JP2014077113A - Flame-retardant resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a flame-retardant resin composition including a carboxyl group-containing modified ester resin, excellent in terms not only of flame retardant bleed-out resistance but also of adhesiveness, heat resistance, elasticity, flexibility, contiguity, electric insulating capacity, humid heat resistance, flame retardance, and flux resistance.SOLUTION: The provided flame-retardant resin composition includes a carboxyl group-containing modified ester resin (A), an aromatic phosphorus compound (B), a saccharide ester compound (C), and a curative (D) consisting of at least one type selected from the group consisting of epoxy group-containing compounds, non-blocked isocyanate compounds, blocked isocyanate compounds, and β-hydroxyalkylamide group-containing compounds.

Description

  The present invention relates to a flame retardant resin composition, and in particular, is excellent in the bleed-out resistance of a flame retardant, and particularly useful as an adhesive and a coating agent used around electronic materials such as a printed wiring board. Flame Retardant Resin, Including Carboxyl Group-Containing Modified Ester Resin that Gives Hardened Products Excellent in Properties, Heat Resistance, Flexibility, Flexibility, Adhesion, Electrical Insulation, Moisture and Heat Resistance, Flame Resistance, and Flux Resistance Relates to the composition.

  In recent years, the development of the electronics field has been remarkable, and in particular, electronic devices have become smaller, lighter, and higher in density, and demands for these performances have become increasingly sophisticated. In order to meet such demands, thinning, multilayering, and high definition of electronic materials including printed wiring boards are being actively studied. Adhesives and coating agents used in these materials , High flexibility, flexibility, adhesion, and high electrical insulation, adhesion, heat, etc. associated with the narrowing of space, which were not required for conventional rigid substrates such as glass epoxy Stability etc. are required. Specific examples of the adhesive / coating agent used around the electronic material include the following (1) to (5).

  (1) Interlayer adhesive: Used to bond circuit boards together, and is in direct contact with copper or silver circuit. It is used between the layers of a multilayer substrate, and there are liquid and sheet-like ones.

  (2) Coverlay film adhesive: used to bond a coverlay film (such as a polyimide film used for the purpose of protecting the outermost surface of a circuit) and an underlying circuit board; In many cases, the adhesive layer is integrated.

  (3) Adhesive for copper-clad film (CCL): used to bond polyimide film and copper foil together. Processing such as etching is performed when the copper circuit is formed.

  (4) Solder resist: used for the purpose of protecting the outermost surface of the circuit, and is formed by applying or bonding to the circuit and then curing. Some are photosensitive and thermosetting.

  (5) Adhesive for reinforcing plate: For the purpose of complementing the mechanical strength of the wiring board, it is used to fix a part of the wiring board to a reinforcing plate made of metal, glass epoxy, polyimide or the like.

  These forms include liquid form and sheet form (previously formed into a film), and the form is appropriately selected according to the application.

  Various studies have been made in order to meet such high demands on electronic material peripheral members, but no material that sufficiently satisfies all the characteristics has been obtained. For example, an adhesive composition mainly comprising an acid value-containing polyester / polyurethane and an epoxy resin is disclosed (Patent Document 1). Although this shows good adhesiveness derived from urethane bonds, it has poor heat resistance because it is difficult to form sufficient crosslinks because the distance between the crosslinks is long, and the amount of epoxy resin is increased to supplement this. In such a case, there is a problem that wettability to the substrate is lowered and adhesive strength is lowered. Furthermore, since the polyester skeleton is used as the main chain, there is a problem that the insulation reliability at high temperature humidification is remarkably inferior.

  Moreover, the adhesive composition containing a urethane modified carboxyl group containing polyester resin, an epoxy resin, and a hardening | curing agent is disclosed (patent document 2). Although this shows good adhesiveness derived from urethane bonds, it has poor heat resistance, and due to the low molecular weight of the urethane resin, there is a poor workability that many protrusions occur when thermosetting with a press or the like. It was a problem. Further, as in Patent Document 1, since the polyester skeleton is used as the main chain, there is a problem that the insulation reliability at high temperature humidification is extremely inferior.

  Moreover, the resin composition containing a polyimide siloxane, a both-ends epoxy siloxane, and a hardening | curing agent is disclosed (patent document 3). Although this system has flexibility specific to siloxane resins and excellent heat resistance, the siloxane skeleton itself has poor adhesion to the substrate, so that sufficient adhesion strength can be obtained by curing with epoxy siloxane having a low crosslinking density. The problem is that it is not possible, and because the distance between the crosslinking points of the epoxy group is large, the problem of poor workability that many protrusions occur when thermosetting with a press or the like is a problem. Further, since the compatibility with other components is remarkably poor, there is a problem that the degree of freedom in designing the composition is poor and the coating film has insufficient resistance as a composition.

  Also disclosed is a thermosetting resin composition mainly composed of an epoxy resin, an NBR rubber containing as little ionic impurities as possible, and a nitrogen-containing phenol novolac resin (Patent Document 4). This adhesive composition has the disadvantages that many NBR rubbers protrude when thermally cured with a press or the like, and the processability is poor. In addition, if a large amount of epoxy resin or phenols is added to compensate for this, the adhesive strength There was a problem that decreased. Furthermore, NBR rubber with as little ionic impurities as possible is expensive and sometimes difficult to use industrially.

  Moreover, the resin composition containing an epoxy resin, a phenol resin, the hardening accelerator for epoxy resins, and an elastomer is disclosed (patent document 5). In this case as well, there is a problem that it is difficult to simultaneously improve the processability deterioration derived from the elastomer and the decrease in the adhesive strength derived from the epoxy / phenol curing system.

  Also disclosed is a resin composition containing polybutadiene which is a flexible skeleton. For example, a polyimide resin having a polybutadiene skeleton is disclosed, and an example in which a resin composition containing the polyimide resin, a polybutadiene polyol, and a blocked isocyanate is used as an overcoat agent for a flexible circuit is disclosed (Patent Document 6). . Moreover, a resin composition (Patent Document 7) in which a polyamidoimide resin having a polybutadiene skeleton and a polysiloxane skeleton and an epoxy resin are blended, or a resin composition (Patent Document 8) in which a polyimide resin having a polybutadiene skeleton and an epoxy resin are blended. It is disclosed. However, these butadiene-based resins require a reaction at a high temperature, cause internal crosslinking due to oxidation unique to the butadiene skeleton, the resin gels during the reaction, and the storage stability as a composition is remarkably high. There was a problem of lowering.

  Further, a proposal focusing on hydrogenated polybutadiene skeleton has been made (Patent Document 9). Since this system uses a composite resin comprising a carboxyl group-containing hydrogenated polybutadiene resin and an acrylic resin having an epoxy group, it has excellent flexibility derived from a hydrogenated polybutadiene skeleton and adhesion to copper. However, since an ester skeleton is introduced when synthesizing the composite resin, there are problems in basic characteristics as an insulating material of a general electric circuit board such as insulation reliability and chemical resistance at high temperature humidification.

  Further, a carboxyl group-containing modified epoxy resin having a chain structure by an ester bond is disclosed (Patent Document 10). This system has an ester bond introduced into the main chain by the polymerization reaction of dibasic acid and diglycidyl ether type epoxy compound, so it has excellent adhesion strength and heat resistance to copper and various substrates, but hydrolysis Since the main chain is an ester skeleton that is inferior in property, there is a problem that the insulation reliability and chemical resistance at high temperature humidification are remarkably inferior. In addition, since dibasic acid is a main raw material, there is a problem in that it is difficult to develop flexibility as compared with a system using urethane resin or NBR rubber, and it is difficult to achieve both heat resistance.

In addition to the above properties, the adhesive / coating agent used around other electronic materials is required to have high flame retardancy. On the other hand, the resin used for the adhesive / coating agent often does not have sufficient flame retardancy as it is, and in such a case, the addition of the flame retardant imparts flame retardancy. Conventionally, flame retardant resin compositions mainly containing halogenated flame retardants and antimony flame retardants have been used, but in recent years, due to the growing awareness of environmental conservation worldwide, containing halogen compounds and antimony compounds. There is an increasing tendency to use flame retardants that do not.

  As flame retardants other than halogen compounds and antimony compounds, there are hydrated metal compounds, nitrogen-based compounds, phosphorus-based compounds, etc., but different defects have been confirmed for each, and no universal one has been proposed yet. Specifically, hydrated metal compounds and nitrogen-based compounds have little adverse effect on electrical properties, etc., but flame retardant performance itself is low, so it is essential to add a large amount, resulting in required substrate adhesion and Flexibility is impaired. Regarding phosphorus-based flame retardants, polyphosphates and phosphinates have high flame retardant properties because of their high phosphorus element concentrations. However, if the amount added is increased in order to obtain the required flame retardancy, flexibility and Deterioration of electrical insulation becomes remarkable. In addition, phosphazene compounds, phosphate ester compounds, phosphaphenanthrene compounds, etc. have relatively high flame retardancy and low risk of lowering flexibility. It had a fatal defect that out (precipitation on the material surface, powder blowing, and exudation) was severe.

  Under such circumstances, attempts have been made to suppress bleedout of phosphazene compounds and phosphate ester compounds.

  For example, a composition comprising a condensed phosphate having a specific structure, a polyester resin, and a polyamide resin is disclosed (Patent Document 11). However, the amount of flame retardant that can be used in this composition without causing bleed-out is 20 parts by weight or less with respect to 100 parts by weight of the resin, which is insufficient to obtain sufficient flame retardant performance.

  Moreover, the phosphazene compound which has a crosslinkable functional group is disclosed (patent documents 12-17). This has succeeded in suppressing the bleed-out by directly crosslinking the phosphorus-based flame retardant, but this also suppresses the flame retardant action accompanied by chemical decomposition of the flame retardant during combustion, resulting in In addition to not being able to obtain sufficient flame retardancy, there was a problem that the flexibility of the molded product was remarkably inferior.

  Moreover, the cyclic | annular phenoxy phosphazene compound which has a specific coupling group and a substituent, and the polymer flame retardant composition containing the same are disclosed (patent document 18). Although this cyclic phenoxyphosphazene compound has improved the bleed out property to some extent by introducing a substituent that enhances the compatibility with the resin, it is difficult to suppress the bleed out when the addition amount is increased. The phosphorus element concentration of the flame retardant itself was significantly reduced, and sufficient flame retardancy was not obtained.

JP-A-11-116930 JP 2007-51212 A JP 2004-91648 A JP 2003-165898 A JP 2007-161811 A JP-A-11-199669 JP 11-246760 A JP 2003-292575 A JP 11-114733 A JP 2005-60662 A JP 2010-241940 A JP-A 64-14239 JP-A 64-14240 Japanese Patent Laid-Open No. 6-247989 JP-A-8-193091 JP 2001-335676 A JP 2008-088217 A JP 2004-018475 A

  The object of the present invention is very excellent in that it has the above-mentioned characteristics, in particular, flame retardancy, electrical insulation, heat resistance, and flexibility, and also has high bleed-out resistance of phosphorus flame retardants, and a printed wiring board. Another object of the present invention is to provide a flame retardant resin composition that can be suitably used as an adhesive and a coating agent used in the vicinity of electronic materials.

  As a result of diligent studies to solve the above problems, the present inventors surprisingly incorporated a carboxyl group-containing modified ester resin having a specific structure, an aromatic phosphorus compound, and a sugar ester compound, It has been found that a flame retardant resin composition having high flame resistance, electrical insulation, moisture and heat resistance and flux resistance and having excellent bleed-out resistance can be obtained, and the present invention has been completed.

That is, the first invention includes a carboxyl group-containing modified ester resin (A), an aromatic phosphorus compound (B), a sugar ester compound (C) and an epoxy group-containing compound, a non-blocked isocyanate compound, a blocked isocyanate compound, And at least one compound (D) selected from β-hydroxyalkylamide group-containing compounds,
An acid anhydride group-containing compound (b) in which the carboxyl group-containing modified ester resin (A) is at least one selected from the polyol compound (a), an alicyclic polybasic acid anhydride, and an aromatic polybasic acid anhydride. ) To produce a carboxyl group-containing ester resin (c),
Reacting the carboxyl group-containing ester resin (c) with an epoxy compound (d) having at least two epoxy groups in one molecule to produce a side chain hydroxyl group-containing modified ester resin (e);
Further, the side chain hydroxyl group-containing modified ester resin (e) is reacted with at least one acid anhydride group-containing compound (b) selected from an alicyclic polybasic acid anhydride and an aromatic polybasic acid anhydride. The present invention relates to a flame retardant resin composition.

  Moreover, 2nd invention is related with said flame-retardant resin composition characterized by the acid value of carboxyl group-containing modified ester resin (A) being 1-100 mgKOH / g.

  The third invention relates to any one of the above flame-retardant resin compositions, wherein the carboxyl group-containing modified ester resin (A) has a weight average molecular weight of 5,000 to 500,000.

  The fourth invention relates to any one of the above flame-retardant resin compositions, wherein the sugar ester compound (C) is a sugar aromatic skeleton-containing carboxylic acid ester compound (C-1).

  The fifth invention relates to any one of the above flame-retardant resin compositions, wherein the sugar aromatic skeleton-containing carboxylic acid ester compound (C-1) is a sucrose benzoic acid ester compound.

  The sixth invention relates to any one of the above flame-retardant resin compositions, wherein the aromatic phosphorus compound (B) is a cyclic phosphazene compound.

  The seventh invention further comprises a thermosetting aid (E) which is at least one selected from an aziridine compound, a carbodiimide group-containing compound, a benzoxazine compound, a phenol resin, imidazoles and dicyandiamide. To any one of the above flame retardant resin compositions.

Moreover, 8th invention is related with the hardened | cured material obtained by hardening one of the said flame-retardant resin compositions by heating.

  Moreover, 9th invention is related with the printed wiring board characterized by having a hardened | cured material obtained by hardening said flame-retardant resin composition by heating.

  According to the present invention, the obtained coating film satisfies adhesiveness, heat resistance, flexibility, flexibility, adhesion, electrical insulation, moist heat resistance, and flux resistance, and has high flame resistance and bleed out resistance. It is possible to provide a flame retardant resin composition having both properties. The flame-retardant resin composition of the present invention comprises an adhesive / coating agent (interlayer adhesive, adhesive for coverlay film, adhesive for copper clad film (CCL), solder resist, reinforcement used around the electronic material. Plate adhesive, electromagnetic wave shielding adhesive) and the like.

  Hereinafter, the flame retardant resin composition of the present invention will be described in detail.

  The carboxyl group-containing modified ester resin of the present invention is an acid anhydride group-containing compound (b) that is at least one selected from a polyol compound (a), an alicyclic polybasic acid anhydride, and an aromatic polybasic acid anhydride. ) [Hereinafter, simply reacting with “an acid anhydride group-containing compound (b)” to produce a carboxyl group-containing ester resin (c), which is combined with the carboxyl group-containing ester resin (c) in one molecule. Is reacted with an epoxy compound (d) having at least two epoxy groups to produce a side chain hydroxyl group-containing modified ester resin (e), and the side chain hydroxyl group-containing modified ester resin (e) is further alicyclic. It can be obtained by reacting an acid anhydride group-containing compound (b) which is at least one selected from the formula polybasic acid anhydrides and aromatic polybasic acid anhydrides. By using grease, physical properties that are very important as adhesives and coating agents used around electronic materials such as printed wiring boards, such as storage stability before curing, flexibility after curing, and insulation reliability Solder heat resistance, solder heat resistance after humidification, etc. can be remarkably improved.

  This uses a polyol compound (a) and at least one acid anhydride group-containing compound (b) selected from an alicyclic polybasic acid anhydride and an aromatic polybasic acid anhydride as starting materials. This is because the flexibility, workability, and the like derived from the polyol compound (a) can be imparted compared to a resin using a polyester skeleton made of a dibasic acid as a main chain as a main chain. In addition, the carboxyl group-containing ester resin (c) is obtained by the polyol compound (a) and at least one acid anhydride group-containing compound (b) selected from an alicyclic polybasic acid anhydride and an aromatic polybasic acid anhydride. Since the ester bond group, which is considered to be inferior in insulation reliability, is protected with a bulky substituent when producing the resin, the insulation reliability and solder heat resistance are higher than those of conventional resins using a polyester skeleton as the main chain. Etc. can be remarkably improved.

  For example, instead of an acid anhydride group-containing compound (b) which is at least one selected from alicyclic polybasic acid anhydrides and aromatic polybasic acid anhydrides, When an acid anhydride group-containing compound that does not belong is used, it is generally possible to obtain a certain degree of adhesive strength and solder heat resistance due to the base material adhesion and heat resistance due to the polarity derived from the ester bond. Under severe conditions, the insulation reliability is poor, and even in terms of solder heat resistance, higher solder heat resistance such as high temperature solder test and solder test in a humidified state cannot be satisfied. In order to solve these problems, generally, a resin having a high Tg (Tg: glass transition temperature) skeleton or a curing agent having a high Tg skeleton is added. In these cases, the entire adhesive layer has a high Tg, Adhesive strength decreases significantly due to a decrease in adhesion to the material.

  On the other hand, the carboxyl group-containing modified ester resin of the present invention is an acid anhydride group-containing compound (a) that is at least one selected from the polyol compound (a), an alicyclic polybasic acid anhydride, and an aromatic polybasic acid anhydride ( When the carboxyl group-containing ester resin (c) is produced by b), the ester bond group is protected with a bulky substituent, and therefore, satisfactory insulation reliability and solder heat resistance are satisfied at the same time. It is possible to show high heat resistance while maintaining high adhesive strength without increasing the resistance.

  In addition, the carboxyl group-containing modified ester resin of the present invention includes polycarbonate polyols, polyester polyols such as alicyclic polyester polyols, polybutadiene polyols (including hydrogenated ones), polyether polyols, By using siloxane polyol, higher electrical insulation and heat resistance can be exhibited. Furthermore, by appropriately selecting an epoxy compound (d) having at least two epoxy groups in one molecule, it is possible to use a polycarbonate skeleton or a polysiloxane skeleton that is generally difficult to adhere to a substrate. Nevertheless, it is possible to show high adhesive strength.

  For example, in general, when a skeleton having excellent heat resistance such as polycarbonate or polysiloxane is used in order to ensure electric insulation, adhesion to a substrate is lowered, so that adhesive strength cannot be ensured. On the other hand, the present invention can solve the trade-off between high electrical insulation and adhesive strength for the above reasons.

  Moreover, since the carboxyl group-containing modified ester resin of the present invention does not require the use of a high Tg raw material, it exhibits excellent flexibility. Generally, a resin having high flexibility tends to have poor heat resistance, but the resin of the present invention is protected by a bulky substituent in the ester bond group in the molecule, so that it is less than a general polyester resin. An acid anhydride group-containing compound that exhibits high heat resistance and is at least one selected from an alicyclic polybasic acid anhydride and an aromatic polybasic acid anhydride for the side chain hydroxyl group-containing modified ester resin (e) Since the thermal crosslinking point is introduced into the main chain by reacting (b), the heat resistance can be further improved by crosslinking.

  For example, a low Tg skeleton or a urethane bond is usually introduced in order to ensure flexibility, but high heat resistance cannot be ensured due to poor heat resistance. Moreover, in order to ensure heat resistance, a high Tg skeleton and a high heat resistant bond are introduced. However, since these generally have poor flexibility, it is impossible to achieve both heat resistance and flexibility.

  On the other hand, the present invention can solve the trade-off between high flexibility and high heat resistance for the reasons described above. In the present invention, the flexibility can be further improved by suitably using a low Tg polycarbonate polyol, polybutadiene polyol, hydrogenated polybutadiene polyol, polyether polyol, or polysiloxane polyol as the polyol compound (a).

  Moreover, the carboxyl group-containing modified ester resin of the present invention can further improve these effects by suitably introducing a trifunctional polyol as the polyol compound (a). Specifically, the introduction of a branched structure increases the cohesive strength of the resin layer, resulting in adhesive strength and heat resistance without any adverse effects on storage stability, processing stability, flexibility, and electrical insulation. Can be improved.

  Hereinafter, the thermosetting resin composition containing the carboxyl group-containing modified ester resin (A) of the present invention will be described in detail.

  The carboxyl group-containing modified ester resin of the present invention is an acid anhydride group-containing compound (b) that is at least one selected from the polyol compound (a), an alicyclic polybasic acid anhydride, and an aromatic polybasic acid anhydride. To produce a carboxyl group-containing ester resin (c), and react the carboxyl group-containing ester resin (c) with an epoxy compound (d) having at least two epoxy groups in one molecule. A chain hydroxyl group-containing modified ester resin (e) is produced, and the side chain hydroxyl group-containing modified ester resin (e) is further selected from at least one selected from an alicyclic polybasic acid anhydride and an aromatic polybasic acid anhydride. It can be obtained by reacting the acid anhydride group-containing compound (b).

  The polyol compound (a) used in the present invention has two or more hydroxyl groups, and further has a repeating unit having a polymerization degree of 2 or more in its structure. In addition, as the polyol compound (a), a compound containing two hydroxyl groups is preferably used, and the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (hereinafter also referred to as “GPC”) is preferably 500 to 50,000. It is a compound of this. Examples of the polyol compound (a) include polyester polyols, polycarbonate polyols, polyether polyols, polybutadiene polyols, and polysiloxane polyols. In the present application, unless otherwise specified, the weight average molecular weight means a polystyrene-reduced weight average molecular weight by GPC measurement.

  Examples of the polyester polyol used in the present invention include a polyester polyol obtained by condensation reaction of a polyfunctional alcohol component and a dibasic acid component. Among the polyfunctional alcohol components, diols include ethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol, triethylene glycol, butylene glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 3,3 '-Dimethylol heptane, polyoxyethylene glycol, polyoxypropylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, octanediol, butylethylpentanediol, 2-ethyl-1,3- Hexanediol, cyclohexanediol, bisphenol A and the like, and as the polyfunctional alcohol component having three or more hydroxyl groups, trimethylolethane, polytrimethylolethane, trimethylol group Bread, poly trimethylol propane, pentaerythritol, poly pentaerythritol, sorbitol, mannitol, arabitol, xylitol, galactitol, glycerol and the like.

  Examples of the dibasic acid component include aliphatic or aromatic dibasic acids such as terephthalic acid, adipic acid, azelaic acid, sebacic acid, phthalic anhydride, isophthalic acid, trimellitic acid, and anhydrides thereof.

  Β-butyrolactone, β-propiolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, ε-caprolactone, γ-caprolactone, γ-heptanolactone, α-methyl-β-propiolactone, etc. Polyester polyols obtained by ring-opening polymerization of cyclic ester compounds such as lactones can also be used.

  Polyester polyols having phosphorus atoms can also be used, specifically, 2- (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-yl) methyl succinic acid or its acid anhydride; A polycondensate with ethylene glycol, or 2- (9,10-dihydro-9-oxa-10-oxide-10-phosphaphenanthrene-10-yl) methylsuccinic acid-bis- (2-hydroxyethyl) -ester, Or the polyester polyol obtained by the polycondensation is mentioned.

  Specifically in the polyester polyol, Kuraray polyol P series of Kuraray Co., Ltd. can be used. Among these, P-1041, P-2041, P-2010, P-2020, P-1030, and P-2030 are preferable because they have insulation reliability and heat resistance.

  The polycarbonate polyols used in the present invention have a structure represented by the following general formula (A) in the molecule.

Formula (A)
— [— R ⁸ —O—CO—] _m —
(In the formula, R ⁸ represents a divalent organic residue, and m represents an integer of 1 or more.)

  The polycarbonate polyol can be obtained, for example, by (1) a reaction between glycol or bisphenol and a carbonate ester, or (2) a reaction in which phosgene is allowed to act on glycol or bisphenol in the presence of an alkali.

  Specific examples of the carbonic acid ester used in the production method (1) include dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate, and propylene carbonate.

  Specific examples of glycols or bisphenols used in the production methods (1) and (2) include ethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol, triethylene glycol, butylene glycol, and 3-methyl-1,5-pentanediol. 2-methyl-1,8-octanediol, 3,3′-dimethylolheptane, polyoxyethylene glycol, polyoxypropylene glycol, propanediol, 1,3-butanediol, 1,4-butanediol, 1, 5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, octanediol, butylethylpentanediol, 2-ethyl-1,3-hexanediol, cyclohexanediol It can be used bisphenols such as bisphenol A, bisphenol F, ethylene oxide to the bisphenols, also bisphenols obtained by adding an alkylene oxide such as propylene oxide. These compounds can be used as one kind or a mixture of two or more kinds.

  Specifically, the Kuraray polyol C series of Kuraray Co., Ltd. can be used in the polycarbonate polyol. Among these, PMHC-1050, PMHC-2050, C-1090, C-2090, C-1065N, C-2065N, C-1015N, and C-2015N are preferable because of their flexibility. In addition, Etanacol UC-100, UM-90 (1/3), UM-90 (1/1), and UM-90 (3/1) manufactured by Ube Industries, Ltd. are preferable because they are excellent in heat resistance.

Examples of the polyether polyol used in the present invention include polymers, copolymers, and graft copolymers of alkylene oxides such as tetrahydrofuran, ethylene oxide, propylene oxide, and butylene oxide;
Polyether polyols obtained by condensation of hexanediol, methylhexanediol, heptanediol, octanediol or mixtures thereof;
Aromatic diols such as bisphenols obtained by adding alkylene oxides such as ethylene oxide and propylene oxide to bisphenol A and bisphenol F;
Using polyhydric alcohols such as trimethylol ethane, polytrimethylol ethane, trimethylol propane, polytrimethylol propane, pentaerythritol, polypentaerythritol, sorbitol, mannitol, arabitol, xylitol, galactitol, glycerin as part of the raw material Synthesized polyethylene oxide, polypropylene oxide, block copolymer or random copolymer of ethylene oxide / propylene oxide, polytetramethylene glycol, block copolymer or random copolymer of tetramethylene glycol and neopentyl glycol, etc. Polyether polyols; those having two or more hydroxyl groups can be used.

  The polybutadiene polyols used in the present invention include, for example, those obtained by hydrogenating unsaturated bonds in the molecule, such as polyethylene polyols, polypropylene polyols, polybutadiene polyols, hydrogenated polybutadiene polyols, polyisoprene polyols, hydrogenated compounds. And polyisoprene polyol.

  Commercially available products of polybutadiene polyol include NISSO PB (G series) from Nippon Soda Co., Ltd., liquid polybutadiene having hydroxyl groups at both ends, such as Poly-Pd from Idemitsu Petrochemical Co., Ltd .; NISSO PB (G series) from Nippon Soda Co., Ltd. ), Hydrogenated polybutadiene having hydroxyl groups at both ends such as polytail H and polytail HA of Mitsubishi Chemical Corporation; liquid C5 polymer having hydroxyl groups at both ends, such as Poly-iP manufactured by Idemitsu Petrochemical Co., Ltd .; Examples include, but are not limited to, Epaul manufactured by Chemical Co., Ltd. and hydrogenated polyisoprene having hydroxyl groups at both ends, such as TH-1, TH-2, and TH-3 manufactured by Kuraray Co., Ltd.

  Examples of the polysiloxane polyols used in the present invention include compounds represented by general formulas (1) and (2).

General formula (1)

(In the formula, X represents a hydroxyl group, R ¹ and R ² each independently represents an alkylene group having 1 to 6 carbon atoms, and n represents an integer of 5 or more.)

General formula (2)

(In the formula, Y represents a hydroxyl group, R ³ represents an alkyl group having 1 to 6 carbon atoms, R ^{4 to} R ⁶ each independently represents an alkylene group having 1 to 6 carbon atoms, and R ⁷ represents a hydrogen atom. Alternatively, it represents an alkyl group having 1 to 6 carbon atoms, and n represents an integer of 5 or more.)

  Among these polyol compounds (a), polyester polyols composed of 1,4-cyclohexanedicarboxylic acid and 3-methyl-1,5-pentanediol, polycarbonate polyols using only 1,6-hexanediol as glycol, Polycarbonate diol using 1,6-hexanediol and 3-methyl-1,5-pentanediol as glycol, 1,9-nonanediol and 2-methyl-1,8-octanediol used as glycol Polycarbonate diol, polytetramethylene glycol, polypropylene glycol, or copolymer polyether polyol, polybutadiene polyol, hydrogenated polybutadiene polyol of tetramethylene glycol and neopentyl glycol Polysiloxane polyols and the like are excellent in flexibility, heat resistance, and hydrolysis resistance of the skeleton, and therefore excellent in electrical insulation, flexibility, heat resistance, moisture resistance, etc. as the carboxyl group-containing modified ester resin of the present invention. Particularly preferred.

  In the present invention, these polyol compounds (a) may be used alone or in combination.

  The present invention is obtained by reacting the polyol compound (a) with at least one acid anhydride group-containing compound (b) selected from alicyclic polybasic acid anhydrides and aromatic polybasic acid anhydrides. The ester bond group in the carboxyl group-containing ester resin (c) to be obtained is protected by a bulky substituent.

  Examples of the acid anhydride group-containing compound (b) which is at least one selected from alicyclic polybasic acid anhydrides and aromatic polybasic acid anhydrides used in the present invention include, for example, methyltetrahydrophthalic anhydride, tetrahydroanhydride Phthalic acid, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, nadic anhydride, methyl nadic anhydride, hydrogenated methyl nadic anhydride, stilendostyrene tetrahydrophthalic anhydride, 3,6-endomethylenetetrahydrophthalic anhydride, Alicyclic dibasic acid anhydrides such as methylendomethylenetetrahydrophthalic anhydride and trialkyltetrahydrophthalic anhydride; Alicyclic polybasic acid anhydrides such as hydrogenated trimellitic acid anhydride and hydrogenated pyromellitic acid anhydride Two aromatics such as phthalic anhydride, tetrabromophthalic anhydride, trimellitic anhydride Motosan anhydride; anhydrides biphenyltetracarboxylic acid dianhydride, diphenylether tetracarboxylic acid dianhydride, and aromatic polybasic acid anhydrides of pyromellitic anhydride, benzophenone tetracarboxylic dianhydride.

  Among these acid anhydride group-containing compounds (b), methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, nadic anhydride, methyl nadic anhydride, hydrogenated methyl anhydride nadic The acid or the like protects the ester bond group, which is considered to be inferior in insulation reliability, with a bulky substituent when the carboxyl group-containing ester resin (c) is produced by reaction with the polyol compound (a). Since the main chain is composed of ester bond groups protected with high substituents, insulation reliability, solder heat resistance, etc. are maintained while maintaining high adhesion compared to conventional resins using a polyester skeleton as the main chain. This is particularly preferable because it can be remarkably improved. Trimellitic anhydride, pyromellitic anhydride, and the like can increase the number of terminal carboxyl groups of the carboxyl group-containing ester resin (c) by reaction with the polyol compound (a), and at least 2 in the following molecule. In the present invention, it is preferable that the molecular weight can be increased in the reaction with the epoxy compound (d) having one epoxy group, and the cohesive strength of the resin is increased by increasing the molecular weight, so that the coating film is maintained while maintaining flexibility. It is preferable in that a tough coating film having excellent resistance can be formed after the formation.

  The hydroxyl group-containing compound (a-1) optionally used in the present invention is a compound having one or more hydroxyl groups, but is a compound excluding the compound belonging to the “polyol compound (a)”. Are, for example, a monoalcohol compound (a-1-1) having one hydroxyl group in the molecule, a diol compound (a-1-2) having two hydroxyl groups in the molecule, and three in the molecule The compound (a-1-3) which has the above hydroxyl groups can be mentioned. These may have both a hydroxyl group and a functional group other than a hydroxyl group in the molecule. Moreover, you may use individually and may use it in combination of multiple.

Examples of the monoalcohol compound (a-1-1) having one hydroxyl group in the molecule include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tertiary butanol, lauryl alcohol, and stearyl. Aliphatic monoalcohols such as alcohol;
Alicyclic monoalcohols such as cyclohexanol;
Aromatic monoalcohols such as benzyl alcohol and fluorenol;
Phenols such as phenol and methoquinone;
Examples of monoalcohol compounds having functional groups other than hydroxyl groups include hydroxyl group-containing carboxylic acid compounds such as 12-hydroxystearic acid, hydroxyl group-containing epoxy compounds such as glycidol, and hydroxyl group-containing oxetane compounds such as oxetane alcohol. Other examples include oligomer-type monoalcohols such as one-end methoxylated polyethylene glycol, one-end methoxylated polypropylene glycol, and caprolactone addition polymer using monoalcohol as an initiator.

  In the present invention, when a monoalcohol compound (a-1-1) having one hydroxyl group in these molecules is used, the end of the resulting carboxyl group-containing ester resin (c) can be sealed, It can be suitably used when it is necessary to adjust the molecular weight, for example, when a low molecular weight carboxyl group-containing modified ester resin is intentionally synthesized. In addition, when a hydroxyl group-containing compound having a functional group other than a hydroxyl group is used, a functional group other than a carboxyl group can be introduced into the terminal of the carboxyl group-containing ester resin (c), so that a carboxyl group-containing modified ester It can be suitably used when terminal modification of the resin is required. In the present invention, in consideration of hydroxyl group reactivity and polymerization control, lauryl alcohol, stearyl alcohol, cyclohexanol, 12-hydroxystearic acid, glycidol and the like are preferably used.

Examples of the diol compound (a-1-2) having two hydroxyl groups in the molecule include ethylene glycol, propylene glycol, 2-methyl-1,3-propanediol, and 2-methyl-2-ethyl. -1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-butyl-2-methyl-1,3-propanediol 2-butyl-2-ethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2-methyl-2,4-pentanediol 1,3,5-trimethyl-1,3-pentanediol, 2-methyl-1,8-octanediol, 3,3′-dimethylolheptane, propanedioe 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, octanediol, 3-butyl-3- Such as ethyl-1,5-pentanediol, 2-ethyl-1,6-hexanediol, cyclohexanediol, cyclohexanedimethanol, tricyclodecane dimethanol, cyclopentadiene dimethanol, dimer diol, hydrogenated bisphenol A, spiroglycol, etc. Aliphatic or alicyclic diols;
1,3-bis (2-hydroxyethoxy) benzene, 1,2-bis (2-hydroxyethoxy) benzene, 1,4-bis (2-hydroxyethoxy) benzene, 4,4′-methylenediphenol, 4, 4 ′-(2-norbornylidene) diphenol, 4,4′-dihydroxybiphenol, o-, m-, and p-dihydroxybenzene, 4,4′-isopropylidenephenol, 1,2-indanediol, 1,3 -Naphthalenediol, 1,5-naphthalenediol, 1,7-naphthalenediol, 9,9'-bis (4-hydroxyphenyl) fluorene, 9,9'-bis (3-methyl-4-hydroxyphenyl) fluorene, etc. Aromatic diols and the like.

  Moreover, the compound which has functional groups other than a hydroxyl group is also mentioned. In addition to the hydroxyl group, examples of the compound containing a tertiary amino group include N, N-bis (2-hydroxypropyl) aniline, N, N-bis (2-hydroxyethyl) aniline, N, N-bis ( 2-hydroxyethyl) methylamine, N, N-bis (2-hydroxyethyl) propylamine, N, N-bis (2-hydroxyethyl) butylamine, N, N-bis (2-hydroxyethyl) hexylamine, N Tertiary amino group-containing diol compounds such as N, N-bis (2-hydroxyethyl) octylamine, N, N-bis (2-hydroxyethyl) benzylamine, and N, N-bis (2-hydroxyethyl) cyclohexylamine Examples of the compound containing a carboxyl group include dimethylol butanoic acid and dimethylol pro Propionic acid, 3-hydroxy salicylic acid, 4-hydroxy salicylic acid, 5-hydroxy acid, such as 2-carboxy-1,4-cyclohexanedimethanol.

  Among them, dimethylolbutanoic acid and dimethylolpropionic acid are reacted with an acid anhydride group-containing compound (b) which is at least one selected from alicyclic polybasic acid anhydrides and aromatic polybasic acid anhydrides. The number of terminal carboxyl groups of the resulting carboxyl group-containing ester resin (c) can be increased, and in the subsequent reaction with the epoxy compound (d) having at least two epoxy groups in one molecule, the molecular weight is increased. This is preferable in the present invention in that it can be performed. In addition, when a tertiary amino group-containing diol compound such as N, N-bis (2-hydroxypropyl) aniline is used, the cohesive force of the finally obtained coating film is increased and the flexibility is maintained. It is preferable at the point that the tough coating film which is more excellent in tolerance can be formed.

Examples of the compound (a-1-3) having 3 or more hydroxyl groups in the molecule include trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, mannitol, arabitol, xylitol, galactitol, glycerin, and the like. The polyhydric alcohol compound is mentioned.

  In the present invention, when the compound (a-1-3) having three or more hydroxyl groups in these molecules is used, the number of terminal carboxyl groups of the resulting carboxyl group-containing ester resin (c) can be increased. Therefore, it becomes possible to increase the molecular weight of the final product and improve the resistance of the cured coating film. Therefore, in the present invention, it may be used as necessary for the purpose of further improving the resistance of the cured coating film. Among these compounds (a-1-3) having three or more hydroxyl groups in the molecule, it is preferable to use trimethylolpropane or pentaerythritol in terms of reaction control.

  Here, the polyol compound (a) and the hydroxyl group-containing compound (a-1) can be used in any proportion according to the purpose in the present invention, and the hydroxyl group in the polyol compound (a) is added to 1.0 mol. On the other hand, the hydroxyl group in the hydroxyl group-containing compound (a-1) is used in a proportion of 0.01 mol to 1.00 mol, preferably 0.05 mol to 0.50 mol. When the hydroxyl group in the hydroxyl group-containing compound (a-1) is used in a proportion of less than 0.01 mol with respect to 1.0 mol of the hydroxyl group in the polyol compound (a) (that is, the polyol compound (a) alone When used), the polyol compound (a) alone can exhibit sufficient insulation reliability, heat resistance, and adhesive strength, but it is difficult to impart higher heat resistance. Moreover, when more than 1.00 mol, the cohesive force of the coating film finally obtained will increase too much, and it exists in the tendency for adhesive strength to fall.

  Moreover, when synthesizing the carboxyl group-containing ester resin (c), the ratio of the reaction of the starting material is included in the polyol compound (a) and the hydroxyl group-containing compound (a-1) to be optionally added. The acid contained in the acid anhydride group-containing compound (b) which is at least one selected from alicyclic polybasic acid anhydrides and aromatic polybasic acid anhydrides when the total number of hydroxyl groups to be added is 1 mol The total of anhydride groups is preferably reacted at a rate of 0.70 mol to 1.30 mol, more preferably at a rate of 0.90 mol to 1.10 mol. When the total of acid anhydride groups is less than 0.70 mol, the amount of carboxyl groups in the resulting carboxyl group-containing ester resin (c) decreases, and the epoxy compound having at least two epoxy groups in the next molecule In the reaction step with (d), sufficient reaction is unlikely to occur, and the weight average molecular weight of the finally obtained carboxyl group-containing modified ester resin (A) may not be sufficiently large. Further, when the total amount of acid anhydride groups is more than 1.30 mol, many side reactions occur when reacting with the epoxy compound (d) having at least two epoxy groups in the next molecule, and during the reaction May cause gelation.

  Moreover, when it is made to react in the ratio close | similar to 1.00 mol within the range of 0.90 mol-1.10 mol, reaction with the epoxy compound (d) which has at least 2 epoxy group in the following 1 molecule. Since the problems as described above are less likely to occur during the process, the weight average molecular weight of the finally obtained carboxyl group-containing modified ester resin (A) can be sufficiently increased, and the heat resistance of the cured coating film can be increased. Flexibility and adhesion can be improved.

  In the present invention, the synthesis conditions of the carboxyl group-containing ester resin (c) are not particularly limited, and can be performed under known conditions. For example, a polyol compound (a) and a solvent [and optionally a hydroxyl group-containing compound (a-1)] are charged into a flask and dissolved uniformly by heating and stirring at 20 to 120 ° C. in a nitrogen stream. An acid anhydride group-containing compound (b), which is at least one selected from cyclic polybasic acid anhydrides and aromatic polybasic acid anhydrides, is added and heated at 50 to 150 ° C. with stirring to form a carboxyl group A containing ester resin (c) can be obtained.

  In the reaction, a tertiary amino group-containing compound or the like may be used as necessary. In addition, the polyol compound (a) charged in the flask in advance before introducing the acid anhydride group-containing compound (b) which is at least one selected from alicyclic polybasic acid anhydrides and aromatic polybasic acid anhydrides ) And the solvent may be heated and stirred at 100 ° C. or higher to remove a part of the solvent. This operation is usually performed to remove water (dehydration treatment) in the system. By this operation, at least one acid selected from alicyclic polybasic acid anhydrides and aromatic polybasic acid anhydrides is used. When the anhydride group-containing compound (b) is reacted, the ring opening reaction of the acid anhydride group by water can be suppressed.

  Next, the epoxy compound (d) having at least two epoxy groups in one molecule of the present invention will be described. The epoxy compound (d) having at least two epoxy groups in one molecule used in the present invention is preferably not particularly limited as long as it is a compound containing two epoxy groups in the molecule. Specifically, for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, bisphenol A / epichlorohydrin type epoxy resin, bisphenol F / epichlorohydrin type epoxy resin , Biphenol-epichlorohydrin type epoxy resin, glycerin-epichlorohydrin adduct polyglycidyl ether, resorcinol diglycidyl ether, polybutadiene diglycidyl ether, hydroquinone diglycidyl ether, dibromoneopentyl glycol diglycidyl ether, neopentyl glycol Diglycidyl ether, hexahydrophthalic acid diglycidyl ester, hydrogenated bisphenol A type diglycidyl ether, dihydroxyan Tracene-type epoxy resin, polypropylene glycol diglycidyl ether, diphenylsulfone diglycidyl ether, dihydroxybenzophenone diglycidyl ether, biphenol diglycidyl ether, diphenylmethane diglycidyl ether, bisphenol full orange glycidyl ether, biscresol full orange glycidyl ether, bisphenoxyethanol full orange Glycidyl ether, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N-diglycidylaniline, N, N-diglycidyltoluidine, JP2004-156024A, JP2004-315595A And an epoxy compound having excellent flexibility disclosed in Japanese Patent Laid-Open No. 2004-323777, and the following formula (1)- Epoxy compounds having a structure represented by 3) and the like.

Formula (1)

Formula (2)

Formula (3)

  Among them, 1,6-hexanediol diglycidyl ether is preferable in the case of imparting flexibility to the finally obtained carboxyl group-containing modified ester resin (A), and the bisphenol A / epichlorohydrin type epoxy resin is the final. It is preferable when the heat resistance is imparted to the carboxyl group-containing modified ester resin (A) obtained in a specific manner. Thus, in the present invention, the epoxy compound (d) having at least two epoxy groups in one molecule can be selected according to the purpose, and these may be used alone or in combination. Use in combination is also preferred.

  Here, the ratio of reacting the carboxyl group-containing ester resin (c) with the epoxy compound (d) having at least two epoxy groups in one molecule is 1.0% of the carboxyl group of the carboxyl group-containing ester resin (c). It is preferable to react the epoxy group in the epoxy compound (d) having at least two epoxy groups in one molecule at a ratio of 0.50 mol to 1.50 mol, and 0.70 mol. It is more preferable to make it react in the ratio of -1.30 mol. When the ratio of the epoxy group in the epoxy compound (d) having at least two epoxy groups in one molecule is less than 0.50 mol with respect to 1.0 mol of the carboxyl group of the carboxyl group-containing ester resin (c), The molecular weight of the carboxyl group-containing modified ester resin (A) finally obtained becomes low, and it becomes difficult to obtain desired coating film resistance and film formability. Moreover, the ratio of the epoxy group in the epoxy compound (d) having at least two epoxy groups in one molecule is more than 1.50 mol with respect to 1.0 mol of the carboxyl group of the carboxyl group-containing ester resin (c). In this case, the amount of the terminal epoxy group is increased, and the acid anhydride group-containing compound (b) which is at least one selected from an alicyclic polybasic acid anhydride and an aromatic polybasic acid anhydride in the final synthesis stage is used. Many side reactions occur during the reaction and may cause gelation during the reaction.

  In the present invention, the conditions for synthesizing the side chain hydroxyl group-containing modified ester resin (e) are not particularly limited, and can be performed under known conditions. For example, a carboxyl group-containing ester resin (c), an epoxy compound (d) having at least two epoxy groups in one molecule, and a solvent are charged in a flask, and heated at 100 to 150 ° C. with stirring to form side chain hydroxyl groups. A group-containing modified ester resin (e) can be obtained. At this time, a catalyst such as triphenylphosphine or a tertiary amino group-containing compound may be used as necessary.

  Next, the carboxyl group-containing modified ester resin (A) of the present invention will be described. The carboxyl group-containing modified ester resin (A) of the present invention is at least one selected from a side chain hydroxyl group-containing modified ester resin (e), an alicyclic polybasic acid anhydride, and an aromatic polybasic acid anhydride. It can be obtained by reacting with a certain acid anhydride group-containing compound (b).

  Here, when synthesizing the carboxyl group-containing modified ester resin (A), at least one acid anhydride group-containing compound selected from alicyclic dipolyacid anhydrides and aromatic polybasic acid anhydrides ( The ratio in which b) is reacted is determined from the alicyclic polybasic acid anhydride and aromatic polybasic acid anhydride when the hydroxyl group in the side chain hydroxyl group-containing modified ester resin (e) is 1.0 mol. It is preferable to react the acid anhydride group in the acid anhydride group-containing compound (b) which is at least one selected at a ratio of 0.05 mol to 1 mol, and a ratio of 0.10 mol to 0.90 mol It is more preferable to make it react with. An acid anhydride group that is at least one selected from alicyclic polybasic acid anhydrides and aromatic polybasic acid anhydrides with respect to 1.0 mol of hydroxyl groups in the side chain hydroxyl group-containing modified ester resin (e). When the ratio of the acid anhydride group in the contained compound (b) is less than 0.05 mol, the modification ratio becomes too small to obtain the effect of introducing a crosslinkable functional group into the main chain.

  In the present invention, the synthesis conditions for the carboxyl group-containing modified ester resin (A) are not particularly limited, and can be performed under known conditions. For example, a side chain hydroxyl group-containing modified ester resin (e) and an acid anhydride group-containing compound (b) that is at least one selected from an alicyclic polybasic acid anhydride and an aromatic polybasic acid anhydride are used in a flask. The carboxyl group-containing modified ester resin (A) can be obtained by charging the solvent and heating at 50 to 100 ° C. with stirring. This reaction proceeds even without a catalyst, but a catalyst such as a tertiary amino group-containing compound may be used if necessary.

  The acid value of the carboxyl group-containing modified ester resin (A) of the present invention is preferably 1 to 100 mgKOH / g, more preferably 5 to 90 mgKOH / g. When the acid value is less than 1 mgKOH / g, there are few carboxyl groups that function as curable groups, and sufficient resistance may not be imparted to the coated film after curing. On the other hand, when the acid value exceeds 100 mgKOH / g, the hardness of the coating film increases, and sufficient adhesive strength may not be obtained. In addition, when the acid value is designed in the range of 1 to 100 mgKOH / g and in the range close to 1 mgKOH / g, the flexibility and adhesion of the obtained coating film are improved, while the design is made in the range close to 100 mgKOH / g. In that case, since the number of crosslinking points increases, the heat resistance of the finally obtained coating film is improved. Thus, in this invention, the acid value of carboxyl group-containing modified ester resin (A) can be adjusted according to the objective within the range of 1-100 mgKOH / g.

  The weight average molecular weight of the carboxyl group-containing modified ester resin (A) of the present invention is preferably 5,000 to 500,000, and more preferably 10,000 to 300,000. If the weight average molecular weight is less than 5000, sufficient solder heat resistance and flexibility may not be obtained. Moreover, when the weight average molecular weight exceeds 500,000, the viscosity at the time of coating and handling may become a subject. In addition, when the weight average molecular weight is designed to be close to 5000 within the range of 5000 to 500000, since the terminal of the resulting resin (that is, carboxyl group) is large, a resin rich in crosslinkability is obtained. The heat resistance of the obtained coating film can be improved. On the other hand, when designing with a value close to 500,000, the finally obtained coating film is excellent in adhesion and flexibility. Thus, in this invention, the weight average molecular weight of carboxyl group-containing modified ester resin (A) can be adjusted according to the objective within the range of 5000-500000.

  The aromatic phosphorus compound (B) of the present invention is not particularly limited as long as it is a compound having a phosphorus element and an aromatic skeleton such as a benzene ring, naphthalene ring, anthracene ring, and phenanthrene ring in one molecule. For example, cyclic phosphazene Compounds, aromatic phosphate compounds, phosphaphenanthrene compounds, and the like.

  Among these, cyclic phosphazene compounds are preferable in that they are excellent in flame retardancy and hydrolysis resistance. The structure of the cyclic phosphazene compound suitably used in the present invention is represented by the following general formula (3) or (4).

General formula (3)

(In the formula, A is hydrogen, methyl group, hydroxyl group, cyano group, amino group, carboxyl group, glycidyloxy group, parahydroxyphenyldimethylmethyl group, paraglycidyloxyphenyldimethylmethyl group, parahydroxyphenylsulfone group, paraglycidyl. A monovalent group selected from the group consisting of an oxyphenylsulfone group, an alkyl group having 2 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, and an aryl group having 2 to 30 carbon atoms, and R is hydrogen, methyl And a monovalent group selected from the group consisting of a group and an alkyl group having 2 to 30 carbon atoms, and n represents an integer of 3 to 15.)

General formula (4)

(In the formula, A is hydrogen, methyl group, hydroxyl group, cyano group, amino group, carboxyl group, glycidyloxy group, parahydroxyphenyldimethylmethyl group, paraglycidyloxyphenyldimethylmethyl group, parahydroxyphenylsulfone group, paraglycidyl. A monovalent group selected from the group consisting of an oxyphenylsulfone group, an alkyl group having 2 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, and an aryl group having 2 to 30 carbon atoms, and B is one carbon atom To 8 alkyl groups, alkenyl groups, cycloalkyl groups, aryl groups, aralkyl groups, alkenyl aryl groups, alkoxy groups, aryloxy groups, aralkyloxy groups, acyloxyalkoxy groups, aryl mercapto groups, alkylamino groups, arylamino groups, An arylglycidyloxy group, or An amino group, R represents hydrogen, a monovalent group selected from the group consisting of alkyl groups of a methyl group and C2-30, n is an integer of 3-15.)

  Examples of such cyclic phosphazene compounds include SPB-100, SPH-100 (above, manufactured by Otsuka Chemical Co., Ltd.), Ravitor FP-100, Ravitor FP-300, Ravitor FP-390 (above, Fushimi Pharmaceutical Co., Ltd.). Manufactured).

  Among them, in general formula (3), it is particularly preferable that A is all hydrogen, A is hydrogen and / or a methyl group, and A is hydrogen and / or a cyano group because of higher flame retardancy. These can also be used individually by 1 type and can also be used in combination of 2 or more type.

  Examples of the aromatic phosphate compound include TPP, TCP, TXP, NDPP, PX-110, CR-733S, CR-741, and PX-200 (all manufactured by Daihachi Chemical Co., Ltd.).

  Examples of the phosphaphenanthrene compound include HCA, HCA-HQ, M-Ester, M-Acid, and SANKO-BCA (manufactured by Sanko Co., Ltd.).

  The addition amount of the aromatic phosphorus compound (B) of the present invention is preferably 10 to 150 parts by weight, preferably 20 to 100 parts by weight, based on 100 parts by weight of the carboxyl group-containing modified ester resin (A). Is particularly preferred. If it is less than 10 parts by weight, the necessary flame retardancy may not be obtained. On the other hand, if the amount is more than 150 parts by weight, the heat resistance may be significantly lowered, and it may be difficult to suppress the bleed-out of the aromatic phosphorus compound (B).

  The sugar ester compound (C) of the present invention is a compound obtained by esterifying a part or all of the hydroxyl groups of the compound (f) having a sugar skeleton with the ester group of the carboxylic acid ester compound (g). Point to.

  Examples of the compound (f) having a sugar skeleton of the present invention include monosaccharides, disaccharides and oligosaccharides. Monosaccharides include tricarbons such as glyceraldehyde and dihydroxyacetone, tetracarbons such as erythrose and erythrulose, pentoses such as ribose and arabinose, hexoses such as glucose and fructose, and seven carbons such as sedheptulose and coliose. Examples include sugars and modified products such as deoxy sugars, uron sugars, amino sugars, sugar alcohols, and sugar alcohol dehydration products, and further structural isomers, stereoisomers, optical isomers, and the like thereof. The disaccharide is not particularly limited as long as it is a dimer composed of one or two of the above monosaccharides, and examples thereof include sucrose (sucrose), lactose (lactose), mannose (malt sugar) and the like. In addition, the oligosaccharide is not particularly limited as long as it is a 3-20 mer composed of one or a combination of two or more of the above monosaccharides, such as 1-kestose, nystose, 1F-fructofuranosyl nystose, etc. Examples include fructooligosaccharides, galactooligosaccharides, and emulsifying oligosaccharides.

  Of these compounds having a sugar skeleton, monosaccharides or disaccharides are preferable from the viewpoint of solubility of the sugar ester compound (C). In addition, from the viewpoint of easy availability, a monosaccharide of pentose and hexose, or a disaccharide comprising one or both of pentose and hexose is more preferable, and glucose, Fructose, sorbitol, sorbitan, sucrose, lactose and maltose are preferred. Furthermore, sucrose is particularly preferable in terms of compatibility between the resulting sugar ester compound (C) and the carboxyl group-containing modified ester resin (A).

  The carboxylic acid ester compound (g) of the present invention is not particularly limited as long as it is a compound having one or more ester groups in one molecule formed by dehydration condensation between a carboxylic acid and methanol or ethanol. And carboxylic acid ester (g-1), aliphatic carboxylic acid ester (g-2) and alicyclic carboxylic acid ester (g-3).

In the carboxylic acid ester (g-1) having an aromatic skeleton, an aromatic skeleton such as a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring may be directly bonded to an ester group carbon, or any linking group may be bonded. For example, benzoic acid, o-methylbenzoic acid, m-methylbenzoic acid, p-methylbenzoic acid, o-ethylbenzoic acid, m-ethylbenzoic acid, p-ethylbenzoic acid. , Salicylic acid, acetylsalicylic acid, p-hydroxybenzoic acid, 1-naphthalenecarboxylic acid, 2-naphthalenecarboxylic acid, 1-phenanthrenecarboxylic acid, 2-phenanthrenecarboxylic acid, 3-phenanthrenecarboxylic acid, 4-phenanthrenecarboxylic acid, 5- Phenanthrenecarboxylic acid, 1-anthracenecarboxylic acid, 2-anthracenecarboxylic acid, 9- Methyl or ethyl esters of aromatic carboxylic acids, such as cement helical carboxylic acid;
Aromatics not directly linked to carboxyl groups such as 2-phenylacetic acid, 3-phenylpropionic acid, 4-phenylbutyric acid, 2-phenoxyacetic acid, 2- (2-phenoxyethoxy) acetic acid, phenylglycine, phenylalanine, tyrosine, and tryptophan Methyl or ethyl ester of a carboxylic acid having a skeleton;
Etc.

  Examples of the aliphatic carboxylic acid ester (g-2) include formic acid, acetic acid, propionic acid, acrylic acid, methacrylic acid, butyric acid, valeric acid, isovaleric acid, caproic acid, stearic acid, oleic acid, linolenic acid, and myristic acid. Examples include methyl or ethyl ester.

  Examples of the alicyclic carboxylic acid (g-3) include cyclohexane carboxylic acid, cyclohexene carboxylic acid, decalin carboxylic acid, abietic acid and isomers thereof, and hydrogenated methyl or ethyl ester.

  Among these carboxylic acid esters (g), a carboxylic acid ester (g-1) having an aromatic skeleton is preferable from the viewpoint of bleeding out suppression performance of the aromatic phosphorus compound. Further, methyl or ethyl ester of benzoic acid is more preferable because it is inexpensive and easily available.

  That is, as the sugar ester compound (C), an aromatic skeleton-containing carboxylic acid ester compound (C-1) is preferable, and a sucrose benzoic acid ester compound is particularly preferable.

  As addition amount with respect to aromatic phosphorus compound (B) of sugar ester compound (C) of this invention, it is preferable to set it as 40-200 weight part with respect to 100 weight part of aromatic phosphorus compound (B), and 60-150 Part by weight is particularly preferred. If it is less than 40 parts by weight, it may be difficult to suppress bleed-out of the aromatic phosphorus compound (B). On the other hand, if the amount is more than 200 parts by weight, the flexibility may decrease.

  Regarding the method of mixing the aromatic phosphorus compound (B) and the sugar ester compound (C) component into the carboxyl group-containing modified ester resin (A), for example, a carboxyl group-containing state in a molten state or a state dissolved in an organic solvent The aromatic phosphorus compound (B) and the sugar ester compound (C) are directly kneaded into the modified ester resin (A) with a disperser or kneader such as a two-roll mill, a three-roll mill, or a twin-screw extruder. It may be mixed, or after being dissolved or suspended in an organic solvent or the like, it may be mixed by stirring with a homodisper or a planetary mixer or by dispersing with a bead mill. At this time, the aromatic phosphorus compound (B) and the sugar ester compound (C) may be compatible with the carboxyl group-containing modified ester resin (A), or are dispersed in the carboxyl group-containing modified ester resin (A). However, the sugar ester compound (C) is compatible with the carboxyl group-containing modified ester resin (A) because the bleedout of the aromatic phosphorus compound (B) can be more efficiently suppressed. It is particularly preferred.

  In the present invention, it is also preferable to add a flame retardant other than the aromatic phosphorus compound (B) as necessary.

Examples of the flame retardant other than the aromatic phosphorus compound (B) include melamine phosphate, melamine polyphosphate, guanidine phosphate, guanidine polyphosphate, ammonium phosphate, ammonium polyphosphate, ammonium amidophosphate, ammonium polyphosphate, Phosphate compounds such as phosphate carbamate and polyphosphate carbamate and polyphosphate compounds;
Phosphoric acid compounds and phosphinic acid compounds and metal salts thereof, phosphorus flame retardants such as phosphine oxide compounds, phosphorane compounds, phosphoramide compounds;
Triazine compounds such as melamine, melam, melem, melon, and melamine cyanurate; nitrogen flame retardants such as cyanuric acid compounds, isocyanuric acid compounds, triazole compounds, tetrazole compounds, diazo compounds, urea;
Silicon-based flame retardants such as silicone compounds and silane compounds, metal hydroxides such as aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, barium hydroxide, calcium hydroxide;
Inorganic flame retardants such as tin oxide, aluminum oxide, magnesium oxide, zirconium oxide, zinc oxide, molybdenum oxide, antimony oxide, nickel oxide, zinc carbonate, magnesium carbonate, calcium carbonate, barium carbonate, zinc borate, hydrated glass;
Etc. In the present invention, flame retardants other than these aromatic phosphorus compounds (B) can be used alone or in combination.

  In the thermosetting resin composition of the present invention, an epoxy group-containing compound, an unblocked isocyanate compound, a blocked isocyanate compound, and a β-hydroxyalkylamide group are contained as a curing agent for the above-described carboxyl group-containing modified ester resin (A). It is characterized by using the compound (D) which is at least 1 type chosen from a compound.

  The epoxy group-containing compound in the present invention is not particularly limited as long as it is a compound containing an epoxy group in the molecule. For example, examples of the compound having one epoxy group in the molecule include compounds such as N-glycidylphthalimide, glycidol, and glycidyl (meth) acrylate. These can be suitably used for the purpose of controlling the crosslink density of the cured product by using together with a compound having two or more epoxy groups in the molecule exemplified below as needed. Examples of the compound containing two or more epoxy groups in the molecule include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, bisphenol A / epichlorohydrin type epoxy resin, Bisphenol F / epichlorohydrin type epoxy resin, bisphenol S / epichlorohydrin type epoxy resin, bisphenol AD / epichlorohydrin type epoxy resin, biphenol / epichlorohydrin type epoxy resin, ethylene oxide adduct of bisphenol A or Propylene oxide adduct epichlorohydrin type epoxy resin, glycerin / epichlorohydrin adduct polyglycidyl ether, naphthalenediol diglycidyl ether, resorcino Rudiglycidyl ether, polybutadiene diglycidyl ether, hydroquinone diglycidyl ether, dibromoneopentyl glycol diglycidyl ether, neopentyl glycol diglycidyl ether, hexahydrophthalic acid diglycidyl ester, hydrogenated bisphenol A type diglycidyl ether, polypropylene glycol diglycidyl Ether, diphenylsulfone diglycidyl ether, dihydroxybenzophenone diglycidyl ether, biphenol diglycidyl ether, diphenylmethane diglycidyl ether, bisphenol full orange glycidyl ether, biscresol full orange glycidyl ether, bisphenoxyethanol full orange glycidyl ether, 1,3-bis ( N, N-diglycidyl Minomethyl) cyclohexane, N, N-diglycidylaniline, N, N-diglycidyltoluidine, Japanese Patent Application Laid-Open Nos. 2004-156024, 2004-315595, and 2004-323777. And an epoxy compound having a structure represented by the following formulas (4) to (6).

Formula (4)

Formula (5)

Formula (6)

  Further, trishydroxyethyl isocyanurate triglycidyl ether, triglycidyl isocyanurate, “jER1031S”, “jER1032H60”, “jER604”, “jER630” manufactured by Mitsubishi Chemical Corporation, phenol novolac type epoxy resin, cresol novolac type epoxy resin, special Dicyclopentadiene type epoxy resin, naphthalene-modified cresol novolac type epoxy resin, diglycidyloxynaphthalene type epoxy resin, polyglycidyl ether of ethylene glycol / epichlorohydrin adduct, pentaerythritol polyglycidyl ether disclosed in JP-A-2001-240654 , Trimethylolpropane polyglycidyl ether, N, N, N ′, N′-tetraglycidyl-m-xylenedia Min, etc. are mentioned. Moreover, the compound which has other thermosetting groups other than an epoxy group can also be used. For example, the silane modified epoxy resin currently disclosed by Unexamined-Japanese-Patent No. 2001-59011 and 2003-48953 is mentioned.

  In particular, isocyanurate ring-containing epoxy compounds such as trishydroxyethyl isocyanurate triglycidyl ether and triglycidyl isocyanurate are preferred because they tend to improve the adhesion strength to polyimide and copper when used in the present invention. Further, “jER1031S”, “jER1032H60”, “jER604”, and “jER630” manufactured by Mitsubishi Chemical Corporation are highly preferable in the present invention because they are multifunctional and have excellent heat resistance. Epoxy compounds and the epoxy compounds described in JP-A Nos. 2004-156024, 2004-315595, and 2004-323777 are preferable because they are excellent in flexibility of the cured coating film. In addition, dicyclopentadiene type epoxy compounds described in JP-A-2001-240654, phenol novolac type epoxy resins, cresol novolac type epoxy resins, naphthalene modified novolak type epoxy resins, biphenol / epichlorohydrin type epoxy resins, etc. In the present invention, it is preferable in terms of durability of a cured coating film including thermosetting, hygroscopicity and heat resistance.

  The isocyanate compound is not particularly limited as long as it is a compound having an isocyanate group in the molecule. Specific examples of the diisocyanate compound include aromatic diisocyanates having 4 to 50 carbon atoms, aliphatic diisocyanates, araliphatic diisocyanates, and alicyclic diisocyanates.

  Examples of the aromatic diisocyanate include 1,3-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6- Tolylene diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, dianisidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4 ', 4 "-Triphenylmethane triisocyanate etc. can be mentioned.

  Examples of the aliphatic diisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, 2 4,4-trimethylhexamethylene diisocyanate and the like.

  Examples of the araliphatic diisocyanate include ω, ω′-diisocyanate-1,3-dimethylbenzene, ω, ω′-diisocyanate-1,4-dimethylbenzene, ω, ω′-diisocyanate-1,4-diethylbenzene, 1 , 4-tetramethylxylylene diisocyanate, 1,3-tetramethylxylylene diisocyanate, and the like.

  Examples of the alicyclic diisocyanate include 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate [also known as isophorone diisocyanate], 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, and 1,4-cyclohexane diisocyanate. , Methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanate methyl) A cyclohexane etc. can be mentioned.

  Specific examples of the isocyanate compound having one or three or more isocyanate groups in the molecule include (meth) acryloyloxyethyl isocyanate, 1,1 as a monofunctional isocyanate having one isocyanate group in one molecule. -Bis [(meth) acryloyloxymethyl] ethyl isocyanate, vinyl isocyanate, allyl isocyanate, (meth) acryloyl isocyanate, isopropenyl-α, α-dimethylbenzyl isocyanate and the like. In addition, 1,6-diisocyanatohexane, isophorone diisocyanate, 4,4′-diphenylmethane diisocyanate, polymeric diphenylmethane diisocyanate, xylylene diisocyanate, tolylene 2,4-diisocyanate, toluene diisocyanate, 2,4-diisocyanic acid Toluene, hexamethylene diisocyanate, 4-methyl-m-phenylene diisocyanate, naphthylene diisocyanate, paraphenylene diisocyanate, tetramethylxylylene diisocyanate, cyclohexylmethane diisocyanate, hydrogenated xylylene diisocyanate, cyclohexyl diisocyanate, tolidine diisocyanate, 2,2 , 4-Trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate Nitrate, m-tetramethylxylylene diisocyanate, p-tetramethylxylylene diisocyanate, diisocyanate ester compounds such as dimer acid diisocyanate and hydroxyl group, carboxyl group, and amide group-containing vinyl monomers are reacted in equimolar amounts. It can be used as an ester compound.

  Examples of the polyfunctional isocyanate having 3 or more isocyanate groups in one molecule include aliphatic polyisocyanates such as aromatic polyisocyanates and lysine triisocyanates, araliphatic polyisocyanates, and alicyclic polyisocyanates. Examples thereof include trimethylolpropane adducts of diisocyanate described above, burettes reacted with water, and trimers having an isocyanurate ring.

  The blocked isocyanate compound is not particularly limited as long as the isocyanate group is an isocyanate compound protected with ε-caprolactam, MEK oxime, or the like. Specifically, the isocyanate group of the isocyanate compound is blocked with ε-caprolactam, MEK oxime, cyclohexanone oxime, pyrazole, 3,5-dimethylpyrazole, diisopropylamine, diethyl malonate, ethyl acetoacetate, phenol, etc. Is mentioned.

  The β-hydroxyalkylamide group-containing compound is not particularly limited as long as it is an amide compound obtained by reacting a carboxyl group of a compound having one or more carboxyl groups with an amino group of ethanolamine or diethanolamine. Is an amide compound obtained by dehydration condensation reaction of ethanolamine or diethanolamine with oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, cyclohexanedicarboxylic acid, etc. can give. Examples of commercially available products include N, N, N ′, N′-tetrakis (2-hydroxyethyl) adipodiamide such as “primid XL-552” manufactured by EMS.

  In the present invention, at least one compound (D) selected from these epoxy group-containing compounds, unblocked isocyanate compounds, and blocked isocyanate compounds may be used alone or in combination. Also good. The amount of the compound (D) that is at least one selected from an epoxy group-containing compound, a non-blocked isocyanate compound, and a blocked isocyanate compound may be determined in consideration of the application of the curable resin composition of the present invention. Although not particularly limited, it is preferably added at a ratio of 0.5 to 100 parts by weight with respect to 100 parts by weight of the carboxyl group-containing modified ester resin (A), preferably 1 to 80 parts by weight. It is more preferable to add in the ratio. By using the compound (D) that is at least one selected from an epoxy group-containing compound, a non-blocked isocyanate compound, and a blocked isocyanate compound, the crosslinking density of the curable resin composition of the present invention is adjusted to an appropriate value. Therefore, various physical properties of the cured coating film can be further improved. When the amount of the compound (D) that is at least one selected from an epoxy group-containing compound, an unblocked isocyanate compound, and a blocked isocyanate compound is less than 0.5 parts by weight, the crosslinking density of the coating film after heat curing is low. In some cases, the desired adhesive strength and heat resistance become insufficient. Further, if the amount used is more than 100 parts by weight, the crosslinking density after heat curing becomes too high, and as a result, the flexibility and flexibility of the coating film may be lowered, and the adhesive strength may be significantly deteriorated. is there.

  Next, the thermosetting aid (E) of the present invention will be described. The thermosetting aid (E) of the present invention is a compound (D) that is at least one selected from the above-mentioned epoxy group-containing compounds, unblocked isocyanate compounds, blocked isocyanate compounds, and β-hydroxyalkylamide group-containing compounds and carboxyls. When the group-containing modified ester resin (A) is subjected to a curing reaction, it is a compound that directly contributes to the curing reaction or a compound that contributes catalytically.

  The compound that directly contributes to the curing reaction as the thermosetting aid (E) represents a compound that has a functional group that can react with heat alone or with a hydroxyl group, amino group, epoxy group, carboxyl group, and the like. Excluded are those belonging to the compound (D), which is at least one selected from a containing compound, an unblocked isocyanate compound, a blocked isocyanate compound, and a β-hydroxyalkylamide group, and the thermosetting resin composition of the present invention It is preferably used in products. Specifically, for example, cyanate ester compounds, aziridine compounds, acid anhydride group-containing compounds, carboxyl group-containing compounds, carbodiimide group-containing compounds, oxetane group-containing compounds, benzoxazine compounds, maleimide compounds, citraconic imide compounds, nadiimide compounds, Allyl nadiimide compound, vinyl ether compound, vinyl benzyl ether resin, thiol compound, melamine compound, guanamine compound, amino resin, phenol resin, alkyd resin, acrylic resin, unsaturated polyester resin, diallyl phthalate resin, silicone resin, xylene resin, furan Resin, ketone resin, triallyl cyanurate resin, resin containing tris (2-hydroxyethyl) isocyanurate, resin containing triallyl trimellitate, Pentadiene resins, such as thermosetting resin by trimerization of aromatic dicyanamide and the like.

Moreover, when using a thermosetting resin as carboxyl group containing modified ester resin (A) of this invention, it is also preferable to add a hardening accelerator further in order to accelerate | stimulate a thermal crosslinking reaction. Although it will not specifically limit as a hardening accelerator if it is a compound which has the effect | action which accelerates | stimulates the crosslinking reaction of carboxyl group-containing modified ester resin (A), For example, a tertiary amine compound and its salts;
Imidazole compounds, diazabicyclo compounds and salts thereof;
Strong acid compounds such as dicyandiamide, diaminomaleonitrile, carboxylic acid hydrazide, phosphine compounds, phosphonium salts, and p-toluenesulfonic acid;
Thermal acid generators such as sulfonium salts;
Lewis acid compounds such as dibutyltin dilaurate;
Metal soaps such as calcium stearate;
Metal catalysts such as 2-ethylhexanoate, naphthenate and acetylacetone complex of manganese, iron, cobalt, nickel, copper, zinc;
Is mentioned. Use of these is preferable because the thermosetting reaction proceeds more efficiently and the coating film has excellent resistance. In the present invention, these curing accelerators can be used alone or in combination.

  In addition to the above, the flame retardant resin composition of the present invention may further include optional components as long as the purpose is not impaired. Foaming agents, preservatives, antibacterial agents, antistatic agents, antiblocking agents, ultraviolet absorbers, infrared absorbers, fillers and the like can be added.

  The present invention will be described more specifically with reference to the following examples. However, the following examples do not limit the scope of rights of the present invention. In the examples, “parts” and “%” mean “parts by weight” and “% by weight”, respectively.

[Production Example 1]
Polycarbonate diol (Kuraray polyol C-2090: Kuraray Co., Ltd .: 3-methyl-1,5-pentanediol / 1) was added to a four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, inlet tube, and thermometer. , 6-hexanediol = 9/1 (molar ratio) copolymerized polycarbonate diol: hydroxyl value = 56 mg KOH / g, Mw = 2000) 292.1 parts, tetrahydrophthalic anhydride (Licacid TH: manufactured by Shin Nippon Rika Co., Ltd.) 44 .9 parts and 350 parts of DPMA (dipropylene glycol monomethyl ether acetate) as a solvent were added, and the mixture was heated to 60 ° C. with stirring in a nitrogen stream and dissolved uniformly. Subsequently, the flask was heated to 110 ° C. and reacted for 3 hours. Then, after cooling to 40 ° C., 62.9 parts of bisphenol A type epoxy resin (YD-8125: manufactured by Tohto Kasei Co., Ltd .: epoxy equivalent = 175 g / eq) and 4 parts of triphenylphosphine as a catalyst were added to 110 ° C. The temperature was raised and reacted for 8 hours. After cooling to room temperature, 11.8 parts of tetrahydrophthalic anhydride was added and reacted at 110 ° C. for 3 hours. After cooling to room temperature, DPMA was added to adjust the solid content to 50% to obtain a carboxyl group-containing modified ester resin (A) solution of the present invention. The weight average molecular weight of the carboxyl group-containing modified ester resin (A) obtained in this production example was 12600, and the acid value of the resin solid content measured was 15.3 mgKOH / g.

[Production Examples 2 to 16, Comparative Production Examples 1 to 4]
Except having replaced with the material shown in Table 1, it carried out similarly to manufacture example 1, and obtained the carboxyl group-containing modified ester resin (A) solution of this invention.

C-2090: Kuraray Co., Ltd .: 3-methyl-1,5-pentanediol / 1,6-hexanediol = 9/1 (molar ratio) copolymerized polycarbonate diol T-5562: Asahi Kasei Chemicals Co., Ltd .: C5C6 Polymerized polycarbonate diol UHC50-200: Ube Industries, Ltd .: 1,6-hexanediol / caprolactone = 5/5 copolymer polycarbonate diol UM90 (1/3): Ube Industries, Ltd .: 1,4-cyclohexanedimethanol / 1,6-hexanediol = 1/3 copolymer polycarbonate diol UM90 (1/1): Ube Industries, Ltd .: 1,4-cyclohexanedimethanol / 1
PTG-2000SN: manufactured by Hodogaya Chemical Co., Ltd .: polytetramethylene glycol GI-2000: manufactured by Nippon Soda Co., Ltd .: hydrogenated polybutadiene glycol (number average molecular weight of about 2100)
Poly-ip: manufactured by Idemitsu Kosan Co., Ltd .: hydroxyl-terminated liquid isoprene (number average molecular weight of about 2500)
KF-6002: Shin-Etsu Chemical Co., Ltd. product: Carbinol modified silicone oil at both ends (weight average molecular weight of about 3000)
P-1041: Kuraray Co., Ltd .: 3-methyl-1,5-pentanediol / 1,4-cyclohexanedicarboxylic acid copolymerized polyester polyol (number average molecular weight of about 1000)
P-2010: Kuraray Co., Ltd .: Aliphatic polyester polyol (number average molecular weight of about 2000)
C-590: Kuraray Co., Ltd .: 3-methyl-1,5-pentanediol / 1,6-hexanediol = 9/1 (molar ratio) copolymerized polycarbonate diol (number average molecular weight of about 600)
C-1090: Kuraray Co., Ltd .: 3-methyl-1,5-pentanediol / 1,6-hexanediol = 9/1 (molar ratio) copolymerized polycarbonate diol (number average molecular weight of about 1000)
TH: Shin Nippon Rika Co., Ltd .: Tetrahydrophthalic anhydride HNA-100: Shin Nippon Rika Co., Ltd .: Methylbicyclo [2.2.1] heptane-2,3-dicarboxylic anhydride SA: Shin Nippon Rika Co., Ltd. Manufactured: Succinic anhydride YD-8125: Toto Kasei Co., Ltd .: Bisphenol A type epoxy resin EX-216L: Nagase ChemteX Corporation: cyclohexanedimethanol diglycidyl ether EX-212L: Nagase ChemteX Corporation: 1, 6-hexanediol diglycidyl ether YX-8800: manufactured by Mitsubishi Chemical Corporation: dihydroxyanthracene type epoxy resin DMBA: dimethylolbutanoic acid 1,6-HD: 1,6-hexanediol

[Production Example 17]
Sucrose as a compound (f) having a sugar skeleton in a four-necked flask equipped with a stirrer, a reflux condenser (circulated with hot water adjusted to 60 ° C.) connected to a vacuum pump, an inlet tube, and a thermometer (Tokyo Chemical Industry Co., Ltd.) 155.6 parts, carboxylic acid ester compound (g) as methyl stearate (Tokyo Chemical Industry Co., Ltd.) 212.3 parts, catalyst as potassium hydroxide (manufactured by Tokyo Chemical Industry Co., Ltd.) 3.0 parts, 525.5 parts of dimethyl sulfoxide (manufactured by Tokyo Chemical Industry Co., Ltd.) as a solvent were charged, and the temperature was raised to 90 ° C. while stirring. Next, the pressure in the reaction system was adjusted to 23 mmHg, and the mixture was boiled for 30 hours at a liquid temperature of 90 ° C. with stirring at 700 rpm. At this time, methanol produced as a by-product in the reaction was distilled out of the system, and dimethyl sulfoxide was condensed and refluxed with a reflux condenser. After completion of the reaction, the reaction solution was transferred to a 1 L eggplant type flask, and dimethyl sulfoxide was distilled off under reduced pressure using an evaporator. 500 parts of ethanol was added to the flask to dissolve the reaction product. Unreacted unreacted sucrose was filtered and transferred to a 2 L beaker, and then 400 parts of liquid paraffin was added and stirred at 80 ° C. to separate 2 L. It was transferred to a funnel and allowed to stand to separate into two layers. Ethanol was distilled off from the separated ethanol layer with an evaporator to obtain sucrose stearate ester (C) at a yield of 89%.

[Production Examples 18 to 25]
Except having replaced with the material shown in Table 2, it carried out similarly to manufacture example 17, and obtained the sugar ester compound (C) of this invention.

Example 1
300 parts by weight of the carboxyl group-containing modified ester resin solution of Production Example 1 as the carboxyl group-containing modified ester resin (A), 50 parts by weight of SPB-100 (Otsuka Chemical Co., Ltd., phenoxyphosphazene) as the aromatic phosphorus compound (B), As a sugar ester compound (C), 50 parts by weight of sucrose stearate obtained in Production Example 1 was added and dispersed with a three-roll mill (manufactured by Inoue Seisakusho Co., Ltd.). To the obtained dispersion, 25 parts by weight of jER-1031S (manufactured by Mitsubishi Chemical Corporation, polyfunctional epoxy resin) was added and mixed as a curing agent (D) to obtain a flame retardant resin composition.

(Examples 2 to 64, Comparative Examples 1 to 16)
Except having prepared with the composition shown to Tables 3-7, it carried out similarly to Example 1, and obtained the flame-retardant resin composition.

JER828: Mitsubishi Chemical Corporation, bisphenol A type epoxy compound jER1031S: Mitsubishi Chemical Corporation, multifunctional epoxy resin EPPN-201L: Nippon Kayaku Co., Ltd., phenol novolac type epoxy resin HP7200: DIC stock Company, dicyclopentadiene type polyfunctional epoxy resin / primid XL-552: manufactured by EMS, β-hydroxylethylamide compound / BL3175: manufactured by Sumika Bayer Urethane Co., Ltd., isocyanurate type blocked isocyanate / BI7982: manufactured by Baxenden Chemicals , Isocyanurate type blocked isocyanate · DICY-7: manufactured by Mitsubishi Chemical Corporation, dicyandiamide · chemitite PZ: manufactured by Nippon Shokubai Co., Ltd., polyfunctional aziridine compound · Ba: Shikoku Chemicals Benzoxazine compound, carbodilite V-07, manufactured by Nisshinbo Co., Ltd., polycarbodiimide compound, EH-4346: ADEKA CORPORATION, imidazole compound, TD-2131: DIC Corporation, phenol novolac resin, OP935: Clariant Aluminum phosphinic acid salt, trade name “Exorit OP935”
・ PM200: Nissan Chemical Industries, Ltd., melamine polyphosphate, trade name “Fosmel 200”
SPB-100: Otsuka Chemical Co., Ltd., cyclic phenoxyphosphazene FP-300: Fushimi Pharmaceutical Co., Ltd., trade name “Ravitor FP-300”
PX-200: manufactured by Daihachi Chemical Co., Ltd., 1,3-phenylene di (2,6-xylenyl phosphate)
-HCA: manufactured by Sanko Co., Ltd., 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide

(1) Bleed-out suppression property The flame-retardant resin compositions of the above examples and comparative examples are dried on a polyimide film having a thickness of 50 μm (manufactured by Toray DuPont, Kapton 200H) so that the film thickness after drying becomes 40 μm. Coated uniformly. Thereafter, the following treatment was performed.
Examples 1 to 76 and Comparative Examples 1 to 32: Drying was performed at 150 ° C. for 1 hour using a hot air drying oven.
The obtained coated product was stored in a constant temperature chamber at 70 ° C. as an accelerated aging test, and the coating film surface state after 100 hours, 500 hours and 1000 hours was visually observed. The results were evaluated according to the following criteria.
A: No abnormality was observed on the coating film surface even after 1000 hours. O: No abnormality was observed on the coating film surface after 500 hours, but bleeding out was confirmed after 1000 hours. Δ: 100 No abnormality was observed on the surface of the coating film after a lapse of time, but bleed out was confirmed after 500 hours. X: Bleed out was confirmed on the surface of the coating film after 100 hours.

(2) Flame retardancy The flame retardant resin compositions of the above examples and comparative examples were dried on a polyimide film (Kapton 100H, manufactured by Toray DuPont Co., Ltd.) with a thickness of 10 μm, 25 μm, and 40 μm, respectively. The coating was uniformly performed. Thereafter, the following treatment was performed.
-It dried at 150 degreeC for 1 hour using the hot air drying oven.
・ Cut the obtained three types of film thickness to 150mm in length and 50mm in width, respectively, wound in the width direction so that the coating surface is on the outside, into a cylindrical shape, long from one end of the cylinder The test sample was marked with a 125 mm mark in the vertical direction. Using this test sample, a vertical flammability test is performed in accordance with the UL-94 thin vertical combustion test standard of Underwriters' Laboratories Inc., and the flame retardancy is evaluated for each coating film thickness. did. The results were evaluated according to the following criteria.

VTM-0: All the following conditions (A) to (E) are satisfied.
(A) The total extinguishing time after 10 times of flame contact is within 50 seconds, 5 test pieces twice each.
(B) A test piece was fired twice for each of five test pieces, and the flame extinguishing time after each flame contact was within 10 seconds.
(C) There is no ignition of the absorbent cotton under 300 mm due to the drop in all the test pieces.
(D) Growing after the second flame contact is within 30 seconds for all specimens.
(E) All specimens are not framing to the clamp.

(Evaluation criteria)
A: All the film thicknesses passed the specification of VTM-0.
○: The film thickness of 10 μm and 25 μm passed the VTM-0 standard, but the film thickness of 40 μm failed the VTM-0 standard.
Δ: VTM-0 specification was passed at a film thickness of 10 μm, but VTM-0 specification was not passed at 25 μm and 40 μm.
X: In all film thicknesses, it did not comply with the provisions of VTM-0.

(3) Flexibility The flame-retardant resin compositions of the above examples and comparative examples were made of copper of a non-adhesive copper-clad laminate (Espanex M, manufactured by Nippon Steel Chemical Co., Ltd.) having a polyimide thickness of 25 μm and a copper foil thickness of 18 μm. On the surface, coating was performed uniformly so that the film thickness after drying was 40 μm. Thereafter, the following treatment was performed.
-It dried at 150 degreeC for 1 hour using the hot air drying oven.
・ A test piece of 100 mm × 40 mm was cut out from the obtained coated material, and a flexibility test was performed using the test piece according to the following procedure. From the number of sets until a crack in the coating film or copper foil was confirmed, It was evaluated as follows.
(procedure)
1. The coated surface was folded 180 °, and the folding position was loaded with a 2 kg weight.
2. 1. With the coated surface facing outward Was bent 180 ° at the same position and was similarly weighted.
3. The coated surface was observed and the presence or absence of the crack of the coating film or copper foil in a bending part was confirmed.
The procedure of 4.1-3 was repeated as 1 set, and the number of sets until a crack generate | occur | produced was confirmed.

(Evaluation criteria)
◎: 20 sets or more ○: 10 sets or more and less than 20 sets △: 5 sets or more and less than 10 sets ×: Less than 5 sets

(4) Insulation reliability A comb-shaped pattern (conductor pattern width / space width = 50 μm / 50 μm) in which a copper circuit is formed on polyimide is uniformly applied on a printed circuit so that the film thickness after drying is 40 μm. did. Thereafter, the following treatment was performed.
-It dried at 150 degreeC for 1 hour using the hot-air drying oven, and produced the test piece for evaluation.
-A DC voltage of 50 V is continuously applied to the conductor circuit of the above test piece in an atmosphere of a temperature of 85 ° C. and a relative humidity of 85%, and the insulation resistance value between the conductors is measured at regular intervals to obtain an insulation resistance value of 10 ⁶ Ω. The time until it became less than was evaluated. The evaluation criteria are as follows.
◎ ・ ・ ・ 2000 hours or more ○ ・ ・ ・ 1000 hours or more and less than 2000 hours Δ ・ ・ ・ 500 hours or more and less than 1000 hours × ・ ・ ・ less than 500 hours

(5) Resistance to Solder Bath Similar to (2) above, a test piece cut out to a width of 10 mm and a length of 65 mm was floated for 1 minute by bringing the polyimide film surface into contact with 260 ° C. molten solder. Thereafter, the appearance of the test piece was visually observed, and the presence or absence of adhesion abnormality such as foaming, floating, and peeling of the adhesive layer was evaluated. This test evaluates the thermal stability of the adhesive layer at the time of solder contact with the appearance. Those with good heat resistance have poor heat resistance, whereas the appearance does not change before and after soldering. Things are subject to foaming and peeling after soldering. These evaluation results were judged according to the following criteria.
◎ ・ ・ ・ No change in appearance
○ ・ ・ ・ “Slight foaming is observed”
△ ... "Bubbling is observed"
× ・ ・ ・ "Strong foaming and peeling are observed"

(6) Flux resistance The thermosetting resin composition is uniformly applied on a polyimide film having a thickness of 75 μm [“Kapton 300H” manufactured by Toray DuPont Co., Ltd.] so that the film thickness after drying becomes 30 μm. The coating was applied and dried and heat-cured at 150 ° C. for 1 hour to prepare a test piece for evaluation. One drop of a weakly active rosin flux (manufactured by Nippon Alpha Metals Co., Ltd., trade name: RM-615) was dropped on the test piece, followed by heat treatment in an oven at 260 ° C. for 3 minutes. After removing the test piece from the oven, the flux was wiped off with isopropyl alcohol, and then judged according to the thickness of the cured film on the polyimide as follows. A thing which does not have a practical problem is (circle).
○: Change in film thickness is 5 μm or less Δ: Change in film thickness is 5-10 μm
X: Change in film thickness of 10 μm or more

  The results of evaluation are shown in Table 8 below.

  As can be seen from the examples and comparative examples in Table 8, in the resin compositions of Comparative Examples 2, 5, 6, 11, and 15, the sugar ester compound (C) was not added or the addition amount was small, or aromatic phosphorus Since the amount of the compound (B) was too large, a relatively significant bleed out of the aromatic phosphorus compound (B) was confirmed in the time course test, and it was clear that the quality stability was lacking. Moreover, the resin composition of Comparative Examples 1-8 is an aliphatic polybasic acid in which the acid anhydride group-containing compound (b) introduced into the main chain or side chain during the synthesis of the carboxyl group-containing modified ester resin (A) Since it was an anhydride, it was confirmed that the insulation reliability and solder heat resistance were greatly reduced. Furthermore, in Comparative Examples 13-16, since low molecular diol was used instead of polyol (a) at the time of the synthesis | combination of carboxyl group-containing modified ester resin (A), the remarkable fall of flexibility was confirmed.

  On the other hand, the flame retardant resin compositions of Examples 1 to 64 had high flame retardancy, flexibility, insulation reliability, solder bath resistance, flux resistance, and excellent bleed-out resistance. These are the characteristics of the carboxyl group-containing modified ester resin (A), which is a feature of the present invention, due to the combined use of the carboxyl group-containing modified ester resin (A), the aromatic phosphorus compound (B), and the sugar ester compound (C). The sugar ester compound (C) without impairing the flexibility, insulation reliability, heat resistance, flux resistance, high flame retardancy imparting ability of the aromatic phosphorus compound (B), and small adverse effects on flexibility and flexibility. ) Acts as a compatibilizing agent for the carboxyl group-containing modified ester resin (A) and the aromatic phosphorus compound (B), and extremely strongly suppresses the bleed out, which was a drawback when using the aromatic phosphorus compound (B). It is thought that it is because. Examples 2-3 and 5-11, in which the sugar ester compound (C) is a sugar-containing aromatic skeleton-containing carboxylic acid ester compound (C-1) and the aromatic phosphorus compound (B) is a cyclic phosphazene compound 13, 15-16, 18-19, 21-25, 27-30, 32, 34-35, 37-41, 43-45, 47-48, 50-51, 53-57, 59-61, 63 In the flame retardant resin composition of ~ 64, particularly excellent bleed-out resistance was confirmed, which was an aromatic skeleton-containing carboxylic acid ester compound (C-) with the aromatic skeleton of the aromatic phosphorus compound (B). This is probably because a relatively strong interaction acts with the aromatic skeleton of 1), and the action as the compatibilizer described above is strengthened. Examples 2 to 6, 8 to 9, 11 to 11 further comprising a thermosetting aid (E) which is at least one selected from an aziridine compound, a carbodiimide group-containing compound, a benzoxazine compound, a phenol resin, imidazoles and dicyandiamide. 12, 14-16, 18-22, 24-25, 27-28, 30-32, 34-38, 40-41, 43-44, 46-48, 50-54, 56-57, 59-60, In 62 to 64, particularly excellent flux resistance, which is presumed to be due to the progress of an effective thermal crosslinking reaction, was confirmed.

  As described above, as can be seen from the examples and comparative examples, the flame retardant resin compositions of the examples include the carboxyl group-containing modified ester resin (A), the aromatic phosphorus compound (B), the sugar ester compound (C), and the curing agent. The combined use of (D) showed good results in all of flame retardancy, flexibility, insulation reliability, flux resistance, solder bath resistance and bleed out resistance.

Claims (9)

Carboxyl group-containing modified ester resin (A), aromatic phosphorus compound (B), sugar ester compound (C), epoxy group-containing compound, unblocked isocyanate compound, blocked isocyanate compound, and β-hydroxyalkylamide A curing agent (D) that is at least one selected from group-containing compounds,
An acid anhydride group-containing compound (b) in which the carboxyl group-containing modified ester resin (A) is at least one selected from the polyol compound (a), an alicyclic polybasic acid anhydride, and an aromatic polybasic acid anhydride. ) To produce a carboxyl group-containing ester resin (c),
Reacting the carboxyl group-containing ester resin (c) with an epoxy compound (d) having at least two epoxy groups in one molecule to produce a side chain hydroxyl group-containing modified ester resin (e);
Further, the side chain hydroxyl group-containing modified ester resin (e) is reacted with at least one acid anhydride group-containing compound (b) selected from an alicyclic polybasic acid anhydride and an aromatic polybasic acid anhydride. A flame retardant resin composition characterized by comprising:   The flame retardant resin composition according to claim 1, wherein the acid value of the carboxyl group-containing modified ester resin (A) is 1 to 100 mgKOH / g.   The flame retardant resin composition according to claim 1 or 2, wherein the carboxyl group-containing modified ester resin (A) has a weight average molecular weight of 5,000 to 500,000.   The flame retardant resin composition according to any one of claims 1 to 3, wherein the sugar ester compound (C) is a sugar aromatic skeleton-containing carboxylic acid ester compound (C-1).   The flame retardant resin composition according to claim 4, wherein the saccharide ester compound (C-1) containing an aromatic skeleton of sugar is a sucrose benzoate compound.   The flame retardant resin composition according to any one of claims 1 to 5, wherein the aromatic phosphorus compound (B) is a cyclic phosphazene compound.   The thermosetting aid (E), which is at least one selected from an aziridine compound, a carbodiimide group-containing compound, a benzoxazine compound, a phenol resin, imidazoles, and dicyandiamide, is further characterized by the above-mentioned. Any one of the flame-retardant resin compositions.   Hardened | cured material obtained by hardening the flame-retardant resin composition in any one of Claims 1-7 by heating.   A printed wiring board comprising a layer made of the cured product according to claim 8.