TWI813829B - Alkali-developable photocurable thermosetting resin composition - Google Patents

Abstract

An object of the present invention is to provide an alkali-developable curable resin composition that can suppress performance degradation even under relatively severe storage conditions. The means of the present invention is an alkali-developable curable resin composition, which is an alkali-developable curable resin composition that constitutes at least a two-component system and contains at least (A) an alkali-soluble resin and (B) a photopolymerized resin having an oxime bond. Initiator, (C) reactive diluent and (D) thermosetting resin, and the aforementioned (B) photopolymerization initiator having an oxime bond is blended in a composition different from the aforementioned (A) alkali-soluble resin , characterized in that at least one type of (E) orthoester compound is blended with the aforementioned (B) photopolymerization initiator having an oxime bond.

Description

Alkali-developable photocurable thermosetting resin composition

The present invention relates to an alkali-developable photocurable thermosetting resin composition, a cured product obtained by curing the composition, and an electronic component having the cured product.

Solder resist has long been used as a protective material for circuits on printed wiring boards. An example of this material composition is an alkali-developable photocurable thermosetting resin composition. (hereinafter also referred to as "curable resin composition"). In the curable resin composition, in order to form a more precise pattern, a photopolymerization initiator with higher sensitivity is sometimes used to increase the sensitivity during exposure and enable photohardening to the deep part of the coating film. As such a photopolymerization initiator, for example, a technology using a photopolymerization initiator having an oxime bond is proposed (Patent Document 1).

On the other hand, a photopolymerization initiator having an oxime bond has a property in which its performance is easily reduced due to contact with a resin having a carboxyl group, and also has a tendency to deteriorate due to contact with a reactive diluent. Doubts about thickening. As a result, the quality of the composition containing it may be impaired. Therefore, the technology of Patent Document 1 is characterized in that a two-component curable resin composition is prepared by combining a photopolymerization initiator having an oxime bond and a resin or reactive diluent having a carboxyl group in separate ingredients are blended. By creating such a two-liquid system, a curable resin composition with excellent storage stability can be provided. [Prior technical literature] [Patent Document]

[Patent Document 1] International Publication No. 2004/048434

[Problem to be solved by the invention]

However, from the viewpoint of exerting its stable performance, a composition containing a compound with high photosensitivity such as the above-mentioned photopolymerization initiator having an oxime bond is expected to have higher quality stability during storage. Therefore, it is possible to provide a curable resin composition with stable quality even after passing through relatively stringent storage conditions, such as transportation by ship, where the temperature is likely to be relatively high, and the transportation period is long. If such storage conditions are assumed, it is considered that the performance of the curable resin composition must be maintained as much as possible even after a continuous period of more than 5 days at approximately 50°C. In this regard, the technology described in Patent Document 1 is a two-liquid system as described above. Therefore, it is possible to suppress the degradation of the performance of the photopolymerization initiator having an oxime bond and to maintain the hardening of the photopolymerization initiator containing this. properties of the resin composition.

However, this technology does not at least assume the following situation: leaving the curable resin composition at 50° C. for more than 5 days. Therefore, an object of the present invention is to provide a curable resin composition that can suppress performance degradation even under such relatively severe storage conditions. [Means to solve the problem]

First, a time-lapse test was conducted on a two-component curable resin composition containing a photopolymerization initiator having an oxime bond at 50°C for 5 days. However, due to the decrease in sensitivity, it could not be processed by exposure and development. to form a pattern.

Therefore, the deterioration mechanism of the photopolymerization initiator having an oxime bond in the curable resin composition was re-investigated. As a result, the following findings were found: The trace amount of water contained in the composition has an oxime bond. The oxime bond in the chemical structure of the photopolymerization initiator brings adverse effects. It is presumed that this moisture decomposes the oxime bond, resulting in the photopolymerization initiator having the oxime bond becoming passivated, and adversely affecting the formation of the hardened film. Then, the adverse effects caused by the presence of moisture are as mentioned above, even if the photopolymerization initiator having an oxime bond, the resin having a carboxyl group, and the reactive diluent are mixed in a two-liquid system of separate components. combination, it is impossible to fully avoid the occurrence of such adverse effects.

From this viewpoint, when blending a photopolymerization initiator having an oxime bond into a two-component curable resin composition, an attempt has been made to blend a dehydrating agent such as zeolite or silica gel together with the photopolymerization initiator. However, they have individual problems such as difficulty in dispersing them in the composition, and therefore they cannot be directly used to suppress the passivation of the photopolymerization initiator having an oxime bond.

Therefore, as a result of further research, it was found that by combining a photopolymerization initiator having an oxime bond with an alkali-soluble resin in separate compositions, and combining a specific orthoester compound with the photopolymerization initiator having an oxime bond When blended together into a curable resin composition, even when stored at 50°C for 5 days, the passivation of the photopolymerization initiator having an oxime bond can be effectively suppressed, thereby improving the storage of the composition. stability, and then complete the present invention.

That is, it was found that the object of the present invention can be solved by the alkali-developable curable resin composition, which is a two-component alkali-developable curable resin composition containing at least (A) an alkali-soluble resin, (B) A photopolymerization initiator having an oxime bond, (C) a reactive diluent and (D) a thermosetting resin, and the aforementioned (B) photopolymerization initiator having an oxime bond is blended with the aforementioned (A) alkali-soluble resin Among different compositions, it is characterized in that at least one type of (E) orthoester compound is blended with the aforementioned (B) photopolymerization initiator having an oxime bond.

Furthermore, in the alkali-developable curable resin composition of the present invention, (E) the orthoester compound is preferably selected from the group consisting of trimethyl orthoformate, triethyl orthoformate, tripropyl orthoformate, and tributyl orthoformate. Ester, trimethyl orthoacetate, triethyl orthoacetate, tripropyl orthoacetate, tributyl orthoacetate, trimethyl orthopropionate, triethyl orthopropionate, propyl orthopropionate and butyl orthopropionate At least one species from the group of esters, preferably at least one species selected from the group consisting of trimethyl orthoformate, triethyl orthoformate and triethyl orthoacetate, preferably triethyl orthoformate. Ethyl ester.

Furthermore, the present invention also provides a cured product obtained by curing the above-mentioned alkali developable curable resin composition and an electronic component having the cured product. [Effects of the invention]

According to the present invention, it is possible to provide "a two-component curable resin composition that can effectively suppress the decrease in performance (such as sensitivity) even after at least 50° C. for 5 days." Therefore, it is suitable for storage under relatively severe conditions such as transportation of the composition by ship.

[The best way to implement the invention]

In the curable resin composition of the present invention, (B) the photopolymerization initiator having an oxime bond and (A) the alkali-soluble resin are blended into separate compositions to form at least a two-liquid system. For example, a main component composition and a hardener composition are separately prepared, and these can be mixed during use. Of course, these compositions can be further customized according to needs, and they can also be made into a three-liquid or higher composition. Examples of components of the main component composition include alkali-soluble resins, reactive diluents, solvents, pigments, and photopolymerization initiators. On the other hand, examples of the components of the curing agent composition include a thermosetting resin, a solvent, a photopolymerization initiator having an oxime bond, and the like.

Then, in the present invention, not only (B) the photopolymerization initiator having an oxime bond is blended into a separate composition from (A) the alkali-soluble resin, but also (E) the orthoester compound and (B) Photopolymerization initiators having an oxime bond are blended together. Based on this, it is speculated that the decomposition of oxime bonds caused by moisture in the composition can be effectively suppressed, that is, the sensitivity can be maintained. The curable resin composition of the present invention blended in this way can effectively suppress the decrease in performance even after at least 50° C. has elapsed for 5 days. Each component is explained below.

[(A) Alkali-soluble resin] (A) The alkali-soluble resin is a resin that contains one or more functional groups among a phenolic hydroxyl group, a thiol group, and a carboxyl group and is soluble in an alkali solution. Preferable examples include those having two or more phenolic hydroxyl groups. Compounds, resins containing carboxyl groups, compounds having phenolic hydroxyl groups and carboxyl groups, and compounds having two or more thiol groups. As (A) the alkali-soluble resin system, a carboxyl group-containing resin or a phenolic hydroxyl group-containing resin can be used, but a carboxyl group-containing resin is preferred.

From the viewpoint of photocurability or development resistance, the carboxyl group-containing resin preferably has an ethylenically unsaturated bond in the molecule in addition to the carboxyl group, but a carboxyl group-containing resin that does not have an ethylenically unsaturated double bond may also be used. resin. As the ethylenically unsaturated bond, acrylic acid or methacrylic acid or derivatives thereof are preferred. Among the carboxyl group-containing resins, preferred are: a carboxyl group-containing resin having a copolymerized structure, a carboxyl group-containing resin having a urethane structure, and a carboxyl group-containing resin using an epoxy resin as a starting material. , a carboxyl group-containing resin using a phenolic compound as a starting material. Specific examples of the carboxyl group-containing resin include the compounds listed below (either an oligomer or a polymer).

(1) React bifunctional or more multifunctional epoxy resin with (meth)acrylic acid, and add phthalic anhydride, tetrahydrophthalic anhydride, or hexahydrophthalic anhydride to the hydroxyl groups present in the side chain. Photosensitive resin containing carboxyl groups obtained from dibasic acid anhydrides such as phthalic anhydride. Here, the bifunctional or more polyfunctional epoxy resin is preferably solid.

(2) Epoxidize the hydroxyl groups of the bifunctional epoxy resin with epichlorohydrin to obtain a multifunctional epoxy resin, and then react (meth)acrylic acid with the multifunctional epoxy resin to add hydroxyl groups to the generated hydroxyl groups. A carboxyl group-containing photosensitive resin obtained from dibasic acid anhydride. Here, the bifunctional epoxy resin is preferably solid.

(3) Compounds having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule and monocarboxylic acids containing unsaturated groups such as (meth)acrylic acid are used as compounds having two or more epoxy groups in one molecule. The reaction product is obtained by reacting an epoxy compound based on the base, and then polybasic acid anhydrides such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromelite dianhydride, and adipic acid are used for the reaction to produce The photosensitive resin containing carboxyl groups is obtained by reacting with the alcoholic hydroxyl group of the substance.

(4) Combine bisphenol A, bisphenol F, bisphenol S, novolak phenol resin, poly-p-hydroxystyrene, condensates of naphthol and aldehydes, and condensates of dihydroxynaphthalene and aldehydes. A reaction product is obtained by reacting a compound having two or more phenolic hydroxyl groups in one molecule with an alkylene oxide such as ethylene oxide or propylene oxide, and then (meth)acrylic acid or the like A carboxyl group-containing photosensitive resin is obtained by reacting an unsaturated group-containing monocarboxylic acid with the reaction product and reacting a polybasic acid anhydride with the obtained reaction product.

(5) A reaction product is obtained by reacting a compound having two or more phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethyl carbonate or propylene carbonate, and then adding the unsaturated group-containing monomer to the reaction product. A carboxyl group-containing photosensitive resin is obtained by reacting a carboxylic acid with the reaction product and reacting a polybasic acid anhydride with the obtained reaction product.

(6) By combining diisocyanate compounds such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, and polycarbonate polyols, polyether polyols, polyester polyols, etc. A polyaddition reaction is performed on diol compounds such as polyols, polyolefin-based polyols, acrylic polyols, bisphenol A-based alkylene oxide adduct diols, and compounds having phenolic hydroxyl groups and alcoholic hydroxyl groups to obtain amines. The urethane resin is a urethane resin containing terminal carboxyl groups obtained by reacting an acid anhydride with the terminal end of the urethane resin.

(7) Carboxyl group-containing urethane is produced by polyaddition reaction between diisocyanate and carboxyl group-containing diol compounds such as dimethylol propionic acid and dimethylol butyric acid. In the synthesis of the resin, a compound having one hydroxyl group and one or more (meth)acrylyl groups in the molecule, such as hydroxyalkyl (meth)acrylate, is added to obtain a terminal (meth)acrylated compound containing Carboxylic urethane resin.

(8) In the synthesis of carboxyl group-containing urethane resin by polyaddition reaction between diisocyanate, carboxyl group-containing diol compound and diol compound, isophorone diisocyanate and pentaerythritol triacrylic acid are added A terminal (meth)acrylated carboxyl group-containing urethane obtained from a compound having one isocyanate group and one or more (meth)acrylyl groups in the molecule of an equimolar reactant of an ester resin.

(9) Obtained by copolymerization of unsaturated carboxylic acids such as (meth)acrylic acid and unsaturated group-containing compounds such as styrene, α-methylstyrene, lower alkyl (meth)acrylate, isobutylene, etc. Photosensitive resin containing carboxyl groups.

(10) React a dicarboxylic acid such as adipic acid, phthalic acid, hexahydrophthalic acid, etc. with a polyfunctional oxetane resin as described below, and add a binary compound to the generated primary hydroxyl group. Acid anhydride is obtained to obtain a polyester resin containing carboxyl groups, and glycidyl (meth)acrylate, α-methylglycidyl (meth)acrylate, etc. are further added to have one epoxy group and one or more epoxy groups in one molecule. A carboxyl group-containing photosensitive resin obtained from a (meth)acrylyl compound.

(11) Carboxyl group-containing photosensitivity obtained by adding a compound having a cyclic ether group and a (meth)acrylyl group in one molecule to the carboxyl group-containing resin in any one of the above (1) to (10) resin.

Note that (meth)acrylate here is a term that collectively refers to acrylate, methacrylate, and mixtures thereof, and the same is true for other similar terms below.

The acid value of the resin containing carboxyl groups is preferably 40 to 150 mgKOH/g. By setting the acid value of the carboxyl group-containing resin to 40 mgKOH/g or more, alkali development becomes good. In addition, by setting the acid value to 150 mgKOH/g or less, normal resist pattern drawing can be easily performed. More preferably, it is 50~130mgKOH/g.

(A) The mass average molecular weight of the alkali-soluble resin varies depending on the resin skeleton, but is preferably in the range of 1,500 to 150,000, and more preferably in the range of 1,500 to 100,000. When the mass average molecular weight is 1500 or more, the tack free performance is good, the moisture resistance of the coating film after exposure is good, and film reduction during development is suppressed, so the decrease in resolution can be suppressed. On the other hand, when the mass average molecular weight is 150,000 or less, the developability is good and the storage stability is also excellent.

In the present invention, the content of (A) alkali-soluble resin is preferably 10 to 60 mass%, and more preferably 20 to 50 mass%, relative to the entire composition. If it is 10 to 60% by mass, the coating film strength is good, the viscosity of the composition is moderate, and the coating properties can be improved.

These (A) alkali-soluble resins can be used individually by 1 type or in combination of 2 or more types.

[(B) Photopolymerization initiator having an oxime bond] As the photopolymerization initiator having an oxime bond (B), for example, well-known ones such as о-acyl oxime ester compounds, sulfonate oxime ester compounds, and ketoxime ether compounds can be used. Examples of commercially available products include CGI-325, TOE-04-A3 (Nihon Chemical Industry Co., Ltd.), Irgacure OXE01 and Irgacure OXE02 (both BASF Japan Co., Ltd.), and N-1919 and NCI-831 ( All are ADEKA Co., Ltd.), etc., but are not limited to them.

The content of (B) the photopolymerization initiator having an oxime bond relative to (A) the alkali-soluble resin is preferably 0.01 to 30 mass %, and more preferably 0.1 to 10 mass %. If (B) the content of the photopolymerization initiator having an oxime bond is 0.01% by mass or more, the photocurability on copper will be good, the coating film will not peel off easily, and the coating film properties such as chemical resistance will be good. . On the other hand, when the content of (B) the photopolymerization initiator having an oxime bond is 30% by mass or less, the light absorption of the (B) photopolymerization initiator having an oxime bond is good and the deep hardening Sex will improve.

[(C) Reactive diluent] The (C) reactive diluent used in the present invention is used to adjust the viscosity of the composition to improve workability, to increase the cross-linking density, and to obtain a coating film having adhesion and the like. Examples of the compound having one or more unsaturated double bonds in one molecule of the reactive diluent system (C) include: (meth)acrylic acid 2-ethylhexyl, (meth)acrylic acid cyclohexyl (meth)acrylic acid alkyl esters such as esters; (meth)acrylic acid hydroxyalkyl esters such as (meth)acrylic acid-2-hydroxyethyl ester and (meth)acrylic acid-2-hydroxypropyl ester; ethanol Mono- or di(meth)acrylates of alkylene oxide derivatives such as glycol, propylene glycol, diethylene glycol, dipropylene glycol, etc.; hexylene glycol, trimethylolpropane, pentaerythritol, ditrimethylolpropane, Polyhydric alcohols such as dipentaerythritol and hydroxyethyl isocyanurate or poly(meth)acrylates of such ethylene oxide or propylene oxide adducts; phenoxyethyl (methyl) Acrylates, polyethoxy di(meth)acrylate of bisphenol A and other phenols, (meth)acrylates of ethylene oxide or propylene oxide adducts; glyceryl diglycidyl ether, triglyceryl ether, etc. (meth)acrylate esters of glyceryl ethers such as hydroxymethylpropane triglyceryl ether and triglycidyl isocyanurate; and melamine (meth)acrylate, etc. Among these, liquid ones are preferred in terms of reactivity and dilution properties.

Moreover, a compound which has an unsaturated double bond in one molecule and further has a carboxyl group can also be used as (C) a reactive diluent. As such a compound, a reaction product of a saturated or unsaturated dibasic acid anhydride and a (meth)acrylic acid ester having one hydroxyl group per molecule can be used. For example, succinic anhydride, maleic anhydride, and phthalic anhydride can be used. , tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, itaconic anhydride, methylendomethylenetetrahydrophthalic anhydride Saturated or unsaturated dibasic acid anhydrides such as phthalic anhydride, and hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, polyethylene glycol mono(methyl) )acrylate, glyceryl di(meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, phenylglyceryl ether Half-esters obtained by reacting (meth)acrylates such as (meth)acrylates with one hydroxyl group per molecule at an equal molar ratio. These (C) reactive diluents can be used alone or in combination of two or more types.

In addition, the content of (C) the reactive diluent is preferably in the range of approximately 2 to 60% by mass relative to the (A) alkali-soluble resin from the viewpoint of the properties and sensitivity of the formed coating film, and The preferred range is 10 to 40% by mass.

[(D) Thermosetting resin] Examples of (D) thermosetting resins include polyfunctional epoxy compounds, polyfunctional oxetane compounds, episulfide resins, and the like having two or more cyclic ether groups and/or cyclic thioethers in the molecule. groups, compounds having two or more isocyanate groups or blocked isocyanate groups in one molecule, such as polyisocyanate compounds and blocked isocyanate compounds, amine resins such as melamine resin and benzoguanamine resin and their derivatives, bismale Well-known thermosetting resins such as acyl imine, oxazine, cyclic carbonate compound, and carbodiimide resin.

As the epoxy resin system, a well-known and commonly used polyfunctional epoxy resin having at least two epoxy groups in one molecule can be used. Epoxy resins can be liquid, solid or semi-solid. Examples of polyfunctional epoxy resins include bisphenol A-type epoxy resin; brominated epoxy resin; novolac-type epoxy resin; bisphenol F-type epoxy resin; hydrogenated bisphenol A-type epoxy resin; and glycidylamine type epoxy resin; hydantoin type epoxy resin; alicyclic epoxy resin; trihydroxytoluene type epoxy resin; dixylenol type or biphenyl type epoxy resin or mixtures thereof; bisphenol S type epoxy resin; bisphenol A novolac epoxy resin; tetrahydroxyphenyl ethane type epoxy resin; complex cyclic epoxy resin; diglycidyl phthalate resin; tetraglycidyl xylyl ethane Alkane resin; naphthyl-containing epoxy resin; epoxy resin with dicyclopentadiene skeleton; glycidyl methacrylate copolymer epoxy resin; cyclohexyl maleimide and glycidyl methacrylate Copolymerized epoxy resin; epoxy modified polybutadiene rubber derivatives; CTBN modified epoxy resin, etc., but are not limited to these. As the epoxy resin system, preferred are bisphenol A type or bisphenol F type novolac type epoxy resin, dixylenol type epoxy resin, biphenyl type epoxy resin, biphenyl novolac type (biphenyl aralkane) base type) epoxy resin, naphthalene type epoxy resin or a mixture of these.

Among them, from the viewpoint of improving resolution and light resistance, an epoxy resin having a hydrogenated cyclic skeleton is preferred.

Examples of the epoxy resin having a hydrogenated cyclic skeleton include YX-8000, YX-8034, and YX-8040 manufactured by Mitsubishi Chemical, ST-3000, ST-4000D manufactured by Nippon Steel Chemical, and EP- 4080 etc.

As explained above, the content of (D) thermosetting resin relative to (A) alkali-soluble resin is preferably in the range of about 30 to 90 mass %, and more preferably in the range of 40 to 70 mass %.

[(E) Orthoester compound] The (E) orthoester compound discovered in the present invention does not react with the substrate or ink components, and after the solder resist composition containing it is coated on the substrate, in the initial drying step It will evaporate and will not remain in the composition. Therefore, not only can the passivation of (B) the photopolymerization initiator having an oxime bond be suppressed, but there is also the following advantage: "There is no concern about adversely affecting the developability or the characteristics of the cured film." As described above, in the present invention, (E) the orthoester compound and (B) the photopolymerization initiator system having an oxime bond are blended into the same system.

Preferable examples of the (E) orthoester compound used in the present invention include trimethyl orthoformate, triethyl orthoformate, tripropyl orthoformate, tributyl orthoformate, trimethyl orthoacetate, and orthoformate. Triethyl acetate, tripropyl orthoacetate, tributyl orthoacetate, trimethyl orthopropionate, triethyl orthopropionate, propyl orthopropionate, butyl orthopropionate. Among them, trimethyl orthoformate, triethyl orthoformate, and triethyl orthoacetate are more preferred, and triethyl orthoformate is most preferred.

(E) The orthoester compound is preferably in the range of 1 to 10% by mass relative to the total amount of the hardener composition in the two-component system in order to efficiently exhibit the performance. The amount of the (E) orthoester compound is preferably contained in an amount in the range of 3 to 6 mass %.

[colorant] As the colorant, well-known ones can be used. Moreover, the colorant system may be used individually by 1 type, and may be used in combination of 2 or more types.

As the colorant, commonly known colorants such as red, blue, green, yellow, white, and black can be used, and any of pigments, dyes, and pigments can be used. More specifically, examples of colorants include those listed below with a color index number (C.I.; issued by The Society of Dyers and Colourists).

Red colorants include monoazo series, disazo series, azo lake series, benzimidazolone series, perylene series, diketopyrrolopyrrole series, condensed azo series, anthraquinone series, and quinacridone series Department etc. Examples of blue colorants include phthalocyanine-based and anthraquinone-based colorants. For pigment-based colorants, compounds classified as pigments can be used. In addition to these, metal-substituted or unsubstituted phthalocyanin compounds can also be used. Green colorants include phthalocyanin-based, anthraquinone-based, and perylene-based colorants. In addition to these, metal-substituted or unsubstituted phthalocyanin compounds may also be used. Examples of the yellow colorant system include monoazo system, disazo system, condensed azo system, benzimidazolone system, isoindolinone system, anthraquinone system, etc. Examples of the white colorant include rutile type or anatase type titanium dioxide. Black colorants include carbon black, black lead, iron oxide, titanium black, iron oxide, anthraquinone, cobalt oxide, copper oxide, manganese, antimony oxide, nickel oxide, perylene, Aniline series, molybdenum sulfide, bismuth sulfide, etc. In addition, depending on the purpose of adjusting the color tone, purple, orange, brown, etc. colorants can also be added.

When the curable resin composition of the present invention is used as a solder resist composition, the content of the colorant is 0.03 to 7 mass % in terms of solid content relative to the total amount of the curable resin composition of the present invention. More preferably, it is 0.05% by mass to 5% by mass.

Here, since the curable resin composition of the present invention can suppress the passivation of (B) the photopolymerization initiator having an oxime bond, it can be suitably used in black masking agents and the like using a highly sensitive photopolymerization initiator. When the curable resin composition of the present invention is used as a black masking agent, etc., the content of the colorant, from the viewpoint of improving the masking properties of the cured product, is greater than the total amount of the curable resin composition of the present invention. , when the colorant is contained at 5 to 50% by mass in terms of solid content, it is preferable because it can achieve both masking and analytical properties. More preferably, it is 10 mass % to 30 mass %. When the curable resin composition of the present invention is used as a black masking agent or the like, the colorant system preferably contains carbon black, and it is preferable to use carbon black and a mixed black colorant in combination. Especially when using carbon black and a mixed black colorant in combination, the total amount of carbon black in the curable resin composition is preferably 4 to 10% by mass in terms of solid content, and the mixed black is preferably The system colorant is set to 8 to 20% by mass.

Furthermore, the so-called mixed black colorant refers to a colorant in which a red colorant, a blue colorant, a green colorant, a yellow colorant, a purple colorant, an orange colorant, etc. are mixed in order to obtain black or a color close to black. And the colorant obtained. In the mixed black colorant system, it is preferable to mix each colorant in advance and then add it to the resin composition. Each colorant constituting the mixed black colorant may be added to the resin composition individually.

[Other ingredients] In the curable resin composition of the present invention, it is of course possible to further incorporate additives as other components as necessary within the scope of the purpose of the present invention. Examples of such components include photopolymerization initiators other than (B) the photopolymerization initiator having an oxime bond, solvents, thermal polymerization inhibitors, ultraviolet absorbers, coupling agents, plasticizers, and flame retardants. , antistatic agent, anti-aging agent, antibacterial and antifungal agent, leveling agent, thickener, adhesion imparting agent, thixotropic viscosity reducing property imparting agent, photoinitiating additive, sensitizer, photobase generator Organic fillers, inorganic fillers, release agents, surface treatment agents, dispersants, dispersion aids, surface modifiers, stabilizers, fluorescent agents, thermoplastic resins, elastomers, urethane beads, etc. body, cellulose resin, etc.

[hardened material] When forming a cured product using the curable composition of the present invention, the composition is applied on a substrate, and after the solvent is evaporated and dried, the obtained resin layer is exposed (light irradiation), whereby the exposed portion ( The part exposed to light) is hardened. Specifically, according to the contact or non-contact method, by forming a patterned mask and using selective active energy rays for exposure, or using a laser direct exposure machine for direct pattern exposure, with alkali Aqueous solution (such as 0.3~3% by mass sodium carbonate aqueous solution) is used to develop the unexposed parts to form a resist pattern. Furthermore, by heating to a temperature of about 100 to 180°C and thermally hardening (post-hardening), it is possible to develop excellent properties such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical properties. Hardened film (hardened material).

[Electronic parts] Furthermore, the present invention also provides electronic components having the above-mentioned hardened material. By using the curable resin composition of the present invention, electronic components with high quality, durability, and reliability can be provided. However, the so-called electronic components in the present invention refer to components used in electronic circuits. In addition to active components such as printed wiring boards, transistors, light-emitting diodes, laser diodes, etc., they also include resistors, Passive parts of capacitors, inductors, connectors, etc.

[Production and use methods of the curable resin composition of the present invention] The curable resin composition of the present invention can be prepared by mixing and dispersing the components of the main component composition and the curing agent composition in designated amounts using, for example, a three-roller mill, etc. The two types of compositions are prepared, and then the two types of compositions are mixed during use.

When forming a coating film using the curable resin composition of the present invention, it can be completed as follows. First, a curable resin composition is applied on a substrate, and after the solvent is evaporated and dried, the obtained resin layer is exposed (light irradiation) to harden the exposed portion (light irradiation portion). Specifically, according to the contact or non-contact method, exposure is performed by forming a patterned mask and using selective active energy rays, or direct pattern exposure is performed using a laser direct exposure machine. After that, the unexposed portion is developed with an alkaline aqueous solution (for example, 0.3 to 3 mass % sodium carbonate aqueous solution) to form a resist pattern. Furthermore, by heating to a temperature of about 100 to 180°C and thermally hardening (post-hardening), it is possible to develop excellent properties such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical properties. Sclerotic membrane.

Here, the curable resin composition of the present invention is, for example, adjusted to a viscosity suitable for the coating method using an organic solvent, and the curable resin composition is prepared by a dip coating method, a flow coating method, a roller coating method, or a rod coating method. After coating on the substrate by methods such as screen printing, curtain coating, etc., the organic solvent contained in the composition is evaporated and dried (pre-drying) at a temperature of approximately 60 to 100°C. A resin layer that is dry to the touch can also be formed.

As the base material, in addition to a printed wiring board or a flexible printed wiring board in which a circuit is formed with copper or the like in advance, phenol paper, epoxy paper, epoxy glass cloth, glass polyimide, Glass cloth/epoxy nonwoven fabric, glass cloth/epoxy paper, epoxy synthetic fiber, fluororesin, polyethylene, polyphenylene ether, polyphenylene ether, cyanate ester, etc. for copper-clad laminates for high-frequency circuits, etc. Copper-clad laminates of all grades of material (FR-4, etc.), and other examples include metal substrates, polyimide films, PET films, polyethylene naphthalate (PEN) films, glass substrates, ceramic substrates, Wafer board etc.

For volatilization drying or thermal hardening, for example, hot air circulation drying ovens, IR ovens, hot plates, convection ovens, etc. can be used (using a heat source with an air heating method by steam and making the hot air in the dryer contact with counter flow) method and by blowing it onto the support through a nozzle).

As an exposure machine used for active energy ray irradiation, any device equipped with a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, a mercury short-arc lamp, etc., and which irradiates ultraviolet rays in the range of 350 to 450 nm can be used. Use a direct rendering device (such as a laser direct imaging device that uses CAD data from a computer to draw an image using a direct laser). As the light source or laser light source of the direct drawing machine, the maximum wavelength only needs to be in the range of 350~410nm. The amount of exposure used to form an image varies depending on the film thickness, etc., but is generally 20~2000mJ/ ^cm2 , and preferably can be set within the range of 20~1500mJ/ ^cm2 .

As a developing method, dipping method, rinsing method, spray method, brush method, etc. can be used; as a developing solution, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, Alkaline aqueous solutions of amines, etc. [Example]

The present invention will be specifically described below by showing examples and comparative examples. However, the present invention is not limited to the following examples and there is no need to elaborate further. However, unless otherwise stated, the "parts" and "%" expressed are based on mass.

A two-component curable resin composition containing a main component composition and a curing agent composition is produced in the following manner.

Example 1 Utilize 100 parts of alkali-soluble resin, 7.2 parts of photopolymerization initiator, 3.8 parts of additives, 28.6 parts of reactive diluent, 3.3 parts of solvent A555, 10.0 parts of carbon black, 10.0 parts of perylene red and 10.0 parts of phthalocyanine blue 3 A roller mill was used for mixing and dispersion, and the main ingredient composition of Example 1 was obtained. On the other hand, 56.7 parts of thermosetting resin, 4.0 parts of photopolymerization initiator A having an oxime bond, 20.0 parts of solvent B, and 4.0 parts of trimethyl orthoformate were mixed and dispersed using a three-roller mill to obtain Hardener composition of Example 1.

Example 2 The main ingredient composition of Example 2 was obtained by the same method as Example 1. On the other hand, the hardener composition of Example 2 was obtained by the same method as Example 1, except that trimethyl orthoformate was replaced with triethyl orthoformate.

Example 3 The main ingredient composition of Example 3 was obtained by the same method as Example 1. On the other hand, the hardener composition of Example 3 was obtained by the same method as Example 1, except that trimethyl orthoformate was replaced with triethyl orthoacetate.

Example 4 The main ingredient composition of Example 4 was obtained by the same method as Example 1. On the other hand, except that the photopolymerization initiator A having an oxime bond was replaced with the photopolymerization initiator B having an oxime bond, the hardener composition of Example 4 was obtained in the same manner as in Example 1. things.

Example 5 The main ingredient composition of Example 5 was obtained by the same method as Example 1. On the other hand, except that the photopolymerization initiator A having an oxime bond was replaced with the photopolymerization initiator B having an oxime bond, the hardener composition of Example 5 was obtained in the same manner as in Example 2. things.

Example 6 The main ingredient composition of Example 6 was obtained by the same method as Example 1. On the other hand, except that the photopolymerization initiator A having an oxime bond was replaced with the photopolymerization initiator B having an oxime bond, the hardener composition of Example 6 was obtained in the same manner as in Example 3. things.

Example 7 The main ingredient composition of Example 6 was obtained by the same method as Example 1. On the other hand, the hardener composition of Example 7 was obtained by the same method as Example 2, except that triethyl orthoformate was replaced with 0.8 parts.

Example 8 The main ingredient composition of Example 6 was obtained by the same method as Example 1. On the other hand, except that triethyl orthoformate was replaced with 9.0 parts, the hardener composition of Example 7 was obtained by the same method as Example 2.

Comparative example 1 Utilize 100 parts of alkali-soluble resin, 7.2 parts of photopolymerization initiator, 3.8 parts of additives, 28.6 parts of reactive diluent, 3.3 parts of solvent A555, 10.0 parts of carbon black, 10.0 parts of perylene red and 10.0 parts of phthalocyanine blue 3 The mixture was mixed and dispersed using a roller mill to obtain the main ingredient composition of Comparative Example 1. On the other hand, 56.7 parts of the thermosetting resin, 4.0 parts of the photopolymerization initiator A having an oxime bond, and 20.0 parts of the solvent B were mixed and dispersed using a three-roll mill to obtain the hardener composition of Comparative Example 1. .

Comparative example 2 The main ingredient composition of Comparative Example 2 was obtained by the same method as Comparative Example 1. On the other hand, the hardener composition of Comparative Example 2 was obtained in the same manner as Comparative Example 1, except that the blending amount of the photopolymerization initiator A having an oxime bond was changed to 8.0 parts.

Comparative example 3 The main ingredient composition of Comparative Example 3 was obtained by the same method as Comparative Example 1. On the other hand, the hardener composition of Comparative Example 3 was obtained in the same manner as Comparative Example 1, except that the blending amount of the photopolymerization initiator A having an oxime bond was changed to 12.0 parts.

Comparative example 4 The main ingredient composition of Comparative Example 4 was obtained by the same method as Comparative Example 1. On the other hand, the hardener composition of Comparative Example 4 was obtained by the same method as Comparative Example 1, except that the photopolymerization initiator A having an oxime bond was replaced with the photopolymerization initiator B having an oxime bond. things.

The compositions of Examples 1 to 8 and Comparative Examples 1 to 4 are shown in Table 1 below. Alkali-soluble resin: CyclomerP (ACA) Z250 (Daicel Co., Ltd.) (Carboxyl-containing acrylic copolymer with an alicyclic skeleton) Photopolymerization initiator: Omnirad TPO (IGM Resins) Additive: BYK-361N (nonionic system Surfactant; BYK Co., Ltd.) Reactive diluent: LR8863 (EO modified trimethylolpropane triacrylate; BASF Japan Co., Ltd.) Solvent A: Dowanol PM (propylene glycol monomethyl ether; Dow Chemical Japan Co., Ltd. Co., Ltd.) Carbon black: MA-100 (carbon black, Mitsubishi Chemical Co., Ltd.) Perylene red (perylene-based red colorant) (CIPigment Red 149) Phthalocyanine blue (phthalocyanin-based blue colorant) (CIPigment Blue 15:3) Thermosetting resin: YX-8034 (hydrogenated bisphenol A type epoxy resin; Mitsubishi Chemical Co., Ltd.) Photopolymerization initiator A with oxime bond: TOE-04-A3 (Nihon Chemical Industry Co., Ltd. Company) Photopolymerization initiator B having an oxime bond: Irgacure OXE02 (BASF Japan Co., Ltd.) Solvent B: Propylene Carbonate (Kanto Chemical Co., Ltd.)

Test example For the respective curable resin compositions of Examples 1 to 8 and Comparative Examples 1 to 4, coating films were prepared from the samples left at 50°C for 7 days, and the sensitivity of the coating films was measured. A test was conducted to confirm to what extent the passivation of the photopolymerization initiator having an oxime bond can be suppressed.

Test method ＜Preparation of coating film＞ The respective main component compositions and hardener compositions of the obtained Examples 1 to 8 and Comparative Examples 1 to 4 were thoroughly mixed, and then applied to the glass with a coater so that the film thickness after drying became 10 μm. Then, they were dried in a hot air circulation drying oven at 80° C. for 30 minutes to form separate coating films (initial stage). On the other hand, separately prepare separate main agent compositions and hardener compositions and place them in a constant temperature bath at 50°C for 7 days. These compositions are also mixed and dried in the same way as above. to make a coating film (after 7 days at 50°C).

<Sensitivity> Adhere Step Tablet (Kodak No.2) to each dried coating film, and use a metal halide lamp exposure machine to expose at an exposure dose of 1000mJ/cm ^2. By 1 mass% After developing the sodium carbonate aqueous solution at 30°C for 1 minute at a spray pressure of 0.2MPa, the sensitivity was evaluated based on the number of remaining segments and the number of glossy segments obtained from the Step Tablet. The results are shown in Table 2 below.

[OD value] The film side of the glass base material (initial stage, 50°C and 7 days later) produced by the above-mentioned coating film production is facing the measuring device and mounted on a transmission density meter (manufactured by SAKATA INX ENG Co., Ltd., model: X-Rite 361T, light source Wavelength: 400~800nm) to evaluate the OD value. The evaluation criteria are as follows. ○···OD value is more than 4 △···OD value is above 3 and below 4 ×···OD value is less than 3

＜Result＞ Regarding the sensitivity, it can be seen that Examples 1 to 8 effectively suppressed the decrease in the number of remaining stages and the number of glossy stages from the initial stage to the decrease in these values after 7 days at 50°C. This is considered to be because the blending of the (E) orthoester compound effectively suppresses the time-dependent passivation of the photopolymerization initiator having an oxime bond. In this way, it was confirmed that the curable resin composition of the present invention has excellent storage stability under relatively severe conditions. In addition, although the description of the evaluation results of the OD value in Table 2 is omitted, the initial OD value of Examples 1 to 8 and the OD value after 7 days at 50°C both exceeded 4 (evaluation standard :〇). Regarding the evaluation results of the OD values of Comparative Examples 1 to 4, the description in Table 2 is similarly omitted. Although the initial OD value showed more than 4 (evaluation standard: 0), after 7 days at 50°C, However, a coating film could not be formed, so evaluation could not be carried out. In this way, since the curable resin composition of the present invention effectively suppresses the time-dependent passivation of the photopolymerization initiator having an oxime bond, the initial OD value and the OD value after 7 days at 50° C. are also unchanged. Variation, may be suitable for use as a black masking agent.

Claims (6)

An alkali-developable curable resin composition, which is an alkali-developable curable resin composition that constitutes at least a two-liquid system and contains at least (A) an alkali-soluble resin, (B) a photopolymerization initiator having an oxime bond, and ( C) reactive diluent and (D) thermosetting resin, and the aforementioned (B) photopolymerization initiator having an oxime bond is blended in a composition different from the aforementioned (A) alkali-soluble resin, which is characterized by: At least one type of (E) orthoester compound is blended with the aforementioned photopolymerization initiator having an oxime bond. The alkali-developable curable resin composition of claim 1, wherein the (E) orthoester compound is selected from the group consisting of trimethyl orthoformate, triethyl orthoformate, tripropyl orthoformate, and tributyl orthoformate. , trimethyl orthoacetate, triethyl orthoacetate, tripropyl orthoacetate, tributyl orthoacetate, trimethyl orthopropionate, triethyl orthopropionate, propyl orthopropionate and butyl orthopropionate At least one of the groups formed. The alkali-developable curable resin composition of claim 1 or 2, wherein the aforementioned (E) orthoester compound is selected from the group consisting of trimethyl orthoformate, triethyl orthoformate, and triethyl orthoacetate. Group at least 1 type. The alkali-developable curable resin composition according to any one of claims 1 to 3, wherein the (E) orthoester compound is triethyl orthoformate. A cured product characterized by being obtained by curing the alkali-developable curable resin composition according to any one of claims 1 to 4. An electronic component characterized by having the hardened object of claim 5.