TWI541281B - A thermosetting resin composition, a hardened product thereof, and a printed circuit board using the same - Google Patents

Description

Thermosetting resin composition, cured product thereof, and printed circuit board using the same

The present invention relates to a thermal hardening of a flexible film which is suitable for forming non-tacky, adhesion to a substrate, folding resistance, low warpage, solder heat resistance, electroless gold plating resistance, electrical insulation, and the like. Resin composition, and a protective film or insulating material formed from the cured product thereof, and the manufacture of a printed circuit board, particularly in the manufacture of a flexible printed circuit board or the manufacture of a tape-and-reel package (Tape-Carrier Package) a protective film or an insulating layer such as a solder resist or an interlayer insulating film, or a protective film for a back electrode of an electroluminescent panel used in a backlight of a liquid crystal display or a display for information display, or a mobile phone or a clock , protective film for display panels such as car audio, IC or super LSI packaging materials.

A solder resist used in the manufacture of a flexible printed circuit board or a tape and reel package uses a bonding type in which a polyimine film called an upper cover film is punched in a mold, and an adhesive is used, or A type of an ultraviolet curable or thermosetting solder resist ink which forms a flexible film by screen printing, or a liquid photo solder resist ink having a flexible film.

However, since the upper cover film has a problem with the followability of the copper foil, it is impossible to form a high-precision pattern. On the other hand, the ultraviolet curable solder resist ink and the liquid photoresist ink have poor adhesion to the polyimide of the substrate, and sufficient flexibility cannot be obtained. Further, since the solder resist ink is hardened and shrunk and the cooling shrinkage after hardening is large, warpage is caused eventually, which becomes a problem.

Further, when an insulating layer is applied onto a substrate on which a circuit is formed and an insulating layer is formed by thermal curing, the step of superposing the substrates after the heat hardening can improve productivity and is preferable. However, the hardening temperature of the thermosetting resin is usually higher than the glass transition temperature Tg of the cured coating film, and since it is in a softened state, there is a problem in that the substrates are bonded to each other when they are superposed immediately after the heat curing. In order to solve such problems, it has been proposed to add an inorganic or organic granular anti-caking agent or the like (see Patent Document 1). However, when a printed circuit board of a high-density circuit is formed, if the agglomerating agent is too large, it may cause an inter-circuit. The insulation is lowered, and conversely, if it is too small, there is a problem that the anti-caking effect cannot be obtained.

[Patent Document 1] JP-A-2007-100038 (Application Patent Application)

Accordingly, an object of the present invention is to provide a thermosetting resin composition which is suitable for forming non-stick properties, adhesion to a substrate, folding resistance, and low in order to solve the problems of the prior art as described above. a flexible film excellent in warpage, solder heat resistance, electroless gold plating resistance, electrical insulation, etc., and a printed circuit board formed of a cured product thereof to form a protective film or an insulating layer at a low cost, in particular, Parts or articles such as flexible printed circuit boards, or tape and reel packaging.

In order to achieve the above object, according to the present invention, there is provided a thermosetting resin composition characterized by containing a cellulose derivative (A).

In a preferred embodiment, the cellulose derivative (A) is solvent-soluble, and the glass transition temperature Tg of the cellulose derivative (A) is preferably 100 ° C or more, more specifically, the heat hardening of the present invention. The resin composition is characterized by containing the above cellulose derivative (A) and a thermosetting compound (B). Preferably, the thermosetting compound (B) is an epoxy resin (B1), and more preferably the thermosetting compound (B) contains a carboxyl group-containing urethane resin (B2).

Moreover, according to the present invention, there is provided a cured product obtained by curing the thermosetting resin composition, and more preferably a cured product obtained by curing the thermosetting resin composition on a tin-plated circuit.

According to still another aspect of the invention, there is provided a printed circuit board comprising a part or all of a hardened film-coated substrate obtained by curing the thermosetting resin composition. Further, the present invention provides a flexible printed circuit board characterized by having a hardened film containing a cellulose derivative (A).

The thermosetting resin composition of the present invention is suitable for forming a non-stick property, adhesion to a substrate, folding resistance, low warpage, solder heat resistance, electroless gold plating resistance, electrical insulation, and the like. Sex film.

Thus, the thermosetting resin composition of the present invention can be used as a protective film or an insulating resin material which is used as a solder resist for use in the manufacture of a flexible brushed circuit board or a tape and reel type package which is excellent in flexibility. Further, the thermosetting resin composition of the present invention can be wound up or overlapped immediately after thermal drying and heat hardening, for example, in a production step of a reel-to-reel. As a result, by using the thermosetting resin composition of the present invention, in various fields as described above, it is possible to produce non-stickiness, adhesion, folding resistance, low warpage, and electrolessness with good productivity at low cost. A flexible protective film excellent in properties such as gold plating resistance, solder heat resistance, and electrical insulating properties.

As described above, the present invention provides a thermosetting resin composition suitable for forming a flexible film excellent in non-stickiness and the like, and is characterized in that it contains a cellulose derivative, but the thermosetting resin composition of the present invention is only required The cured product exhibits the above characteristics and is not limited to a specific constituent component, and is basically considered to have various forms containing a thermosetting component. In addition to the cellulose derivative (A) and the thermosetting compound (B), the curing accelerator (C) may be contained, and if necessary, a filler or the like may be contained, and the types and blending of the components may be combined. A cured product of the above characteristics can be obtained by the amount or the like. The cured product of the above-mentioned characteristics can be easily obtained by referring to the examples and comparative examples described later by those skilled in the art, and therefore detailed description is omitted. However, the main constituent components of the thermosetting resin composition of the present invention will be briefly described below.

(A) cellulose derivatives

The cellulose derivative (A) used in the present invention is preferably one which is soluble in an organic solvent and has a high glass transition temperature (Tg). The cellulose derivative is exemplified by a cellulose ether, a carboxymethyl cellulose, a cellulose ester or the like which will be described later.

The cellulose ether is exemplified by ethyl cellulose, hydroxyalkyl cellulose, etc., and the commercial products of ethyl cellulose are exemplified by ETOCEL (registered trademark) 4, ETOCEL 7, ETOCEL 10, ETOCEL 14, ETOCEL 20, ETOCEL 45, ETOCEL. 70, ETOCEL 100, ETOCEL 200, ETOCEL 300 (both trade names manufactured by The Dow Chemical Company), METOLOSE SM, METOLOSE 60SH, METOLOSE 65SH, METOLOSE 90SH, METOLOSE SEB, METOLOSE SNB (All are the trade names manufactured by Shin-Etsu Chemical Co., Ltd.) and so on.

Further, commercially available products of carboxymethyl cellulose are exemplified by CMCAB-641-0.2 (trade name manufactured by Eastman Co., Ltd.), SUNLOSE F, SUNNOSE A, SUNNOSE P, SUNNOSE S, and SUNNOSE B (all of which are Japanese paper chemicals ( Share) the name of the product manufactured).

Further, a cellulose derivative which is a cellulose ester obtained by esterifying a hydroxyl group of cellulose with an organic acid is specifically exemplified by a compound represented by the following formula (1).

(In the formula, R represents hydrogen or an organic acid ester group, and is composed of at least two or more selected from the group consisting of hydrogen and an organic acid ester, and n is an integer of 1 or more, and the upper limit is limited by the molecular weight described later).

The cellulose ester represented by the above formula (1) has a hydroxyl group content of 0 to 6 wt% with respect to the cellulose resin, and as the organic acid ester, the ethyl sulfonate content is 0 to 40 wt%, and the content of propyl sulfonate or / and butyl sulfonate A range of 0 to 55 wt% is preferred. Here, [wt%] is the weight % of hydrogen or organic acid ester relative to the weight of cellulose.

Commercial products of such cellulose esters, as for cellulose acetate, for example, CA-398-3, CA-398-6, CA-398-10, CA-398-30, CA-394-60S, etc. Cellulose acetate butyrates are exemplified by CAB-551-0.01, CAB-551-0.2, CAB-553-0.4, CAB-531-1, CAB-500-5, CAB-381-0.1, CANB-381- 0.5, CAB-381-2, CAB-381-20, CAB-381-20BP, CAB-321-0.1, CAB-171-15, etc., as for cellulose acetate propionate, CAP-504-0.2, CAP-482-0.5, CAP-482-20 (the above cellulose derivatives are all trade names manufactured by Eastman Corporation) and the like. Among these, cellulose acetate butyrate and cellulose acetate propionate are preferred from the viewpoint of solubility of the solvent, and cellulose acetate is preferred from the viewpoint of odor. Ester propionate.

The number average molecular weight of the cellulose derivative is not particularly limited, but is preferably from 5,000 to 500,000, more preferably from 10,000 to 100,000. When the molecular weight is less than the above range, it is difficult to obtain the non-stickiness of the coating film after drying, and on the other hand, when it is larger than the above range, the solubility in the solvent and the compatibility are likely to be deteriorated.

Further, the glass transition temperature Tg of the cellulose derivative is preferably 70 ° C or more, less than 200 ° C, more preferably 100 ° C or more, and less than 180 ° C. When the glass transition temperature is less than 70 ° C, it is difficult to obtain sufficient non-stickiness. On the other hand, when it is 200 ° C or more, the folding resistance of the cured coating film may be impaired.

Further, the glass transition temperature Tg of the present specification means a glass transition temperature measured by a thermomechanical analysis (DSC) according to the method described in "5.17.5 DSC method" of JIS C6481:1996.

The cellulose derivative used in the present invention is derived from a natural product, which is preferable in terms of depletion of the fossil fuel. Further, the starting material used in the cellulose derivative of the present invention can also be produced from recycled articles such as recycled pulp, and can provide a composition which is preferable in terms of the environmental surface of CO ₂ reduction.

The cellulose derivative (A) as described above may be used singly or in combination of two or more. The amount of the cellulose derivative (A) is preferably from 1 to 50 parts by mass, more preferably from 2 to 40 parts by mass, per 100 parts by mass of the thermosetting compound (B) described later. When the amount of the cellulose derivative (A) is less than 1 part by mass, it is difficult to form a flexible hardened film excellent in non-stickiness and the like, and on the other hand, when it exceeds 50 parts by mass, mechanical properties of the cured product are likely to be caused. Reduced poorly.

(B) Thermosetting compound

The thermosetting compound (B) used in the present invention may be an epoxy resin, a urethane resin, a polyester resin, a polyurethane having a hydroxyl group, an amine group or a carboxyl group, a polyester, or a polycarbonate. A thermosetting resin conventionally used, such as a polyhydric alcohol, a phenol resin, an acrylic copolymer resin, a vinyl resin, a polyamide, a polyamidimide, an oxazine resin, or a cyanate ester. Further, as the curing agent corresponding to these, an isocyanate, an amine, a phenol or the like can be used (blocked).

Among these thermosetting compounds, an epoxy resin (B1) and a curing agent reactive with an epoxy resin are preferably used in combination from the viewpoint of adhesion and insulation reliability. Further, the combination of the epoxy resin (B1) and the carboxyl group-containing urethane resin (B2) is preferable in terms of low warpage and insulation reliability.

(B1) epoxy resin

Specific examples of the epoxy resin are, for example, a difunctional epoxy resin, such as a bisphenol A type epoxy resin, a hydrogenated bisphenol A type epoxy resin, a brominated bisphenol A type epoxy resin, and a bisphenol F type epoxy resin. , bisphenol S type epoxy resin, bisxylenol type epoxy resin, biphenol type epoxy resin, etc., and trifunctional or higher polyfunctional epoxy resin is exemplified by novolak type epoxy resin, phenol novolak type Epoxy resin, cresol novolak type epoxy resin, N-glycidyl type epoxy resin, phenolic phenol type epoxy resin of bisphenol A, bisphenol type epoxy resin, phenol novolac type epoxy Resin, chelating epoxy resin, glyoxal epoxy resin, epoxy resin containing amine group, rubber modified epoxy resin, dicyclopentadiene phenol epoxy resin, diglycidyl benzene a formate resin, a heterocyclic epoxy resin, a tetraglycidyl xylylene ethane ethane resin, an oxime modified epoxy resin, an ε-caprolactone modified epoxy resin, or the like. Further preferred epoxy resins which are easy to obtain a cured product of high Tg are N-glycidyl epoxy resin, bisphenol phenol epoxy resin, biphenol phenol epoxy resin, tetraglycidyl xylene oxime A ethane resin, a nonyl ethane type epoxy resin, a dicyclopentadiene phenol type epoxy resin, an epoxy resin containing a naphthalene skeleton, and the like. Specifically, the indophenol type epoxy resin is exemplified by GTR-1800 (manufactured by Nippon Kayaku Co., Ltd.), and the dicyclopentadiene phenol type epoxy resin is exemplified by HP-7200H (Daily Ink Chemical Industry Co., Ltd. The epoxy resin having a naphthalene skeleton is exemplified by HP-4032D, EXA-7240, EXA-4700, and EXA-4770 (all manufactured by Dainippon Ink Chemical Industry Co., Ltd.), and has a xanthene skeleton. The epoxy resin is exemplified by EXA-7335 (manufactured by Dainippon Ink Chemical Industry Co., Ltd.), and the bisphenol novolac epoxy resin is exemplified by NC-3000 (manufactured by Nippon Kayaku Co., Ltd.) by using these polyfunctional compounds. Base epoxy resin or other trifunctional and tetrafunctional epoxy resins can improve solder heat resistance and other characteristics. Among these epoxy resins, a solid epoxy resin is preferred.

Further, in order to impart flame retardancy, an epoxy resin in which a halogen or a phosphorus atom such as chlorine or bromine is introduced into the structure may be used.

(B2) a urethane resin containing a carboxyl group

The carboxyl group-containing urethane resin (B2) which can be used in the present invention is exemplified by a diisocyanate compound (a) and a polyol compound (b), and a compound having one carboxyl group and two alcoholic hydroxyl groups in one molecule ( c) The winner of the reaction. At this time, it is also possible to use a reaction stopper to stabilize the terminal. As the reaction stopper, a monohydroxy compound such as an aliphatic alcohol or a monohydroxy mono(meth)acrylate compound may be used, or an isocyanate group addition reaction or condensation reaction with an alcoholic hydroxyl group, an amine group, a thiol group or the like may be used. Various reaction stop agents known in the art such as a monocarboxylic acid obtained as a functional group. Further, in the above reaction, the compound (d) having one alcoholic hydroxyl group and one or more phenolic hydroxyl groups in the molecule, which is one of the functions of the reaction terminator, is reacted, and has a carboxyl group-containing amine group at the terminally introduced phenolic hydroxyl group. Since the ethyl formate resin causes a reaction between the epoxy resin and the phenol group which are expected to have heat resistance in addition to the carboxyl group, it is preferable in the case where welding heat resistance or the like is required.

The diisocyanate compound (a) which is a constituent component of the carboxyl group-containing urethane resin (B2) which can be used in the present invention can be a conventionally known diisocyanate, but it is preferably used from the viewpoint of low warpage. An isocyanate compound having an aromatic ring.

Specific examples of the isocyanate compound having no aromatic ring are, for example, an aliphatic diisocyanate such as hexamethylene diisocyanate or a branched aliphatic diisocyanate such as trimethylhexamethylene diisocyanate or isophorone diisocyanate. (o-, m- or p-)-hydroxylene diisocyanate, methylene bis(cyclohexyl isocyanate), cyclohexane-1,3-dimethylene diisocyanate, cyclohexane-1,4-diene An alicyclic diisocyanate such as a diisocyanate. Among these, hexamethylene diisocyanate of an aliphatic diisocyanate and trimethylhexamethylene diisocyanate of a branched aliphatic diisocyanate are preferable. These diisocyanate compounds which do not have an aromatic ring may be used individually or in mixture of 2 or more types. When these diisocyanate compounds are used, a cured product excellent in low warpage can be obtained. Further, an aromatic diisocyanate can also be used within a range that does not impair the film properties.

The polyol component (b) which is a constituent component of the carboxyl group-containing urethane resin (B2) which can be used in the present invention can be used in various conventionally known polyols, and is not limited to a specific compound, but it is preferably used. Polycarbonate-based polyol such as carbonate diol, polyether-based polyol, polyester-based polyol, polyolefin-based polyol, polybutadiene-based polyol, polyisoprene-based polyol, hydrogenation A polybutadiene-based polyol, a hydrogenated iso-pentadiene-based polyol, an acrylic polyol, a bisphenol A-based alkylene oxide adduct diol, a phosphorus-containing polyol, or the like. The polycarbonate diol is exemplified by a polycarbonate diol (b-1) containing a repeating unit derived from one or two or more kinds of linear aliphatic diols as a constituent unit, and one or more kinds thereof are contained. The repeating unit of the alicyclic diol is used as a constituent unit of the polycarbonate diol (b-2), or a repeating unit containing a diol derived from both a linear aliphatic diol and an alicyclic diol as a constituent Unit of polycarbonate diol (b-3).

Specific examples of the polycarbonate diol (b-1) containing a repeating unit derived from one or two or more kinds of linear aliphatic diols as a constituent unit are exemplified by, for example, 1,6-hexanediol. Polycarbonate diol, polycarbonate diol derived from 1,5-pentanediol and 1,6-hexanediol, polycarbonate derived from 1,4-butanediol and 1,6-hexanediol Ester diol, polycarbonate diol derived from 3-methyl-1,5-pentanediol and 1,6-hexanediol, from 1,9-nonanediol and 2-methyl-1,8 - octanediol derived polycarbonate diol or the like.

Specific examples of the above-mentioned polycarbonate diol (b-2) containing a repeating unit derived from one or two or more kinds of alicyclic diols as constituent units are exemplified by, for example, 1,4-cyclohexanedimethanol. Polycarbonate diol.

Specific examples of the polycarbonate diol (b-3) having a repeating unit derived from a diol derived from both a linear aliphatic diol and an alicyclic diol as a constituent unit are exemplified by, for example, 1,6- A diol diol derived from hexanediol and 1,4-cyclohexane methanol or the like.

The polycarbonate diol containing the repeating unit of the linear aliphatic diol as a constituent unit tends to have low warpage and excellent flexibility. In addition, the polycarbonate diol containing a repeating unit derived from an alicyclic diol as a constituent unit tends to have excellent tin plating resistance and solder heat resistance. In view of the above, these polycarbonate diols may be used in combination of two or more kinds, or a repeating unit containing a diol derived from both a linear aliphatic diol and an alicyclic diol may be used as a constituent unit. Carbonate diol. From the viewpoint of exhibiting low warpage or flexibility, balance with solder heat resistance or tin plating resistance, it is preferred to use a copolymerization ratio of a linear aliphatic diol and an alicyclic diol in terms of a mass ratio. It is a polycarbonate diol of 3:7 to 7:3.

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

The bisphenol A-based alkylene oxide adduct diol is exemplified by an ethylene oxide adduct of bisphenol A, a propylene oxide adduct, a butylene oxide adduct, etc., but preferably those of the above. It is a propylene oxide adduct of bisphenol A.

Specific examples of the phosphorus-containing polyol are exemplified by FC-450 (manufactured by Asahi Kasei Co., Ltd.), M-Ester (manufactured by Sanko Co., Ltd.), and M-Ester-Hp (manufactured by Sanko Co., Ltd.). By using these phosphorus-containing polyols, a phosphorus compound can be introduced into the urethane resin to impart flame retardancy.

In the present invention, a constituent component of a carboxyl group-containing urethane resin (B2), and a compound (c) having one carboxyl group and two alcoholic hydroxyl groups in one molecule is exemplified as a dimethylol group. Propionic acid, dimethylol butyric acid, and the like. The carboxyl group can be easily introduced into the urethane resin by using the compound having a carboxyl group and two or more alcoholic hydroxyl groups.

Next, as the compound having an alcoholic hydroxyl group as the above-mentioned stopper, various conventionally known monohydroxy compounds can be used. For example, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, second butanol, third butanol, pentanol, hexanol, octanol, 2-hydroxyl (meth)acrylate Ethyl ester, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, cyclohexanedimethanol mono(meth)acrylate, lactone or alkylene oxide addition of each of the above (meth)acrylates , glyceryl di(meth)acrylate, trimethylol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, bis(trimethylol)propane Tris(meth)acrylate, allyl alcohol, allyloxyethanol, glycolic acid, hydroxypyruvate, etc., but are not limited thereto.

Further, the compound (d) having one alcoholic hydroxyl group and one or more phenolic hydroxyl groups in the above molecule is used for introducing a phenolic hydroxyl group into the ethyl urethane, and has an end as a polyurethane. The function of the blocking agent, in particular, a compound having an alcoholic hydroxyl group and a phenolic hydroxyl group obtained by reacting with an isocyanate in a molecule functions as a reaction stopper. Specific examples of the compound (d) are exemplified by, for example, hydroxymethylphenol, hydroxymethylcresol, hydroxymethyl-di-tert-butylphenol, p-hydroxyphenyl-2-methanol, p-hydroxyphenyl group. 3-propanol, p-hydroxyphenyl-4-butanol, hydroxyethyl cresol, 2,6-dimethyl-4-hydroxymethylphenol, 2,4-dimethyl-6-hydroxyl Phenolic, 2,3,6-trimethyl-4-hydroxymethylphenol, 2-cyclohexyl-4-hydroxymethyl-5-methylphenol, 4-methyl-6-hydroxymethylbenzene-1 a hydroxyalkylphenol such as 2-diol, 4-(1,1-dimethylethyl)-6-hydroxymethylbenzene-1,2-diol, or a hydroxyalkyl cresol; hydroxybenzoic acid a phenol having a carboxyl substituent such as hydroxyphenylbenzoic acid or hydroxyphenoxybenzoic acid, and an esterified product of ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol or the like; The monoethylene oxide adduct of phenol, the monopropylene oxide adduct of bisphenol, p-hydroxyphenylethyl alcohol, etc., but it is not limited to these. These compounds (d) may be used singly or in combination of two or more.

The weight average molecular weight of the carboxyl group-containing urethane resin (B2) is preferably from 500 to 100,000, more preferably from 8,000 to 50,000. Here, the weight average molecular weight is a value converted into polystyrene by gel permeation chromatography. When the weight average molecular weight of the carboxyl group-containing urethane resin (B2) is less than 500, the elongation, flexibility, and strength of the cured film are impaired, and on the other hand, solubility in a solvent exceeding 100,000 is obtained. If it is lowered, even if the dissolved viscosity is too high, the restriction on the use surface is large.

Further, the acid value of the carboxyl group-containing urethane resin (B2) is preferably in the range of 10 to 120 mgKOH/g, more preferably 20 to 80 mgKOH/g. When the acid value is less than 10 mgKOH/g, the reactivity with the thermosetting component is lowered, which may impair the heat resistance. On the other hand, when the acid value exceeds 120 mgKOH/g, the properties such as alkali resistance and electrical properties of the cured film may be lowered as the resist. Further, the resin acid value is a value measured in accordance with JIS K5407.

In the thermosetting resin composition of the present invention, the thermosetting compound (B) to be blended with the carboxyl group-containing urethane resin (B2) may be used in addition to the epoxy resin (B1). An oxetane resin (B3) or the like having two or more oxetanyl groups obtained by reacting a carboxyl group (or a phenolic hydroxyl group) of the carboxyl group-containing urethane resin (B2).

The thermosetting compound (B) as described above may be used singly or in combination of two or more. The compounding amount of the thermosetting compound (B) is preferably in the range of 20 to 99% by mass, preferably 30 to 95% by mass based on the total amount of the composition. Further, when the epoxy resin (B1) and the carboxyl group-containing urethane resin (B2) are used in combination, the carboxyl group-containing urethane resin is preferably 50 to 2000 with respect to 100 parts by mass of the epoxy resin. The parts by mass are preferably in the range of 100 to 1000 parts by mass.

The hardening accelerator (C) used in the present invention is a member that promotes a thermosetting reaction, and is used to further improve properties such as adhesion, chemical resistance, and heat resistance. Specific examples of the hardening accelerator are, for example, imidazole and derivatives thereof (for example, 2MZ, 2E4MZ, C11Z, C17Z, 2PZ, 1B2MZ, 2MZ-CN, 2E4MZ-CN, C11Z-CN, manufactured by Siguo Chemical Industry Co., Ltd.). 2PZ-CN, 2PHZ-CN, 2MZ-CNS, 2E4MZ-CNS, 2PZ-CNS, 2MZ-AZINE, 2E4MZ-AZINE, C11Z-AZINE, 2MA-OK, 2P4MHZ, 2PHZ, 2P4BHZ, etc.); acetamidine, benzene And guanamine such as guanamine; diaminodiphenylmethane, m-phenylenediamine, m-xylylenediamine, diaminodiphenylphosphonium, diaminodiamine, urea, urea derivative, Polyamines such as melamine and polybasic hydrazine; organic acid salts and/or epoxy adducts; amine complexes of boron trifluoride; ethylenediamine-S-triazine, 2,4- Triazine derivatives such as diamino-S-triazine and 2,4-diamino-6-dimethylphenyl-S-triazine; trimethylamine, triethanolamine, N,N-dimethyloctylamine , N-benzyldimethylamine, pyridine, N-methylmorpholine, hexa(N-methyl)melamine, 2,4,6-gin (dimethylaminophenol), hydrazine methyl hydrazine, m- Amines such as aminophenols; polyvinylphenol, polyvinylphenol bromide, phenol novolac resin, alkylphenol novolac Polyphenols such as resins; organic phosphines such as tributylphosphine, triphenylphosphine, and cyano-2-ethylphosphine; tri-n-butyl (2,5-dihydroxyphenyl)phosphonium bromide, ten a sulfonium salt such as hexaalkyltributylphosphonium chloride; a quaternary ammonium salt such as benzyltrimethylammonium chloride or phenyltributylammonium chloride; the above-mentioned polybasic acid anhydride; diphenyliodonium tetrafluoride Borate, triphenylsulfonium hexafluoroantimonate, 2,4,6-triphenylthiopyridinium hexafluorophosphate, Ciba. Photopolymerization catalysts such as IRUGACURE (registered trademark) 261 manufactured by Specialty Chemicals Co., Ltd., OPTOMER-SP-170 manufactured by ADEKA Co., Ltd.; styrene-maleic anhydride resin; phenyl isocyanate and dimethylamine A conventionally used hardening accelerator or hardening agent such as a molar reactant, or an organic polyisocyanate such as toluene diisocyanate or isophorone diisocyanate, or a molar reactant such as dimethylamine.

These hardening accelerators (C) may be used singly or in combination of two or more. The use of the hardening accelerator (C) is not necessary, but it is preferably used in an amount of 0.1 to 25 parts by mass based on 100 parts by mass of the above thermosetting compound (B). When it exceeds 25 parts by mass, it is not preferable because the sublimation component of the hardened material is increased.

The thermosetting resin composition of the present invention can be a cellulose derivative (A) or a thermosetting compound (B) by using a kneading machine such as a disperser, a kneader, a triaxial roll mill, a bead mill or the like. The oxygen resin (B1), the carboxyl group-containing urethane resin (B2), and the like, and optionally the hardening accelerator (C), a filler, and the like are dissolved or dispersed. In this case, a solvent inert to the epoxy group or the phenolic hydroxyl group can also be used. These inert solvents are preferably organic solvents.

The organic solvent is such that the cellulose derivative (A), the thermosetting compound (B) (epoxy resin (B1), a carboxyl group-containing urethane resin (B2), etc.) are easily dissolved or dispersed, or adjusted. It is used in a viscosity suitable for coating. The organic solvent can be exemplified by, for example, toluene, xylene, ethylbenzene, nitrobenzene, cyclohexane, isophorone, diethylene glycol dimethyl ether, ethylene glycol diethyl ether, carbitol acetic acid Ester, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, dipropylene glycol methyl ether acetate, diethylene glycol ethyl ether acetate, methyl methoxypropionate, methoxy propyl Ethyl acetate, 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 hydrazine, chloroform, dichloromethane, and the like. The amount of the organic solvent to be formulated can be appropriately set depending on the desired viscosity.

The thermosetting resin composition of the present invention may contain a conventionally used thiol compound as needed to enhance adhesion to a substrate such as polyimide. Examples of thiol compounds are 2-mercaptopropionic acid, trimethylolpropane ginseng (2-thiopropionate), 2-mercaptoethanol, 2-aminothiophenol, 3-mercapto-1,2,4-tri A decane coupling agent containing a mercapto group such as oxazole or 3-mercaptopropyltrimethoxydecane. These may be used alone or in combination of two or more. The amount of the thermosetting compound (B) is preferably 10 parts by mass or less per 100 parts by mass of the compounding amount. When the amount of the thiol compound is more than the above range, the epoxy group (reacting with the epoxy group) of the above epoxy resin necessary for the crosslinking reaction is consumed, which causes a decrease in the crosslinking density.

The thermosetting resin composition of the present invention may further contain at least one filler selected from the group consisting of inorganic fillers and organic fillers for the purpose of improving properties such as adhesion, hardness, and heat resistance as needed. Examples of the inorganic filler are barium sulfate, calcium carbonate, barium titanate, cerium oxide, amorphous cerium oxide, talc, limestone, mica powder, etc., and organic fillers are exemplified by polyoxyn powder, nylon powder, fluorine powder, and the like. Among the above fillers, those having a low hygroscopicity and a low volume expansion property are preferably cerium oxide. The cerium oxide may be melted, crystallized, or a mixture of these, but in particular, in the case of cerium oxide which is surface-treated such as a coupling agent, it is preferred because it can improve electrical insulation. The average particle diameter of the filler is preferably 25 μm or less, more preferably 10 μm or less, still more preferably 3 μm or less. The amount of the inorganic and/or organic filler to be added is preferably 300 parts by mass or less, and preferably 5 to 150 parts by mass per 100 parts by mass of the thermosetting compound (B). When the compounding amount of the filler exceeds the above ratio, the folding resistance of the hardened film is lowered and is not appropriate.

Further, in the thermosetting resin composition of the present invention, other additives or coloring agents other than the above components may be added as long as the effects of the present invention are not impaired. Examples of additives include asbestos, organic bentonite, montmorillonite and other tackifiers, polyfluorene-based, fluorine-based defoamers, advection agents, glass fibers, carbon fibers, boron nitride fibers and other fiber-reinforced materials. Phthalocyanine. Blue, turnip. Green, iodine. Green, diazo yellow, titanium oxide, carbon black, and the like. In addition, according to the need to add known conventional thermal polymerization inhibitors, UV absorbers, decane coupling agents, plasticizers, foaming agents, flame retardants, antistatic agents, anti-aging agents, antibacterial. Mold inhibitors, etc.

The thermosetting resin composition having the above composition may be applied to a printed substrate, or may be used for a dry film or a prepreg, in addition to various methods known in the art such as a curtain coating method, a roll coating method, a spray coating method, and a dip coating method. Various forms and uses. Various solvents can be used depending on the method of use or use, but it is also possible to use not only a good solvent but also a weak solvent depending on the conditions.

Further, the thermosetting resin composition of the present invention can be applied to a flexible circuit board or a tape-and-reel package or an electroluminescence panel formed by a screen by a screen printing method, for example, by heating to 120 to 180 ° C. The temperature is excellent, such as warpage, adhesion to the substrate, folding resistance, low warpage, electroless gold plating resistance, solder heat resistance, electrical insulation, etc., by hardening shrinkage and cooling shrinkage. Solder resist film or protective film.

[Examples]

The invention is specifically described below by way of examples and comparative examples, but the invention is not limited by the following examples. In addition, the following [parts] and [%] are all based on quality unless otherwise specified.

Synthesis Example 1 Synthesis of Thermosetting Resin (Polyurethane Containing Carboxyl Group)

Injecting 360 g (0.45 m) of polycarbonate diol derived from 1,5-pentanediol and 1,6-hexanediol (number average molecular weight 800) into a reaction vessel equipped with a stirring device, a thermometer, and a condenser As a compound having two or more alcoholic hydroxyl groups, 81.4 g (0.55 mol) of dimethylolbutanoic acid, and 11.8 g (0.16 mol) of n-butanol were used as molecular weight modifiers (reaction stoppers). Next, 200.9 g (1.08 mol) of trimethylhexamethylene diisocyanate was injected as an isocyanate compound having no aromatic ring, and the mixture was heated to 60 ° C with stirring, and then stopped, and heated again when the temperature in the reaction vessel began to decrease. Stirring was continued at 80 ° C, and it was confirmed by infrared absorption spectrum that the absorption spectrum (2280 cm ^-1 ) of the isocyanate group disappeared as the end of the reaction. Next, carbitol acetate was added to make the solid content 60% by weight, and a carboxyl group-containing polyurethane having a viscous liquid of a diluent was obtained. The solid content of the obtained carboxyl group-containing polyurethane was 49.8 mgKOH/g.

Examples 1 to 5 and Comparative Example 1

The thermosetting resin composition was prepared by kneading three times at room temperature by a triaxial roll at the respective components and the mixing ratio shown in Table 1.

The following various characteristics were evaluated by the following methods for the hardened film of each of the above thermosetting resin compositions. The results are shown in Table 2.

(1) non-stickiness

Each of the thermosetting resin compositions of the above Examples 1 to 5 and Comparative Example 1 was screen-printed and printed on KAPTON 100EN (polyamide film manufactured by Toray Dupont Co., Ltd., thickness: 25 μm). It was thermally hardened at 120 ° C for 60 minutes (dry film thickness 15 μm). The hardened film is placed upside down and placed on a hot plate heated to a specified temperature. KAPTON 100EN was placed thereon, and after placing a 100-gram hammer for 30 seconds, KAPTON was lifted between the hammer and the coating film. The temperature at which adhesion or sticking occurred at this time was observed and evaluated on the following basis.

◎: No sticking or sticking at 80 °C.

○: No sticking or sticking at 60 °C. Attached at 80 ° C.

△: No adhesion or sticking at 40 °C. Attached at 60 ° C.

×: Adhesion and sticking occurred at 40 ° C or less.

(2) Adhesion

Each of the thermosetting resin compositions of the above Examples 1 to 5 and Comparative Example 1 was screen-printed and printed on KAPTON 100EN (polyamide film manufactured by Toray Dupont Co., Ltd., thickness: 25 μm). After heat curing at 120 ° C for 60 minutes, thermal hardening was carried out at 125 ° C for 7.5 hours (dry film thickness 15 μm). The adhesion of the hardened film was measured by peeling test using a celesta adhesive tape, and the presence or absence of peeling of the solder resist layer was confirmed, and the evaluation was performed on the following basis.

○: Not peeled at all.

△: A little peeling.

×: There is peeling.

(3) folding resistance

Each of the thermosetting resin compositions of the above Examples 1 to 5 and Comparative Example 1 was screen-printed and printed on KAPTON 100EN (polyamide film manufactured by Toray Dupont Co., Ltd., thickness: 25 μm). After heat curing at 120 ° C for 60 minutes, thermal hardening was carried out at 125 ° C for 7.5 hours (dry film thickness 15 μm). The obtained hardened film was bent at 180° and evaluated on the following basis.

○: The hardened film has no cracks.

△: There is a little crack in the hardened film.

×: The hardened film has cracks.

(4) Low warpage

Each of the thermosetting resin compositions of the above Examples 1 to 5 and Comparative Example 1 was screen-printed and printed on KAPTON 100EN (polyamide film manufactured by Toray Dupont Co., Ltd., thickness: 25 μm). After heat curing at 120 ° C for 60 minutes, thermal hardening was carried out at 125 ° C for 7.5 hours (dry film thickness 15 μm). After cooling, the obtained hardened film was cut into 50 × 50 mm, and the warpage of the four corners was measured to obtain an average value, and the evaluation was performed on the following basis.

◎: Those whose warpage is less than 1 mm.

○: Warpage of 1 mm or more and less than 4 mm.

△: Warpage of 4 mm or more and less than 7 mm.

×: A warp of 7 mm or more.

(5) Electroless gold plating resistance

Each of the thermosetting resin compositions of the above Examples 1 to 5 and Comparative Example 1 was printed on a copper polyimide substrate (ESPERNEX manufactured by Nippon Steel Co., Ltd.) in a pattern, and at 120 ° C. The test piece (dry film thickness 15 μm) was obtained by heat hardening for 60 minutes. Using the obtained test piece, electroless gold plating was performed in the procedure described later, and the resistance of electroless gold plating was evaluated by the following criteria.

○: The hardened film is not bulged, peeled, or discolored.

△: The hardened film is slightly bulged, peeled, and discolored.

×: The hardened film is bulged, peeled, and discolored.

Electroless gold plating steps:

1. Degreasing: The test piece was immersed in an acidic degreasing liquid (manufactured by Japan MAC DERMID Co., Ltd., a 20 vol% aqueous solution of Metex L-5B) at 30 ° C for 3 minutes.

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

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

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

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

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

7. Catalyst imparting: The test piece was immersed in a catalyst liquid (10 vol% aqueous solution of metal plate activator 350 manufactured by MELTEX) at 30 ° C for 3 minutes.

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 (MELUPLATE Ni-865M, manufactured by MELTEX Co., Ltd., 20 vol% aqueous solution) at 85 ° C and pH = 4.6 for 30 minutes.

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

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 liquid (Eolexex UP 15 vol%, a gold potassium cyanide 3 wt% aqueous solution manufactured by MELTEX) at 85 ° C and pH = 6 for 30 minutes.

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

14. Hot water washing: The test piece was immersed in warm water of 60 ° C, washed thoroughly for 3 minutes, and then thoroughly dehydrated and dried.

(6) Electrical insulation

Each of the thermosetting resin compositions of the above Examples 1 to 5 and Comparative Example 1 was subjected to a tin-plated polyimine substrate having an L/S (line/space ratio) of 15/15 μm (Sumitomo Metal Mine) A coating film was formed on the tin-coated substrate of the manufactured S'PERFLEX, and was thermally cured at 120 ° C for 60 minutes, and then thermally cured at 125 ° C for 7.5 hours (dry film thickness 15 μm). The electrical insulation properties of the obtained hardened film were 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 60V, measured at room temperature

◎: The insulation resistance value after humidification was 1012 Ω or more, and no migration occurred.

○: The insulation resistance value after humidification was less than 1012 Ω and 109 Ω or more, and no migration occurred.

△: The insulation resistance value after humidification was 109 Ω or more, and migration occurred.

×: The insulation resistance value after humidification is 108 Ω or less, and migration occurs.

(7) Chemical resistance

Each of the thermosetting resin compositions of the above Examples 1 to 5 and Comparative Example 1 was subjected to a tin-plated polyimine substrate having an L/S (line/space ratio) of 15/15 μm (Sumitomo Metal Mine) A coating film was formed on the tin-coated substrate of the manufactured S'PERFLEX, and was thermally cured at 120 ° C for 60 minutes, and then thermally cured at 125 ° C for 7.5 hours (dry film thickness 15 μm). The obtained hardened film was immersed in N-methylpyrrolidone for 30 minutes, and the solvent was wiped off. Then, a peeling test was performed by using a cellophane adhesive tape, and the presence or absence of the soldering layer peeling was confirmed, and it evaluated on the following basis.

○: Not peeled at all.

△: There was a little peeling.

×: There is peeling.

The evaluation results are shown in Table 2 below.

As is clear from the results shown in the above Table 2, the non-tacky property of the hardened film formed of the thermosetting insulating composition containing the cellulose derivative of the present invention, the adhesion to the substrate, the folding resistance, Low warpage, electroless gold plating resistance, and excellent insulation reliability. On the other hand, when the cured film is formed of the thermosetting insulating composition of Comparative Example 1 containing no cellulose derivative, there is no problem in adhesion to the substrate, folding resistance, electroless gold plating resistance, and electrical insulating properties. But not sticky.

The thermosetting insulating composition containing a cellulose derivative of the present invention can be cured at a low temperature and is excellent in non-stickiness, and is excellent in electroless gold plating resistance, and has excellent insulation reliability in a micro-circuit substrate which has been previously tin-plated. It is suitable for flexible circuit boards, especially for COF (film over-film) insulating protective film.

Examples 6 to 10 and Comparative Example 2

The thermosetting resin composition was prepared by kneading three times at room temperature three times at the room temperature and the blending ratio shown in Table 3.

The following various characteristics were evaluated by the following methods for the hardened film of each of the above thermosetting resin compositions. The results are shown in Table 4.

(8) non-stickiness

Each of the thermosetting resin compositions of the above Examples 6 to 10 and Comparative Example 2 was printed on a printed circuit board (thickness: 1.6 mm), and thermally dried at 80 ° C for 30 minutes (dry film thickness: 20 μm). Next, for double-sided printing, pattern printing is performed on the back side of the dried substrate. At this time, the adhesion or sticking of the first printed film to the aluminum step was observed and evaluated on the following basis.

○: No sticking or sticking.

×: There are stickers and sticky marks.

(9) Adhesion

The thermosetting resin compositions of the above Examples 6 to 10 and Comparative Example 2 were each printed on a printed circuit board (thickness: 1.6 mm), thermally dried at 80 ° C for 30 minutes, and then thermally cured at 150 ° C. 30 minutes (dry film thickness 20 μm). The adhesion of the hardened film to the copper was evaluated by using a celesta adhesive tape and confirming the peeling of the solder resist layer by a peeling test, and the evaluation was performed on the following basis.

○: Not peeled at all.

△: A little peeling.

×: There is peeling.

(10) Solder heat resistance

The thermosetting resin compositions of the above Examples 6 to 10 and Comparative Example 2 were each printed on a printed circuit board (thickness: 1.6 mm), thermally dried at 80 ° C for 30 minutes, and then thermally cured at 150 ° C. 30 minutes (dry film thickness 20 μm). The rosin-based flux was applied onto the obtained hardened film, and immersed in a solder bath at 260 ° C to remove the flux. After drying, the tape peeling test was performed, and the state of the cured film was evaluated by the following criteria.

○: There was no peeling even after immersion for 10 seconds.

△: It was slightly peeled off in 10 seconds, but it was not peeled off after immersion for 5 seconds.

×: After the immersion for 5 seconds, the hardened film was peeled off.

Examples 11 to 15 and Comparative Example 3

The thermosetting resin composition was prepared by kneading three times at room temperature three times at room temperature in the respective components and blending ratios shown in Table 5.

The following various characteristics were evaluated by the following methods for the hardened film of each of the above thermosetting resin compositions. The results are shown in Table 6.

(11) non-stickiness

Each of the thermosetting resin compositions of the above Examples 11 to 15 and Comparative Example 3 was screen-printed and printed on KAPTON 100H (polyimide film manufactured by Toray Dupont Co., Ltd., thickness: 25 μm). It was thermally dried at 80 ° C for 30 minutes (dry film thickness 20 μm). Ten sheets of the obtained substrates were stacked, and allowed to stand at room temperature at 25 ° C for 1 hour. The overlapping substrates were peeled off, and the attachment or sticking at this time was observed and evaluated on the following basis.

◎: No sticking or sticking.

○: No attachment, a little sticky mark.

△: There are stickers and sticky marks.

×: The coating film was transferred to the substrate.

(12) Adhesion

Each of the thermosetting resin compositions of the above Examples 11 to 15 and Comparative Example 3 was separately printed on KAPTON 100H (polyimine film manufactured by Toray Dupont Co., Ltd., thickness: 25 μm) at 80 ° C. After hot drying for 30 minutes, it was thermally hardened at 150 ° C for 30 minutes (dry film thickness 20 μm). The adhesion of the hardened film was evaluated by the peeling test using a spheroidal adhesive tape to confirm the peeling of the solder resist layer, and the evaluation was performed on the following basis.

○: Not peeled at all.

△: A little peeling.

×: There is peeling.

(13) folding resistance

Each of the thermosetting resin compositions of the above Examples 11 to 15 and Comparative Example 3 was screen-printed and printed on KAPTON 100H (polyimide film manufactured by Toray Dupont Co., Ltd., thickness: 25 μm). After heat drying at 80 ° C for 30 minutes, heat curing was carried out at 150 ° C for 30 minutes (dry film thickness 20 μm). The obtained hardened film was bent at 180° and evaluated on the following basis.

○: The hardened film has no cracks.

△: There is a little crack in the hardened film.

×: The hardened film has cracks.

(14) Low warpage

Each of the thermosetting resin compositions of the above Examples 11 to 15 and Comparative Example 3 was screen-printed and printed on KAPTON 100H (polyimide film manufactured by Toray Dupont Co., Ltd., thickness: 25 μm). After heat drying at 80 ° C for 30 minutes, heat curing was carried out at 150 ° C for 30 minutes (dry film thickness 20 μm). After cooling, the obtained hardened film was cut into 50 × 50 mm, and the warpage of the four corners was measured to obtain an average value, and the evaluation was performed on the following basis.

○: Warp 0 mm or more, less than 4 mm.

△: Warpage of 4 mm or more and less than 7 mm.

×: A warp of 7 mm or more.

(15) Solder heat resistance

The thermosetting resin compositions of the above Examples 11 to 15 and Comparative Example 3 were each printed on a printed circuit board (thickness: 1.6 mm), thermally dried at 80 ° C for 30 minutes, and then thermally cured at 150 ° C. 30 minutes (dry film thickness 20 μm). The rosin-based flux was applied onto the obtained hardened film, and immersed in a solder bath at 260 ° C to remove the flux. After drying, the tape peeling test was performed, and the state of the cured film was evaluated by the following criteria.

○: There was no peeling even after immersion for 10 seconds.

△: It was slightly peeled off in 10 seconds, but it was not peeled off after immersion for 5 seconds.

×: After the immersion for 5 seconds, the hardened film was peeled off.

Claims (6)

A thermosetting resin composition characterized by containing a cellulose derivative (A) having a glass transition temperature Tg of 70 ° C or more and less than 200 ° C and a thermosetting compound (B), and the aforementioned cellulose derivative (A) A solvent-soluble cellulose ester, and the thermosetting compound (B) contains an epoxy resin (B1). The thermosetting resin composition of the first aspect of the invention, wherein the thermosetting compound (B) contains a carboxyl group-containing urethane resin (B2). A cured product characterized by being cured by a thermosetting resin composition according to claim 1 or 2. A cured product characterized in that the thermosetting resin composition of claim 1 or 2 is hardened on a tin-plated circuit. A printed circuit board characterized by partially or wholly part of a hardened film-coated substrate formed by curing a thermosetting resin composition according to claim 1 or 2. The printed circuit board of claim 5, wherein the hardened film is a solder resist.