KR101184552B1 - Urethane oligomer, thermosetting resin composition containing the same and cured product thereof - Google Patents

Abstract

The present invention comprises a urethane resin suitable for forming a flexible film having excellent adhesion to a substrate, cutting resistance, low warpage, solder heat resistance, electroless gold plating resistance, electrical insulation, and the like, a thermosetting resin composition containing the same, and a cured product thereof. Provided are a printed wiring board on which a protective film or an insulating layer is formed.

The primary amino group-containing urethane oligomer is obtained by reacting (a) a polyisocyanate compound, (b) a compound having two or more alcoholic hydroxyl groups, and (c) a primary amino group-containing compound. Preferably, the primary amino group is bonded to the alicyclic or aliphatic constituent unit of the urethane oligomer, and the isocyanate component of the urethane oligomer is aliphatic or alicyclic diisocyanate. In addition, the compound (b) is preferably a polycarbonate diol. The thermosetting resin composition contains (A) the said primary amino group containing urethane oligomer and (B) the thermosetting compound.

Primary amino group, urethane oligomer, thermosetting resin composition

Description

Urethane oligomer, thermosetting resin composition containing this, and its hardened | cured material {URETHANE OLIGOMER, THERMOSETTING RESIN COMPOSITION CONTAINING THE SAME AND CURED PRODUCT THEREOF}

The present invention provides an amino group-containing urethane oligomer suitable for forming a flexible coating having excellent adhesion to a substrate, corrosion resistance, low warpage, solder heat resistance, electroless gold plating resistance, electrical insulation, and the like, and a thermosetting resin composition containing the same, and a cured product thereof. A protective film or insulating material comprising a protective film or an insulating layer such as a soldering resist or an interlayer insulating film used for the manufacture of a printed wiring board, in particular for the manufacture of a flexible printed wiring board or a tape carrier package, or the backlight or information of a liquid crystal display. It is useful for the back electrode protective film of an electroluminescent panel used for a display, etc., the protective film of display panels, such as a mobile telephone, a clock, and a car stereo, IC, an ultra-LSI sealing material, etc.

As a soldering resist used for manufacture of a flexible printed wiring board or a tape carrier package, a polyimide film called a coverlay film is punched with a mold according to a pattern, and then a type of adhesive or a film having flexibility is formed. The type which apply | coats ultraviolet-curable or thermosetting soldering resist ink by screen printing, or the liquid photosolder resist ink type which forms a flexible film is used.

However, with a coverlay film, since the traceability with copper foil has a problem, a high-precision pattern cannot be formed. On the other hand, in ultraviolet curable soldering resist ink and liquid photosolder ink, adhesiveness with a base material polyimide is bad, and sufficient flexibility is not acquired. Moreover, since the shrinkage | contraction of the soldering resist ink and the cooling contraction after hardening are large, a curvature arises and it becomes a problem.

In addition, as a conventional thermosetting solder resist ink, there is an epoxy resin resist ink composition containing an epoxy resin and a long chain dibasic anhydride as essential components disclosed in Japanese Patent Publication No. 5-75032 (Patent Document 1). When it adjusts to provide flexibility to the film formed, there exists a problem that adhesiveness with a base material polyimide worsens, and plating resistance, PCT resistance, and solder heat resistance fall.

 Therefore, Japanese Patent Laid-Open No. 2006-117922 (Patent Document 2) discloses a urethane bond formed by the reaction of a polycarbonate diol (a) with a polyisocyanate (b) having two or more carboxyl groups in one molecule of (A). A thermosetting resin composition comprising a polyurethane having and a (B) thermosetting component is proposed. By using such a carboxyl group-containing urethane resin in combination with an epoxy resin as the thermosetting component, the above-described problems of the conventional solder resist ink can be solved, but there are still points to be improved in characteristics such as solder heat resistance.

[Patent Document 1] Japanese Patent Application Laid-Open No. 5-75032 (Patent Claims)

[Patent Document 2] Japanese Patent Laid-Open No. 2006-117922 (claims)

Accordingly, an object of the present invention is to solve the problems of the prior art as described above, and is suitable for forming a flexible film having excellent adhesion to a substrate, corrosion resistance, low warpage, solder heat resistance, electroless gold plating resistance, electrical insulation, and the like. Provided is a urethane resin and a thermosetting resin composition containing the same, thereby providing a printed wiring board, particularly a flexible printed wiring board or a tape carrier package or the like, having a protective film or insulating layer formed of its cured material at a relatively low cost. There is.

In order to achieve the above object, according to the present invention, there is provided a urethane oligomer containing a primary amino group in a molecule. In a preferred embodiment, the primary amino group is bonded to the alicyclic or aliphatic constituent unit of the urethane oligomer, and the isocyanate component of the urethane oligomer is preferably aliphatic or alicyclic diisocyanate.

In a more specific preferred embodiment, there is provided a urethane resin obtained by reacting (a) a polyisocyanate compound, (b) a compound having two or more alcoholic hydroxyl groups, and (c) a compound containing a primary amino group. Preferably, the compound (b) having two or more alcoholic hydroxyl groups is a polycarbonate diol.

Moreover, according to this invention, the thermosetting resin composition characterized by containing the urethane oligomer which contains a primary amino group in (A) molecule | numerator, and (B) thermosetting compound.

In a preferable embodiment, it is preferable that the said thermosetting compound (B) is an epoxy resin, and also contains (C) hardening accelerator further. Moreover, it may contain an inorganic and / or organic filler, and may contain an organic solvent as needed.

Moreover, according to this invention, the hardened | cured material formed by hardening | curing the said thermosetting resin composition, and the printed wiring board in which one part or all part of the surface was coat | covered with this hardened | cured material are also provided.

The urethane resin of the present invention is characterized in that it is a urethane oligomer containing a primary amino group in a molecule. This amino group-containing urethane oligomer has high reactivity derived from a primary amino group and excellent adhesiveness with a base material, and since an oligomer has a urethane structure, it shows the outstanding flexibility. For these reasons, even when a polyfunctional epoxy resin having a high performance or the like is used as the thermosetting component of the thermosetting resin composition, it is excellent in low warpage resistance and cut resistance and further improves solder heat resistance. Moreover, the urethane resin of this invention is obtained by making (a) polyisocyanate compound, (b) compound which has two or more alcoholic hydroxyl groups, and (c) the compound containing a primary amino group react as a preferable aspect. In the urethane oligomer thus obtained, the reaction is controlled so that the primary amino group remains at the terminal of the molecule, and the storage stability can be improved. Moreover, since it has a primary amino group in the terminal of a urethane oligomer, characteristics, such as solder heat resistance, can be improved further by hardening reaction with a thermosetting component.

Therefore, the urethane oligomer of the present invention is suitable for forming a flexible film having excellent adhesion to substrates, corrosion resistance, low warpage, solder heat resistance, electroless gold plating resistance, electrical insulation and the like.

Moreover, the thermosetting resin composition of this invention which contains such a urethane oligomer containing a primary amino group with a thermosetting compound is a protective film, such as a soldering resist used for manufacture of a flexible printed wiring board and a tape carrier package which is excellent in flexibility, or an insulating resin. It is useful as a material. Moreover, since the film obtained from such a thermosetting resin composition does not bend after thermosetting, attachment of a component or a chip to a flexible printed wiring board or a tape carrier package is easy. Therefore, by using the thermosetting resin composition of this invention, the flexible protective film excellent in various characteristics, such as adhesiveness, abrasion resistance, low curvature, electroless gold plating resistance, solder heat resistance, electrical insulation, etc., can be formed efficiently at low cost.

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching in order to achieve the said subject, the present inventors made it react with (a) a polyisocyanate compound, (b) the compound which has two or more alcoholic hydroxyl groups, and (c) the compound containing a primary amino group, The obtained amino group-containing urethane oligomer has excellent adhesiveness with the base material mentioned as a characteristic derived from an amino group, and at the time of thermosetting, the amino group causes a crosslinking reaction with a functional group of a thermosetting compound, for example, an epoxy group of an epoxy resin, It has been found that the properties such as solder heat resistance can be improved. In general, the lower the crosslinking density of the resin, the greater the flexibility of the formed film, and the less the warpage of the film after thermosetting. However, when crosslinking density becomes low, the characteristics, such as solder heat resistance, plating resistance, and chemical resistance, of the film obtained will also fall easily. In this invention, the high reactivity derived from a primary amino group and adhesiveness with a base material can be improved by using an amino group containing urethane oligomer. Moreover, since it has the outstanding flexibility derived from a urethane structure, it becomes possible to use the high Tg epoxy resin, polyfunctional epoxy resin, etc. which have a high performance generally considered to be difficult to use for the soldering resist for flexible board | substrates, It has been found that properties such as solder heat resistance can be improved while maintaining low warpage.

Hereinafter, each component of the amino group containing urethane oligomer of this invention and the thermosetting resin composition containing this is demonstrated in detail.

First, the urethane oligomer (A) of the present invention is reacted with (a) a polyisocyanate compound, (b) a compound having two or more alcoholic hydroxyl groups, and (c) a compound containing a primary amino group, It is preferable that it is a urethane oligomer which has the amino group introduce | transduced at the terminal.

The said urethane oligomer (A), for example, in the case of the said preferable urethane oligomer, makes (a) polyisocyanate compound and (b) compound which has two or more alcoholic hydroxyl groups react as a 1st reaction, and then 2nd It is preferable to react (c) the compound containing a primary amino group as reaction.

The reaction proceeds without a catalyst by stirring and mixing at room temperature to 100 ° C, but it is preferably heated to 70 to 100 ° C in order to increase the reaction rate.

As said polyisocyanate compound (a), conventionally well-known various polyisocyanate can be used and it is not limited to a specific compound. As a specific example of the (branched) aliphatic or alicyclic isocyanate (a) used when synthesize | combining the said preferable urethane oligomer, For example, branched aliphatic diisocyanate, such as aliphatic diisocyanate, such as hexamethylene diisocyanate, and trimethylhexamethylene diisocyanate, etc. , Isophorone diisocyanate, (o, m, or p) -hydrogenated xylylene diisocyanate, methylenebis (cyclohexyl isocyanate), cyclohexane-1,3-dimethylene diisocyanate, cyclohexane-1,4- Alicyclic diisocyanate, such as dimethylene diisocyanate, etc. are mentioned. Among these, hexamethylene diisocyanate which is aliphatic diisocyanate and trimethylhexamethylene diisocyanate which is branched aliphatic diisocyanate are preferable. Moreover, diisocyanate which has an aromatic ring, such as (o, m, or p)-xylylene diisocyanate, can also be used. These diisocyanate can be used individually or in mixture of 2 or more types. When these diisocyanate is used, the hardened | cured material excellent in low curvature can be obtained.

Next, as the compound (b) having two or more alcoholic hydroxyl groups, various conventionally known polyols can be used. Although not limited to a specific compound, polycarbonate-based polyols such as polycarbonate diols, polyether-based polyols, and poly Ester polyol, polyolefin polyol, polybutadiene polyol, polyisoprene polyol, hydrogenated polybutadiene polyol, hydrogenated isoprene polyol, acrylic polyol, bisphenol A alkylene oxide adduct diol, phosphorus containing polyol, carboxyl group and two or more A compound having an alcoholic hydroxyl group, a phenolic hydroxyl group, a compound having two or more alcoholic hydroxyl groups, and the like can be preferably used. As a polycarbonate diol, the polycarbonate diol (b-1) which comprises the repeating unit derived from 1 type, or 2 or more types of linear aliphatic diol as a structural unit, and comprises the repeating unit derived from 1 type or 2 or more types of alicyclic diols The polycarbonate diol (b-3) which contains as a structural unit the repeating unit derived from the polycarbonate diol (b-2) contained as a unit, or the diol of both linear aliphatic diol and alicyclic diol is mentioned. The compound (b) having two or more alcoholic hydroxyl groups may be used alone or in combination of two or more thereof.

As a specific example of the polycarbonate diol (b-1) which contains as a structural unit the repeating unit derived from the said 1 type, or 2 or more types of linear aliphatic diol, For example, polycarbonate diol derived from 1, 6- hexanediol, Polycarbonate diols derived from 1,5-pentanediol and 1,6-hexanediol, polycarbonate diols derived from 1,4-butanediol and 1,6-hexanediol, 3-methyl-1,5-pentanediol and Polycarbonate diols derived from 1,6-hexanediol, polycarbonate diols derived from 1,9-nonanediol and 2-methyl-1,8-octanediol, and the like.

As a specific example of the polycarbonate diol (b-2) which contains as a structural unit the repeating unit derived from the said 1 type, or 2 or more types of alicyclic diol, For example, polycarbonate diol derived from 1, 4- cyclohexane dimethanol Etc. can be mentioned.

As a specific example of the polycarbonate diol (b-3) which contains as a structural unit the repeating unit derived from the diol of both said linear aliphatic diol and alicyclic diol, for example, 1, 6- hexanediol and 1, 4- And polycarbonate diols derived from cyclohexanedimethanol.

Polycarbonate diols containing a repeating unit derived from the linear aliphatic diol as a structural unit tend to be excellent in low smoothness and flexibility. Moreover, the polycarbonate diol which contains the repeating unit derived from an alicyclic diol as a structural unit becomes high in crystallinity, and it exists in the tendency which is excellent in tin plating resistance and solder heat resistance. In the above aspect, these polycarbonate diol can use 2 or more types in combination, or can use the polycarbonate diol which contains the repeating unit derived from the diol of both linear aliphatic diol and alicyclic diol as a structural unit. In order to balance low warpage and flexibility and solder heat resistance and tin plating resistance, it is preferable to use polycarbonate diol having a copolymerization ratio of linear aliphatic diol and alicyclic diol in a mass ratio of 3: 7 to 7: 3. Do.

The polycarbonate diol preferably has a number average molecular weight of 200 to 5,000, but the polycarbonate diol contains a repeating unit derived from a linear aliphatic diol and an alicyclic diol as a structural unit, and copolymerization of a linear aliphatic diol and an alicyclic diol. When the ratio is 3: 7 to 7: 3 by mass ratio, those having a number average molecular weight of 400 to 2,000 are preferable.

Examples of the bisphenol A-based alkylene oxide adduct include ethylene oxide adducts, propylene oxide adducts, and butylene oxide adducts of bisphenol A. Among these, propylene oxide adducts of bisphenol A are preferable.

Specific examples of the phosphorus-containing polyol include FC-450 (manufactured by Asahi Denka Kogyo Co., Ltd.), M-ester (Ester) (manufactured by Sanco Co., Ltd.), M-ester-HP (manufactured by Sanco Co., Ltd.), and the like. Can be. By using these phosphorus containing polyols, a phosphorus compound can be introduce | transduced in a urethane resin and flame retardance can be provided.

As a specific example of the compound which has the said carboxyl group and two or more alcoholic hydroxyl groups, dimethylol propionic acid, dimethylol butanoic acid, etc. are mentioned. By using the compound which has these carboxyl groups and 2 or more alcoholic hydroxyl groups, a carboxyl group can be introduce | transduced easily in a urethane resin.

As a specific example of the compound (c) containing a primary amino group used by this invention, For example, aliphatic polyamines, such as diaminobutane, hexamethylenediamine, trimethylhexamethylenediamine, and 2-methylpentamethylenediamine, isophoronediamine, And alicyclic polyamines such as 1,3-bisaminomethylcyclohexane, bis (4-aminocyclohexyl) methane, norbornenediamine, and 1,2-diaminocyclohexane.

It is preferable that it is 500-100,000, and, as for the weight average molecular weight of the said amino group containing urethane oligomer (A), 8,000-50,000 are more preferable. Here, a weight average molecular weight is the value of polystyrene conversion measured by the gel permeation chromatography. If the weight average molecular weight of the amino group-containing urethane oligomer (A) is less than 500, the elongation, flexibility, and strength of the cured film may be impaired, while if it exceeds 100,000, not only the solubility in the solvent is lowered, but also the viscosity is high even when dissolved. Since it becomes too high, the restriction becomes large in terms of use.

In the thermosetting resin composition of this invention, as a thermosetting compound (B) mix | blended with the said amino group containing urethane oligomer (A), the epoxy group, oxetanyl group, etc. which can react with the amino group of the urethane resin which is the said (A) component are mentioned. Although the epoxy resin and oxetane compound which have two or more in 1 molecule can be used preferably, epoxy resin is especially preferable.

As a specific example of an epoxy resin, for example, bisphenol-A epoxy resin, hydrogenated bisphenol-A epoxy resin, brominated bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, bisphenol S-type epoxy resin, novolak-type epoxy resin, phenol no Volac type epoxy resin, cresol novolac type epoxy resin, N-glycidyl type epoxy resin, novolac type epoxy resin of bisphenol A, bixylenol type epoxy resin, biphenol type epoxy resin, chelate type epoxy resin, glyoxal type epoxy Resin, amino-group-containing epoxy resin, rubber modified epoxy resin, dicyclopentadiene phenolic epoxy resin, diglycidyl phthalate resin, heterocyclic epoxy resin, tetraglycidyl xylenoylethane resin, silicone modified epoxy resin, ε- A caprolactone modified epoxy resin, etc. are mentioned.

As an epoxy resin which the hardened | cured material of a more preferable high Tg is easy to obtain, an N-glycidyl-type epoxy resin, a bixylenol-type epoxy resin, a biphenol type epoxy resin, tetraglycidyl xylenoyl ethane resin, tetrakisphenol ethane type epoxy A resin, a dicyclopentadiene phenolic epoxy resin, a naphthalene skeleton containing epoxy resin, etc. are mentioned, Specifically, GTR-1800 (made by Nippon Kayaku Co., Ltd.) and dicyclopenta which are tetrakisphenol ethane type epoxy resins is mentioned. HP-7200 (manufactured by Dainippon Ink & Chemicals Co., Ltd.), a dienephenolic epoxy resin, HP-4032D, EXA-7240, EXA-4700, and EXA-4770 (all Dainippon Inks Inc.) are epoxy resins having a naphthalene skeleton. Manufactured by Kaku Kogyo Co., Ltd., EXA-7335 (manufactured by Dainippon Ink & Chemicals Co., Ltd.), an epoxy resin having a xanthene skeleton, and NC-3000 (manufactured by Nippon Kayaku Co., Ltd.), a biphenol novolac epoxy resin. ), These By using a polyfunctional epoxy resin, another trifunctional and tetrafunctional epoxy resin, etc., characteristics, such as solder heat resistance, can be improved.

Further, for imparting flame retardancy, those in which atoms such as halogens such as chlorine and bromine and phosphorus are introduced into the structure thereof may be used.

In the thermosetting resin composition of this invention, the said thermosetting compound (B) is used individually or as a mixture of 2 or more types. It is preferable that the compounding quantity is 5-1000 mass parts with respect to 100 mass parts of amino group containing urethane oligomers which are said (A) component, Preferably it is the ratio of 10-500 mass parts. If it is less than 5 mass parts, the solder heat resistance of the cured film of a thermosetting resin composition may become inadequate, On the other hand, when it exceeds 1000 mass parts, the various characteristics at the time of using it as an insulating protective film of a flexible printed wiring board (FPC), especially an electrical insulation This tends to get worse.

The hardening accelerator (C) used by this invention promotes a thermosetting reaction, and is used in order to further improve characteristics, such as adhesiveness, chemical-resistance, and heat resistance. As a specific example of such a hardening accelerator, imidazole and its derivatives (for example, Shikoku Kasei Kogyo Co., Ltd. make, 2MZ, 2E4MZ, C11Z, C17Z, 2PZ, 1B2MZ, 2MZ-CN, 2E4MZ-CN, C11Z-CN, 2PZ-CN, 2PHZ-CN, 2MZ-CNS, 2E4MZ-CNS, 2PZ-CNS, 2MZ-AZINE, 2E4MZ-AZINE, C11Z-AZINE, 2MA-OK, 2P4MHZ, 2PHZ, 2P4BHZ, etc.); Guanamines such as acetoguanamine and benzoguanamine; Polyamines such as diaminodiphenylmethane, m-phenylenediamine, m-xylenediamine, diaminodiphenylsulfone, dicyandiamide, urea, urea derivatives, melamine and polybasic hydrazide; Organic acid salts and / or epoxy adducts thereof; Amine complexes of boron trifluoride; Triazine derivatives such as ethyldiamino-S-triazine, 2,4-diamino-S-triazine and 2,4-diamino-6-xylyl-S-triazine; Trimethylamine, triethanolamine, N, N-dimethyloctylamine, N-benzyldimethylamine, pyridine, N-methylmorpholine, hexa (N-methyl) melamine, 2,4,6-tris (dimethylaminophenol), tetra Amines such as methylguanidine and m-aminophenol; Polyphenols such as polyvinylphenol, polyvinylphenol bromide, phenol novolak and alkylphenol novolak; Organic phosphines such as tributylphosphine, triphenylphosphine and tris-2-cyanoethylphosphine; Phosphonium salts such as tri-n-butyl (2,5-dihydroxyphenyl) phosphonium bromide and hexadecyltributylphosphonium chloride; Quaternary ammonium salts such as benzyltrimethylammonium chloride and phenyltributylammonium chloride; The polybasic acid anhydride; Diphenyl iodonium tetrafluoroborate, triphenylsulfonium hexafluoro antimonate, 2,4,6-triphenylthiopyryllium hexafluorophosphate, Irgacure (trademark) made by Ciba Specialty Chemicals Co., Ltd. 261, photocationic polymerization catalysts such as Optimer SP-170 manufactured by Adeka Corporation; Styrene-maleic anhydride resins; Known conventional hardening accelerators or hardeners, such as equimolar reactants of phenyl isocyanate and dimethylamine, and organic polyisocyanate, such as tolylene diisocyanate and isophorone diisocyanate, and equimolar reactants of dimethylamine, are mentioned.

These hardening accelerators (C) can be used individually or in mixture of 2 or more types. Although the use of a hardening accelerator (C) is not essential, Especially when it is going to accelerate hardening, it can use in the range of 0.1-25 mass parts with respect to 100 mass parts of said thermosetting compounds (B). When it exceeds 25 mass parts, since the sublimable component from the hardened | cured material increases, it is unpreferable.

The thermosetting resin composition of the present invention comprises the above-mentioned amino group-containing urethane oligomer (A), thermosetting compound (B), and a curing accelerator (C) or a filler, if necessary, for example, a disper, a kneader, a triaxial roll mill. Obtained by dissolving or dispersing using a bead mill or the like. At this time, you may use the solvent inactive with respect to an epoxy group or phenolic hydroxyl group. As such an inert solvent, an organic solvent is preferable.

An organic solvent is used in order to melt | dissolve or disperse the said amino-group containing urethane oligomer (A) and a thermosetting compound (B) easily, or to adjust to the viscosity suitable for coating. As an organic solvent, for example, toluene, xylene, ethylbenzene, nitrobenzene, cyclohexane, isophorone, diethylene glycol dimethyl ether, ethylene glycol diethyl ether, carbitol acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate , Dipropylene glycol methyl ether acetate, diethylene glycol ethyl ether acetate, methyl methoxypropionate, ethyl methoxypropionate, methyl ethoxypropionate, ethyl ethoxypropionate, ethyl acetate, n-butyl acetate, isoamyl acetate, ethyl lactate , Acetone, methyl ethyl ketone, cyclohexanone, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, γ-butyrolactone, dimethyl sulfoxide, chloroform and methylene chloride Can be mentioned. The compounding quantity of an organic solvent can be set suitably according to a desired viscosity.

The thermosetting resin composition of this invention can contain the compound which has a carboxyl group and / or phenolic hydroxyl group for the purpose of improving the adhesiveness, hardness, heat resistance, etc. in the range which does not impair the effect of this invention. As a compound which has a carboxyl group and / or a phenolic hydroxyl group, all compounds can be used as long as it has a carboxyl group and / or a phenolic hydroxyl group, Although it is not limited to a specific thing, Among these, for example, the following resin is preferable. Do.

(1) carboxyl group-containing resin obtained by copolymerizing an unsaturated carboxylic acid and a compound having an unsaturated double bond,

(2) a carboxyl group-containing resin obtained by reacting a polyfunctional epoxy compound with a saturated or unsaturated monocarboxylic acid and reacting the resulting secondary hydroxyl group with a polybasic acid anhydride,

(3) carboxyl group-containing resin obtained by making polybasic acid anhydride react with a hydroxyl-group containing polymer,

(4) carboxyl group-containing resin obtained by addition reaction of four kinds of compounds with a polyisocyanate compound, a polyol compound, a compound having two or more alcoholic hydroxyl groups and one carboxyl group, and a compound having one hydroxyl group,

(5) polyfunctional phenolic resin,

(6) phenolic hydroxyl group-containing resin obtained by addition reaction of three kinds of compounds of polyisocyanate compound, polyol compound, compound having alcoholic hydroxyl group and phenolic hydroxyl group, and

(7) A polyisocyanate compound, a polyol compound, obtained by addition reaction of four kinds of compounds with a compound having two or more alcoholic hydroxyl groups and one carboxyl group, and a compound having an alcoholic hydroxyl group and a phenolic hydroxyl group Carboxyl group and phenolic hydroxyl group containing resin.

Among these, the carboxyl group-containing resins of the above (4), (6) and (7) having a urethane structure in order to improve properties such as adhesion, hardness, heat resistance, etc. without impairing the flexibility and low warpage of the cured product obtained. It is especially preferable to mix | blend.

The thermosetting resin composition of this invention can contain a well-known conventional mercapto compound in order to improve adhesiveness with base materials, such as a polyimide, as needed. Examples of the mercapto compound include 2-mercaptopropionic acid, trimethylolpropane tris (2-thiopropionate), 2-mercaptoethanol, 2-aminothiophenol, 3-mercapto-1,2,4-triazole, Mercapto group containing silane coupling agents, such as 3-mercapto- propyl trimethoxysilane, etc. are mentioned. These may be used independently, respectively and may be used in combination of 2 or more type. The compounding quantity is suitable for the range of 10 mass parts or less per 100 mass parts of thermosetting resin compositions of this invention. When the compounding quantity of a mercapto compound exceeds the said range, since the epoxy group of the said epoxy resin required for a crosslinking reaction is consumed (reacts with an epoxy group), and a crosslinking density falls, it is unpreferable.

The thermosetting resin composition of this invention can contain an inorganic and / or organic filler further in order to improve characteristics, such as adhesiveness, hardness, and heat resistance, as needed. Examples of the inorganic fillers include barium sulfate, calcium carbonate, barium titanate, silicon oxide, amorphous silica, talc, clay, mica powder, and the like, and silicon powder, nylon powder, fluorine powder, and the like can be given. Among the fillers, silica is particularly excellent in low hygroscopicity and low volume expandability. Although silica may be a mixture of these regardless of melting | fusing and crystallinity, especially in the case of silica surface-treated with a coupling agent etc., since electrical insulation can be improved, it is preferable. It is preferable that the average particle diameter of a filler is 25 micrometers or less, More preferably, it is 10 micrometers or less, More preferably, it is 3 micrometers or less. The compounding quantity of these inorganic and / or organic fillers is suitable 300 mass parts or less per 100 mass parts of thermosetting resin compositions of this invention, Preferably it is the ratio of 5-150 mass parts. When the compounding quantity of a filler exceeds the said ratio, the corrosion resistance of a cured film falls and it is unpreferable.

Moreover, in the thermosetting resin composition of this invention, other additives and coloring agents other than the said component can also be added unless the effect of this invention is impaired. Examples of the additive include thickeners such as asbestos, organic bentonite and montmorillonite, silicone-based and fluorine-based antifoaming agents, leveling agents, fiber reinforcing materials such as glass fibers, carbon fibers and boron nitride fibers, and the like. Iodine green, disazo yellow, titanium oxide, carbon black and the like. If necessary, known conventional thermal polymerization inhibitors, ultraviolet absorbers, silane coupling agents, plasticizers, foaming agents, flame retardants, antistatic agents, anti-aging agents, antibacterial and flavoring agents, and the like can be added.

The thermosetting resin composition having the composition as described above can be applied to a printed board by various conventionally known methods such as curtain coating method, roll coating method, spray coating method and dip coating method, as well as various forms such as dry film or prepreg, Can be used for purposes. Various solvents may be used depending on the method of use and use thereof, but in some cases, not only a good solvent but also a poor solvent may be used.

Further, the thermosetting resin composition of the present invention is applied to a flexible printed wiring board, a tape carrier package or an electroluminescent panel formed with a circuit by a screen printing method, and cured by shrinkage by heating to a temperature of 120 to 180 ° C., for example. A soldering resist film or a protective film is formed that is not warped by cooling shrinkage and that is excellent in adhesion to the substrate, corrosion resistance, low warpage, electroless gold plating resistance, solder heat resistance, electrical insulation, and the like.

<Examples>

Although an Example and a comparative example are shown to the following and this invention is concretely demonstrated to it, of course, this invention is not limited to the following Example. In addition, it is a mass reference | standard unless it mentions specially in "part" and "%" below.

Synthesis Example 1 <Synthesis example of amino group-containing urethane oligomer>

280 g of hexamethylene diisocyanate was added to 300 g of dimethylformamide as a polyisocyanate in the reaction container provided with a stirring apparatus, a thermometer, and a capacitor, and it stirred at room temperature. After the flask was mixed uniformly, the solution was raised to 70 ° C. and a polycarbonate diol derived from 1,5-pentanediol and 1,6-hexanediol as a compound having two or more alcoholic hydroxyl groups (Ube Alpine ( Note) 800 g of Manufacture, PCDL800, and number average molecular weight 800) were added with stirring, followed by stirring at 70 ° C for 15 hours to obtain a urethane oligomer.

Subsequently, 330 g of dimethylformamide and 130 g of norbornene diamine were charged into a reaction vessel equipped with a stirring device, a thermometer, and a condenser, stirred at room temperature, and after confirming that the flask was mixed uniformly, the urethane obtained before. 540 g of the oligomer was added in portions over 2 hours, and the reaction temperature was raised from room temperature to 70 ° C. Furthermore, the reaction temperature was maintained at 70 ° C and stirred for 5 hours. The infrared absorption spectrum confirmed that the absorption spectrum (2280 cm ^-1 ) of the isocyanate group was lost, and the reaction was terminated to obtain an amino group-containing urethane oligomer (hereinafter abbreviated as varnish A) having a solid content of 67% by weight.

Synthesis Example 2 <Synthesis example of carboxyl group-containing urethane oligomer>

Polycarbonate diol derived from 1,5-pentanediol and 1,6-hexanediol as a compound having two or more alcoholic hydroxyl groups in a reaction vessel equipped with a stirring device, a thermometer and a condenser (manufactured by Ube Koyama Co., Ltd.) , PCDL800, 360 g of number average molecular weight 800), 81.4 g of dimethyl olbutanoic acid, and 11.8 g of n-butanol were added as a reaction terminator. Next, 151.2 g of hexamethylene diisocyanate was added thereto, heated to 60 ° C while stopping with stirring, and heated again at the time when the temperature in the reaction vessel began to decrease, continued stirring at 80 ° C, and an isocyanate group in the infrared absorption spectrum. It was confirmed that the absorption spectrum of (2280 cm ^-1 ) was lost and the reaction was terminated. Next, carbitol acetate was added so that solid content might be 50 weight%, and the carboxyl group-containing urethane oligomer (it abbreviates as varnish B hereafter) which is a viscous liquid containing a diluent was obtained. The acid value of solid content of the obtained urethane oligomer was 51.0 mgKOH / g.

Synthesis Example 3 <Synthesis example of urethane oligomer>

Polycarbonate diol derived from 1,5-pentanediol and 1,6-hexanediol as a compound having two or more alcoholic hydroxyl groups in a reaction vessel equipped with a stirring device, a thermometer and a condenser (manufactured by Ube Koyama Co., Ltd.) , PCDL800, 800 g of a number average molecular weight 800) and 11.8 g of n-butanol were added. Next, 151.2 g of hexamethylene diisocyanate was added thereto, heated to 60 ° C while stopping with stirring, and heated again at the time when the temperature in the reaction vessel began to decrease, continued stirring at 80 ° C, and an isocyanate group in the infrared absorption spectrum. It was confirmed that the absorption spectrum of (2280 cm ^-1 ) was lost and the reaction was terminated. Next, carbitol acetate was added so that solid content might be 50 weight%, and the urethane oligomer (it abbreviates as varnish C hereafter) which is a viscous liquid containing a diluent was obtained.

Examples 1 to 8 and Comparative Examples 1 and 2

It mixed with the triaxial roll mill at room temperature by each component and compounding ratio shown in Table 1, and manufactured the thermosetting resin composition. The obtained thermosetting resin composition was coated on the board | substrate by screen printing, and thermosetting was performed at 150 degreeC for 60 minutes.

About the cured film of each said thermosetting resin composition, the following various characteristics were evaluated with the following method. The results are shown in Table 2.

(1) adhesion

Each of the thermosetting resin compositions of Examples 1 to 8 and Comparative Examples 1 and 2 was totally printed by Kapton 100H (polyimide film manufactured by Toray DuPont Co., Ltd., 25 μm thick) by screen printing, and then 60 minutes at 150 ° C. Heat curing. The adhesiveness of the hardened film was confirmed by the presence or absence of the peeling of the resist layer by the peeling test using a cellophane adhesive tape, and the following references | standards evaluated.

(Circle): No peeling at all.

(Triangle | delta): There exists a peeling slightly.

X: There exists peeling.

(2) heat resistance

Each of the thermosetting resin compositions of Examples 1 to 8 and Comparative Examples 1 and 2 was totally printed by Kapton 100H (polyimide film manufactured by Toray DuPont Co., Ltd., 25 μm thick) by screen printing, and then 60 minutes at 150 ° C. Heat curing. The obtained cured film was bent 180 ° and evaluated according to the following criteria.

(Circle): A thing with a crack in a hardened film.

(Triangle | delta): A thing with a crack in a hardened film slightly.

X: There exists a crack in a hardened film.

(3) low warpage

Each of the thermosetting resin compositions of Examples 1 to 8 and Comparative Examples 1 and 2 was totally printed by Kapton 100H (polyimide film manufactured by Toray DuPont Co., Ltd., 25 μm thick) by screen printing, and then 60 minutes at 150 ° C. Heat curing. After cooling, the obtained cured film was cut out to 50x50 mm, the curvature of four corners was measured, the average was calculated | required, and the following references | standards evaluated.

○: warpage is less than 1 mm.

(Triangle | delta): It is thing whose curvature is 1 or more and less than 5 mm.

X: curvature is 5 mm or more.

(4) electroless gold plating resistance

Each thermosetting resin composition of the said Examples 1-8 and Comparative Examples 1 and 2 was pattern-printed on the printed circuit board (thickness 1.6mm), respectively, and was thermosetted at 150 degreeC for 60 minutes, and the test piece was obtained. Using the obtained test piece, electroless gold plating was performed at the process mentioned later, and electroless gold plating tolerance was evaluated on the following references | standards.

○: The cured film has no swelling, peeling, or discoloration.

(Triangle | delta): A thing with a swelling, peeling, and discoloration a little in a cured film.

X: A thing with swelling, peeling, and discoloration in a cured film.

Electroless Gold Plating Process:

1. Degreasing: The test piece was immersed for 30 minutes in 30 degreeC acidic degreasing liquid (made by Nippon McDermid, 20 volume% aqueous solution of Metex L-5B).

2. Water washing: The test piece was immersed in running water for 3 minutes.

3. Soft etching: The test piece was immersed in 14.3 weight% of ammonium persulfate aqueous solution for 1 minute at room temperature.

4. Water washing: The test piece was immersed in running water for 3 minutes.

5. Acid immersion: The test piece was immersed in 10 volume% sulfuric acid aqueous solution for 1 minute at room temperature.

6. Water washing: The test piece was immersed in running water for 30 seconds to 1 minute.

7. Catalyst provision: The test piece was immersed for 30 minutes in 30 degreeC catalyst liquid (10 volume% aqueous solution of the Meltex Corporation make, metal plate activator 350).

8. Water washing: The test piece was immersed in running water for 3 minutes.

9. Electroless Nickel Plating: The test piece was immersed in a nickel plating solution (manufactured by Meltex Co., Ltd., Melplate Ni-865M, 20% by volume aqueous solution) having a pH of 4.6 for 30 minutes.

10. Acid immersion: The test piece was immersed in 10 volume% aqueous sulfuric acid solution for 1 minute at room temperature.

11. Water washing: The test piece was immersed in running water for 30 seconds to 1 minute.

12. Electroless Gold Plating: The test piece was immersed in a gold plating solution (manufactured by Meltex Co., Ltd., Ourore's UP 15% by volume, 3% by weight aqueous potassium cyanide solution) having a pH of 6 for 30 minutes.

13. Water washing: The test piece was immersed in running water for 3 minutes.

14. Hot water: The test piece was immersed in warm water at 60 ° C., washed with water for 3 minutes sufficiently, and dried well to dry water.

(5) solder heat resistance

Each thermosetting resin composition of the said Examples 1-8 and Comparative Examples 1 and 2 was pattern-printed on the printed circuit board (thickness 1.6mm), respectively, and was thermosetted at 150 degreeC for 60 minutes. The rosin-type flux was apply | coated to the obtained hardened film, it was immersed in 260 degreeC solder tank for 10 second, and the state of the hardened film was evaluated based on the following references | standards.

(Double-circle): A thing which does not swell, peel, or discolor a cured film even if it repeats immersion twice for 10 second.

○: The cured film has no swelling, peeling, or discoloration.

(Triangle | delta): A thing with a swelling, peeling, and discoloration a little in a cured film.

X: A thing with swelling, peeling, and discoloration in a cured film.

(6) electrical insulation

The thermosetting resin compositions of Examples 1 to 8 and Comparative Examples 1 and 2 were each prepared with a coating film on a polyimide substrate (Shinnex Tetsu Co., Ltd., Espanex) having L / S = 20/20 µm, respectively. And thermoset at 150 ° C. for 60 minutes. The electrical insulation of the obtained hardened film was evaluated under the following conditions and criteria.

Humidification conditions: temperature 120 ° C, humidity 85% RH, applied voltage 60 V, 100 hours

Measurement conditions: 60 seconds measuring time, 60 V applied voltage

(Circle): The insulation resistance value after humidification is 109 ohms or more, and there is no migration of copper.

(Triangle | delta): Insulation resistance value 109 ohms or more after humidification, and there exists copper migration.

X: Insulation resistance after humidification 108 ohms or less, copper migration exists.

The following various characteristics were evaluated on the board | substrate which line tin plating process was performed about the cured film of each said thermosetting resin composition by the following method. The results are shown in Table 3.

(7) Tin Plated Adhesiveness

Polyimide substrate (Sumitomo Kinzoku Kosan Co., Ltd.) which tin-plated L / S (line / space) = 15/15 micrometers of each thermosetting resin composition of the said Examples 1-8 and Comparative Examples 1 and 2, respectively The coating film was manufactured on the board | substrate which tin-plated on S'PERFLEX), and it thermosetted at 120 degreeC for 60 minutes, and then thermosetted at 125 degreeC for 7.5 hours. The adhesiveness on the tin plating of this hardened film was confirmed by the presence or absence of the peeling of the resist layer by the peeling test using a cellophane adhesive tape, and the following references | standards evaluated.

(Circle): No peeling at all.

(Triangle | delta): There exists a peeling slightly.

X: There exists peeling.

(8) electrical insulation

Polyimide substrate (Sumitomo Kinzoku Kosan Co., Ltd. product) which tin-treated each thermosetting resin composition of the said Examples 1-5 and Comparative Example 1 with L / S (line / space) = 15 / 15micrometer, respectively The coating film was manufactured on the board | substrate which tin-plated to S'PERFLEX), and it thermosetted at 120 degreeC for 60 minutes, and then thermosetted at 125 degreeC for 7.5 hours. The electrical insulation of the obtained hardened film was evaluated under the following conditions and criteria.

Humidification conditions: temperature 120 ° C, humidity 85% RH, applied voltage 60 V, 100 hours

Test conditions: Measurement time 60 seconds, applied voltage 60 V, measured at room temperature

(Circle): The insulation resistance value after humidification is 109 ohms or more, and there is no migration.

(Triangle | delta): The insulation resistance value after humidification is 109 ohms or more, and there exist migration.

X: Insulation resistance after humidification 108 ohms or less, migration generate | occur | produces.

As is clear from the results shown in Tables 2 and 3 above, the cured coating film formed from the thermosetting resin composition of the present invention was excellent in adhesion to the substrate, corrosion resistance, low warpage, electroless gold plating resistance, solder heat resistance, and electrical insulation. . Moreover, also on the board | substrate which performed the line tin plating process, the favorable result was obtained. On the other hand, in Comparative Examples 1 and 2 using urethane oligomers (varnishes B and C) containing no amino groups, there was no problem in adhesion, substrate resistance, and low warpage to the substrate, but the electroless gold plating resistance, the solder heat resistance, and the electrical Insulation was inferior.

Claims (10)

Primary amino groups in a molecule | numerator manufactured by reaction with (A) (a) polyisocyanate compound, (b) compound which has 2 or more alcoholic hydroxyl groups, and (c) compound containing a primary amino group Containing Urethane oligomers, and (B) 1 or more types of thermosetting compounds chosen from an epoxy resin and an oxetane compound It contains, The thermosetting resin composition for printed wiring boards. The thermosetting resin composition for a printed wiring board according to claim 1, wherein the thermosetting compound (B) is an epoxy resin. Furthermore, (C) hardening accelerator is contained, The thermosetting resin composition for printed wiring boards of Claim 1 characterized by the above-mentioned. The thermosetting resin composition for a printed wiring board according to claim 1, further comprising an inorganic and / or organic filler. Hardened | cured material formed by hardening | curing the thermosetting resin composition of Claim 1, and applying to a printed wiring board. The printed wiring board in which one part or all part of the surface was coat | covered with the hardened | cured material of the thermosetting resin composition of Claim 1. delete delete delete delete