KR20170012050A - Curable resin composition, dry film, cured product and printed wiring board - Google Patents

Abstract

Provided are a curable resin composition having excellent thermal resistance and elongation rate of a cured product, a dry film having a resin layer obtained from the composition, a cured product of the composition or the resin layer of the dry film, and a printed wiring board having the cured product. The curable resin composition comprises: (A) a resin containing a carboxyl group; (B) a thermosetting component; and (C) a boric acid ester compound.

Description

TECHNICAL FIELD [0001] The present invention relates to a curable resin composition, a dry film, a cured product and a printed wiring board,

The present invention relates to a curable resin composition, a dry film, a cured product and a printed wiring board.

In the printed wiring board, a solder resist is formed on a substrate having a conductor layer of a circuit pattern. Conventionally, various curable resin compositions have been proposed as the material of the permanent protective film such as the interlayer insulating material of the printed wiring board and the coverlay of the flexible printed wiring board, not limited to such solder resist.

For example, Patent Document 1 discloses a photosensitive curable resin composition for a permanent resist comprising a polymer having a carboxyl group, a photopolymerizable compound having an ethylenic unsaturated bond, and a photopolymerization initiator. As a material of the permanent protective film, a thermosetting resin composition is also known (for example, Patent Document 2).

The permanent protective film as described above is required to have resistance to deterioration such as peeling and cracking, that is, reliability even in a severe environment. One of the characteristics for achieving high reliability is heat resistance. For example, the solder resist needs solder heat resistance. In addition, a printed wiring board that can be used in a high-temperature environment, for example, a printed wiring board for vehicle mounting, requires a permanent protective film having high heat resistance. In the case where the permanent protective film is patterned by cutting the cured product by laser processing, it is necessary to impart heat resistance so as not to be deteriorated by the laser beam.

Another characteristic for achieving high reliability is an elongation percentage. When the elongation percentage is low, cracks tend to occur due to the impact. Further, in the case of patterning by laser machining, there is a fear that a crack is generated due to the opening by the laser machining.

Japanese Patent Laid-Open No. 2005-99647 (claims) Japanese Patent Application Laid-Open No. 2011-63653 (claims)

Accordingly, an object of the present invention is to provide a curable resin composition which is excellent in heat resistance and elongation of a cured product, a dry film having a resin layer obtained from the composition, a cured resin layer of the composition or the dry film, and a printed wiring board having the cured product I have to.

The inventors of the present invention have conducted intensive studies in view of the above, and as a result, found that the above problems can be solved by blending a boric acid ester compound, and the present invention has been accomplished.

That is, the curable resin composition of the present invention is characterized by containing (A) a carboxyl group-containing resin, (B) a thermosetting component, and (C) a boric acid ester compound.

The curable resin composition of the present invention preferably contains a liquid epoxy resin as the (B) thermosetting component.

The curable resin composition of the present invention preferably further comprises a photopolymerization initiator.

The curable resin composition of the present invention is preferably used for forming a solder resist, a coverlay, or an interlayer insulating material.

The dry film of the present invention is characterized by having a resin layer obtained by applying the curable resin composition to a film and drying the film.

The cured product of the present invention is characterized by being obtained by curing the resin layer of the curable resin composition or the dry film.

The printed wiring board of the present invention is characterized by having the cured product.

According to the present invention, there is provided a curable resin composition which is excellent in heat resistance and elongation of a cured product, a dry film having a resin layer obtained from the composition, a cured product of the composition or the resin layer of the dry film, and a printed wiring board having the cured product .

1 is a schematic side view showing two test tubes used for liquid phase determination of a thermosetting component.

The curable resin composition of the present invention is characterized by containing (A) a carboxyl group-containing resin, (B) a thermosetting component, and (C) a boric acid ester compound.

In the curable resin composition of the present invention, the addition of the boric acid ester compound (C) not only improves the heat resistance and elongation, but also improves the drying management width in the case of the alkali developing type photo-curable resin composition.

The dry management width (also referred to as "development life") is the width of a drying condition in which development defects do not occur in the drying step after the alkali developing type photo-curable resin composition is applied to a substrate before development. If the drying control width is short, it should be dried at a definite drying temperature and drying time. In an actual manufacturing process, it is not easy to shorten the drying time, and as a result, it becomes difficult to pattern the film with good developing properties. Conventionally, the alkali developing type photocurable resin composition used for forming a solder resist having high heat resistance has a problem that the drying management width is short. It is considered that the cause of the short dry management width of such an alkali developing type photocurable resin composition is a thermosetting component to be blended for imparting high heat resistance. For example, as compared with the case where a solid or powdered epoxy resin is used as the thermosetting component, the use of a liquid epoxy resin increases the reactivity and can remarkably improve the high heat resistance, but the occurrence of thermal blurring easily occurs Therefore, the drying management width is shortened. Further, in the case of containing melamine or the like in order to improve the high heat resistance, thermal blur easily occurs. However, as described above, according to the present invention, it is possible to obtain an alkali-developable photocurable resin composition excellent in dry management width.

When the curable resin composition of the present invention is an alkali developing type photo-curable resin composition, even when a liquid thermosetting component, particularly a liquid epoxy resin, which has a problem that thermal blurring is likely to occur is blended, Do.

Further, by mixing the boric acid ester compound (C), adhesion between the cured product and the copper circuit of the printed wiring board can be improved.

Hereinafter, the components contained in the curable resin composition of the present invention will be described in detail.

[(A) Resin containing a carboxyl group]

The carboxyl group of the carboxyl group-containing resin enables the thermosetting reaction with the (B) thermosetting component to be enabled. In addition, by the carboxyl group, alkali development becomes possible. From the viewpoints of photo-curability and resistance to development, it is preferable to have an ethylenically unsaturated bond in the molecule other than a carboxyl group, but only a carboxyl group-containing water not having an ethylenically unsaturated double bond may be used. As the ethylenically unsaturated double bond, those derived from acrylic acid or methacrylic acid or a derivative thereof are preferable.

In the curable resin composition of the present invention, the carboxyl group-containing resin (A) preferably has at least one of a phenol novolak type, a bisphenol novolak type and a cresol novolak type structure from the viewpoint of heat resistance. In addition to the solder heat resistance, (A) the carboxyl group-containing resin is more preferably a phenol novolak-type structure from the viewpoint of adhesiveness of the underfill. For example, underfill for wire bonding or flip chip mounting is used It can be suitably used for a printed wiring board for mounting.

Specific examples of the carboxyl group-containing resin include the following compounds (any of oligomers and polymers) listed below.

(1) a method in which a (meth) acrylic acid is reacted with a bifunctional or higher polyfunctional epoxy resin to obtain a carboxyl group containing a dibasic acid anhydride such as phthalic anhydride, tetrahydrophthalic anhydride or hexahydrophthalic anhydride added to the hydroxyl groups present in the side chain Photosensitive resin. Here, the bifunctional or higher polyfunctional epoxy resin is preferably a solid.

(2) a carboxyl group-containing photosensitive resin obtained by reacting a polyfunctional epoxy resin obtained by epoxidizing a hydroxyl group of a bifunctional epoxy resin with epichlorohydrin, with (meth) acrylic acid and adding a dibasic acid anhydride to the generated hydroxyl group. Here, the bifunctional epoxy resin is preferably a solid.

(3) reacting an epoxy compound having two or more epoxy groups in one molecule with a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule and an unsaturated group-containing monocarboxylic acid such as (meth) acrylic acid And reacting the resulting alcoholic hydroxyl group of the reaction product with a polybasic acid anhydride such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, or adipic anhydride.

(4) A process for producing a polyurethane resin, which comprises the steps of mixing a bisphenol A, a bisphenol F, a bisphenol S, a novolac phenol resin, poly-p-hydroxystyrene, a condensate of naphthol and an aldehyde, a condensate of dihydroxynaphthalene and an aldehyde A reaction product obtained by reacting a compound having two or more phenolic hydroxyl groups with an alkylene oxide such as ethylene oxide or propylene oxide is reacted with a monocarboxylic acid containing an unsaturated group such as (meth) acrylic acid to obtain a reaction product A carboxyl group-containing photosensitive resin obtained by reacting a polybasic acid anhydride.

(5) reacting a reaction product obtained by reacting a compound having two or more phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate, with an unsaturated group-containing monocarboxylic acid , And a reaction product obtained is reacted with a polybasic acid anhydride.

(6) A process for producing a polyisocyanate compound, which comprises reacting a diisocyanate compound such as an aliphatic diisocyanate, a branched aliphatic diisocyanate, an alicyclic diisocyanate or an aromatic diisocyanate with a polycarbonate-based polyol, a polyether- , A terminal carboxyl group-containing urethane resin obtained by reacting an acid anhydride at the terminal of a urethane resin by a heavy-chain reaction of a diol compound such as a bisphenol A-based alkylene oxide adduct diol, a phenolic hydroxyl group and a compound having an alcoholic hydroxyl group Suzy.

(7) In the synthesis of a carboxyl group-containing urethane resin by diisocyanate and a carboxyl group-containing dialcohol compound containing a carboxyl group such as dimethylolpropionic acid or dimethylolbutyric acid and a diol compound, a hydroxyalkyl (meth) acrylate or the like A carboxyl group-containing urethane resin obtained by adding a compound having one hydroxyl group and at least one (meth) acryloyl group in a molecule to a terminal (meth) acrylate.

(8) In the synthesis of a carboxyl group-containing urethane resin by the reaction of a diisocyanate with a carboxyl group-containing dialcohol compound and a diol compound, an isomeric reaction product of isophorone diisocyanate and pentaerythritol triacrylate, (Meth) acryloyl group-containing urethane resin obtained by adding a compound having two or more isocyanato groups and at least one (meth) acryloyl group.

(9) A carboxyl group-containing photosensitive resin obtained by copolymerization of an unsaturated carboxylic acid such as (meth) acrylic acid with an unsaturated group-containing compound such as styrene,? -Methylstyrene, lower alkyl (meth) acrylate or isobutylene.

(10) A carboxyl group-containing polyester resin obtained by reacting a polyfunctional oxetane resin with a dicarboxylic acid such as adipic acid, phthalic acid, or hexahydrophthalic acid, and adding a dibasic acid anhydride to the resulting primary hydroxyl group.

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

Here, (meth) acrylate is generically referred to as acrylate, methacrylate and a mixture thereof, and the same applies to other similar expressions below.

Since the carboxyl group-containing resin (A) has a large number of carboxyl groups in the side chain of the backbone polymer, development with a dilute alkaline aqueous solution becomes possible.

The acid value of the carboxyl group-containing resin (A) is suitably in the range of 30 to 200 mgKOH / g, more preferably in the range of 30 to 150 mgKOH / g, and particularly preferably in the range of 45 to 120 mgKOH / g. When the acid value of the carboxyl group-containing resin is 30 mgKOH / g or more, the alkali develops satisfactorily. On the other hand, when the acid value is 200 mgKOH / g or less, dissolution of the exposed portion by the developer can be suppressed, , It is possible to inhibit dissolution and peeling in the developing solution without distinction between the exposed portion and the unexposed portion, whereby a patterned resist can be satisfactorily drawn.

The weight average molecular weight Mw (weight average molecular weight in terms of polystyrene) of the carboxyl group-containing resin (A) measured by gel permeation chromatography (GPC), for example, is different from resin skeleton but is larger than 4,000 150,000 or less, more preferably 5,000 to 100,000. When the weight average molecular weight is more than 4,000, the touch-tack drying performance is good, the wettability in the coated film after exposure is good, the film reduction during development can be suppressed, and the decrease in resolution can be suppressed. On the other hand, when the weight average molecular weight is 150,000 or less, developability is improved.

[(B) Thermal curing component]

The thermosetting component (B) may be any one that reacts with the carboxyl-containing resin (A), and examples thereof include an epoxy compound, an amino resin, an oxetane compound, and an isocyanate compound. Among them, an epoxy compound is preferable. Examples of the epoxy compound include a bifunctional epoxy resin having two epoxy groups in the molecule and a polyfunctional epoxy resin having a large number of epoxy groups in the molecule. From the viewpoint of heat resistance, the thermosetting component is preferably liquid.

Examples of the epoxy compound include epoxidized vegetable oil; Bisphenol A type epoxy resin; Hydroquinone type epoxy resins, bisphenol type epoxy resins, and thioether type epoxy resins; Brominated epoxy resin; Novolak type epoxy resins; Biphenol novolak type epoxy resins; Bisphenol F type epoxy resin; Hydrogenated bisphenol A type epoxy resin; Glycidylamine type epoxy resins; Hidanto dolphin epoxy resin; Alicyclic epoxy resins; Trihydroxyphenylmethane type epoxy resin; Biscylenol type or biphenol type epoxy resins or mixtures thereof; Bisphenol S type epoxy resin; Bisphenol A novolak type epoxy resin; Tetraphenylol ethane type epoxy resin; Heterocyclic epoxy resins; Diglycidyl phthalate resin; Tetraglycidylsilanoy ethane resin; A naphthalene group-containing epoxy resin; An epoxy resin having a dicyclopentadiene skeleton; Glycidyl methacrylate copolymer epoxy resin; A copolymerized epoxy resin of cyclohexylmaleimide and glycidyl methacrylate; Epoxy-modified polybutadiene rubber derivatives, CTBN-modified epoxy resins, and the like, but are not limited thereto. From the viewpoint of reactivity, an epoxy compound having two or more functional groups is preferable.

The epoxy compound may be a solid epoxy resin, a semi-solid epoxy resin, or a liquid epoxy resin, but a liquid epoxy resin is preferable. In the present specification, the solid epoxy resin refers to an epoxy resin which is solid at 40 占 폚, and the semi-solid epoxy resin refers to an epoxy resin which is solid at 20 占 폚 and liquid at 40 占 폚, ≪ / RTI > In this specification, the definitions of solid, semi-solid and liquid phase are also based on other thermoset components.

The determination of the liquid phase shall be made in accordance with the Attachment 2 (Method for Confirmation of Liquid Phase) of the Japanese Ministry of Justice (1989 Decree of the Japanese Autonomy Law No.1) concerning the testing and properties of dangerous substances.

(1) Device

Constant temperature bath:

Use a stirrer, heater, thermometer, automatic thermostat (temperature controllable to ± 0.1 ℃) and a depth of 150mm or more.

In the determination of the epoxy resin used in the examples described later, all of 22 liters of tap water were mixed with a low-temperature constant-temperature water bath (type BU300) and a charging type thermostatting thermometer (type BF500) (Type BF500) to the set temperature (20 ° C or 40 ° C) by turning on the power of the thermometer (type BF500) attached to the thermometer (type BU300) , But can be used for any device that can make the same adjustments.

examiner:

As shown in Fig. 1, a test tube was made of a plain cylindrical transparent glass having an inner diameter of 30 mm and a height of 120 mm. Markers 31 and 32 were attached at the positions of 55 mm and 85 mm from the bottom of the tube, The inlet of the test tube is sealed with a rubber stopper 33b having the same size and the same mark as that of the liquid phase determination test tube 30a sealed with the cap 33a and having a hole for inserting and supporting a thermometer in the center, A temperature measuring test tube 30b in which a thermometer 34 is inserted into a rubber stopper 33b is used. Hereinafter, a line drawn at a height of 55 mm from the bottom of the tube is referred to as an "A line", and a line at a height of 85 mm from the bottom of the tube is referred to as a "B line".

As the thermometer 34, a temperature range of 0 to 50 占 폚 is to be measured, while a thermometer 34 (SOP-58 scale range: 20 to 50 占 폚) specified in JIS B7410 (1982) It may be possible.

(2) Procedure of the test

A sample left to stand for 24 hours or more at atmospheric pressure at a temperature of 20 ± 5 ° C was placed in a liquid phase determination test tube 30a shown in Figure 1 (a) and a temperature measurement test tube 30b shown in Figure 1 (b) Put in line. The two test tubes 30a and 30b are placed upright in the low-temperature and constant-temperature water bath so that the line B is below the water surface. The thermometer should have its lower end 30 mm below the A line.

After the sample temperature reaches the set temperature ± 0.1 ℃, the sample remains unchanged for 10 minutes. After 10 minutes, the test tube 30a for liquid phase determination was taken out from the low-temperature constant-temperature water bath and immediately dropped horizontally on a horizontal test bench. The time at which the tip of the liquid surface in the test tube was moved from line A to line B was measured with a stop- Record. The sample is judged to be liquid if the measured time is within 90 seconds at the set temperature, and is determined to be solid when it exceeds 90 seconds.

Examples of the solid epoxy resin include naphthalene type epoxy resins such as HP-4700 (naphthalene type epoxy resin) manufactured by DIC, EXA4700 (tetrafunctional naphthalene type epoxy resin) manufactured by DIC, NC-7000 (polyfunctional solid epoxy resin containing naphthalene skeleton) manufactured by Nippon Kayaku Co., Epoxy resin; An epoxy compound (trisphenol type epoxy resin) of a condensate of a phenol such as EPPN-502H (trisphenol epoxy resin) and an aromatic aldehyde having a phenolic hydroxyl group; Dicyclopentadiene aralkyl type epoxy resins such as Epiclon HP-7200H (multifunctional solid epoxy resin containing dicyclopentadiene skeleton) manufactured by DIC Corporation; Biphenylaralkyl type epoxy resins such as NC-3000H (polyfunctional solid epoxy resin containing biphenyl skeleton) manufactured by Nippon Kayaku Co., Ltd.; Biphenyl / phenol novolak type epoxy resins such as NC-3000L manufactured by Nippon Kayaku Co., Ltd.; Novolak type epoxy resins such as Epiclon N660 manufactured by DIC, Epiclon N690, and EOCN-104S manufactured by Nippon Kayaku Co., Ltd.; Biphenyl type epoxy resins such as YX-4000 manufactured by Mitsubishi Chemical Corporation; Phosphorus-containing epoxy resin such as TX0712 manufactured by Shin-Etsu Chemical Co., Ltd.; And tris (2,3-epoxypropyl) isocyanurate such as TEPIC manufactured by Nissan Chemical Industries, Ltd.

Examples of the semi-solid epoxy resin include Epiclon 860, Epiclon 900-IM, Epiclon EXA-4816, Epiclon EXA-4822 manufactured by DIC, Araldite AER280 manufactured by Asahi Shiba Co., A bisphenol A type epoxy resin such as jER834, jER872, ELA-134 manufactured by Sumitomo Chemical Co., Ltd.; Naphthalene-type epoxy resins such as Epiclon HP-4032 manufactured by DIC Corporation; And phenol novolak type epoxy resins such as Epiclon N-740 manufactured by DIC Corporation.

Examples of the liquid epoxy resin include epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, phenol novolak type epoxy resin, tert-butyl-catechol type epoxy resin, glycidylamine type epoxy resin, Epoxy resins, and alicyclic epoxy resins.

When the curable resin composition of the present invention is an alkali-developable photo-curable resin composition, the amount of the epoxy compound is preferably 1 to 100 parts by mass relative to 100 parts by mass of the (A) carboxyl group-containing resin. In this range, the curability is improved and various general characteristics such as solder heat resistance are improved. Further, sufficient toughness is obtained, and storage stability is not lowered. More preferably, it is 2 to 70 parts by mass.

When a liquid epoxy resin is used, the ratio of the liquid epoxy resin to (A) 100 parts by mass of the carboxyl group-containing resin is preferably 5 to 50 parts by mass, more preferably 5 to 40 parts by mass. When the proportion of the liquid epoxy resin is in the range of 5 to 50 parts by mass, the heat resistance is more excellent, and in the case of the alkali developing type photocurable resin composition, the developing property is excellent.

Examples of the amino resin include melamine resin, benzoguanamine resin and the like. For example, methylolmelamine compounds, methylolbenzoguanamine compounds, methylol glycol uril compounds, and methylol urea compounds. The alkoxymethylated melamine compound, the alkoxymethylated benzoguanamine compound, the alkoxymethylated glycoluril compound, and the alkoxymethylated urea compound may be used in combination with the respective methylolmelamine compounds, methylolbenzoguanamine compounds, methylolglycoluril compounds, and methylol urea compounds Methylol group into an alkoxymethyl group. The kind of the alkoxymethyl group is not particularly limited, and examples thereof include a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, and a butoxymethyl group. Particularly, a melamine derivative having a formalin concentration of 0.2% or less which is friendly to human body and environment is preferable.

Examples of the oxetane compound include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [ Methyl-3-oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) (3-ethyl-3-oxetanyl) methyl methacrylate, (3-methyl-3-oxetanyl) methyl methacrylate, Or polyfunctional oxetanes such as polytetrafluoroethylene, polytetrafluoroethylene, polytetrafluoroethylene, polytetrafluoroethylene, polytetrafluoroethylene, polytetrafluoroethylene, polytetrafluoroethylene, polytetrafluoroethylene, , And the like, and the like. Other examples include copolymers of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate.

As the isocyanate compound, a polyisocyanate compound having a plurality of isocyanate groups in the molecule can be used. As the polyisocyanate compound, for example, aromatic polyisocyanate, aliphatic polyisocyanate or alicyclic polyisocyanate is used. Specific examples of the aromatic polyisocyanate include 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-xylylene diisocyanate, m-xylylene diisocyanate and 2,4-tolylene dimer. Specific examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-methylene bis (cyclohexyl isocyanate) and isophorone diisocyanate. Specific examples of the alicyclic polyisocyanate include bicycloheptane triisocyanate. Examples of the isocyanate compound adduct, burette and isocyanurate include the above-mentioned isocyanate compounds. The isocyanate compound may be a block isocyanate compound in which the isocyanate group is protected by a blocking agent to temporarily inactivate it.

As the thermosetting component (B), thermosetting components other than the above can be used, and a maleimide compound, a benzoxazine resin, a carbodiimide resin, a cyclocarbonate compound, an episulfide resin and the like can be used have. Further, as the thermosetting component (B), at least one of imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, Imidazole derivatives such as sol, 1-cyanoethyl-2-phenylimidazole, and 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; Amines such as dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine and 4- Compounds, hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; (2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (both trade names of imidazole compounds, manufactured by Shikoku Chemical Industry Co., Ltd.) U-CAT3503N and U-CAT3502T (trade names of block isocyanate compounds of dimethylamine), DBU, DBN, U-CATSA102 and U-CAT5002 (both bicyclic amidine compounds and salts thereof) . Further, it is also possible to use one or more compounds selected from the group consisting of guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, Azine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine isocyanuric acid adduct (B) a thermosetting component, which functions also as an adhesion promoter. The thermosetting component (B) may be used alone or in combination of two or more.

As the thermosetting component (B), it is preferable to include melamine. Since the melamine and (C) boric acid ester compound are bonded, the combination of melamine and (C) boric acid ester compound is more effective in extending the dry control width.

The blending amount of the thermosetting component (B) is preferably 5 to 250 parts by mass, more preferably 10 to 230 parts by mass per 100 parts by mass of the (A) carboxyl group-containing resin. When the compounding amount of the thermosetting component is within the above range, the heat resistance is better and the strength of the cured coating film is also good.

[(C) Boric acid ester compound]

As the boric acid ester compound (C), known boric acid ester compounds can be used. For example, low-volatility triphenyl borate or cyclic boric acid ester can be given. Preferably a cyclic boric acid ester compound. The cyclic boric acid ester compound means that boron is contained in the cyclic structure, and 2,2'-oxybis (5,5'-dimethyl-1,3,2-oxaborinane) is particularly preferable. Examples of the boric acid ester compound include trimethyl borate, triethyl borate, tripropyl borate, tributyl borate and the like, in addition to triphenyl borate and cyclic boric acid ester compounds. However, since the boric ester compound has high volatility, The effect of the storage stability of the composition at the time may not be sufficient. The boric acid ester compound may be used singly or in combination of two or more.

Examples of commercially available products of the boric acid ester compound (C) include Hyboron BC1, Hyboron BC2, Hyboron BC3, Hyboron BCN (all manufactured by Boron International), Cure Duct L-07N (manufactured by Shikoku Chemicals Co., Ltd.) .

The amount of the boric acid ester compound (C) is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 3 parts by mass based on 100 parts by mass of the (A) carboxyl group-containing resin.

(Photopolymerization initiator)

The curable resin composition of the present invention may contain a photopolymerization initiator. The photopolymerization initiator is not particularly limited, and a known photopolymerization initiator can be used. For example, benzoin such as benzoin, benzyl, benzoin methyl ether, benzoin ethyl ether, benzoin n-propyl ether, benzoin isopropyl ether and benzoin n-butyl ether; Benzoin alkyl ethers; Benzophenones such as benzophenone, p-methylbenzophenone, Michler's ketone, methylbenzophenone, 4,4'-dichlorobenzophenone, and 4,4'-bisdiethylaminobenzophenone; Acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, N, N-dimethylaniline, N, N-diethylamino-1- (4- Acetophenones such as N-dimethylaminoacetophenone; Thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-di Thioxanthones such as isopropylthioxanthone; Anthraquinones such as anthraquinone, chloroanthraquinone, 2-methyl anthraquinone, 2-ethyl anthraquinone, 2-tert-butyl anthraquinone, 1-chloro anthraquinone, 2-amylanthraquinone and 2-aminoanthraquinone; Ketal such as acetophenone dimethyl ketal and benzyl dimethyl ketal; Benzoic acid esters such as ethyl-4-dimethylaminobenzoate, 2- (dimethylamino) ethylbenzoate and p-dimethylbenzoic acid ethyl ester; (9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-2-yl) Oxime esters such as 3-yl] -, 1- (O-acetyloxime); Bis (cyclopentadienyl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) phenyl) titanium, bis (cyclopentadienyl) Titanocenes such as bis [2,6-difluoro-3- (2- (1-phenyl-1-yl) ethyl) phenyl] titanium; Acylphosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide; Phenyl disulfide, 2-nitrofluorene, butyloline, anisooin ethyl ether, azobisisobutyronitrile, tetramethylthiuram disulfide, and the like. Among them, acetophenones, thioxanthones and oxime esters (hereinafter also referred to as "oxime ester-based photopolymerization initiators") are preferable. One type of photopolymerization initiator may be used alone, or two or more types may be used in combination.

The blending amount of the photopolymerization initiator is preferably 0.01 to 20 parts by mass relative to 100 parts by mass of the (A) carboxyl group-containing resin. In this range, the photocurability on copper is sufficient, the curability of the coating film is improved, the coating film properties such as chemical resistance are improved, and the deep curing property is also improved. More preferably, it is 0.5 to 15 parts by mass based on 100 parts by mass of the (A) carboxyl group-containing resin.

It is preferable to use thioacetic acid (hereinafter also referred to as " thioxanthone photopolymerization initiator ") in combination with other photopolymerization initiators since the sensitivity to light during exposure can be improved. Among the above-mentioned thioxanthone photopolymerization initiators, 2,4-diethylthioxanthone is more preferably used. The blending amount of the thioxanthene photopolymerization initiator is preferably 0.05 to 2 parts by mass, more preferably 0.1 to 1 part by mass based on 100 parts by mass of the (A) carboxyl group-containing resin. If the amount is in the range of 0.05 to 2 parts by mass, the effect of improving the sensitivity is large, and as a result, the undercut can be suppressed easily and outgas is hardly generated.

When the oxime ester-based photopolymerization initiator is used, the blending amount is preferably 0.01 to 5 parts by mass based on 100 parts by mass of the (A) carboxyl group-containing resin. This range is because the photocurability on copper is sufficient, the curability of the coating film is improved, the coating film properties such as chemical resistance are improved, and the deep curing property is also improved. In addition, the oxime ester-based photopolymerization initiator generates a base by light irradiation, so that the thermosetting property is improved and the cured property after heat curing such as gold plating resistance and solder heat resistance can be further improved. The blending amount of the oxime ester-based photopolymerization initiator is more preferably 0.5 to 3 parts by mass based on 100 parts by mass of the (A) carboxyl group-containing resin.

(Photo-curing component)

The curable resin composition of the present invention may contain a photo-curing component. As the photocurable component, it is preferable to use a photoreactive monomer. The photoreactive monomer is a compound having at least one ethylenic unsaturated group in the molecule. The photoreactive monomer is to assist the photocuring of the carboxyl group-containing resin by irradiation with active energy rays.

Examples of the compound to be used as the photoreactive monomer include polyester (meth) acrylate, polyether (meth) acrylate, urethane (meth) acrylate, carbonate Methacrylate, and the like. Specific examples thereof include hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; Diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol and propylene glycol; Acrylamides such as N, N-dimethyl acrylamide, N-methylol acrylamide and N, N-dimethylaminopropylacrylamide; Aminoalkyl acrylates such as N, N-dimethylaminoethyl acrylate and N, N-dimethylaminopropyl acrylate; Polyhydric alcohols such as hexanediol, trimethylol propane, pentaerythritol, dipentaerythritol and tris-hydroxyethylisocyanurate, or ethylene oxide adducts thereof, propylene oxide adducts, or? -Caprolactone adducts Polyhydric acrylates; Polyfunctional acrylates such as phenoxy acrylate, bisphenol A diacrylate and ethylene oxide adducts or propylene oxide adducts of these phenols; Polyhydric acrylates of glycidyl ethers such as glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylol propane triglycidyl ether and triglycidyl isocyanurate; The present invention is not limited to the above. The polyol such as polyether polyol, polycarbonate diol, hydroxyl-terminated polybutadiene and polyester polyol may be directly acrylated or acrylated with urethane acrylate through a diisocyanate and melamine Acrylate and the respective methacrylates corresponding to the acrylate.

In addition, epoxy acrylate resins obtained by reacting acrylic acid with polyfunctional epoxy resins such as cresol novolak type epoxy resins, and epoxy acrylate resins obtained by reacting hydroxy acrylates such as pentaerythritol triacrylate with iso An epoxy urethane acrylate compound obtained by reacting a half urethane compound of a diisocyanate such as phthalone diisocyanate or the like may be used as a photoreactive monomer. Such an epoxy acrylate resin can improve photo-curability without deteriorating the touch-dry composition.

The photocuring component may be used alone or in combination of two or more. The blending amount of the photo-curable component is preferably 1 to 15 parts by mass with respect to 100 parts by mass of the (A) carboxyl group-containing resin. In this range, the photocurability is improved, and pattern formation is facilitated by the alkali development after irradiation with active energy rays, and the strength of the coating film is improved. More preferably, it is 1 to 10 parts by mass.

(Inorganic filler)

The curable resin composition of the present invention may contain an inorganic filler for the purpose of improving properties such as adhesion, hardness and heat resistance. Examples of inorganic fillers include calcium carbonate, magnesium carbonate, fly ash, dehydrated sludge, natural silica, synthetic silica, kaolin, clay, calcium oxide, magnesium oxide, titanium oxide, zinc oxide, barium sulfate, calcium hydroxide, aluminum hydroxide, , Talc, mica, hydrotalcite, aluminum silicate, magnesium silicate, calcium silicate, calcined talc, wollastonite, potassium titanate, magnesium sulfate, calcium sulfate, magnesium phosphate, sepiolite, zonolite, aluminum borate , Silica glass ball, silica flour, glass balloon, silica, seasonal slag, copper, iron, iron oxide, carbon black, Sendust, alnico magnets and various ferrites, cement, glass powder, neodymium, diatomaceous earth, Antimony, magnesium oxysulfate, aluminum hydrate, hydrated gypsum, alum, and the like. Examples of the inorganic filler include fiber reinforcing materials such as organic bentonite, montmorillonite, glass fiber, carbon fiber and boron nitride fiber. The inorganic filler may be used alone or in combination of two or more.

The average particle diameter (D50) of the inorganic filler is preferably 25 占 퐉 or less, more preferably 10 占 퐉 or less, further preferably 3 占 퐉 or less. Here, D50 is a particle diameter at a cumulative volume of 50% obtained by using a laser diffraction scattering particle size distribution measurement method based on the Mie scattering theory. More specifically, the particle size distribution of the fine particles can be measured with a laser diffraction scattering type particle size distribution measuring device, and the median diameter of the fine particles is determined as an average particle size. The measurement sample can be preferably one in which fine particles are dispersed in water by ultrasonic waves. As the laser diffraction particle size distribution measuring apparatus, LA-500 manufactured by Horiba Seisakusho Co., Ltd. and the like can be used.

The blending amount of the inorganic filler is preferably 50 to 400 parts by mass, more preferably 80 to 350 parts by mass, relative to 100 parts by mass of the (A) carboxyl group-containing resin from the viewpoint of forming a coating film of the curable resin composition.

(Organic solvent)

In the curable resin composition of the present invention, a known organic solvent may be added to adjust the viscosity of the composition or to adjust viscosity for application to a substrate or a film. Examples of the solvent include toluene, xylene, ethyl acetate, butyl acetate, methanol, ethanol, isopropyl alcohol, isobutyl alcohol, 1-butanol, diacetone alcohol, ethylene glycol monobutyl ether, propylene glycol monoethyl ether, Ether acetate, terpineol, methyl ethyl ketone, carbitol, carbitol acetate, butyl carbitol, butyl carbitol acetate and the like. The organic solvent may be used alone or in combination of two or more.

(Other optional components)

The curable resin composition of the present invention may contain known additives in the field of electronic materials. Examples of additives include additives such as thermal polymerization inhibitors, ultraviolet absorbers, silane coupling agents, plasticizers, flame retardants, antistatic agents, antioxidants, antibacterial and antifungal agents, antifoaming agents, leveling agents, organic fillers, thickeners, Photoinitiator, photoinitiator, and sensitizer.

The curable resin composition of the present invention may be a single solution or may be two or more solutions. In the case of two or more liquids, for example, a boric acid ester compound (C) may be compounded in any one of the (A) the base containing the carboxyl group-containing resin and (B) the curing agent containing the thermosetting component.

The curable resin composition of the present invention may be in the form of a dry film having a film and a resin layer containing the curable resin composition formed on the film. In the case of dry film formation, the curable resin composition of the present invention is diluted with the above organic solvent, adjusted to an appropriate viscosity, and then subjected to a heat treatment such as a comma coater, blade coater, lip coater, rod coater, squeeze coater, reverse coater, transfer roll coater, Spray coating or the like on a carrier film (support) at a uniform thickness and then dried at a temperature of usually 50 to 130 ° C for 1 to 30 minutes to obtain a film. The thickness of the coating film is not particularly limited, but is generally appropriately selected in the range of 10 to 150 占 퐉, preferably 20 to 60 占 퐉 in film thickness after drying.

As the carrier film, a plastic film is used, and it is preferable to use a plastic film such as a polyester film such as polyethylene terephthalate, a polyimide film, a polyamideimide film, a polypropylene film, and a polystyrene film. The thickness of the carrier film is not particularly limited, but is generally appropriately selected in the range of 10 to 150 mu m.

It is preferable to laminate a peelable cover film on the surface of the film for the purpose of preventing the adherence of dust to the surface of the film after the resin layer is formed on the carrier film using the curable resin composition of the present invention . As the peelable cover film, for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper, or the like can be used. When the cover film is peeled off, It is good if the adhesive strength to the film is smaller.

The curable resin composition of the present invention can be prepared, for example, by a method such as dip coating, flow coating, roll coating, bar coating, screen printing, curtain coating , And the organic solvent contained in the composition is volatilized and dried (dried) at a temperature of about 60 to 100 캜 to form a tacky dry film. Further, in the case of a dry film obtained by applying the above composition onto a carrier film, drying and winding the film as a film, the resin layer is brought into contact with the substrate by a laminator or the like, and then the carrier film is peeled off to form a resin layer on the substrate .

As the base material, there may be used a base material such as paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth / nonwoven epoxy, glass cloth / paper epoxy, synthetic fiber epoxy, fluorine / polyethylene / poly (FR-4 and the like), other polyimide films, PET films, glass substrates, ceramics, and the like using materials such as copper clad laminate for high frequency circuit using phenylene ether, polyphenylene oxide, cyanate ester, A substrate, a wafer plate, and the like.

The volatile drying after application of the curable resin composition of the present invention can be carried out by hot air circulation drying furnace, IR hot plate, convection oven or the like (hot air in the dryer is contacted by countercurrent contact , And a method of spraying onto a support by a nozzle) can be used.

The curable resin composition of the present invention is heated to a temperature of, for example, about 140 to 180 DEG C to thermally cure the resin composition so that (A) the carboxyl group-containing resin and (B) the thermosetting component react with each other to produce heat resistance, chemical resistance, A cured coating film excellent in various properties such as adhesion, electrical characteristics and the like can be formed.

In the case where the curable resin composition of the present invention is an alkali developing type, the coating film obtained after the curable resin composition is applied and the solvent is volatilized and dried is subjected to exposure (irradiation with active energy rays) Part) is cured. Alternatively, a pattern exposure may be performed by a contact type (or noncontact type) through a photomask having a pattern formed thereon by an active energy ray directly or by a laser direct exposure apparatus, and the unexposed portion may be exposed in a dilute alkali aqueous solution (for example, 0.3 To 3 wt% aqueous sodium carbonate solution) to form a resist pattern.

The exposure apparatus used for the active energy ray irradiation may be a device which mounts a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a mercury short arc lamp, etc. and irradiates ultraviolet rays in the range of 350 to 450 nm, A drawing apparatus (for example, a laser direct imaging apparatus for directly drawing an image with a laser by CAD data from a computer) can be used. As the laser light source of the direct shot, a gas laser or a solid laser may be used if laser light having a maximum wavelength in the range of 350 to 410 nm is used. The exposure dose for image formation varies depending on the film thickness and the like, but may be generally within the range of 20 to 800 mJ / cm 2, preferably 20 to 600 mJ / cm 2.

As the developing method, a dipping method, a shower method, a spray method, a brush method, or the like can be used. As the developing solution, an aqueous alkali solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, have.

The curable resin composition of the present invention is suitable for forming a permanent insulation cured film such as a solder resist, a coverlay, and an interlayer insulating layer of a printed wiring board or a flexible printed wiring board.

[ Example ]

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples. In the following, " parts " and "% " are on a mass basis unless otherwise specified.

[Synthesis and adjustment of carboxyl group-containing resin]

(A-1: Synthesis of a carboxyl group-containing resin having a phenol novolak structure)

190 parts (1 equivalent) of phenol novolak type epoxy resin (P-201, epoxy equivalent 190 g / eq, manufactured by Nippon Kayaku Co., Ltd.), 140.1 parts of carbitol acetate and 60.3 parts of solvent naphtha were charged into a flask, And dissolved. The obtained solution was once cooled to 60 占 폚, and 72 parts (1 mole) of acrylic acid, 0.5 part of methylhydroquinone and 2 parts of triphenylphosphine were added and heated to 100 占 폚 for about 12 hours to obtain an acid value of 0.2 mgKOH / g. < / RTI > Thereto was added 80.6 parts (0.53 mol) of tetrahydrophthalic anhydride, heated to 90 占 폚 and reacted for about 6 hours to obtain a resin solution having a solid acid value of 60 mgKOH / g and a solid content concentration of 65.8%. Hereinafter, it is referred to as a varnish A-1.

(A-2: Synthesis of carboxyl group-containing resin having cresol novolak type structure)

220 parts (1 equivalent) of cresol novolac epoxy resin (EOCN-104S, epoxy equivalent: 220 g / eq), 140.1 parts of carbitol acetate and 60.3 parts of solvent naphtha were charged into a flask, And dissolved. The obtained solution was once cooled to 60 占 폚, and 72 parts (1 mole) of acrylic acid, 0.5 part of methylhydroquinone and 2 parts of triphenylphosphine were added and heated to 100 占 폚 for about 12 hours to obtain an acid value of 0.2 mgKOH / g. < / RTI > Thereto was added 80.6 parts (0.53 mol) of tetrahydrophthalic anhydride, heated at 90 DEG C and reacted for about 6 hours to obtain a resin solution having a solid content acid value of 85 mgKOH / g and a solid content concentration of 65.8%. Hereinafter, it is referred to as varnish A-2.

(A-3: Adjustment of carboxyl group-containing copolymer resin)

(ACA) Z250 (acid value: 70.0 mgKOH / g, solid content concentration: 45%) manufactured by Daicel Chemical Industries, Ltd. was used. Hereinafter, it is referred to as varnish A-3.

[Examples 1 to 14, Comparative Examples 1 and 2]

The above resin solution (varnish) was compounded with various components shown in Table 1 in the ratio shown in Table 1 (mass part), preliminarily mixed in a stirrer, and kneaded with a three-roll mill to prepare a curable resin composition Respectively.

<Development Life>

Each of the curable resin compositions of Examples 1 to 11 and Comparative Examples 1 and 2 was applied on the entire surface by screen printing on a patterned copper foil substrate and ultraviolet ray irradiation light having a wavelength of 365 nm was irradiated through a photomask, Cm 2 at a spraying pressure of 2 kg / cm &lt; 2 &gt; for 60 seconds using a developing solution at 80 DEG C for 30 seconds, Respectively.

○: What was able to completely develop

X: Could not develop

<Resistance to gold plating>

Each of the curable resin compositions of Examples 1 to 11 and Comparative Examples 1 and 2 was applied on the entire surface by screen printing on a patterned copper foil substrate, dried at 80 DEG C for 30 minutes, and cooled to room temperature. A solder resist pattern was exposed to the substrate at an optimum exposure dose using an exposure apparatus equipped with a high pressure mercury lamp (short arc lamp), and development was performed for 60 seconds under the condition of a 1 wt% Na ₂ CO ₃ aqueous solution at 30 캜 at a spray pressure of 2 kg / To obtain a resist pattern. This substrate was irradiated with ultraviolet rays under the condition of an integrated exposure dose of 1000 mJ / cm 2 in a UV conveyer, and then cured by heating at 150 ° C for 60 minutes. Electroless nickel plating bath and electroless gold plating bath were used for the obtained printed board (evaluation board), plating was performed under conditions of nickel 0.5 탆 and gold 0.03 탆, and peeling of the resist layer The presence or absence of penetration of plating or plating was evaluated, and the presence or absence of peeling of the resist layer was evaluated by tape peeling.

For each of the curable resin compositions of Examples 12 to 14, the entire surface was coated on a copper foil substrate by screen printing and then cured by heating at 150 DEG C for 60 minutes. Existence of peeling of the resist layer was evaluated in the same manner as in Example 1 except that the printed substrate (evaluation substrate) thus obtained was used.

The criteria are as follows.

◎: No peeling

○: Partially peeled but within 3 sites

△: Peeling around the edge portion

X: Expansion, peeling

&Lt; Soldering heat resistance &

Each of the curable resin compositions of Examples 1 to 11 and Comparative Examples 1 and 2 was applied on the entire surface of the substrate so as to have a thickness of 20 탆 after being dried by screen printing and dried for 30 minutes in a hot air circulation type drying furnace at 80 캜 , And allowed to cool to room temperature. The substrate was exposed at an optimum exposure dose using a high-pressure mercury lamp mounted exposure apparatus (mercury short arc lamp exposure apparatus, manufactured by Oak Seascus Co., Ltd.), and was exposed under the conditions of a temperature of 30 캜, a spray pressure of 0.2 MPa, a developer of 1% by mass sodium carbonate aqueous solution For 60 seconds to obtain a pattern. The substrate was irradiated with ultraviolet rays under the condition of an integrated exposure dose of 1000 mJ / cm 2 in a UV conveyer, and then cured by heating at 160 캜 for 60 minutes. The optimum exposure dose was exposed through a step tablet (T4105C, manufactured by Stouffer Co.) at the time of exposure, and when the number of stages of the remaining step tablets after development was 8, the optimum exposure dose was obtained. The obtained printed substrate (evaluation substrate) was coated with a rosin-based flux and immersed in a solder bath set at 260 占 폚 for 30 seconds. The test substrate was washed with an organic solvent, and then subjected to a peeling test using a cellophane adhesive tape, and evaluated according to the following criteria.

For each of the curable resin compositions of Examples 12 to 14, the entire surface was coated on a copper foil substrate by screen printing and then cured by heating at 150 DEG C for 60 minutes. A peeling test was carried out in the same manner as in Example 1 except that the printed substrate (evaluation substrate) thus obtained was used.

◎: No peeling

○: Partially peeled but within 3 sites

△: Peeling around the edge portion

X: Expansion, peeling

<Insulation resistance>

Each of the curable resin compositions of Examples 1 to 14 and Comparative Examples 1 and 2 was coated with an IPC interdigital B pattern and cured in the same manner as in the gold plating resistance evaluation to obtain a cured resin composition of 90% RH, 25 to 65 占 폚, After the daily humidification, the insulation resistance value after 1 minute at 500 V DC was observed.

○: 10 ¹² Ω or more

Δ: 10 ¹¹ Ω or more and less than 10 ¹² Ω

×: less than 10 ¹¹ Ω

&Lt; Tensile strength, elongation >

Each of the curable resin compositions of Examples 1 to 11 and Comparative Examples 1 and 2 was applied to the entire surface of the glossy surface of the copper foil, followed by drying at 80 캜 for 30 minutes, followed by cooling to room temperature. The curable resin composition on the copper foil was exposed to the entire surface at an optimal exposure dose using an exposure apparatus equipped with a high-pressure mercury lamp (short arc lamp). Subsequently, the curable resin composition on the copper foil was irradiated with ultraviolet rays under the conditions of an integrated exposure dose of 1000 mJ / cm2 in a UV conveyer, and then heated at 150 DEG C for 60 minutes and cured to obtain a cured product.

On the other hand, each of the curable resin compositions of Examples 12 to 14 was applied to the entire surface of the glossy surface of the copper foil and cured at 180 캜 for 90 minutes to obtain a cured product.

The copper foil was removed from each cured product obtained as described above, cut with a test piece having a width of about 5 mm and a length of about 80 mm, and a tensile tester (Autograph AGS-100N, manufactured by Shimadzu Seisakusho Co., Ltd.) Were measured.

The measurement conditions were a sample width of about 10 mm, a point-to-point distance of about 40 mm, a tensile speed of 1.0 mm / min, and an elongation to break.

The tensile strength was evaluated based on the following criteria.

◎: Greater than 7%

○: greater than 5% and less than 7%

?: Greater than 3% and not more than 5%

<Peel strength>

The entire surface of each of the curable resin compositions of Examples 1 to 11 and Comparative Examples 1 and 2 was coated on the glossy surface of the copper foil which had been subjected to surface treatment (manufactured by MAK Co., Ltd., CZ-8101, etching amount: about 1.0 탆) in advance, For 30 minutes, and allowed to cool to room temperature. The curable resin composition on the copper foil was exposed to the entire surface at an optimal exposure dose using an exposure apparatus equipped with a high-pressure mercury lamp (short arc lamp). Subsequently, the curable resin composition on the copper foil was irradiated with ultraviolet rays under the condition of an integrated exposure dose of 1000 mJ / cm2 in a UV conveyer, and then heated at 150 DEG C for 60 minutes to cure the cured resin composition to obtain a cured product.

On the other hand, each of the curable resin compositions of Examples 12 to 14 was applied to the entire surface of a copper foil which had been previously subjected to surface treatment (Macros, CZ-8101, etching amount: about 1.0 탆) and cured at 180 캜 for 60 minutes to have a cured film Copper foil was made.

Each of the thus-obtained cured copper foil-shaped cured films was coated with an adhesive (Araldite), and then subjected to pressing and heating at a pressure of 0.5 MPa and a temperature of 60 캜 by a press machine to prepare a copper evaluation board.

The obtained copper evaluation substrate was inserted into a depth of about 10 mm x about 80 mm at a depth reaching the cured film, and the end portion was slightly peeled to secure the exposed portion. Then, it was held with a jig for gripping, and a tensile tester (Autograph AGS-100N) was used to measure the peel strength. The measurement conditions were a room temperature and a tensile speed of 50 mm / min, and an average load at the time of peeling 35 mm was measured. The peel strength was evaluated based on the following criteria.

?: Greater than 10 N

?: Greater than 7N and less than 10N

?: Larger than 5N and not larger than 7N

<PCBT Resistance>

Each of the cured resin compositions of Examples 1 to 14 and Comparative Examples 1 and 2 was applied in a comb pattern having a copper thickness of 18 占 퐉 and L / S of 100 占 퐉 / 100 占 퐉 and cured in the same manner as in the gold plating resistance evaluation In the bath temperature; 121 ° C, humidity; 97%, and a voltage of 30 V was applied thereto. 10 ⁶ Ω or less was measured as the end point of the measurement, and the connectable time was measured.

◎: 200 hours or more

○: 150 hours or more and less than 200 hours

B: 100 hours or more and less than 150 hours

X: Less than 100 hours

&Lt; Adhesion of underfill &

The evaluation board subjected to electroless plating in the gold plating resistance evaluation was treated with plasma (gas Ar / O ₂ : output: 350 W, degree of vacuum: 300 mTorr) for 60 seconds to apply underfill (DENA TITE R3003EX, manufactured by Nagase ChemteX) After curing at 160 DEG C for one hour and further reflow at 260 DEG C for 3 times and further at 121 DEG C under 2 atmospheric pressure and 100% humidity for 100 hours, the adhesiveness between the underfill and the resist layer was measured by a push gauge Evaluation was carried out according to the following criteria.

?: 100 N or more

?: 80 N or more and less than 100 N

?: 60 N or more and less than 80 N

X: less than 60 N

* 1: Photosensitive carboxyl group-containing resin (PN (phenol novolak type epoxy resin) / AA (acrylic acid) / THPA (tetrahydrophthalic anhydride)) having a skeleton of phenol novolac type

* 2: Photosensitive carboxyl group-containing resin (CN (cresol novolak type epoxy resin) / AA (acrylic acid) / THPA (tetrahydrophthalic anhydride)) having a cresol novolak-

* 3: Carboxyl group-containing copolymer resin (Cyclomer P (ACA) Z250 manufactured by Daicel Chemical Industries, Ltd.)

* 4: Irgacure 907 (2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one manufactured by BASF Japan)

* 5: DETX-S (2,4-diethylthioxanthone) manufactured by Nippon Kayaku Co.,

* 6: Irgacure OXE02 (ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-

* 7: B-30 manufactured by Sakai Chemical Industry Co., Ltd.

* 8: SO-E2 manufactured by Admatechs Co.

* 9: 2,2'-oxybis (5,5'-dimethyl-1,3,2-oxaborinane)

* 10: Diethylene glycol monoethyl ether acetate

* 11: Aromatic hydrocarbons (Solvesso 150)

* 12: N-730A (phenol novolak type epoxy resin, liquid epoxy resin) manufactured by DIC Corporation

* 13: jER828 (bisphenol A type epoxy resin, liquid epoxy resin) manufactured by Mitsubishi Chemical Corporation,

* 14: N-770 (phenol novolak type epoxy resin, solid epoxy resin) manufactured by DIC Corporation

* 15: 2PHZ (2-phenyl-4,5-dihydroxymethylimidazole) manufactured by Shikoku Chemicals,

* 16: Dipentaerythritol hexaacrylate (manufactured by Kyoeisha Chemical Co., Ltd.)

* 17: Trimethylolpropane triacrylate (manufactured by Nippon Kayaku Co., Ltd.)

From the results shown in Table 1, it was found that the curable resin compositions of Examples 1 to 14 were excellent in heat resistance and elongation of the cured product. Further, in the case of the compositions of Examples 1 to 11, which are the alkali-developable photocurable resin compositions, excellent development properties can be obtained even when the development life is evaluated under the above-mentioned drying conditions. On the other hand, the curable resin compositions of Comparative Examples 1 and 2, which did not contain the boric acid ester compound (C), were poor in heat resistance and elongation percentage of the cured product.

Claims (7)

(A) a carboxyl group-containing resin,
(B) a thermosetting component, and
(C) a boric acid ester compound. The curable resin composition according to claim 1, wherein the (B) thermosetting component comprises a liquid epoxy resin. The curable resin composition according to claim 1 or 2, further comprising a photopolymerization initiator. The curable resin composition according to any one of claims 1 to 3, which is for forming a solder resist, a coverlay or an interlayer insulating material. A dry film having a resin layer obtained by applying the curable resin composition according to any one of claims 1 to 4 to a film and drying the film. A cured product obtained by curing the resin layer of the curable resin composition according to any one of claims 1 to 4 or the dry film according to claim 5. A printed wiring board having the cured product according to claim 6.

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