TWI704174B - Curable resin composition, dry film, cured product, and printed wiring board - Google Patents

Abstract

The subject of the present invention is to provide a curable resin composition having excellent heat resistance and elongation of the 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 with the cured product.

As a solution, the present case is to provide a curable resin composition, etc., characterized by including (A) a carboxyl group-containing resin, (B) a thermosetting component, and (C) a borate compound.

Description

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

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

In the printed wiring board, a solder resist layer is formed on a substrate with a conductor layer of a circuit pattern. Not limited to the solder mask, various curable resin compositions have been proposed as materials for permanent protective films such as interlayer insulating materials for printed wiring boards or back adhesive films for flexible printed wiring boards.

For example, Patent Document 1 discloses a photosensitive curable resin composition for permanent photoresist, which contains a polymer having a carboxyl group, a photopolymerizable compound having an ethylenically unsaturated bond, and a photopolymerization initiator. Agent. Furthermore, as a material of a permanent protective film, a thermosetting resin composition is also known (for example, Patent Document 2).

For the above-mentioned permanent protective film, even in a harsh environment, it is required to have resistance to deterioration such as peeling or cracking, that is, reliability. One of the characteristics for achieving high reliability is heat resistance. For example, the solder mask must have solder heat resistance. In addition, printed wiring boards that can be used in high-temperature environments, such as printed wiring boards for vehicles, A permanent protective film with high heat resistance is also required. In addition, when cutting off the hardened material by laser processing and patterning the permanent protective film, heat resistance must be imparted in order not to deteriorate it due to laser heat.

As other characteristics for achieving high reliability, elongation is cited. The lower the elongation, the easier it is to break due to impact. In addition, when patterning is performed by laser processing, there is a risk of cracking due to the opening of the laser processing.

[Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Application Publication No. 2005-99647 (Scope of Patent Application)

[Patent Document 2] Japanese Patent Application Publication No. 2011-63653 (Scope of patent application)

Here, the object of the present invention is to provide a curable resin composition having excellent heat resistance and elongation of the cured product, a dry film having a resin layer obtained from the composition, and a resin layer of the composition or the dry film A cured product and a printed wiring board having the cured product.

In view of the above-mentioned results of careful research It has been found that the above-mentioned problems can be solved by blending a borate compound, and the present invention has been further completed.

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

In the curable resin composition of the present invention, it is preferable to include a liquid epoxy resin as the aforementioned (B) thermosetting component.

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

The curable resin composition of the present invention is suitable for forming a solder mask, a back adhesive film, or an interlayer insulating material.

The dry film of the present invention is characterized by having a resin layer obtained by coating the aforementioned curable resin composition on a film and drying it.

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

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

According to the present invention, it is possible to provide a curable resin composition having excellent heat resistance and elongation of the 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 with the cured product.

31‧‧‧Marking

32‧‧‧Marking

33a‧‧‧Rubber bolt

30a, 30b‧‧‧Test tube

33b‧‧‧Rubber bolt

34‧‧‧Thermometer

[Fig. 1] A schematic side view showing two test tubes used for judging the liquid state of thermosetting components.

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 borate compound.

In the curable resin composition of the present invention, by blending (C) a borate compound, not only the heat resistance and elongation are improved, but also when it is an alkali-developing photocurable resin composition, the drying management range can be improved.

Drying management range (also called development period) refers to the drying conditions under which development defects will not occur in the drying step before development after the alkali-developing photocurable resin composition is applied to the substrate Amplitude. If the drying management range is short, it must be dried at a limited drying temperature and drying time. In the actual manufacturing process, it is not easy to shorten the drying time and manage it. As a result, it becomes difficult to have good visualization and patterning. In the past, the alkali-developing type photocurable resin composition used in the formation of a high heat-resistant solder resist and the like has a problem of a short drying control range. The reason for the short drying control range of the alkali-developing photocurable resin composition is considered to be the thermosetting component blended in order to impart high heat resistance. For example, as a thermosetting component, compared with the use of solid or powder epoxy resin, if liquid epoxy resin is used, the reactivity will increase. Plus, the high heat resistance can also be significantly improved. However, since thermal atomization is more likely to occur, the drying management range will be shortened. In addition, in order to improve high heat resistance, when melamine or the like is contained, thermal atomization is likely to occur. However, as described above, according to the present invention, it is possible to obtain an alkali-developing photocurable resin composition having an excellent drying management range.

When the curable resin composition of the present invention is an alkali-developing photocurable resin composition, it is mixed with a liquid thermosetting component that is prone to thermal fogging, especially when liquid epoxy resin is used for drying management The range is also excellent.

In addition, by blending (C) a borate compound, the adhesion between the cured product and the copper circuit of the printed wiring board can be further improved.

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

[(A) Resin containing carboxyl group]

The carboxyl group contained in the carboxyl group-containing resin can undergo a thermosetting reaction with the thermosetting component (B). Moreover, alkali imaging can also be obtained by the carboxyl group. From the standpoint of photocurability or development resistance, in addition to the carboxyl group, it is better to have ethylenically unsaturated bonds in the molecule, but it is also possible to use only carboxyl group-containing resins that do not have ethylenically unsaturated double bonds . As the ethylenically unsaturated double bond, acrylic acid, methacrylic acid or derivatives derived from these are preferred.

In the curable resin composition of the present invention, (A) the carboxyl group-containing resin has a phenol novolak type and a biphenyl from the viewpoint of heat resistance. At least any one of phenol novolak type and cresol novolak type is preferable. Moreover, (A) the resin containing carboxyl groups, in addition to the solder heat resistance and the adhesiveness of the underfill, a phenol novolak type structure is more preferable, and it can be suitably used in, for example, wire bonding applications. For mounting or flip chip mounting, it is used in printed wiring boards that use underfill.

As a specific example of the resin containing a carboxyl group, the compound (it may be either an oligomer or a polymer) enumerated below is mentioned.

(1) Reaction of a bifunctional or more multifunctional epoxy resin with (meth)acrylic acid, and adding phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, etc. to the hydroxyl group present in the side chain A carboxyl group-containing photosensitive resin of acid anhydride. Here, the bifunctional or higher polyfunctional epoxy resin is preferably a solid.

(2) A carboxyl group-containing photosensitive resin in which a dibasic acid anhydride is added to the hydroxyl group formed by the reaction of the polyfunctional epoxy resin epoxidized with epichlorohydrin and (meth)acrylic acid to the hydroxyl group of the bifunctional epoxy resin. Here, the bifunctional epoxy resin is preferably solid.

(3) Epoxy compounds having two or more epoxy groups in one molecule, compounds having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule, and unsaturated groups such as (meth)acrylic acid The reaction of monocarboxylic acid, the reaction of alcoholic hydroxyl group of the resulting reaction product with maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipic anhydride and other polybasic acid anhydrides, resulting in carboxyl-containing photosensitive Resin.

(4) Make bisphenol A, bisphenol F, bisphenol S, novolac type phenolic resin, poly-P-hydroxystyrene, condensate of naphthol and aldehydes, dihydroxy Compounds having two or more phenolic hydroxyl groups in one molecule, such as condensates of naphthalene and aldehydes, reaction products obtained by reacting with alkylene oxides such as ethylene oxide and propylene oxide, and (meth)acrylic acid A carboxyl-containing photosensitive resin obtained by reacting an unsaturated group-containing monocarboxylic acid and reacting the resulting reaction product with a polybasic acid anhydride.

(5) The 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 and propylene carbonate is reacted with an unsaturated group-containing monocarboxylic acid to make A carboxyl group-containing photosensitive resin obtained by reacting the obtained reaction product with a polybasic acid anhydride.

(6) Combining diisocyanate compounds such as aliphatic diisocyanate, branched aliphatic diisocyanate, alicyclic diisocyanate, aromatic diisocyanate, etc., with polycarbonate-based polyol, polyether-based polyol, and polyester-based polyol , Polyolefin polyols, acrylic polyols, bisphenol A alkylene oxide adduct diols, compounds with phenolic hydroxyl groups and alcoholic hydroxyl groups and other diol compounds formed by the complex addition reaction A urethane resin containing a terminal carboxyl group formed by the reaction of the end of a carbamate resin with an acid anhydride.

(7) Carboxyl-containing urethane resin formed by the compound addition reaction of diisocyanate, carboxyl-containing diethanol compounds such as dimethylolpropionic acid, dimethylolbutyric acid, and glycol compounds In the synthesis of hydroxyalkyl (meth)acrylates, compounds with one hydroxyl group and one or more (meth)acrylic groups in the molecule are added, and the resulting (meth)acrylated terminal containing carboxyl group Urethane resin.

(8) Add isophorone diisocyanate and pentaerythritol triacrylic acid in the synthesis of diisocyanate, carboxyl-containing diethanol compound, and diol compound compound addition reaction to form carboxyl-containing urethane resin Mole reactants such as esters, etc., are compounds having one isocyanate group and one or more (meth)acrylic acid groups in the molecule, and the resulting terminal (meth)acrylated carboxyl group contains a urethane resin.

(9) Unsaturated carboxylic acid such as (meth)acrylic acid, copolymerized with styrene, α-methylstyrene, lower alkane (meth)acrylate, isobutylene and other unsaturated group-containing compounds. Photosensitive resin with carboxyl group.

(10) The polyfunctional propylene oxide resin is reacted with dicarboxylic acids such as adipic acid, phthalic acid, and hexahydrophthalic acid, and the carboxyl group-containing polyester is added to the produced first-stage hydroxyl group with dibasic acid anhydride Resin.

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

And, here, (meth)acrylate refers to a term that collectively refers to acrylate, methyl acrylate, and mixtures thereof, and the following other similar expressions are also the same.

(A) The resin containing carboxyl group is in the main chain. The side chain of the polymer has many carboxyl groups, so it can be developed with diluted alkaline aqueous solution.

In addition, (A) the acid value of the carboxyl-containing resin is suitably in the range of 30 to 200 mgKOH/g, more preferably 30 to 150 mgKOH/g, and particularly preferably in the range of 45 to 120 mgKOH/g. With If the acid value of the resin with carboxyl group is more than 30mgKOH/g, the alkali development is better. On the other hand, if the acid value is less than 200mgKOH/g, in order to suppress the dissolution of the exposed part caused by the developer, it can suppress the decrease of the time limit More than necessary, or due to different circumstances, the exposed part and the unexposed part can be dissolved and peeled with the developer solution without distinction, and a patterned photoresist can be drawn well.

In addition, the weight average molecular weight Mw (weight average molecular weight in terms of polystyrene) of (A) carboxyl-containing resin measured by gel permeation chromatography (GPC) varies depending on the resin skeleton, but is greater than 4,000 and 150,000 or less, more preferably in the range of 5,000 to 100,000. If the weight average molecular weight is greater than 4,000, the non-stick performance is good, and the moisture resistance of the coating film after exposure is good, the film reduction during development is suppressed, and the reduction in resolution can be suppressed. On the other hand, when the weight average molecular weight is 150,000 or less, the developability is good.

[(B) Thermal hardening component]

The (B) thermosetting component may be any one that can react with (A) the carboxyl group-containing resin, and examples include epoxy compounds, amine resins, propylene oxide compounds, and isocyanate compounds. Among them, epoxy compounds are preferred. Examples of the epoxy compound include a bifunctional epoxy resin having two epoxy groups in the molecule, and a multifunctional epoxy resin having many epoxy groups in the molecule. In addition, from the viewpoint of heat resistance, the thermosetting component is preferably in a liquid form.

Examples of the aforementioned epoxy compounds include epoxidized vegetable oils; bisphenol A type epoxy resins; hydroquinone type epoxy resins, bisphenol type epoxy resins Grease and thioether epoxy resin; brominated epoxy resin; novolac epoxy resin; biphenol novolac epoxy resin; bisphenol F epoxy resin; water-added bisphenol A epoxy resin; shrinkage Glycerolamine type epoxy resin; Hydantoin type epoxy resin; Alicyclic epoxy resin; Trishydroxyphenylmethane type epoxy resin; Dixylenol type or biphenol type epoxy resin or a mixture of these ; Bisphenol S type epoxy resin; Bisphenol A novolac type epoxy resin; Tetrahydroxyphenyl ethane type epoxy resin; Heterocyclic epoxy resin; Diglycidyl phthalate resin; Tetraglycidyl xylene Ethane resin; epoxy resin with naphthyl group; epoxy resin with dicyclopentadiene skeleton; glycidyl methacrylate copolymer epoxy resin; cyclohexyl maleimide and glycidyl methyl Acrylate copolymerized epoxy resin; epoxy modified polybutadiene rubber derivative, CTBN modified epoxy resin, but not limited to these. From the viewpoint of reactivity, an epoxy compound having two or more functions is preferred.

The epoxy compound may be any of a solid epoxy resin, a semi-solid epoxy resin, and a liquid epoxy resin, but a liquid epoxy resin is preferred. In this specification, solid epoxy resin means an epoxy resin that is solid at 40°C, and semi-solid epoxy resin means an epoxy resin that is solid at 20°C and liquid at 40°C. Liquid epoxy resin means an epoxy resin that is liquid at 20°C. In this specification, the definitions of solid, semi-solid, and liquid are also subject to other thermosetting components.

The determination of the liquid state is based on the "Method of Confirming Liquid State" in Annex 2 of the Provincial Order (Autonomous Provincial Order No. 1 of the First Year of Heisei) concerning the test and properties of dangerous substances.

(1) Device

Constant temperature water tank:

Use a blender, heater, thermometer, automatic temperature regulator (the temperature can be controlled at ±0.1°C) and a depth of 150mm or more.

In addition, in the determination of the epoxy resin used in the following examples, a combination of a low-temperature constant-temperature water tank (model BU300) manufactured by Yamato Scientific Co., Ltd. and an input thermostat (model BF500) was used, and approximately 22 liters of tap water was used. Enter the low temperature constant temperature water tank (type BU300), turn on the power of the Thermo mate (type BF500) assembled here, set it to the set temperature (20℃ or 40℃), and fine-tune the water temperature to the setting with the Thermo mate (type BF500) The temperature is ±0.1℃, and any device that can perform the same adjustment can also be used.

Test tube:

As the test tube, as shown in Figure 1, a flat-bottomed cylindrical transparent glass with an inner diameter of 30mm and a height of 120mm was used. The heights from the bottom of the tube at 55mm and 85mm were marked with markings 31 and 32 respectively. The test tube 30a is sealed with a rubber plug 33a, and the test tube 30a is of the same size and marked with markings, and is chiseled in the center for insertion. The rubber plug 33b supporting the hole of the thermometer seals the test nozzle, and the temperature measurement test tube 30b of the thermometer 34 is inserted into the rubber plug 33b. Hereinafter, the marking line at a height of 55mm from the bottom of the tube is called "A line", and a marking line with a height of 85mm from the tube bottom is called "B line".

As the thermometer 34, JIS B7410 (1982) "Petroleum type test The test glass thermometer is required for freezing point measurement (SOP-58 scale range 20~50℃), as long as it can measure the temperature range of 0~50℃.

(2) The implementation sequence of the test

The samples that have been placed for more than 24 hours under atmospheric pressure at a temperature of 20±5°C are placed in the test tube 30a for liquid state determination shown in Figure 1(a) and the test tube 30b to A for temperature measurement shown in Figure 1(b). line. The two test tubes 30a, 30b are erected and placed in a low-temperature constant-temperature water tank so that the line B is under the water surface. The lower end of the thermometer is 30mm below the A line.

After the sample temperature reaches the set temperature ±0.1°C, keep this state for 10 minutes. After 10 minutes, take the test tube 30a for judging the liquid state from the low-temperature constant-temperature water tank and place it directly on a horizontal test bench. Use a stopwatch to measure the time for the tip of the liquid level in the test tube to move from line A to line B. , And record. The sample is judged as liquid when the measurement time is within 90 seconds at the set temperature, and is judged as solid when the measurement time exceeds 90 seconds.

Examples of solid epoxy resins include HP-4700 (naphthalene-type epoxy resin) manufactured by DIC, EXA4700 (4-functional naphthalene-type epoxy resin) manufactured by DIC, and NC-7000 (containing naphthalene skeleton) manufactured by Nippon Kayaku Co., Ltd. Multifunctional solid epoxy resin) and other naphthalene type epoxy resins; EPPN-502H (ginseng phenol epoxy resin) manufactured by Nippon Kayaku Co., Ltd., and epoxides of condensation products of phenols and aromatic aldehydes with phenolic hydroxyl groups ( Ginseng phenol type epoxy resin); Epiclon HP-7200H (multifunctional solid epoxy resin containing dicyclopentadiene skeleton) manufactured by DIC, etc. dicyclopentadiene arane type epoxy resin; Japan Biphenylarane type epoxy resin such as NC-3000H (multifunctional solid epoxy resin containing biphenyl skeleton) manufactured by Honkayaku Corporation; Biphenyl/phenol novolak type ring such as NC-3000L manufactured by Nippon Kayaku Corporation Oxygen resin; Epiclon N660, Epiclon N690 manufactured by DIC, EOCN-104S manufactured by Nippon Kayaku Co., Ltd. Novolac type epoxy resin; YX-4000 manufactured by Mitsubishi Chemical Corporation, etc. Biphenyl type epoxy resin; Nippon Steel & Sumikin Chemical Phosphorus-containing epoxy resin manufactured by the company TX0712; ginseng (2,3-epoxypropyl) isocyanurate manufactured by Nissan Chemical Industry Co., Ltd. TEPIC, etc.

Examples of semi-solid epoxy resins include Epiclon 860, Epiclon 900-IM, Epiclon EXA-4816, Epiclon EXA-4822 manufactured by DIC Corporation, Araldite AER280 manufactured by Asahi Chiba Corporation, Epotohto YD-134 manufactured by Totoh Chemical Co., Ltd., and Mitsubishi Chemical Corporation. Bisphenol A type epoxy resins such as jER834, jER872, and ELA-134 manufactured by Sumitomo Chemical Industries; Naphthalene type epoxy resins such as Epiclon HP-4032 manufactured by DIC; Phenolic novolacs such as Epiclon N-740 manufactured by DIC Type epoxy resin etc.

Examples of liquid epoxy resins include bisphenol A epoxy resins, bisphenol F epoxy resins, bisphenol AF epoxy resins, phenol novolac epoxy resins, and tert-butyl-catechol Type epoxy resin, glycidylamine type epoxy resin, aminophenol type epoxy resin, alicyclic epoxy resin, etc.

When the curable resin composition of the present invention is an alkali-developing photocurable resin composition, the blending amount of the aforementioned epoxy compound is preferably 1-100 parts by mass relative to 100 parts by mass of (A) carboxyl-containing resin . because If it is in this range, the hardenability will be improved, and the solder heat resistance will be better in various general characteristics. Moreover, it is because sufficient strength and toughness can be obtained, and the storage stability will not decrease. More preferably, it is 2 to 70 parts by mass.

In addition, when a liquid epoxy resin is used, the ratio of the liquid epoxy resin is preferably 5 to 50 parts by mass, and more preferably 5 to 40 parts by mass relative to 100 parts by mass of (A) carboxyl group-containing resin. When the ratio of the liquid epoxy resin is 5 to 50 parts by mass, the heat resistance is more excellent, and when it is an alkali-developing photocurable resin composition, the developability is excellent.

Examples of amine resins include melamine resins and benzoguanamine resins. For example, there are methylol melamine compounds, methylol benzoguanamine compounds, methylol acetylene carbamide compounds, and methylol urea compounds. In addition, alkoxymethylated melamine compounds, alkoxymethylated benzoguanamine compounds, alkoxymethylated acetylene carbamide compounds, and alkoxymethylated urea compounds can be separated into methylol melamine compounds and methylol The methylol groups of the benzoguanamine compounds, methylol acetylene carbamide compounds and methylol urea compounds are changed to alkoxymethyl groups. The type of alkoxymethyl is not particularly limited, but it can be methoxymethyl, ethoxymethyl, propoxymethyl, butoxymethyl, and the like. In particular, melamine derivatives with a formaldehyde concentration of 0.2% or less which are excellent for the human body or the environment are preferable.

Examples of the aforementioned propylene oxide compound include bis[(3-methyl-3-oxetanylmethoxy)methyl]ether, bis[(3-ethyl-3-oxetanylmethoxy)methyl Base]ether, 1,4-bis[(3-methyl-3-oxetanylmethoxy)methyl]benzene, 1,4-bis[(3-ethyl-3-oxetanylmethoxy) )Methyl)benzene, (3-methyl-3-oxetanyl)methacrylate, (3-ethyl-3-oxetanyl) Methacrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate or these oligomers In addition to polyfunctional propylene oxides such as materials or copolymers, there are also propylene oxide and novolac resins, poly(p-hydroxystyrene), cardo structure bisphenols, calixarene, Aromatic cups, or ether compounds of resins with hydroxyl groups such as semisiloxane. Other examples include copolymers of unsaturated monomers having propylene oxide rings and alkyl (meth)acrylates.

As the aforementioned 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 aromatic polyisocyanates include 4,4'-diphenylmethane diisocyanate, 2,4-tolylphenyl diisocyanate, 2,6-tolylphenyl diisocyanate, naphthalene-1,5 -Diisocyanate, o-diisocyanate, m-diisocyanate and 2,4-tolyl dimer. Specific examples of aliphatic polyisocyanates include tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-methylene diisocyanate (Cyclohexyl isocyanate) and isophorone diisocyanate. As a specific example of alicyclic polyisocyanate, bicycloheptane diisocyanate is mentioned. And there are adducts, biuret compounds, and isocyanurate compounds of the isocyanate compounds listed previously. The aforementioned isocyanate compound may also be a blocked isocyanate compound in which the isocyanate group is protected by a blocking agent and temporarily inert.

(B) The thermosetting component can also use well-known and commonly used thermosetting components other than the above, and it is also possible to use maleimide compounds and benzoxazines. Resin, carbodiimide resin, cyclic carbonate compound, epoxy sulfide resin, etc. In addition, as the (B) thermosetting component, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole and other imidazole derivatives; dicyandiamine, benzyldimethylamine, 4 -(Dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzyl Amine compounds such as amines, hydrazine compounds such as dihydrazine adipic acid and dihydrazine sebacate; phosphorous compounds such as triphenylphosphorus, etc., as commercially available ones include, for example, 2MZ manufactured by Shikoku Chemical Industry Co., Ltd. -A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (all are trade names of imidazole compounds), U-CAT3503N, U-CAT3502T (all are trade names of dimethylamine blocked isocyanate compounds) manufactured by San-apro ), DBU, DBN, U-CATSA102, U-CAT5002 (all are bicyclic amidine compounds and their salts), etc. Moreover, guanamine, acetguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloxyethyl-S-triazine, 2-vinyl-4, 6-Diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine. Isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine. Compounds that also function as adhesion imparting agents, such as S-triazine derivatives such as isocyanuric acid adducts, are used as (B) thermosetting components. (B) A thermosetting component may be used individually by 1 type, and may be used in combination of 2 or more types.

As the (B) thermosetting component, it is preferable to contain melamine. Melamine and (C) borate compound will bond, so the combination of melamine and (C) borate compound will be effective due to the extension of the drying management range.

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

[(C)Borate compound]

(C) As the borate compound, a known borate compound can be used. Examples include terphenyl boric acid or cyclic borate esters which have relatively low volatility. It is preferably a cyclic borate compound. The cyclic boronic acid ester compound means that boron is contained in the cyclic structure, especially 2,2'-oxybis(5,5'-dimethyl-1,3,2-oxaborole) is preferred . As borate compounds, in addition to terphenyl borate or cyclic borate compounds, there are, for example, trimethyl borate, triethyl borate, tripropyl borate, tributyl borate, etc. However, due to these boron The acid ester compound has high volatility, and the effect is sometimes insufficient in terms of the storage stability of the composition at high temperature. A borate compound may be used individually by 1 type, and may be used in combination of 2 or more types.

Commercial products of (C) borate compounds include, for example, Hiboron BC1, Hiboron BC2, Hiboron BC3, Hiboron BCN (all manufactured by Boron International), and Cure duct L-07N (manufactured by Shikoku Chemical Co., Ltd.) )Wait.

(C) The blending amount of the borate compound is preferably 0.01 to 5 parts by mass, and more preferably 0.05 to 3 parts by mass relative to 100 parts by mass of the carboxyl group-containing resin (A).

(Photopolymerization initiator)

The curable resin composition of the present invention may have a photopolymerization initiator. The photopolymerization initiator is not particularly limited, and known and commonly used photopolymerization initiators can be used. For example, benzoin such as benzoin, benzyl, benzoin methyl ether, benzoin ethyl ether, benzoin n-propyl ether, benzoin isopropyl ether, benzoin n-butyl ether, etc.; benzoin alkyl ethers; benzophenone , P-methylbenzophenone, Michele ketone, methyl benzophenone, 4,4'-dichlorobenzophenone, 4,4'-diethylaminobenzophenone, etc. Benzophenones; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichlorobenzene Ethyl ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholin-1-propanone, 2-benzyl-2-dimethyl Acetophenones such as amino-1-(4-morpholinylphenyl)-butanone-1, N,N-dimethylaminoacetophenone; thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone, etc. Thioxanthones; scallion, chloroscallion, 2-methyl scallion, 2-ethyl scallion, 2-tert-butyl scallion, 1-chloro scallion, 2-pentyl scallion, 2 -Amino scallions and other scallions; acetophenone dimethyl ketal, benzyl dimethyl ketal, and other ketals; ethyl-4-dimethylaminobenzoate, 2-( Benzoic acid esters such as dimethylamino) ethyl benzoate and p-dimethyl ethyl benzoate; 1.2-octanedione, 1-[4-(phenylthio)-,2-( O-benzyl oxime)], ethyl ketone, 1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-,1-(0-ethyl Oxime) and other oxime esters; bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrolyl-1-yl)phenyl ) Titanocenes such as titanium, bis(cyclopentadienyl)-bis[2,6-difluoro-3-(2-(1H-pyrrol-1-yl)ethyl)phenyl]titanium; 2,4,6-trimethylbenzyl diphenyl phosphine oxide, bis(2,4,6-trimethylbenzyl)-phenyl phosphine oxide, etc.; disulfide Benzene 2-nitrile, heptanone, anisyl ketone ethyl ether, azobisisobutyronitrile, sulfur blue, etc. Among them, acetophenones, thioxanthones, and oxime esters (hereinafter also referred to as "oxime ester-based photopolymerization initiator") are preferred. A photopolymerization initiator may be used individually by 1 type, and may be used in combination of 2 or more types.

The blending amount of the photopolymerization initiator is 0.01 to 20 parts by mass relative to 100 parts by mass of the (A) carboxyl group-containing resin. The reason is that if it is in this range, the photocuring properties on copper will be sufficient, the curability of the coating film will be good, the coating properties such as chemical resistance will be improved, and the deep curability will also be improved. More preferably, it is 0.5-15 mass parts with respect to 100 mass parts of resin containing a carboxyl group (A).

In order to increase the sensitivity to light during exposure, thioxanthones (hereinafter also referred to as "thioxanthone-based photopolymerization initiators") and other photopolymerization initiators are preferably used in combination. As the thioxanthone-based photopolymerization initiator, among the above, it is more preferable to use 2,4-diethylthioxanthone. The blending amount of the thioxanthone-based photopolymerization initiator is based on 100 parts by mass of the (A) carboxyl group-containing resin, preferably 0.05 to 2 parts by mass, more preferably 0.1 to 1 part by mass. This is because if it is in the range of 0.05 to 2 parts by mass, the sensitivity improvement effect is greater, and as a result, undercutting is easily suppressed, and outgassing is difficult to generate.

When the oxime ester-based photopolymerization initiator is used, the blending amount is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the (A) carboxyl group-containing resin. The reason is that if it is in this range, the light hardening on the copper will be sufficient, the hardening of the coating film will be good, the coating characteristics such as chemical resistance will be improved, and the deep part will be hard. The chemistry will also improve. In addition, the oxime ester-based photopolymerization initiator generates bases due to light irradiation, so the thermal curability is improved, and the properties of the cured product after thermal curing such as gold plating resistance or 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 with respect to 100 parts by mass of the (A) carboxyl group-containing resin.

(Light hardening ingredients)

The curable resin composition of the present invention may contain a photocuring component. As the photocuring component, a photoreactive monomer is preferably used. The photoreactive monomer is a compound having one or more ethylenically unsaturated groups in the molecule. The photoreactive monomer will help the light hardening of the carboxyl-containing resin under the irradiation of activation energy rays.

As the compound used as the aforementioned photoreactive monomer, there are, for example, well-known and commonly used polyester (meth)acrylate, polyether (meth)acrylate, urethane (meth)acrylate, and carbonic acid. Ester (meth)acrylate, epoxy (meth)acrylate, etc. Specifically, there are hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, propylene glycol, etc. Diacrylates of diols; N,N-dimethyl acrylamide, N-methylol acrylamide, N,N-dimethylaminopropyl acrylamide and other acrylamides; N , N-dimethylaminoethyl acrylate, N,N-dimethylaminopropyl acrylate and other amino alkyl acrylates; hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, ginseng -Hydroxyethyl isocyanurate and other polyols or these ethylene oxide adducts, propylene oxide adducts, or ε- Polyacrylates such as caprolactone adducts; polyacrylates such as phenoxy acrylates, bisphenol A diacrylates, and these phenols ethylene oxide adducts or propylene oxide adducts Acrylic esters; polyvalent acrylates of glycidyl ether such as glycerol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, triglycidyl isocyanurate, etc. Class; not limited to the foregoing, but also include the direct acrylate of polyether polyol, polycarbonate diol, hydroxyl-terminated polybutadiene, polyester polyol and other polyols, or the intermediary of diisocyanate for urethane Acid ester acrylated acrylates, melamine acrylates, and methyl acrylates corresponding to the aforementioned acrylates.

Furthermore, an epoxy acrylate resin in which a polyfunctional epoxy resin such as a cresol novolak type epoxy resin and acrylic acid reacts, or the hydroxyl group of the epoxy acrylate resin and a hydroxy acrylate such as pentaerythritol triacrylate and the like The epoxy urethane acrylate compound and the like after the reaction of the half urethane compound of the diisocyanate such as isophorone diisocyanate is used as a photoreactive monomer. Such an epoxy acrylate resin does not reduce the dryness to the touch of a finger, and can improve the photocurability.

The photohardening component may be used individually by 1 type, and may be used in combination of 2 or more types. The blending amount of the light-curing component is preferably 1 to 15 parts by mass relative to 100 parts by mass of (A) carboxyl group-containing resin. The reason is that if it is in this range, the photocurability will be improved, and the pattern formation will be easier by the alkali imaging after activation energy ray irradiation, and the coating film strength will be improved. More preferably, it is 1-10 mass parts.

(Inorganic filler)

The curable resin composition of the present invention may also contain an inorganic filler for the purpose of improving adhesion, hardness, heat resistance and other characteristics. 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, and hydroxide Calcium, aluminum hydroxide, aluminum oxide, magnesium hydroxide, mica, hydromica, hydrotalcite, aluminum silicate, magnesium silicate, calcium silicate, fired mica, wollastonite, potassium titanate, magnesium sulfate, calcium sulfate , Phosphoric acid, magnesium, sepiolite, vermiculite, boron nitride, aluminum borate, hollow silica, glass fragments, hollow glass, silica, steel slag, copper, iron, iron oxide, carbon black, aluminum ferrosilicon Powder, alnico magnet, magnetic powder of various fertilizer particles, etc., cement, glass powder, Neuberg silica, diatomaceous earth, antimony trioxide, magnesium oxysulfate, aluminum hydrate, hydrated gypsum, alum, etc. . In addition, as inorganic fillers, there are fiber reinforced materials such as organic bentonite, montmorillonite, glass fiber, carbon fiber, and boron nitride fiber. An inorganic filler may be used individually by 1 type, and may be used in combination of 2 or more types.

The average particle diameter (D50) of the inorganic filler is 25 μm or less, more preferably 10 μm or less, and more preferably 3 μm or less. Here, D50 means the particle size in 50% of the cumulative volume obtained by the laser refraction scattering particle size distribution method based on the Mie scattering theory. More specifically, a laser refraction scattering type particle size distribution measuring device can be used to produce the particle size distribution of fine particles on a volume basis, and the center diameter can be measured as the average particle size. The measurement sample can preferably be used to disperse fine particles in water by ultrasonic waves. As a laser refraction particle size distribution measuring device, it can Use LA-500 manufactured by Horiba Manufacturing Co., Ltd. etc.

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

(Organic solvents)

In the curable resin composition of the present invention, in order to adjust the viscosity of the composition or to adjust the viscosity for coating on a substrate or a film, a known and commonly used organic solvent may also be included. Examples include toluene, xylene, ethyl acetate, butyl acetate, methanol, ethanol, isopropanol, isobutanol, 1-butanol, diacetone alcohol, ethylene glycol monobutyl ether, propylene glycol monoethyl ether , Propylene glycol monomethyl ether acetate, pinoresinol, methyl ethyl ketone, carbitol, carbitol acetate, butyl carbitol, butyl carbitol acetate, etc. An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more types.

(Other optional ingredients)

The curable resin composition of the present invention may also be blended with additives that are well-known and commonly used in the field of electronic materials. As additives, there are thermal polymerization inhibitors, ultraviolet absorbers, silane coupling agents, plasticizers, flame retardants, anti-charge agents, anti-aging agents, and antibacterial agents. Antifungal agents, defoamers, leveling agents, organic fillers, tackifiers, adhesion imparting agents, thixotropy imparting agents, coloring agents, photoinitiating additives, sensitizers, etc.

The curable resin composition of the present invention may also be one component, or Can be more than 2 liquids. When it is two or more liquids, for example, (C) a borate compound can be blended with either of the main agent containing (A) a carboxyl group-containing resin and the curing agent containing (B) a thermosetting component.

The curable resin composition of the present invention can be in the form of a dry film, and the film is provided with a thin film and a resin layer composed of the aforementioned curable resin composition formed on the thin film. When forming a dry film, the curable resin composition of the present invention is diluted with the aforementioned organic solvent, and adjusted to an appropriate viscosity, using a chipping wheel coater, knife coater, die lip coater, rod coater, and press Extrusion coater, reverse coater, transfer roll coater, gravure coater, spray coater, etc. coat the carrier film (support) to a uniform thickness, usually drying at a temperature of 50~130℃ for 1~ In 30 minutes, a film can be obtained. The coating film thickness is not particularly limited. Generally, the film thickness after drying can be appropriately selected in the range of 10 to 150 μm, preferably 20 to 60 μm.

As the carrier film, there are plastic films, polyester films such as polyethylene terephthalate, polyimide film, polyimide imide film, polypropylene film, polystyrene film, etc. Better. There is no particular limitation on the thickness of the supporting film, and generally it is appropriately selected within the range of 10 to 150 μm.

After forming a resin layer using the curable resin composition of the present invention on a carrier film, for the purpose of preventing dust from adhering to the film surface, it is preferable to laminate a peelable cover film on the film surface. As the peelable cover film, for example, polyethylene film, polytetrafluoroethylene film, polypropylene film, surface-treated paper, etc. can be used. When peeling the cover film, only The adhesive force between the film and the carrier film is smaller than the adhesive force between the film and the cover film.

The curable resin composition of the present invention is adjusted to a viscosity suitable for the coating method with, for example, the aforementioned organic solvent, and is applied to the substrate by dip coating, flow coating, roll coating, rod coating, and screen printing. Coating method, curtain coating method, etc., by volatilizing and drying the organic solvent contained in the composition at a temperature of about 60-100°C (temporary drying), a non-sticky coating film can be formed. And, it is to apply the aforementioned composition on a carrier film and dry it as a film. When the dry film is rolled, it is attached with a laminator or the like so that the resin layer is in contact with the substrate, and then the carrier film Peeling can form a resin layer on the substrate.

As the aforementioned substrates, in addition to printed wiring boards or flexible printed wiring boards with preformed circuits, paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth/non-fiber Cloth epoxy, glass cloth/paper epoxy, synthetic fiber epoxy, fluorine. Polyethylene. Polyphenylene sulfide, polyphenylene ether. Copper-clad laminates of all grades (FR-4, etc.) of materials such as cyanate esters and other copper-clad laminates for high-frequency circuits. In addition, polyimide films, PET films, glass substrates, Ceramic substrates, wafer boards, etc.

The volatilization drying performed after coating the curable resin composition of the present invention can be carried out using a hot air circulating drying furnace, IR furnace, hot plate, convection oven, etc. (using a heat source equipped with a method of heating air by steam to heat the hot air in the dryer The method of contact with the flow and the method of blowing the nozzle to the support).

The curable resin composition of the present invention is heated to a temperature of about 140 to 180°C and thermally cured, and (A) a resin containing a carboxyl group reacts with (B) a thermosetting component to form heat resistance, A hardened coating film with excellent chemical resistance, moisture absorption resistance, adhesion, and electrical properties.

When the curable resin composition of the present invention is an alkali-developing type, by applying the curable resin composition and evaporating and drying the solvent, the resulting coating film is exposed (irradiation of activation energy rays), and the exposed portion (activated The part irradiated with energy rays will harden. In addition, contact (or non-contact) mode is used to form a patterned mask, which is exposed with selective activation energy lines or directly patterned with a laser direct exposure machine, and the unexposed area is diluted with alkaline aqueous solution (For example, 0.3~3wt% carbonated soda water solution) for imaging, which can form a photoresist pattern.

As the exposure machine used for the aforementioned activation energy ray irradiation, any device equipped with a high-pressure mercury lamp bulb, ultra-high pressure mercury lamp bulb, metal halide bulb, mercury short-arc lamp, etc., and irradiates ultraviolet rays in the range of 350 to 450 nm, and further, It is also possible to use a direct drawing device (for example, a laser direct imaging device that draws an image directly with a laser from CAD data from a computer). As the laser light source for direct scanners, any of gas lasers and solid lasers can also be used as long as the laser light with a maximum wavelength of 350~410nm is used. The amount of exposure used to form the image will vary depending on the film thickness, etc., but generally it can be set in the range of 20~800mJ/cm ² , preferably in the range of 20~600mJ/cm ² .

As the aforementioned developing method, the immersion method, shower method, spray method, brushing method, etc. can be used, and as the developing solution, hydroxide can be used. Alkaline aqueous solutions of potassium, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines, etc.

The curable resin composition of the present invention is suitable for the formation of permanent insulating cured films such as solder masks, adhesive films and interlayer insulating layers of printed wiring boards or flexible printed wiring boards.

[Example]

Hereinafter, the present invention will be explained in detail using examples, but the present invention is not limited to the following examples. In addition, below, "parts" and "%" are all quality standards as long as there are no exceptions.

[Synthesis and adjustment of carboxyl-containing resin]

(A-1: Synthesis of carboxyl-containing resin with phenol novolak type structure)

Put 190 parts (1 equivalent) of phenol novolak type epoxy resin (manufactured by Nippon Kayaku Co., P-201, epoxy equivalent 190g/eq), 140.1 parts of carbitol acetate, and 60.3 parts of solvent naphtha into the test In the bottle, heat to 90°C and stir to dissolve. The resulting solution was first cooled to 60°C, 72 parts of acrylic acid (1 mol), 0.5 part of methylhydroquinone, and 2 parts of triphenylphosphorus were added, heated to 100°C, and reacted for about 12 hours to obtain an acid value of 0.2mgKOH/g reactant. Here, 80.6 parts (0.53 mol) of tetrahydrophthalic anhydride was added, heated to 90° C., and reacted for about 6 hours to obtain a resin solution with a solid acid value of 60 mgKOH/g and a solid concentration of 65.8%. Hereinafter, it is called Varnish A-1.

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

Put cresol novolac type epoxy resin (Nippon Kayaku Co., Ltd., EOCN-104S, epoxy equivalent 220g/eq) 220 parts (1 equivalent), 140.1 parts of carbitol acetate, and 60.3 parts of solvent naphtha Put it into the test bottle, heat to 90°C, stir and dissolve. The resulting solution was first cooled to 60°C, 72 parts of acrylic acid (1 mol), 0.5 part of methylhydroquinone, and 2 parts of triphenylphosphorus were added, heated to 100°C, and reacted for about 12 hours to obtain an acid value of 0.2mgKOH/g reactant. 80.6 parts (0.53 mol) of tetrahydrophenol anhydride was added here, heated to 90° C., and reacted for about 6 hours to obtain a resin solution with a solid acid value of 85 mgKOH/g and a solid concentration of 65.8%. Hereinafter, it is referred to as varnish A-2.

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

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

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

The above-mentioned resin solution (varnish) is blended with the various ingredients shown in Table 1 in the proportions (parts by mass) shown in Table 1, after pre-mixing with a mixer, kneading with 3 rolls to prepare a curable resin Composition.

<Development period>

The curable resin compositions of Examples 1 to 11 and Comparative Examples 1 and 2 were coated on a copper foil substrate with a pattern formed by screen printing, and passed through a photomask using an integrated light meter manufactured by ORC Manufacturing Co., Ltd. Irradiate 750mJ/cm ² of ultraviolet light with wavelength of 365nm, use this as a test product, dry it at 80°C for 30 minutes, and develop it for 60 seconds under a spraying pressure of 2kg/cm ² with a developing solution. Visually judge the state of the unexposed parts removed.

○: Can be fully developed

×: Cannot develop

<Gold plating resistance>

The curable resin compositions of Examples 1 to 11 and Comparative Examples 1 and 2 were completely coated on a patterned copper foil substrate by screen printing, dried at 80° C. for 30 minutes, and allowed to cool to room temperature. Use an exposure device equipped with a high-pressure mercury lamp (short-arc lamp) on this substrate to expose the solder mask pattern with the most appropriate exposure amount. A 1wt% Na ₂ CO ₃ aqueous solution at 30°C is sprayed at a pressure of 2 kg/cm ² Perform development for 60 seconds to obtain a photoresist pattern. After this substrate was irradiated with ultraviolet rays under the conditions of a cumulative exposure amount of 1000 mJ/cm ² in a UV conveyor belt furnace, it was heated at 150° C. for 60 minutes and cured. The obtained printed circuit board (evaluation board) was electroplated under the conditions of 0.5μm nickel and 0.03μm gold using commercially available electroless nickel plating bath and electroless gold plating bath, and evaluated the photoresist layer by stripping After the peeling or the penetration of plating, the peeling of the photoresist layer is evaluated by tape peeling.

Regarding each curable resin composition of Examples 12 to 14, after being coated on a copper foil substrate by screen printing, it was heated at 150° C. for 60 minutes and cured. Except using the printed circuit board (evaluation board) obtained in this way, it carried out similarly to Example 1, and evaluated the presence or absence of peeling of a photoresist layer.

The criterion is as follows.

◎: No peeling

○: Some peeling but within 3 places

△: There is peeling around the part of the blade

×: Swelling, peeling

<Solder Heat Resistance>

The curable resin compositions of Examples 1 to 11 and Comparative Examples 1 and 2 were coated on the substrate by screen printing to a thickness of 20μm after drying, and dried in a hot air circulating drying oven at 80°C for 30 minutes After that, let it cool to room temperature. This substrate was exposed with the most appropriate exposure amount using a high-pressure mercury lamp-equipped exposure device (mercury short-arc lamp equipped with an exposure machine made by ORC Manufacturing Co., Ltd.), and temperature: 30°C, spray pressure: 0.2 MPa, developer: 1% by mass Under the condition of sodium carbonate aqueous solution, the image was developed for 60 seconds to obtain the pattern. Furthermore, this substrate was irradiated with ultraviolet rays under the conditions of a cumulative exposure amount of 1000 mJ/cm ² in a UV conveyor belt furnace, and then heated at 160° C. for 60 minutes and cured. The most appropriate amount of exposure is when the exposure is carried out through a trapezoid (T4105C manufactured by Stouffer), and the number of remaining trapezoids after development is 8 as the most appropriate exposure. The resulting printed circuit board (evaluation board) was coated with a rosin-based flux and immersed in a solder tank set at 260°C for 30 seconds. After washing the test substrate with an organic solvent, a peeling test of the Celofan adhesive tape was performed, and the evaluation was performed based on the following criteria.

Regarding each curable resin composition of Examples 12 to 14, after being coated on a copper foil substrate by screen printing, it was heated at 150° C. for 60 minutes and cured. Except that the printed circuit board (evaluation board) thus obtained was used, a peel test was performed in the same manner as in Example 1.

◎: No peeling

○: Some peeling but within 3 places

△: There is peeling around the part of the blade

×: Swelling, peeling

<Insulation resistance>

The curable resin compositions of Examples 1 to 14 and Comparative Examples 1 and 2 were coated on the IPC comb-shaped pattern B, and cured in the same manner as in the gold plating resistance evaluation above, at 90%RH, 25~65℃ After applying externally to DC100V and humidifying for 7 days, observe the insulation resistance value after 1 minute at DC500V.

○: 10 ¹² Ω or more

△: 10 ¹¹ Ω or more, less than 10 ¹² Ω

×: Less than 10 ¹¹ Ω

<Tensile strength, elongation>

The curable resin compositions of Examples 1 to 11 and Comparative Examples 1 and 2 were coated on the entire surface of the copper foil, dried at 80°C for 30 minutes, and left to cool to room temperature. An exposure device equipped with a high-pressure mercury lamp (short arc lamp) is used to fully expose the curable resin composition on the copper foil with the most appropriate exposure amount. Next, the curable resin composition on the copper foil was irradiated with ultraviolet rays in a UV conveyor belt furnace under the conditions of an accumulated exposure amount of 1000 mJ/cm ² , and then heated at 150° C. for 60 minutes and cured to obtain a cured product.

On the other hand, each curable resin composition of Examples 12 to 14 was coated on the gloss surface of a copper foil and cured at 180° C. for 90 minutes to obtain a cured product.

The copper foil was removed from each hardened product obtained as described above and cut into test pieces with a width of approximately 5 mm and a length of approximately 80 mm, and a tensile tester (manufactured by Shimadzu Corporation, Autograph AGS-100N) was used to measure the breaking point elongation.

The measurement conditions are that the sample width is about 10 mm, the distance between the fulcrums is about 40 mm, the stretching speed is 1.0 mm/min, and the elongation until breaking is the elongation at break.

The tensile strength was evaluated from the following criteria.

◎: greater than 7%

○: Greater than 5% and less than 7%

△: greater than 3% and less than 5%

<Peel strength>

All the curable resin compositions of Examples 1 to 11 and Comparative Examples 1 and 2 were coated on the gloss surface of copper foil previously surface-treated (made by MEC, CZ-8101, etching amount about 1.0 μm), Dry at 80°C for 30 minutes and let cool to room temperature. An exposure device equipped with a high-pressure mercury lamp (short arc lamp) is used to fully expose the curable resin composition on the copper foil with the most appropriate exposure amount. Next, the curable resin composition on the copper foil was irradiated with ultraviolet rays in a UV conveyor belt furnace under the conditions of an accumulated exposure amount of 1000 mJ/cm ² , and then heated at 150° C. for 60 minutes and cured to obtain a cured product.

On the other hand, each curable resin composition of Examples 12 to 14 was coated on the copper foil previously surface-treated (MEC, CZ-8101, etching amount about 1.0μm), and cured at 180°C In 60 minutes, a copper foil with a hardened film is produced.

The cured film on the copper foil obtained as described above was respectively coated with an adhesive (Araldite), and then a copper-clad evaluation substrate was prepared with a press machine under a pressure of 0.5 MPa and a temperature of 60° C. and heating.

Cut the obtained copper-clad evaluation substrate with a size of about 10mm×about 80mm to reach the depth of the hardened film. After peeling off the end slightly and ensuring that it can be grasped, grasp it with a grasping jig and use a tensile test A machine (manufactured by Shimadzu Corporation, Autograph AGS-100N) was used to measure the peel strength. The measurement conditions are at room temperature, the tensile speed is set to 50mm/min, and the average load at 35mm peeling is measured. The peel strength was evaluated from the following criteria.

◎: Greater than 10N

○: Greater than 7N and less than 10N

△: Greater than 5N and less than 7N

<PCBT resistance>

The hardened resin compositions of Examples 1 to 14 and Comparative Examples 1 and 2 were applied to a comb-shaped pattern with a copper thickness of 18 μm, L/S: 100 μm/100 μm, and cured in the same manner as in the gold plating resistance evaluation mentioned above. Put the substrate into the tank and keep the temperature at 121℃, keep the humidity at 97% and apply DC30V, set the resistance value; 10 ⁶ Ω or less as the end point of the measurement, and determine the continuous time.

◎: More than 200 hours

○: 150 hours or more but less than 200 hours

△: more than 100 hours but less than 150 hours

×: Less than 100 hours

<Adhesion of bottom filling>

The evaluation substrate that will be subjected to electroless gold plating in the above-mentioned gold plating resistance evaluation is treated with plasma (gas Ar/O ₂ : output: 350W, vacuum degree: 300mTorr) for 60 seconds and coated with underfill (DENA TITE R3003iEX Nagasechemtex) Manufacture), harden at 160℃ for 1h, and then perform 3 times of reflow at 260℃ peak, and then pressurize and cook for 100h at 121℃, 2 atmospheres, and 100% humidity, and then seal the bottom filling with the photoresist layer The performance was measured with a push gauge, and the evaluation was performed on the following basis.

◎: 100N or more

○: 80N or more but less than 100N

△: Above 60N but less than 80N

×: less than 60N

Cyclomer P(ACA)Z250)*4：BASF Japan公司製Irgacure 907(2-甲基-1-[4-(甲硫基)苯基]-2-嗎啉基丙烷-1-基)*5：日本化藥公司製DETX-S(2,4-二乙基噻吨酮)*6：BASF Japan公司製IrgacureOXE02(乙酮,1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-,1-(0-乙醯肟))*7：堺化學公司製B-30 *8：Admatechs公司製SO-E2 *9：2,2’-氧基雙(5,5’-二甲基-1,3,2-氧硼雜環)*10：二乙二醇單乙基醚乙酸酯*11：芳香族烴(Solvesso 150)*12：DIC公司製N-730A(苯酚酚醛清漆型環氧樹脂，液狀環氧樹脂)*13：三菱化學公司製jER828(雙酚A型環氧樹脂，液狀環氧樹脂)*14：DIC公司製N-770(苯酚酚醛清漆型環氧樹脂，固態環氧樹脂)*15：四國化成公司製2PHZ(2-苯基-4,5-二羥基甲基咪唑)*16：二季戊四醇六丙烯酸酯(共榮社化學公司製)*17：三羥甲基丙烷三丙烯酸酯(日本化藥公司製)

Cyclomer P(ACA)Z250)*4: Irgacure 907 (2-methyl-1-[4-(methylthio)phenyl]-2-morpholin-1-yl) manufactured by BASF Japan Corporation*5: DETX-S (2,4-Diethylthioxanthone) manufactured by Nippon Kayaku Co., Ltd. *6: IrgacureOXE02 (ethyl ketone, 1-[9-ethyl-6-(2-methylbenzamide) manufactured by BASF Japan Group)-9H-carbazol-3-yl]-,1-(0-acetoxime)) *7: B-30 manufactured by Sakai Chemical Co., Ltd. *8: SO-E2 manufactured by Admatechs Co., Ltd. *9: 2,2'-Oxybis(5,5'-dimethyl-1,3,2-oxaborole heterocycle)*10: diethylene glycol monoethyl ether acetate*11: aromatic hydrocarbon (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: DIC N-770 (phenol novolac epoxy resin, solid epoxy resin) manufactured by the company *15: 2PHZ (2-phenyl-4,5-dihydroxymethylimidazole) manufactured by Shikoku Chemical Co., Ltd. *16: dipentaerythritol Acrylate (manufactured by Kyoeisha Chemical Co., Ltd.) *17: Trimethylolpropane triacrylate (manufactured by Nippon Kayaku Co., Ltd.)

From the results shown in Table 1 above, it can be seen that the curable resin compositions of Examples 1-14 have excellent heat resistance and elongation of the cured products. And, it is the group of Examples 1 to 11 of the alkali-developing photocurable resin composition In the finished product, even if the development period is evaluated under the above-mentioned drying conditions, good developability can be obtained, so the drying management range is excellent. On the other hand, the curable resin compositions of Comparative Examples 1 and 2 that do not contain the (C) borate compound have poor heat resistance and elongation of the cured product.

31‧‧‧Marking

32‧‧‧Marking

33a‧‧‧Rubber bolt

30a‧‧‧Test tube

33b‧‧‧Rubber bolt

34‧‧‧Thermometer

Claims (7)

An alkali-developing curable resin composition comprising (A) a resin containing a carboxyl group, (B) a thermosetting component, and (C) a curable resin composition of a borate compound. The aforementioned (A) contains The carboxyl group resin has at least any one of a phenol novolak type, a bisphenol novolak type, and a cresol novolak type. The aforementioned (B) thermosetting component contains a compound that reacts with the aforementioned carboxyl group-containing resin, and melamine, the aforementioned (C) The borate compound is terphenyl borate and/or cyclic borate. The alkali-developing type curable resin composition of claim 1, wherein the thermosetting component (B) includes a liquid epoxy resin. The alkali-developing curable resin composition according to claim 1, which further contains a photopolymerization initiator. Such as the alkali-developing curable resin composition of any one of claims 1 to 3, which is used for the formation of solder resist, adhesive film or interlayer insulating material. A dry film having a resin layer obtained by coating and drying the alkali-developing curable resin composition according to any one of claims 1 to 4 on the film. A cured product obtained by curing the alkali-developing curable resin composition according to any one of claims 1 to 4 or the resin layer of the dry film according to claim 5. A printed wiring board having a hardened product as claimed in claim 6.

Images