JP2017025290A - Curable resin composition, dry film, cured product and printed wiring board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable resin composition having excellent heat resistance and an elongation rate of a cured product, a dry film having a resin layer obtained from the composition, a cured product of the composition or of the resin layer of the dry film, and a printed wiring board having the cured product.SOLUTION: The curable resin composition comprises (A) a carboxyl group-containing resin, (B) a thermosetting component, and (C) a boric acid ester compound.SELECTED DRAWING: Figure 1

Description

  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 base material having a conductor layer of a circuit pattern. In the past, various curable resin compositions have been proposed as materials for permanent protective films such as interlayer insulating materials for printed wiring boards and coverlays for flexible printed wiring boards.

  For example, Patent Document 1 discloses a photosensitive curable resin composition for a permanent resist that includes a polymer having a carboxyl group, a photopolymerizable compound having an ethylenically unsaturated bond, and a photopolymerization initiator. ing. A thermosetting resin composition is also known as a material for the permanent protective film (for example, Patent Document 2).

  The permanent protective film as described above is required to have resistance to deterioration such as peeling and cracking even in a severe environment, that is, reliability. One of the characteristics for achieving high reliability is heat resistance. For example, solder resist requires solder heat resistance. In addition, a printed wiring board that can be used in a high-temperature environment, for example, an in-vehicle printed wiring board, also requires a highly heat-resistant permanent protective film. Moreover, when patterning a permanent protective film by scraping the cured product by laser processing, it is necessary to impart heat resistance so as not to be deteriorated by laser heat.

  Another characteristic for achieving high reliability is elongation. If the elongation is low, cracks are likely to occur due to impact. Further, when patterning is performed by laser processing, there is a risk that cracks may occur due to openings by laser processing.

Japanese Patent Laying-Open No. 2005-99647 (Claims) JP 2011-63653 A (Claims)

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

  As a result of intensive studies in view of the above, the present inventor has found that the above problems can be solved by blending a borate ester compound, and has completed the present invention.

  That is, the curable resin composition of the present invention comprises (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 thermosetting component (B).

  The curable resin composition of the present invention preferably further contains 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 it.

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

  The printed wiring board of this invention has the said hardened | cured material, It is characterized by the above-mentioned.

  According to the present invention, a curable resin composition 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 a resin layer of the dry film, And the printed wiring board which has this hardened | cured material can be provided.

It is a schematic side view which shows the two test tubes used for liquid determination of the thermosetting component.

  The curable resin composition of the present invention comprises (A) a carboxyl group-containing resin, (B) a thermosetting component, and (C) a borate ester compound.

  In the curable resin composition of the present invention, by blending the (C) boric acid ester compound, not only the heat resistance and the elongation rate are improved, but in the case of an alkali development type photocurable resin composition, The drying management width is also improved.

  The drying management width (also referred to as development life) is a width of a drying condition in which development failure does not occur in a drying process performed after applying the alkali development type photocurable resin composition to a substrate and before development. If the drying control width is short, it must be dried with a limited drying temperature and drying time. In an actual manufacturing process, it is not easy to manage the drying time short, and as a result, it becomes difficult to perform patterning with good developability. Conventionally, the alkali development type photocurable resin composition used for forming a high heat-resistant solder resist or the like has a problem that the drying control width is short. It is thought that the cause of the short drying control width of such an alkali development type photocurable resin composition is a thermosetting component blended for imparting high heat resistance. For example, compared to the case of using a solid or powder epoxy resin as a thermosetting component, the use of a liquid epoxy resin can increase the reactivity and significantly improve the high heat resistance, Therefore, the drying management width is shortened. Moreover, in order to improve high heat resistance, when it contains melamine etc., it becomes easy to produce a hot fog. However, as described above, according to the present invention, an alkali-developable photocurable resin composition having an excellent dry management width can be obtained.

  When the curable resin composition of the present invention is an alkali-developable photocurable resin composition, it is a case where a liquid thermosetting component, particularly a liquid epoxy resin, which has a problem that heat fog easily occurs. Even with excellent drying control range.

  Moreover, by mix | blending (C) boric-ester compound, the adhesiveness of hardened | cured material and the copper circuit of a printed wiring board can also be improved.

  Hereinafter, the component which the curable resin composition of this invention contains is explained in full detail.

[(A) Carboxyl group-containing resin]
By the carboxyl group which carboxyl group-containing resin has, thermosetting reaction with (B) thermosetting component can be enabled. Moreover, alkali development is also enabled by the carboxyl group. From the viewpoint of photocurability and development resistance, it is preferable to have an ethylenically unsaturated bond in the molecule in addition to the carboxyl group, but only use a carboxyl group-containing resin that does not have an ethylenically unsaturated double bond. May be. As the ethylenically unsaturated double bond, those derived from acrylic acid, methacrylic acid or derivatives thereof are preferable.

  In the curable resin composition of the present invention, the (A) carboxyl group-containing resin 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. The (A) carboxyl group-containing resin preferably has a phenol novolac type structure from the viewpoint of adhesion of underfill in addition to solder heat resistance. For example, an undercoat such as wire bonding mounting or flip chip mounting It can be suitably used for a printed wiring board for mounting using a fill.

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

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

(2) A carboxyl group in which a polyfunctional epoxy resin obtained by epoxidizing the hydroxyl group of a bifunctional epoxy resin with epichlorohydrin is reacted with (meth) acrylic acid, and a dibasic acid anhydride is added to the resulting hydroxyl group. Contains photosensitive resin. Here, the bifunctional epoxy resin is preferably solid.

(3) An epoxy compound having two or more epoxy groups in one molecule is combined with a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule, and (meth) acrylic acid or the like. Reacting with a saturated carboxylic acid containing monocarboxylic acid, the resulting reaction product has many alcoholic hydroxyl groups such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and adipic anhydride. A carboxyl group-containing photosensitive resin obtained by reacting a basic acid anhydride.

(4) Two or more per molecule such as bisphenol A, bisphenol F, bisphenol S, novolac type phenol resin, poly-p-hydroxystyrene, condensate of naphthol and aldehydes, condensate of dihydroxynaphthalene and aldehydes Reaction obtained by reacting an unsaturated group-containing monocarboxylic acid such as (meth) acrylic acid with a reaction product obtained by reacting a compound having a phenolic hydroxyl group with an alkylene oxide such as ethylene oxide or propylene oxide A carboxyl group-containing photosensitive resin obtained by reacting a product with a polybasic acid anhydride.

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

(6) Diisocyanate compounds such as aliphatic diisocyanate, branched aliphatic diisocyanate, alicyclic diisocyanate, aromatic diisocyanate, polycarbonate polyol, polyether polyol, polyester polyol, polyolefin polyol, acrylic polyol, bisphenol A type A terminal carboxyl group-containing urethane resin obtained by reacting an acid anhydride with a terminal of a urethane resin by a polyaddition reaction of a diol compound such as an alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.

(7) During synthesis of a carboxyl group-containing urethane resin by a polyaddition reaction between a diisocyanate, a carboxyl group-containing dialcohol compound such as dimethylolpropionic acid or dimethylolbutyric acid, and a diol compound, a molecule such as hydroxyalkyl (meth) acrylate A carboxyl group-containing urethane resin in which a compound having one hydroxyl group and one or more (meth) acryloyl groups is added and terminally (meth) acrylated.

(8) During synthesis of a carboxyl group-containing urethane resin by polyaddition reaction of a diisocyanate, a carboxyl group-containing dialcohol compound, and a diol compound, an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate, etc. A carboxyl group-containing urethane resin obtained by adding a compound having two isocyanate groups and one or more (meth) acryloyl groups, and then terminally (meth) acrylating.

(9) Carboxy group-containing photosensitivity obtained by copolymerization of unsaturated carboxylic acid such as (meth) acrylic acid and unsaturated group-containing compound such as styrene, α-methylstyrene, lower alkyl (meth) acrylate, and isobutylene. resin.

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

  Here, (meth) acrylate is a generic term for acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions.

  (A) Since the carboxyl group-containing resin has a 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 (A) carboxyl group-containing resin is suitably in the range of 30 to 200 mgKOH / g, more preferably 30 to 150 mgKOH / g, and particularly preferably 45 to 120 mgKOH / g. When the acid value of the carboxyl group-containing resin is 30 mgKOH / g or more, alkali development is good. 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, so that the line becomes thinner than necessary. In some cases, it is possible to satisfactorily draw a patterned resist by suppressing dissolution and peeling with a developer without distinction between an exposed portion and an unexposed portion.

  In addition, the weight average molecular weight Mw (polystyrene equivalent weight average molecular weight) of the (A) carboxyl group-containing resin measured by, for example, gel permeation chromatography (GPC) varies depending on the resin skeleton. It is preferably greater than 000 and less than or equal to 150,000, more preferably in the range of 5,000 to 100,000. When the weight average molecular weight is larger than 4,000, the tack-free performance is good, the moisture resistance of the coated film after exposure is good, the film loss during development is suppressed, and the resolution can be suppressed from decreasing. On the other hand, if the weight average molecular weight is 150,000 or less, the developability is good.

[(B) Thermosetting component]
(B) As a thermosetting component, what is necessary is just what reacts with (A) carboxyl group-containing resin, and an epoxy compound, an amino resin, an oxetane compound, an isocyanate compound, etc. are mentioned. Among these, an epoxy compound is preferable. As an epoxy compound, the bifunctional epoxy resin which has two epoxy groups in a molecule | numerator, the polyfunctional epoxy resin which has many epoxy groups in a molecule | numerator, etc. are mentioned. From the viewpoint of heat resistance, the thermosetting component is preferably liquid.

  Examples of the epoxy compound include epoxidized vegetable oils; bisphenol A type epoxy resins; hydroquinone type epoxy resins, bisphenol type epoxy resins, thioether type epoxy resins; brominated epoxy resins; novolac type epoxy resins; biphenol novolac type epoxy resins; Epoxy resin; Hydrogenated bisphenol A type epoxy resin; Glycidylamine type epoxy resin; Hydantoin type epoxy resin; Alicyclic epoxy resin; Trihydroxyphenylmethane type epoxy resin; Bixylenol type or biphenol type epoxy resin or a mixture thereof; S type epoxy resin; bisphenol A novolac type epoxy resin; tetraphenylolethane type epoxy resin; heterocyclic epoxy resin; Rate resin; Tetraglycidylxylenoylethane resin; Naphthalene group-containing epoxy resin; Epoxy resin having dicyclopentadiene skeleton; Glycidyl methacrylate copolymer epoxy resin; Copolymer epoxy resin of cyclohexylmaleimide and glycidyl methacrylate; Examples thereof include, but are not limited to, polybutadiene rubber derivatives and CTBN-modified epoxy resins. From the viewpoint of reactivity, a bifunctional or higher functional epoxy compound 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 preferable. In this specification, a solid epoxy resin refers to an epoxy resin that is solid at 40 ° C., and a semi-solid epoxy resin refers to an epoxy resin that is solid at 20 ° C. and is liquid at 40 ° C. Means an epoxy resin that is liquid at 20 ° C. In the present specification, other thermosetting components are also applied to the definitions of solid, semi-solid, and liquid.

Judgment of liquid state shall be made in accordance with the second “Liquid Confirmation Method” of the Ministerial Ordinance on Dangerous Goods Testing and Properties (Ministry of Local Government Ordinance No. 1 of 1989)
(1) Equipment constant temperature water bath:
A thing equipped with a stirrer, a heater, a thermometer, and an automatic temperature controller (with temperature control at ± 0.1 ° C.) having a depth of 150 mm or more.
In the determination of the epoxy resin used in the examples to be described later, a combination of a low temperature thermostatic water bath (model BU300) manufactured by Yamato Scientific Co., Ltd. and a thermostat (model BF500) of a charging type thermostatic apparatus (model BF500) is used. Is put into a low temperature constant temperature water bath (model BU300), the thermomate (model BF500) assembled to this is turned on and set to a set temperature (20 ° C or 40 ° C), and the water temperature is set to a set temperature ± 0.1 ° C. Although fine adjustment was performed with a thermomate (model BF500), any apparatus capable of the same adjustment can be used.

Test tube:
As shown in FIG. 1, the test tube is made of a flat bottom cylindrical transparent glass having an inner diameter of 30 mm and a height of 120 mm, and marked lines 31 and 32 are respectively provided at heights of 55 mm and 85 mm from the tube bottom. The test tube 30a for liquid judgment with the test tube 30a sealed with a rubber plug 33a is the same size as that of the test tube 30a. The rubber plug 33b is similarly provided with a marked line and a hole for inserting and supporting a thermometer in the center. A test tube 30b for temperature measurement in which the mouth of the test tube is sealed and a thermometer 34 is inserted into the rubber plug 33b is used. Hereinafter, a marked line having a height of 55 mm from the tube bottom is referred to as “A line”, and a marked line having a height of 85 mm from the tube bottom is referred to as “B line”.
As the thermometer 34, the one for freezing point measurement (SOP-58 scale range 20-50 ° C) specified in JIS B7410 (1982) "Petroleum test glass thermometer" is used, but the temperature is 0-50 ° C. It is sufficient if the range can be measured.

(2) Test procedure The liquid test tube 30a shown in FIG. 1 (a) and the temperature measurement test shown in FIG. 1 (b) were prepared for 24 hours or more at atmospheric pressure of 20 ± 5 ° C. Insert up to line A in each tube 30b. The two test tubes 30a and 30b are left standing in a low temperature constant temperature water tank so that the line B is below the water surface. The thermometer has its lower end 30 mm below the A line.
The state is maintained as it is for 10 minutes after the sample temperature reaches the set temperature ± 0.1 ° C. Ten minutes later, the test tube 30a for liquid judgment is taken out of the low-temperature water bath and immediately tilted horizontally on a horizontal test stand, and the time when the tip of the liquid level in the test tube has moved from the A line to the B line is measured with a stopwatch. Measure and record. A sample is determined to be liquid when the measured temperature is 90 seconds or less at a set temperature, and solid when it exceeds 90 seconds.

  As the solid epoxy resin, 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., Ltd. Naphthalene-type epoxy resins such as EPPN-502H (trisphenol epoxy resin) manufactured by Nippon Kayaku Co., Ltd. Epoxidized products (trisphenol-type epoxy resins) of condensation products of phenols and aromatic aldehydes having a phenolic hydroxyl group; Dicyclopentadiene aralkyl epoxy resin such as Epiklon HP-7200H (dicyclopentadiene skeleton-containing polyfunctional solid epoxy resin) manufactured by Nippon Kayaku Co., Ltd .; biphenyl aralkyl such as NC-3000H (biphenyl skeleton-containing polyfunctional solid epoxy resin) manufactured by Nippon Kayaku Co., Ltd. Type Epoxy Resin; biphenyl / phenol novolak type epoxy resin such as NC-3000L manufactured by Nippon Kayaku; novolak type epoxy resin such as Epicron N660 and Epicron N690 manufactured by DIC, EOCN-104S manufactured by Nippon Kayaku; YX- manufactured by Mitsubishi Chemical Corporation Biphenyl type epoxy resin such as 4000; Phosphorus-containing epoxy resin such as TX0712 manufactured by Nippon Steel & Sumikin Chemical Co .; Tris (2,3-epoxypropyl) isocyanurate such as TEPIC manufactured by Nissan Chemical Industries, Ltd.

  As semi-solid epoxy resin, DIC Corporation Epicron 860, Epicron 900-IM, Epicron EXA-4816, Epicron EXA-4822, Asahi Ciba Araldite AER280, Toto Kasei Epoto YD-134, Mitsubishi Chemical Corporation jER834, jER872, bisphenol A type epoxy resin such as ELA-134 manufactured by Sumitomo Chemical Co., Ltd .; naphthalene type epoxy resin such as Epicron HP-4032 manufactured by DIC; phenol novolac type epoxy resin such as Epicron N-740 manufactured by DIC .

  Liquid epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, glycidylamine type epoxy resin, aminophenol type epoxy resin And alicyclic epoxy resins.

  When the curable resin composition of the present invention is an alkali development type photocurable resin composition, the compounding amount of the epoxy compound is 1 to 100 parts by mass with respect to 100 parts by mass of the (A) carboxyl group-containing resin. preferable. This is because, within this range, curability is improved and general characteristics such as solder heat resistance are improved. Moreover, it is because sufficient toughness is obtained and storage stability does not fall. More preferably, it is 2-70 mass parts.

  Moreover, when using a liquid epoxy resin, it is preferable that the ratio of a liquid epoxy resin is 5-50 mass parts with respect to 100 mass parts of (A) carboxyl group-containing resin, and it is more preferable that it is 5-40 mass parts. preferable. 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 development type photocurable resin composition, the developability is excellent.

  Examples of amino resins include melamine resins and benzoguanamine resins. For example, there are methylol melamine compounds, methylol benzoguanamine compounds, methylol glycoluril compounds and methylol urea compounds. Furthermore, the alkoxymethylated melamine compound, the alkoxymethylated benzoguanamine compound, the alkoxymethylated glycoluril compound and the alkoxymethylated urea compound have the methylol group of the respective methylolmelamine compound, methylolbenzoguanamine compound, methylolglycoluril compound and methylolurea compound. Obtained by conversion to an alkoxymethyl group. The type of the alkoxymethyl group is not particularly limited and can be, for example, a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a butoxymethyl group, or the like. In particular, a melamine derivative having a formalin concentration which is friendly to the human body and the environment is preferably 0.2% or less.

  Examples of the oxetane compound include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, 1,4-bis [(3-methyl-3 -Oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3-oxetanyl) methyl acrylate, (3-ethyl-3-oxetanyl) methyl In addition to polyfunctional oxetanes such as acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate and oligomers or copolymers thereof, oxetane alcohol and novolac resin, poly ( p-hydroxystyrene), cardo-type bisphenol , Calixarenes, calix resorcin arenes or etherified products such as the resin having a hydroxyl group such as silsesquioxane and the like. In addition, a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate is also included.

  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- Examples include xylylene diisocyanate and 2,4-tolylene dimer. Specific examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-methylenebis (cyclohexyl isocyanate), and isophorone diisocyanate. Specific examples of the alicyclic polyisocyanate include bicycloheptane triisocyanate. In addition, adduct bodies, burette bodies and isocyanurate bodies of the isocyanate compounds mentioned above may be mentioned. The isocyanate compound may be a blocked isocyanate compound in which an isocyanate group is protected by a blocking agent and temporarily deactivated.

(B) The thermosetting component may be a known and commonly used thermosetting component other than those described above, and a maleimide compound, a benzoxazine resin, a carbodiimide resin, a cyclocarbonate compound, an episulfide resin, or the like can be used. (B) As thermosetting component, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, Imidazole derivatives such as 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N- Amine compounds such as dimethylbenzylamine and 4-methyl-N, N-dimethylbenzylamine, hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; phosphorus compounds such as triphenylphosphine may be used and are commercially available. As an example For example, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (both trade names of imidazole compounds) manufactured by Shikoku Kasei Kogyo Co., Ltd. Compound trade names), DBU, DBN, U-CATSA102, U-CAT5002 (both bicyclic amidine compounds and salts thereof), and the like. Guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-4,6-diamino-S-triazine, 2-vinyl-4,6-diamino Compounds that also function as adhesion-imparting agents, such as S-triazine / isocyanuric acid adducts and S-triazine derivatives such as 2,4-diamino-6-methacryloyloxyethyl-S-triazine / isocyanuric acid adducts (B ) It can also be used as a thermosetting component. (B) A thermosetting component may be used individually by 1 type, and may be used in combination of 2 or more type.
(B) The thermosetting component preferably contains melamine. Since the melamine and the (C) borate compound are combined, the combination of the melamine and the (C) borate compound is effective by extending the drying control range.

  (B) As for the compounding quantity of a thermosetting component, 5-250 mass parts is preferable with respect to 100 mass parts of (A) carboxyl group-containing resin, and 10-230 mass parts is more preferable. When the blending 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 better.

[(C) Boric acid ester compound]
(C) As a boric acid ester compound, a well-known boric acid ester compound can be used. For example, triphenyl borate or cyclic borate having low volatility can be used. A cyclic borate compound is preferred. The cyclic borate ester compound is a compound in which boron is contained in a cyclic structure, and 2,2′-oxybis (5,5′-dimethyl-1,3,2-oxaborinane) is particularly preferable. Examples of boric acid ester compounds include trimethyl borate, triethyl borate, tripropyl borate, tributyl borate, and the like other than triphenyl borate and cyclic borate compounds. Since the compound has high volatility, the effect may not be sufficient for the storage stability of the composition particularly at high temperatures. A boric acid ester compound may be used individually by 1 type, and may be used in combination of 2 or more type.

(C) Examples of commercially available boric acid ester compounds include high boron BC1, high boron BC2, high boron BC3, high boron BCN (all of which are manufactured by Boron International), cure duct L-07N (manufactured by Shikoku Kasei Kogyo Co., Ltd.), and the like. Can be mentioned.

The compounding amount of the (C) boric acid ester compound is preferably 0.01 to 5 parts by mass, and 0.05 to 3 parts by mass with respect to 100 parts by mass of the (A) carboxyl group-containing resin. More preferred.

(Photopolymerization initiator)
The curable resin composition of the present invention may contain a photopolymerization initiator. A photoinitiator is not specifically limited, A well-known and usual photoinitiator can be used. For example, benzoins such as benzoin, benzyl, benzoin methyl ether, benzoin ethyl ether, benzoin n-propyl ether, benzoin isopropyl ether, benzoin n-butyl ether; benzoin alkyl ethers; benzophenone, p-methylbenzophenone, Michler's ketone, methylbenzophenone, Benzophenones such as 4,4′-dichlorobenzophenone and 4,4′-bisdiethylaminobenzophenone; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloro Acetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propano Acetophenones such as 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, N, N-dimethylaminoacetophenone; thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2, Thioxanthones such as 4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone; anthraquinone, chloroanthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, Anthraquinones such as 1-chloroanthraquinone, 2-amylanthraquinone and 2-aminoanthraquinone; Ketals such as acetophenone dimethyl ketal and benzyldimethyl ketal; Ethyl Benzoic acid esters such as -4-dimethylaminobenzoate, 2- (dimethylamino) ethyl benzoate, and p-dimethylbenzoic acid ethyl ester; 1.2-octanedione, 1- [4- (phenylthio)-, 2- ( O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime) and other oxime esters; bis (Η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) phenyl) titanium, bis (cyclopentadienyl) -bis [2, Titanocenes such as 6-difluoro-3- (2- (1-pyr-1-yl) ethyl) phenyl] titanium; 2,4,6-trimethylbenzoyldi Acylphosphine oxides such as phenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide; phenyl disulfide 2-nitrofluorene, butyroin, anisoin ethyl ether, azobisisobutyronitrile, tetramethylthiuram A disulfide etc. can be mentioned. Among these, acetophenones, thioxanthones, and oxime esters (hereinafter also referred to as “oxime ester photopolymerization initiators”) are preferable. A photoinitiator may be used individually by 1 type and may be used in combination of 2 or more type.
It is preferable that the compounding quantity of a photoinitiator is 0.01-20 mass parts with respect to 100 mass parts of (A) carboxyl group-containing resin. This is because, within this range, the photocurability on copper is sufficient, the curability of the coating film is good, the coating film properties such as chemical resistance are improved, and the deep curability is also improved. . More preferably, it is 0.5-15 mass parts with respect to 100 mass parts of (A) carboxyl group-containing resin.

  Since the sensitivity to light during exposure can be improved, it is preferable to use thioxanthones (hereinafter also referred to as “thioxanthone photopolymerization initiators”) in combination with other photopolymerization initiators. Among the above, 2,4-diethylthioxanthone is more preferable as the thioxanthone photopolymerization initiator. The blending amount of the thioxanthone photopolymerization initiator is preferably 0.05 to 2 parts by mass, more preferably 0.1 to 1 part by mass with respect to 100 parts by mass of the (A) carboxyl group-containing resin. It is because the effect of a sensitivity improvement is large and it becomes easy to suppress an undercut as a result as it is the range of 0.05-2 mass parts, and it becomes difficult to produce an outgas.

  The amount of the oxime ester photopolymerization initiator used is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the (A) carboxyl group-containing resin. This is because, within this range, the photocurability on copper is sufficient, the curability of the coating film is good, the coating film properties such as chemical resistance are improved, and the deep curability is also improved. . In addition, since a base is generated by light irradiation in the oxime ester photopolymerization initiator, the thermosetting property is improved, and the properties of the cured product such as gold plating resistance and solder heat resistance can be further improved. . The amount of the oxime ester 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.

(Photocuring component)
The curable resin composition of the present invention may contain a photocurable component. As the photocuring component, it is preferable to use a photoreactive monomer. A photoreactive monomer is a compound having one or more ethylenically unsaturated groups in the molecule. The photoreactive monomer assists photocuring of the carboxyl group-containing resin by irradiation with active energy rays.

  Examples of the compound used as the photoreactive monomer include known and commonly used polyester (meth) acrylate, polyether (meth) acrylate, urethane (meth) acrylate, carbonate (meth) acrylate, epoxy (meth) acrylate, and the like. It is done. Specifically, 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; N, N-dimethylacrylamide Acrylamides such as N-methylol acrylamide and N, N-dimethylaminopropyl acrylamide; aminoalkyl acrylates such as N, N-dimethylaminoethyl acrylate and N, N-dimethylaminopropyl acrylate; hexanediol, trimethylolpropane, Polyhydric alcohols such as pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate or the like Polyvalent acrylates such as idoid adducts, propylene oxide adducts, or ε-caprolactone adducts; phenoxy acrylates, bisphenol A diacrylates, and polyhydric acrylates such as ethylene oxide adducts or propylene oxide adducts of these phenols Polyglycerides of glycidyl ethers such as glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylol propane triglycidyl ether, triglycidyl isocyanurate; Acrylates in which polyols such as polyols are directly acrylated or urethane acrylated via diisocyanate And melamine acrylate, and methacrylates corresponding to the acrylate.

  Furthermore, an epoxy acrylate resin obtained by reacting acrylic acid with a polyfunctional epoxy resin such as a cresol novolac type epoxy resin, and further a hydroxy acrylate such as pentaerythritol triacrylate and a diisocyanate such as isophorone diisocyanate on the hydroxyl group of the epoxy acrylate resin. An epoxy urethane acrylate compound or the like obtained by reacting a half urethane compound may be used as a photoreactive monomer. Such an epoxy acrylate resin can improve photocurability without deteriorating the touch drying property.

  A photocuring component may be used individually by 1 type, and may be used in combination of 2 or more type. It is preferable that the compounding quantity of a photocuring component is 1-15 mass parts with respect to 100 mass parts of (A) carboxyl group-containing resin. This is because, within this range, photocurability is improved, and pattern formation is facilitated and coating film strength is improved by alkali development after irradiation with active energy rays. More preferably, it is 1-10 mass parts.

(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. 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 , Alumina, magnesium hydroxide, talc, mica, hydrotalcite, aluminum silicate, magnesium silicate, calcium silicate, calcined talc, wollastonite, potassium titanate, magnesium sulfate, calcium sulfate, magnesium phosphate, sepiolite, zonolite, nitriding Boron, aluminum borate, silica balloon, glass flake, glass balloon, silica, iron slag, copper, iron, iron oxide, carbon black, sendust, alnico magnet, magnetic powders such as various ferrites, cement DOO, glass powder, Noiburugu siliceous earth, diatomaceous earth, antimony trioxide, magnesium oxysulfate, hydrated aluminum, hydrated gypsum, alum, and the like. In addition, examples of the inorganic filler include fiber reinforcements 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 type.

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

  The blending amount of the inorganic filler is preferably 50 to 400 parts by mass, and 80 to 350 parts by mass with respect 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. More preferred.

(Organic solvent)
The curable resin composition of the present invention may contain a known and commonly used organic solvent for adjusting the viscosity of the composition or for adjusting the viscosity for application to a substrate or a film. For example, toluene, xylene, ethyl acetate, butyl acetate, methanol, ethanol, isopropyl alcohol, isobutyl alcohol, 1-butanol, diacetone alcohol, ethylene glycol monobutyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, terpineol, methyl ethyl ketone Carbitol, carbitol acetate, butyl carbitol, butyl carbitol acetate and the like. An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more type.

(Other optional ingredients)
You may mix | blend a well-known and usual additive in the field | area of an electronic material with the curable resin composition of this invention. Additives include thermal polymerization inhibitors, UV absorbers, silane coupling agents, plasticizers, flame retardants, antistatic agents, anti-aging agents, antibacterial / antifungal agents, antifoaming agents, leveling agents, organic fillers, Examples include thickeners, adhesion promoters, thixotropic agents, colorants, photoinitiator aids, and sensitizers.

  The curable resin composition of the present invention may be one liquid or two or more liquids. In the case of using two or more liquids, for example, (C) a boric acid ester compound can be blended with either (A) a main agent containing a carboxyl group-containing resin and (B) a curing agent containing a thermosetting component.

  The curable resin composition of this invention can also be made into the form of the dry film provided with the film and the resin layer which consists of the said curable resin composition formed on this film. When forming a dry film, the curable resin composition of the present invention is diluted with the above-mentioned organic solvent to adjust to an appropriate viscosity, and a comma coater, blade coater, lip coater, rod coater, squeeze coater, reverse coater, transfer roll coater. A film can be obtained by applying a uniform thickness on a carrier film (support) with a gravure coater, spray coater or the like, and drying usually at a temperature of 50 to 130 ° C. for 1 to 30 minutes. Although there is no restriction | limiting in particular about a coating film thickness, Generally, it is 10-150 micrometers by the film thickness after drying, Preferably it selects suitably in the range of 20-60 micrometers.

  As the carrier film, a plastic film is used, and a plastic film such as a polyester film such as polyethylene terephthalate, a polyimide film, a polyamideimide film, a polypropylene film, or a polystyrene film is preferably used. Although there is no restriction | limiting in particular about the thickness of a carrier film, Generally, it selects suitably in the range of 10-150 micrometers.

  After forming a resin layer using the curable resin composition of the present invention on a carrier film, a cover film that can be peeled off from the surface of the film is used for the purpose of preventing dust from adhering to the surface of the film. It is preferable to laminate. 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, and when the cover film is peeled off, the adhesive strength between the film and the carrier film is exceeded. What is necessary is just to have a smaller adhesive force between the membrane and the cover film.

  The curable resin composition of the present invention is adjusted to a viscosity suitable for the coating method with the organic solvent, for example, on the substrate, dip coating method, flow coating method, roll coating method, bar coater method, screen printing method, A tack-free coating film can be formed by applying the organic solvent contained in the composition at a temperature of about 60 to 100 ° C. by volatile drying (preliminary drying) at a temperature of about 60 to 100 ° C. Further, in the case of a dry film that is applied on a carrier film, dried and wound up as a film, after laminating the resin layer so as to contact the substrate with a laminator or the like, by peeling the carrier film, A resin layer can be formed on the substrate.

  Examples of the base material include printed circuit boards and flexible printed circuit boards in which circuits are formed in advance, paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth / non-woven cloth epoxy, glass cloth / paper epoxy, synthetic fiber. Copper graded laminates of all grades (FR-4 etc.) and other polyimides using materials such as epoxy, fluorine, polyethylene, polyphenylene ether, polyphenylene oxide, cyanate ester, etc. A film, a PET film, a glass substrate, a ceramic substrate, a wafer plate, etc. can be mentioned.

  Volatile drying performed after applying the curable resin composition of the present invention may be performed by using a hot air circulation drying furnace, an IR furnace, a hot plate, a convection oven or the like (a hot air in a dryer using an air heating type heat source using steam). Can be carried out by using a counter current contact method and a method of spraying a nozzle on a support.

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

  When the curable resin composition of the present invention is of the alkali development type, the coating film obtained after applying the curable resin composition and evaporating and drying the solvent is exposed (irradiated with active energy rays). The exposed portion (the portion irradiated by the active energy ray) is cured. Further, by a contact method (or a non-contact method), exposure is selectively performed with an active energy ray through a photomask having a pattern formed thereon or direct pattern exposure is performed by a laser direct exposure machine, and an unexposed portion is diluted with a dilute alkaline aqueous solution (for example, 0.3 The resist pattern is formed by development with a 3 wt% sodium carbonate aqueous solution.

As an exposure machine used for the active energy ray irradiation, a high-pressure mercury lamp lamp, an ultra-high pressure mercury lamp lamp, a metal halide lamp, a mercury short arc lamp, etc. are mounted, and any apparatus that irradiates ultraviolet rays in the range of 350 to 450 nm may be used. Furthermore, a direct drawing apparatus (for example, a laser direct imaging apparatus that directly draws an image with a laser using CAD data from a computer) can also be used. As a laser light source of the direct drawing machine, either a gas laser or a solid laser may be used as long as laser light having a maximum wavelength in the range of 350 to 410 nm is used. The amount of exposure for image formation varies depending on the film thickness and the like, but is generally 20 to 800 mJ / cm ² , preferably 20 to 600 mJ / cm ² .

  The developing method can be a dipping method, a shower method, a spray method, a brush method or the like, and as a developer, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, Alkaline aqueous solutions such as ammonia and amines can be used.

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

  EXAMPLES Hereinafter, although this invention is demonstrated in detail using an Example, this invention is not limited to the following Example. In the following description, “parts” and “%” are all based on mass unless otherwise specified.

[Synthesis and preparation of carboxyl group-containing resin]
(A-1: Synthesis of a carboxyl group-containing resin having a phenol novolac type structure)
A flask was charged with 190 parts (1 equivalent) of a phenol novolac type epoxy resin (Nippon Kayaku Co., Ltd., P-201, epoxy equivalent of 190 g / eq), 140.1 parts of carbitol acetate, and 60.3 parts of solvent naphtha. Heated and stirred at 0 ° C. to dissolve. The obtained solution is once cooled to 60 ° C., 72 parts (1 mol) of acrylic acid, 0.5 part of methylhydroquinone and 2 parts of triphenylphosphine are added, heated to 100 ° C., reacted for about 12 hours, and acid value Yielded a reaction of 0.2 mg KOH / g. To this was added 80.6 parts (0.53 mol) of tetrahydrophthalic anhydride, heated to 90 ° C., reacted for about 6 hours, and a resin solution having a solid content acid value of 60 mg KOH / g and a solid content concentration of 65.8%. Got. Hereinafter, it is referred to as Varnish A-1.

(A-2: Synthesis of carboxyl group-containing resin having a cresol novolac type structure)
Cresole novolac type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., EOCN-104S, epoxy equivalent 220 g / eq) 220 parts (1 equivalent), carbitol acetate 140.1 parts, and solvent naphtha 60.3 parts were charged in a flask, 90 Heated and stirred at 0 ° C. to dissolve. The obtained solution is once cooled to 60 ° C., 72 parts (1 mol) of acrylic acid, 0.5 part of methylhydroquinone and 2 parts of triphenylphosphine are added, heated to 100 ° C., reacted for about 12 hours, and acid value Yielded a reaction of 0.2 mg KOH / g. To this was added 80.6 parts (0.53 mol) of tetrahydrophthalic anhydride, heated to 90 ° C., reacted for about 6 hours, and a resin solution having a solid content acid value of 85 mgKOH / g and a solid content concentration of 65.8%. Got. Hereinafter, it is referred to as varnish A-2.

(A-3: Preparation of carboxyl group-containing copolymer resin)
Cyclomer P (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) is blended in the proportions (parts by mass) shown in Table 1 together with various components shown in Table 1, premixed with a stirrer, kneaded with a three-roll mill, and curable resin composition A product was prepared.

<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 of a patterned copper foil substrate by screen printing, and each was irradiated with an ultraviolet light having a wavelength of 365 nm through a photomask. The test piece was irradiated with 750 mJ / cm ² using an integrated light meter manufactured by Seisakusho Co., Ltd., dried at 80 ° C. for 30 minutes, and developed with each developer at a spray pressure of ² kg / cm ² for 60 seconds. The state where the unexposed part was removed was visually judged.
○: Completely developed ×: Undeveloped

<Gold plating 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 a patterned copper foil substrate by screen printing, dried at 80 ° C. for 30 minutes, and allowed to cool to room temperature. This substrate is exposed to a solder resist pattern at an optimum exposure amount using an exposure apparatus equipped with a high-pressure mercury lamp (short arc lamp), and a 1 wt% Na ₂ CO ₃ aqueous solution at 30 ° C. is applied for 60 seconds under a spray pressure of 2 kg / cm ^2. Development was performed to obtain a resist pattern. This substrate was irradiated with ultraviolet rays under a condition of an integrated exposure amount of 1000 mJ / cm ^{2 in} a UV conveyor furnace, and then cured by heating at 150 ° C. for 60 minutes. Using the commercially available electroless nickel plating bath and electroless gold plating bath, the obtained printed circuit board (evaluation board) is plated under the conditions of nickel 0.5 μm and gold 0.03 μm, and tape peeling After evaluating the presence or absence of peeling of the resist layer and the presence or absence of plating penetration, the presence or absence of peeling of the resist layer was evaluated by tape peeling.
About each curable resin composition of Examples 12-14, after apply | coating the whole surface by screen printing on a copper foil board | substrate, it heated and hardened | cured for 60 minutes at 150 degreeC. Except for using the printed board (evaluation board) thus obtained, the presence or absence of peeling of the resist layer was evaluated in the same manner as in Example 1.
The judgment criteria are as follows.
◎: No peeling ○: Partially peeled, but within 3 points △: Peeled around the edge part ×: Swelled and peeled

<Solder heat resistance>
Each surface of each of the curable resin compositions of Examples 1 to 11 and Comparative Examples 1 and 2 was applied onto a substrate by screen printing so that the film thickness after drying was 20 μm, and was 30 in a hot air circulation drying oven at 80 ° C. After drying for a minute, it was allowed to cool to room temperature. This substrate is exposed at an optimum exposure amount using an exposure apparatus equipped with a high-pressure mercury lamp (exposure machine manufactured by Oak Manufacturing Co., Ltd. equipped with a mercury short arc lamp), temperature: 30 ° C., spray pressure: 0.2 MPa, developer: 1% by mass. Development was performed for 60 seconds under the condition of an aqueous sodium carbonate solution to obtain a pattern. Further, this substrate was irradiated with ultraviolet rays under a condition of an integrated exposure amount of 1000 mJ / cm ^{2 in} a UV conveyor furnace, and then cured by heating at 160 ° C. for 60 minutes. The optimum exposure amount was exposed through a step tablet (T4105C manufactured by Stouffer, Inc.) at the time of exposure, and the optimum exposure amount was obtained when the number of step tablet steps remaining after development was eight. About the obtained printed circuit board (evaluation board | substrate), the rosin-type flux was apply | coated and it immersed in the solder tank set to 260 degreeC for 30 second. After the test substrate was washed with an organic solvent, a peeling test using a cellophane adhesive tape was performed, and the following criteria were evaluated.
About each curable resin composition of Examples 12-14, after apply | coating the whole surface by screen printing on a copper foil board | substrate, it heated and hardened | cured for 60 minutes at 150 degreeC. A peeling test was performed in the same manner as in Example 1 except that the printed circuit board (evaluation board) thus obtained was used.
◎: No peeling ○: Partially peeled, but within 3 points △: Peeled around the edge part ×: Swelled and peeled

<Insulation resistance>
Each of the curable resin compositions of Examples 1 to 14 and Comparative Examples 1 and 2 was applied to an IPC comb B pattern, cured in the same manner as in the gold plating resistance evaluation, and 90% RH, 25 to 65 ° C., and DC 100V. After the application of humidification for 7 days, the insulation resistance value after 1 minute was observed at 500 VDC.
○: 10 ¹² Ω or more Δ: 10 ¹¹ Ω or more and less than 10 ¹² Ω x: less than 10 ¹¹ Ω

<Tensile strength and elongation>
Each curable resin composition of Examples 1 to 11 and Comparative Examples 1 and 2 was applied to the entire glossy surface of the copper foil, dried at 80 ° C. for 30 minutes, and allowed to cool to room temperature. The entire surface of the curable resin composition on the copper foil was exposed with an optimum exposure amount using an exposure apparatus equipped with a high-pressure mercury lamp (short arc lamp). Next, the curable resin composition on the copper foil was irradiated with ultraviolet rays under a condition of an integrated exposure amount of 1000 mJ / cm ^{2 in} a UV conveyor furnace, and then cured by heating at 150 ° C. for 60 minutes to obtain a cured product. .
On the other hand, each curable resin composition of Examples 12 to 14 was applied to the entire glossy surface of the copper foil and cured at 180 ° C. for 90 minutes to obtain a cured product.
Copper foil is removed from each cured product obtained as described above, cut into test pieces having a width of about 5 mm and a length of about 80 mm, and a tensile tester (manufactured by Shimadzu Corporation, Autograph AGS-100N) is used. The elongation at break was measured.
The measurement conditions were a sample width of about 10 mm, a fulcrum distance of about 40 mm, a pulling speed of 1.0 mm / min, and the elongation rate until breakage was the elongation at breakage point.
The tensile strength was evaluated according to the following criteria.
◎: Greater than 7% ○: Greater than 5% and 7% or less △: Greater than 3% and 5% or less

<Peel strength>
Each of the curable resin compositions of Examples 1 to 11 and Comparative Examples 1 and 2 was applied on the entire glossy surface of a copper foil that had been previously surface-treated (MEC, CZ-8101, etching amount: about 1.0 μm). And dried at 80 ° C. for 30 minutes and allowed to cool to room temperature. The entire surface of the curable resin composition on the copper foil was exposed with an optimum exposure amount using an exposure apparatus equipped with a high-pressure mercury lamp (short arc lamp). Next, the curable resin composition on the copper foil was irradiated with ultraviolet rays under a condition of an integrated exposure amount of 1000 mJ / cm ^{2 in} a UV conveyor furnace, and then cured by heating at 150 ° C. for 60 minutes to obtain a cured product. .
On the other hand, each curable resin composition of Examples 12 to 14 was applied to the entire surface of a copper foil that had been subjected to surface treatment (MEC, CZ-8101, etching amount: about 1.0 μm) and cured at 180 ° C. for 60 minutes. Thus, a copper foil having a cured film was produced.
After applying an adhesive (araldite) to the cured film on each copper foil obtained as described above, evaluation of copper tension was performed with a press at a pressure of 0.5 MPa and a temperature of 60 ° C. A substrate was created.
The obtained copper-clad evaluation board is cut to a depth of about 10 mm × about 80 mm to reach the cured film, and the end is peeled off a little to secure a grip, and then gripped with a gripping jig. The peel strength was measured using (manufactured by Shimadzu Corporation, Autograph AGS-100N). The measurement conditions were room temperature, the pulling speed was 50 mm / min, and the average load when peeling 35 mm was measured. The peel strength was evaluated according to the following criteria.
◎: Greater than 10N ○: Greater than 7N and 10N or less △: Greater than 5N and 7N or less

<PCBT resistance>
Each cured resin composition of Examples 1 to 14 and Comparative Examples 1 and 2 was applied to an L / S having a copper thickness of 18 μm: a comb pattern having a thickness of 100 μm / 100 μm, and the substrate cured in the same manner as the gold plating resistance was evaluated. It was put in an environment maintained at an internal temperature of 121 ° C. and a humidity of 97%, DC 30 V was applied, and the connection time was measured with a resistance value of 10 ⁶ Ω or less as the measurement end point.
◎: 200 hours or more ○: 150 hours or more and less than 200 hours Δ: 100 hours or more and less than 150 hours ×: Less than 100 hours

<Underfill adhesion>
The evaluation substrate plated with electroless gold in the gold plating resistance evaluation is treated with plasma (gas Ar / O ₂ : output: 350 W, vacuum degree: 300 mTorr) for 60 seconds, and underfill (DENA TITE R3003iEX manufactured by Nagase ChemteX Corporation). ), Cured at 160 ° C. for 1 h, and further subjected to 260 ° C. peak reflow three times, further at 121 ° C., 2 atm, and 100% humidity for 100 h, and then the adhesion between the underfill and the resist layer The properties were measured with a push gauge and evaluated according to the following criteria.
◎: 100N or more ○: 80N or more and less than 100N Δ: 60N or more and less than 80N ×: Less than 60N

＊１：フェノールノボラック型の骨格を有する感光性カルボキシル基含有樹脂（ＰＮ（フェノールノボラック型エポキシ樹脂）／ＡＡ（アクリル酸）／ＴＨＰＡ（テトラヒドロフタル酸無水物））
＊２：クレゾールノボラック型の骨格を有する感光性カルボキシル基含有樹脂（ＣＮ（クレゾールノボラック型エポキシ樹脂）／ＡＡ（アクリル酸）／ＴＨＰＡ（テトラヒドロフタル酸無水物））
＊３：カルボキシル基含有共重合樹脂（ダイセル化学工業社製のサイクロマーＰ（ＡＣＡ）Ｚ２５０）
＊４：ＢＡＳＦジャパン社製イルガキュア９０７（２−メチル−１−［４−（メチルチオ）フェニル］−２−モルフォリノプロパン−１−オン）
＊５：日本化薬社製ＤＥＴＸ−Ｓ（２，４−ジエチルチオキサントン）
＊６：ＢＡＳＦジャパン社製イルガキュアＯＸＥ０２（エタノン，１−［９−エチル−６−（２−メチルベンゾイル）−９Ｈ−カルバゾール−３−イル］−，１−（０−アセチルオキシム））
＊７：堺化学社製Ｂ−３０
＊８：アドマテックス社製ＳＯ−Ｅ２
＊９：２，２’−オキシビス（５，５’−ジメチル−１，３，２−オキサボリナン）
＊１０：ジエチレングリコールモノエチルエーテルアセテート
＊１１：芳香族炭化水素（ソルベッソ１５０）
＊１２：ＤＩＣ社製Ｎ−７３０Ａ（フェノ−ルノボラック型エポキシ樹脂、液状エポキシ樹脂）
＊１３：三菱化学社製ｊＥＲ８２８（ビスフェノールＡ型エポキシ樹脂、液状エポキシ樹脂）
＊１４：ＤＩＣ社製Ｎ−７７０（フェノ−ルノボラック型エポキシ樹脂、固形エポキシ樹脂）
＊１５：四国化成社製２ＰＨＺ（２−フェニル−４，５−ジヒドロキシメチルイミダゾール）
＊１６：ジペンタエリスリトールヘキサアクリレート（共栄社化学社製）
＊１７：トリメチロールプロパントリアクリレート（日本化薬社製）

* 1: Photosensitive carboxyl group-containing resin having a phenol novolac type skeleton (PN (phenol novolak type epoxy resin) / AA (acrylic acid) / THPA (tetrahydrophthalic anhydride))
* 2: Photosensitive carboxyl group-containing resin having a cresol novolac type skeleton (CN (cresol novolac type epoxy resin) / AA (acrylic acid) / THPA (tetrahydrophthalic anhydride))
* 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-morpholinopropan-1-one) manufactured by BASF Japan
* 5: Nippon Kayaku DETX-S (2,4-diethylthioxanthone)
* 6: BASF Japan Irgacure OXE02 (ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime))
* 7: Sakai Chemical B-30
* 8: Admatechs SO-E2
* 9: 2,2′-oxybis (5,5′-dimethyl-1,3,2-oxaborinane)
* 10: Diethylene glycol monoethyl ether acetate * 11: Aromatic hydrocarbon (Sorvesso 150)
* 12: DIC's N-730A (phenol novolac type epoxy resin, liquid epoxy resin)
* 13: Mitsubishi Chemical Corporation jER828 (bisphenol A epoxy resin, liquid epoxy resin)
* 14: N-770 manufactured by DIC (phenol novolac type epoxy resin, solid epoxy resin)
* 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 result shown in the said Table 1, it turns out that the curable resin composition of Examples 1-14 is excellent in the heat resistance and elongation rate of hardened | cured material. Moreover, in the case of the composition of Examples 1-11 which is an alkali development type photocurable resin composition, even if development life is evaluated on the said drying conditions, since favorable developability is obtained, it is excellent in a dry management width | variety. I understand that. On the other hand, the curable resin compositions of Comparative Examples 1 and 2 not containing (C) the boric acid ester compound were inferior in heat resistance and elongation rate of the cured product.

Claims (7)

(A) a carboxyl group-containing resin,
(B) a thermosetting component, and
(C) A curable resin composition comprising a borate ester compound.   The curable resin composition according to claim 1, comprising a liquid epoxy resin as the thermosetting component (B).   Furthermore, a photoinitiator is contained, The curable resin composition of Claim 1 or 2 characterized by the above-mentioned.   The curable resin composition according to claim 1, wherein the curable resin composition is used for forming a solder resist, a coverlay, or an interlayer insulating material.   It has a resin layer obtained by apply | coating and drying the curable resin composition of any one of Claims 1-4 on a film, The dry film characterized by the above-mentioned.   A cured product obtained by curing the curable resin composition according to any one of claims 1 to 4 or the dry film resin layer according to claim 5.   A printed wiring board comprising the cured product according to claim 6.

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