~330g/eq)

*12: Thermosetting component, Epolight 40E manufactured by Kyoeisha Chemical Co., Ltd., ethylene glycol diglycidyl ester*13: Thermosetting component, Duranate MF-B60B manufactured by Asahi Kasei Chemical Co., Ltd., blocked isocyanate*14 : 2-Phenyl-4,5-dihydroxymethylimidazole, curezol 2PHZ-PW manufactured by Shikoku Chemical Industry Co., Ltd. *15: CIPigment Blue 15: 3 *16: CIPigment Yellow 147 *17: Silicone-based defoamer , KS-66 manufactured by Shin-Etsu Chemical Co., Ltd. *18: Dispersant, DISPERBYK-191 manufactured by BYK・JAPAN Corporation *19: Organic acid, 2,2'-thiodiacetic acid manufactured by Kanto Chemical Co., Ltd. *20: Filler, Sakai Chemical Industry Co., Ltd. Baryace B-30, barium sulfate *21: Filler, Admatechs Co., Ltd. SO-E2, spherical silica *22: Filler, Nippon Talc Co., Ltd. SG-2000, talc *23 : Filler, spherical silver powder (maximum particle size 30 μm or less, average particle size 2 μm, and the average particle size is the average particle size of 10 random particles observed with an electron microscope (SEM) at 10,000 times.) * 24: Solvent, Ipzole 150 manufactured by Idemitsu Kosan Co., Ltd., petroleum-based solvent

As shown in the above Table 1, it can be seen that the contact angles A and C of water are 75.0° or more, and the change rates R ₈₀ (Examples 1-7) and R ₉₀ (Examples 8-9) of the contact angle are 3.0 or less The photosensitive resin compositions of Examples 1 to 9 can not only obtain high resolution of the coating film after formal hardening, but also prevent the contamination of the developing solution in the developing step or the clogging of the developing device caused by deposits. The photosensitive resin composition. On the other hand, it can be seen that with the photosensitive resin compositions of Comparative Examples 1 and 2, since the contact angles A and C of water are less than 75.0°, even if the rate of change of the contact angle R ₈₀ (Comparative Examples 1-2), R ₉₀ (Comparative Example 4) is below 3.0, and the high resolution of the coating film after formal hardening cannot be obtained. At the same time, it can also prevent the contamination of the developing solution in the developing step or the clogging of the developing device caused by sediment. Photosensitive resin composition. Also, it can be seen that with the photosensitive resin compositions of Comparative Examples 3 and 5, although the contact angles A and C of water are 75.0° or more, due to the change rate of the contact angle R ₈₀ (Comparative Example 3), R ₉₀ (Comparative Example Example 5) If it exceeds 3.0, it is impossible to obtain a photosensitive resin composition that satisfies the high resolution of the coating film after the official hardening, and can also prevent the contamination of the developing solution in the developing step or the clogging of the developing device caused by deposits .

(Specific resistance value) On a PET film (LUMIRROR T60 thickness 125 μm manufactured by Toray Co., Ltd.), each composition of Examples 6 and 9 was coated on the entire surface using a 380-mesh polyester screen, and then circulated in hot air. Drying oven (DF610 manufactured by Yamato Science Co., Ltd.) was performed at 80° C. for 30 minutes to form a dry coating film with good dryness to the touch. After that, the obtained dried coating film was formed by using an exposure device equipped with a metal halide lamp as a light source (HMW-680-GW20 manufactured by ORC MANUFACTURING CO., LTD.), and forming a conductive pattern circuit with an interval of 4 mm x 100 mm. Use the negative image mask to expose the pattern with the optimum exposure. Here, the optimum exposure dose is defined as using an exposure device equipped with a metal halide lamp for the dry coating film obtained above, a trapezoidal plate with a separation sensitivity of 21, and using 0.2% by mass Na ₂ at a liquid temperature of 30°C. When CO ₃ aqueous solution is developed for 60 seconds under the condition of a spray pressure of 0.2 MPa, the remaining pattern of the trapezoidal plate becomes the exposure amount of 6 stages. Next, image development and water washing were performed using an aqueous sodium carbonate solution having a Na ₂ CO ₃ concentration of 0.2% by mass at a liquid temperature of 30°C. Finally, it was made to harden at 150 degreeC x 60 minutes, and the test piece for specific resistance evaluation was produced. The resistance value and the film thickness were measured using the test piece, and the specific resistance was calculated. As a result of calculation, Examples 6 and 9 both obtained a low specific resistance value of 4.0×10 ^-5 (Ω·cm). From the above, it can be seen that the use of an organic acid such as 2,2'-thiodiacetic acid in a conductive resin composition becomes more conductive.

Claims (5)

A photosensitive resin composition, which is a photosensitive resin composition containing an alkali-soluble resin and a conductive filler, characterized in that the coating film formed by coating the photosensitive resin composition is carried out at 80°C for 40 minutes The contact angle of water on the dry coating film after drying is A (°), and the contact angle of water on the dry coating film after drying the coating film formed by coating the photosensitive resin composition at 80°C for 70 minutes When the contact angle is B(°), A is 75.0° or more, and the rate of change R ₈₀ represented by R ₈₀ (%)=|(BA)/A|×100 is 3.0 or less. A photosensitive resin composition, which is a photosensitive resin composition containing an alkali-soluble resin and a conductive filler, characterized in that the coating film formed by coating the photosensitive resin composition is carried out at 90°C for 20 minutes The contact angle of water on the dry coating film after drying is C (°), and the contact angle of water on the dry coating film after drying the coating film formed by coating the photosensitive resin composition at 90°C for 35 minutes When the contact angle is D (°), C is 75.0° or more, and the rate of change R ₉₀ represented by R ₉₀ (%)=|(DC)/C|×100 is 3.0 or less. A dry film, characterized in that it has a resin layer obtained by coating and drying the photosensitive resin composition described in claim 1 or 2 on a film. A cured product characterized in that it is obtained by curing the photosensitive resin composition described in Claim 1 or 2, or the resin layer of the dry film described in Claim 3. A printed wiring board characterized in that it has the cured product described in Claim 4.