JP2010013528A - Polyester resin, photo curable-thermosetting resin composition, photo curable-thermosetting resin layer, ink, adhesive, and printed circuit board - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a modified polyester resin having an ethylenically unsaturated double bond contributing to photo-curability and a photo curable-thermosetting resin composition by using the same. <P>SOLUTION: This polyester resin excellent in flame retardant property and adhesion, having a hard segment and a soft segment in a main chain, and a carboxyl group based on an acid dianhydride, and also containing a phosphorus atom contributing to flame retardance in the main chain or a side chain can be obtained, and also the modified polyester resin having the ethylenically unsaturated double bond contributing to the photo-curability is obtained by reacting the above resin with a (meth)acrylic monomer having a functional group capable of reacting with the above carboxyl group. By using these resin compositions, it is possible to obtain an ink or an adhesive excellent in flame retardance, alkali-developing property, sensitivity, soldering heat resistance, flexibility, etc., and further it is possible to obtain an automobile component, a printed circuit board used for an electric utensil, etc., by using them, and these are very effective. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention comprises a polyester resin having a hard group and a soft segment in the main chain, and further a carboxyl group based on an acid dianhydride and containing a phosphorus atom in the main chain or side chain, and a functional group that reacts with the carboxyl group. Modified polyester resin obtained by reacting a (meth) acrylic monomer having a group, a photocurable / thermosetting resin composition using the same, a photocurable / thermosetting layer, an ink, an adhesive, and The present invention relates to a printed circuit board.

  In recent years, film adhesives have been used in various fields, and in particular, used for bonding printed wiring boards. Among them, the demand for adhesives for cover films of flexible printed wiring boards (FPC), bonding between FPCs and hard substrates, bonding sheets used for bonding FPCs, adhesives for flat cables, and the like is expanding.

  For example, recently, flat cables have been widely used from the viewpoint of reducing the weight of automobile parts and wiring parts of household electrical appliances and reducing costs. This flat cable adhesive is often composed of three layers of polyethylene terephthalate (PET), a plastic film layer such as vinyl chloride and polyimide, an adhesive, and a metal foil such as copper. That is, the adhesive is required to exhibit adhesiveness to both the plastic film and the metal foil, and is required to have durability.

  In addition, when it is used after being bent for a long time or used in a bent portion, it requires mechanical properties such as considerably high bending resistance.

  However, the conventionally proposed adhesives have not been able to satisfy such a demand for increasing sophistication.

  In OA equipment and home appliances, polymer materials (resin materials) may ignite due to abnormal heating due to malfunction of parts, which may cause a fire. (Nonflammability and flame retardancy) is required. In such a situation, in order to impart a higher degree of flame retardancy, it is necessary not only to make the molding material flame retardant, but also to achieve flame retardant for adhesives and inks used there. .

  In order to realize the conventional flame retardancy, methods for introducing halogen atoms into the resin skeleton and methods using a halogen flame retardant and antimony trioxide in combination with the resin have been used for adhesives. .

  However, the use of halogen atoms and flame retardants containing halogen atoms has been increasingly restricted due to concerns about the generation of dioxins during incineration, and in particular, in Europe, attaching eco-labels indicating that halogens are not used in products. There is a movement.

  Generally, non-halogen (halogen-free) technology that achieves low toxicity, low smoke generation, and flame retardancy includes a method of adding a phosphorus-based flame retardant such as a phosphate ester. In order to develop flammability, it is necessary to add a large amount of these flame retardants, which is not practical, and when added in a large amount, properties such as adhesiveness, mechanical properties, and heat resistance are reduced. In addition, there may be a problem that the flame retardant itself bleeds out and the adhesiveness decreases with time.

  In FPC and printed wiring boards, a liquid or film solder resist agent is used for circuit protection and solder adhesion prevention during mounting. As the solder resist agent, the development film type for forming a pattern by a photolithography method can obtain high dimensional accuracy, so that the demand is increasing.

  Solder resist agents that have been developed so far include those that use an epoxy resin, but when the epoxy resin is used as the main component, the resulting cured product is practically inferior in flexibility. Have problems.

  In Patent Document 1, a curable resin obtained by adding a polybasic acid anhydride to a reaction product of a novolak-type epoxy compound and an unsaturated monocarboxylic acid, a photopolymerization initiator, a photopolymerizable monomer, and 1 An epoxy resin composition containing a polyfunctional epoxy resin having two or more epoxy groups in the molecule has been disclosed, but there has been a problem that sufficient flexibility has not been obtained.

  Various attempts have been made to improve flexibility. For example, a novolac epoxy compound is reacted with a phenol compound and / or a naphthol compound and an unsaturated group-containing monocarboxylic acid, and a polybasic acid anhydride is further reacted. A solder resist containing a reaction product obtained by reacting a product and an epoxy compound as an essential component is disclosed (for example, see Patent Document 2). Although this solder resist gives flexibility to the formed cured film and crack resistance is solved, there is a problem in that it is difficult to form a clear resist pattern image due to insufficient alkali developability. ing.

  Further, a reaction product obtained by reacting an epoxy compound selected from a bisphenol F-type epoxy compound or a rubber-modified epoxy compound with an unsaturated group-containing monocarboxylic acid and further reacting with a polybasic acid anhydride, and a curing agent as an essential component And a reaction product obtained by reacting a bisphenol type polyfunctional epoxy compound having a specific structure with an unsaturated group-containing monocarboxylic acid and further reacting with a polybasic acid anhydride. And a solder resist containing an epoxy compound (see, for example, Patent Document 4).

  However, the above-mentioned solder resist gives flexibility to the formed cured film and solves crack resistance, but since both have low sensitivity to ultraviolet rays (light), the resolution of the formed image is low. There is a concern that the low density and sufficient high density mounting required in the next generation cannot be sufficiently handled.

  In this way, when flexibility is imparted to the cured film formed to solve crack resistance, generally alkali developability is greatly reduced, and basic performance as a solder resist ink used in the production of printed wiring boards It is extremely difficult to achieve a good balance between dryness to touch, alkali developability, sensitivity, soldering heat resistance, and adhesion to the base material, and there is currently no satisfactory content. is there.

JP-A 61-243869 Japanese Patent Laid-Open No. 11-315107 JP-A-11-242331 JP 2001-278947 A

  Therefore, the present invention has a carboxyl group based on a hard segment and a soft segment, acid dianhydride in the main chain, and further contains a polyester resin containing a phosphorus atom in the main chain or side chain, and the carboxyl group A modified polyester resin having an ethylenically unsaturated double bond that reacts with a (meth) acrylic monomer having a functional group to react to contribute to photocurability, and photocuring / heat using the modified polyester resin An object is to provide a curable resin composition. Furthermore, by using the photocurable / thermosetting resin composition, an object is to provide a printed circuit board or the like used in inks and adhesives, automobile parts using these, and electrical appliances. And

  As a result of intensive studies to solve the above problems, the present inventors have found the following polyester resins and the like, and have completed the present invention.

That is, the polyester resin of the present invention, at least two or more ester bonds and hard segments based on the ester bond-containing diol oligomer A ₁ having hydroxyl groups at both ends, at least two carbonate groups and hydroxyl groups on both ends a polyester resin C containing a soft segment based on carbonate-containing diol oligomer a ₂ having a residual carboxyl group-containing segment B based on dianhydride, wherein the hard segments, and the soft segment, the combined with the remaining carboxyl group-containing segment B based on dianhydride constitute the polyester resin C, the glass transition temperature of the ester bond-containing diol oligomer a ₁ is, exceed 0 ° C., and a number average molecular weight , 600-4000, The glass transition temperature of the serial carbonate groups-containing diol oligomer _{A 2} is, is at 0 ℃ or less and a number average molecular weight is 800 to 4000, the molar ratio of the oligomer _{A 1} and the oligomer _{A 2 (A} 1 / A ₂ ) is 1/9 to 9/1, and the molar ratio B / (A ₁ + A ₂ ) of the acid dianhydride B, the oligomer A ₁ and the oligomer A ₂ is 65/100 to 98/100. Or 135/100 to 102/100, the number average molecular weight of the polyester resin C is 2000 to 10000, and the polyester resin C contains 0.5 to 7% by weight of phosphorus atoms. .

Polyester resin of the present invention, the ester bond-containing diol oligomer A ₁ is a hydroxyl group in the diol compound, it is preferably obtained by reacting the carboxyl groups of the dicarboxylic acid compound.

  In the polyester resin of the present invention, the dicarboxylic acid compound is preferably an imide group-containing dicarboxylic acid oligomer.

Polyester resin of the present invention, the carbonate group-containing diol oligomer A ₂ is preferably polycarbonate diols.

Polyester resin of the present invention, the carbonate group-containing diol oligomer A ₂ is preferably a phosphorus-containing polycarbonate diol.

The modified polyester resin of the present invention is a polyester resin D obtained by reacting a residual carboxyl group in the polyester resin with a (meth) acrylic monomer having a functional group that reacts with the residual carboxyl group, the modified resin A part of the residual carboxyl group remains in the main chain of the polyester resin D, the side chain of the modified polyester resin D has an ethylenically unsaturated double bond, and the acid value of the modified polyester resin D Is 350 to 2000 equivalent / 10 ⁶ g, and the number average molecular weight is preferably 2500 to 10,000.

  In the modified polyester resin of the present invention, the functional group of the (meth) acrylic monomer is preferably a glycidyl group and / or a hydroxyl group.

  The photocurable / thermosetting resin composition of the present invention contains the modified polyester resin D, the (meth) acrylic monomer E, and the epoxy resin F, and the (( It is preferable that 5-30 parts by weight of the (meth) acrylic monomer E and 5-50 parts by weight of the epoxy resin F are contained.

  The photocurable / thermosetting resin composition of the present invention preferably further contains a flame retardant.

  The photocurable / thermosetting layer of the present invention is preferably obtained by reacting the photocurable / thermosetting resin composition.

  The ink of the present invention preferably uses the photocurable / thermosetting resin composition.

  It is preferable to use the photocurable / thermosetting resin composition for the adhesive of the present invention.

  The printed circuit board of the present invention preferably has the photocurable / thermosetting layer on the surface of the circuit board.

  The present invention has a hard segment and a soft segment in the main chain, a carboxyl group based on acid dianhydride, and further contains a phosphorus atom that contributes to flame retardancy in the main chain or side chain. Polyester resin excellent in flowability, adhesion, and fluidity required at the time of adhesion can be obtained, and (meth) acrylic monomer having a functional group that reacts with the carboxyl group is reacted to be photocured A modified polyester resin having an ethylenically unsaturated double bond that contributes to the properties can be obtained. In addition, by using a photocurable / thermosetting resin composition using these, it is possible to obtain an ink or an adhesive having excellent flame retardancy, alkali developability, sensitivity, solder heat resistance, flexibility, and the like. Furthermore, it is possible to obtain automobile parts using these, printed circuit boards used for electrical appliances, and the like, which are effective.

  Hereinafter, embodiments of the present invention will be described in detail.

<Polyester resin>
Polyester resin of the present invention includes a hard segment based on the ester bond-containing diol oligomer A ₁ having at least two ester bonds and hydroxyl groups at both ends, at least two or more carbonate groups and hydroxyl groups on both ends a soft segment based on carbonate-containing diol oligomer a _2, a polyester resin C containing a residual carboxyl group-containing segment B based on dianhydride and, in the main chain of the polyester resin C, an ester bond, the remaining It has a carboxyl group and a carbonate group.

  By having a hard segment in the main chain of the polyester resin C, it is possible to provide solder heat resistance after curing, improve coating film hardness, and impart scratch resistance. Moreover, by having a soft segment, bending resistance, low warpage, and flexibility can be imparted. Further, by including both the hard segment and the soft segment, it is possible to achieve both heat resistance, scratch resistance, flex resistance, low warpage, and flexible mechanical characteristics. Furthermore, since the carboxyl group remains in the main chain of the polyester resin C, alkali solubility (alkali developability in the photoresist manufacturing process) can be realized. In addition, ester bonds and carbonate groups are effective without causing a resin decomposition reaction called so-called copper damage using copper used for a printed circuit board as a catalyst, like ether bonds.

The glass transition temperature of the ester bond-containing diol oligomer A ₁ is greater than 0 ° C., preferably 20 ° C. or higher, more preferably 30 ° C. or higher, more preferably 40 ° C. or higher. When it is less than 0 ° C., there is a problem that heat resistance is deteriorated and coating film hardness is lowered, which is not preferable.

The glass transition temperature of the carbonate group-containing diol oligomer A ₂ is less than 0 ° C., preferably -5 ° C. or less, more preferably -10 ° C. or less. When the temperature is 0 ° C. or higher, the flexibility is inferior, and when bent, cracks are generated, which is not preferable.

The number average molecular weight of the ester bond-containing diol oligomer A ₁ having hydroxyl groups at both ends in the polyester resin C used in the present invention is 600 to 4000, and preferably 800 to 3000. If it is less than 600, it does not function as a hard segment, and there is a problem that heat resistance and coating film hardness are inferior. On the other hand, if it exceeds 4000, the solubility in an alkali developer becomes insufficient, and development becomes impossible, which is not preferable.

The number average molecular weight of the carbonate group-containing diol oligomer A ₂ having hydroxyl groups at both ends in the polyester resin C used in the present invention is 800 to 4000, preferably 1000 to 3500, and more preferably 1200 to 3000. . When it is less than 800, it does not function as a soft segment, and there is a problem that heat resistance characteristics and coating film hardness are inferior. On the other hand, if it exceeds 4000, the solubility in an alkali developer becomes insufficient, and development becomes impossible, which is not preferable.

The polyester resin C used in the present invention is preferably obtained by reacting the ester bond-containing diol oligomer A ₁ with a hydroxyl group in the diol compound and a carboxyl group in the dicarboxylic acid compound. The ester bond-containing diol oligomer A ₁ has to have an ester bond, polyethylene glycol, polypropylene glycol, as compared to ether oligomer of polytetramethylene glycol characterized of excellent heat resistance. Further, the hydroxyl group and the carboxyl group react to generate an ester bond. The segment based on the ester bond-containing diol oligomer A ₁ becomes a portion serves as a so-called hard segment, thereby contributing to the solder heat resistance and surface tack-free.

Also, the ester bond-containing diol oligomer A ₁ is preferably a polyesterimide diols oligomer. The ester bond-containing diol oligomer A ₁ has to have an ester bond and an imide bond, polyethylene glycol, polypropylene glycol, as compared to ether oligomer of polytetramethylene glycol characterized of excellent heat resistance. The segment based on the ester bond-containing diol oligomer A ₁ becomes a portion serves as a so-called hard segment, thereby contributing to the solder heat resistance and surface tack-free. The polyesterimide diol oligomer is preferably obtained by reacting the diol compound with an imide group-containing dicarboxylic acid oligomer as the dicarboxylic acid compound.

Polyester resin C used in the present invention, the carbonate group-containing diol oligomer A ₂ is a hydroxyl group in the diol compound, it is preferably obtained by reacting the carboxyl groups of the dicarboxylic acid compound. The hydroxyl group and the carboxyl group react to form an ester bond. The carbonate group-containing diol oligomer A ₂ has to have an ester bond or carbonate groups, polyethylene glycol, polypropylene glycol, as compared to ether oligomer of polytetramethylene glycol characterized of excellent heat resistance. Further, ester bond-containing segment based on the carbonate group-containing diol oligomer A ₂ becomes a moiety serves as a so-called soft segment, thereby contributing to such flexibility.

Further, the polyester resin C is produced by a method of producing at least two ester bonds and ester bond-containing diol oligomer A ₁ having hydroxyl groups at both ends, at least two ester bonds and hydroxyl groups at both ends. a carbonate group-containing diol oligomer a ₂ having, it is preferable to react the dianhydride. Wherein the ester bond-containing diol oligomer A _1, via the carbonate group-containing diol oligomer A ₂ and acid dianhydride, by reacting, a hard segment bets can be coupled soft segment, both characteristics Can be incorporated and is effective.

Examples of the diol compounds that can be used as a component of the oligomer _{A 1,} specifically, for example, ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 2,4-dimethyl-2-ethyl hexane-1, 3-diol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 2-ethyl-2-butyl-1,3-propanediol, 2-ethyl-2-isobutyl-1,3-propane Diol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 2,2,4-trimethyl-1 1,6-hexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexane Dimethanol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 1,9-nonanediol, dimer diol, hydrogenated dimer diol, tricyclodecandiol, tricyclodecane dimethylol, spiroglyco -Ethylene, hydrogenated bisphenol A, hydrogenated bisphenol A ethylene oxide adduct and propylene oxide adduct. Examples of the trihydric or higher polyhydric alcohol include pentaerythritol, dipentaerythritol, tripentaerythritol, glycerin, trimethylolpropane, trimethylolethane, 1,3,6-hexanetriol, and the like. . Furthermore, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and the like can be used as the polyether polyol, but the degree of polymerization must be such that the effects of the present invention are not impaired. In addition, these compounds may be used independently and may mix and use 2 or more types.

The oligomer A ₁ in order to function as a hard segment, it is desirable glass transition temperature is high. Wherein as a constituent of the oligomer A _1, by using a diol compound of short chain (glycol), there is a tendency that it is possible to increase the glass transition temperature of the segments based on the oligomer A _1. Examples of the short-chain glycol include ethylene glycol, propylene glycol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 2-ethyl-2-butyl-1,3-propanediol, and 2-ethyl. Examples include 2-isobutyl-1,3-propanediol.

The dicarboxylic acid compounds used in the ester bond-containing diol oligomer A _1, as long as it is a compound having two carboxyl groups is not particularly limited, for example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, Pimelic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, dodecanedicarboxylic acid, tetradecanedicarboxylic acid, hexadecanedicarboxylic acid, 3-cyclobutanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2,5-norbornanedicarboxylic acid, saturated aliphatic dicarboxylic acids exemplified by dimer acid, etc., or ester-forming derivatives thereof, fumaric acid, maleic acid , Itacon Unsaturated aliphatic dicarboxylic acids exemplified by acids and the like, or ester-forming derivatives thereof, orthophthalic acid, isophthalic acid, terephthalic acid, diphenic acid, 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1, 5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 4,4′-biphenyldicarboxylic acid, 4,4′-biphenylsulfone dicarboxylic acid, 4,4′-biphenylether dicarboxylic acid 1,2-bis (phenoxy) ethane-p, p′-dicarboxylic acid, pamoic acid, anthracene dicarboxylic acid and the like, and aromatic dicarboxylic acids and ester-forming derivatives thereof. In addition, these compounds may be used independently and may mix and use 2 or more types.

  Among the above dicarboxylic acid compounds, the use of aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, aliphatic dicarboxylic acids such as sebacic acid and azelaic acid, physical properties of the resulting polyester resin, etc. It is preferable at this point, and another dicarboxylic acid compound can be made into a structural component as needed.

  Polyvalent carboxylic acids other than these dicarboxylic acid compounds can be used as long as they do not impair the characteristics of the present invention. For example, ethanetricarboxylic acid, propanetricarboxylic acid, butanetetracarboxylic acid, pyromellitic acid, Examples include merit acid, trimesic acid, 3,4,3 ′, 4′-biphenyltetracarboxylic acid, and ester-forming derivatives thereof.

The ester bond-containing diol oligomer A ₁ is by reacting a diol compound and a dicarboxylic acid compound, can be produced. As the production method, a known method can be used. For example, a diol compound (in addition, a polyhydric alcohol can be used as long as the characteristics are not impaired in the present invention) and a dicarboxylic acid compound. When the esterification reaction is carried out using, the molar ratio (diol compound / dicarboxylic acid) is preferably 2.2 / 1 to 1.8 / 1, more preferably 2/1 to 1.9 / 1. is there. When the range exceeds 2.2 / 1, it takes an excessive amount of time for esterification, and a great amount of energy is consumed for removing unnecessary diol compounds (glycols). In addition to the hydroxyl group, a carboxyl group is generated, and an ester bond-containing diol oligomer that does not contribute to the reaction between the acid dianhydride of the present invention and the hydroxyl group is generated, which is not preferable. What is adjusted to the above range is charged into an autoclave and subjected to esterification at 180 to 240 ° C., and then the system is gradually evacuated in the presence of a catalyst at 230 to 270 ° C. to distill the diol compound out of the system. To obtain an ester bond-containing diol oligomer having a desired number average molecular weight.

When polymerizing the ester bond-containing diol oligomer A _1, as a polymerization catalyst, for example, as the inorganic compound, antimony compound, germanium compound, tin compound, aluminum compound, and a titanium compound.

  Examples of the titanium compound include tetra-n-propyl titanate, tetraisopropyl titanate, tetra-n-butyl titanate, tetraisobutyl titanate, tetra-tert-butyl titanate, tetracyclohexyl titanate, tetraphenyl titanate, and tetrabenzyl titanate. In particular, the use of tetra-n-butyl titanate is preferred.

Further, as the ester bond-containing diol oligomer A _1, it is preferably a polyesterimide diols oligomer. The method for producing the polyesterimide diol oligomer is not particularly limited, and a known method can be applied. For example, after esterifying an acid-terminated polyimide oligomer (imide group-containing dicarboxylic acid oligomer) with a large excess of diol compound (glycol), deglycolization and polycondensation are performed by heating and decompression to obtain the polyesterimide diol oligomer. Can be manufactured.

  The acid-terminated polyimide oligomer (imide group-containing dicarboxylic acid oligomer) is, for example, an acid anhydride (polyhydric acid anhydride) and a diamine, and the molar ratio between them is preferably acid anhydride / diamine = 100 / 50- It can be obtained by reacting at 100/95, more preferably acid anhydride / diamine = 100/50 to 100/90. When the molar ratio exceeds 100/50, an acid anhydride that does not contribute to the reaction remains, and there is a problem that a by-product is produced during esterification. If it is less than 100/95, the number average molecular weight of the acid-terminated polyimide oligomer becomes too high, and the solubility of the polyester resin or modified polyester resin obtained by using this becomes low in alkali, and the alkali developability tends to decrease. . Moreover, if it is less than 100/100, an amine-terminated polyimide oligomer is mainly produced and esterified with a diol compound (glycol), whereby the polyesterimide diol oligomer cannot be obtained.

  The polyesterimide diol oligomer can be produced, for example, by the following method. In a reaction vessel equipped with a stirrer and a thermometer, a diamine is dissolved in a polymerization solvent, and a polyvalent carboxylic acid anhydride is gradually added thereto, and 0 to 90 ° C, preferably 0.5 to 70 ° C. The polyimide precursor oligomer is obtained by stirring for -20 hours, preferably 1-10 hours. Under the present circumstances, it is preferable that the diamine density | concentration at the time of reaction start is 5 to 50 weight%, Preferably it is 10 to 40 weight%. The polyimide precursor oligomer generates a dehydration reaction by heating to obtain an acid-terminated polyimide oligomer (imide group-containing dicarboxylic acid oligomer). The reaction temperature and reaction time are 100 to 180 ° C., preferably 120 to 170 ° C. for 0.5 to 20 hours, preferably 1 to 10 hours. It is desirable that both terminal groups of the obtained acid-terminated polyimide oligomer (imide group-containing dicarboxylic acid oligomer) are carboxyl groups. An esterification reaction is carried out with an acid-terminated polyimide oligomer having a carboxyl group (imide group-containing dicarboxylic acid oligomer) and a diol compound (glycol). It is preferable that reaction temperature and time are 180-240 degreeC, More preferably, it is 190-230 degreeC, 1-6 hours are preferable, More preferably, it is 2-5 hours. The diol compound (glycol) used for esterification may be used as a solvent for the reaction for obtaining the polyimide precursor oligomer, or may be added during the esterification reaction. When the esterification is completed, the polyesterimide diol oligomer can be obtained.

  Although a catalyst is not required for imidation of the polyimide precursor oligomer, it is useful to use a polymerization catalyst at the time of polycondensation for the production of the polyesterimide diol oligomer after completion of esterification. Examples of the polymerization catalyst include inorganic compounds such as antimony compounds, germanium compounds, tin compounds, aluminum compounds, and titanium compounds.

  Examples of the titanium compound include tetra-n-propyl titanate, tetraisopropyl titanate, tetra-n-butyl titanate, tetraisobutyl titanate, tetra-tert-butyl titanate, tetracyclohexyl titanate, tetraphenyl titanate, and tetrabenzyl titanate. In particular, the use of tetra-n-butyl titanate is preferred.

  The number average molecular weight of the polyesterimide diol oligomer is preferably 600 to 4000, and more preferably 800 to 3000. If the number average molecular weight is less than 600, physical and chemical strength and durability of the coating film tend not to be secured. On the other hand, if the number average molecular weight exceeds 4000, the number average molecular weight of the modified polyester resin becomes too high. Solubility becomes low, and alkali developability tends to decrease.

  Examples of acid anhydrides (polyhydric carboxylic acid anhydrides and / or derivatives thereof) that can be used as raw materials for the polyesterimide diol oligomer include aromatic tricarboxylic acid anhydrides, aromatic tetracarboxylic acid anhydrides, aliphatic and alicyclic groups. Mention may be made of trivalent or tetravalent polycarboxylic acid anhydrides such as tetracarboxylic acid anhydrides.

  Examples of the aromatic tricarboxylic acid anhydride and / or derivatives thereof include trimellitic acid anhydride, 3,4,4′-benzophenone tricarboxylic acid anhydride, 3,4,4′-biphenyltricarboxylic acid anhydride, butane. -1,2,4-tricarboxylic acid anhydride, naphthalene-1,2,4-tricarboxylic acid anhydride.

  Examples of the aromatic tetracarboxylic acid anhydride and / or its derivative include pyromellitic dianhydride, ethylene glycol bisanhydro trimellitate, propylene glycol bisan hydrotrimellitate, 1,4-butanediol bisan. Alkylene glycol bisanhydro trimellitates such as hydrotrimellitate, hexamethylene glycol bisan hydrotrimellitate, polyethylene glycol bisanhydro trimellitate, polypropylene glycol bisan hydrotrimellitate, 3,3 ′, 4 4'-benzophenonetetracarboxylic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,4,5 , 8-Naphthalenetetracarboxylic acid di- Water, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic acid Dianhydride, m-terphenyl-3,3 ′, 4,4′-tetracarboxylic dianhydride, 4,4′-oxydiphthalic dianhydride, 1,1,1,3,3,3-hexa Fluoro-2,2-bis (2,3- or 3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3- or 3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis [4- (2,3- or 3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis [ 4- (2,3- or 3,4-dicarboxyphenoxy) phenyl] pro Emissions dianhydride, 1,3-bis (3,4-carboxyphenyl) -1,1,3,3-tetramethyldisiloxane dianhydride, and the like.

  Examples of the aliphatic and alicyclic tetracarboxylic acids and / or derivatives thereof include butane-1,2,3,4-tetracarboxylic dianhydride and pentane-1,2,4,5-tetracarboxylic acid. Dianhydride, cyclobutanetetracarboxylic dianhydride, hexahydropyromellitic dianhydride, cyclohex-1-ene-2,3,5,6-tetracarboxylic dianhydride, 3-ethylcyclohex-1- Ene-3- (1,2), 5,6-tetracarboxylic dianhydride, 1-methyl-3-ethylcyclohexane-3- (1,2), 5,6-tetracarboxylic dianhydride, 1 -Methyl-3-ethylcyclohex-1-ene-3- (1,2), 5,6-tetracarboxylic dianhydride, 1-ethylcyclohexane-1- (1,2), 3,4-tetra Carboxylic dianhydride, 1-p Pyrcyclohexane-1- (2,3), 3,4-tetracarboxylic dianhydride, 1,3-dipropylcyclohexane-1- (2,3), 3- (2,3) -tetracarboxylic acid bis Anhydride, dicyclohexyl-3,4,3 ′, 4′-tetracarboxylic dianhydride, bicyclo [2.2.1] heptane-2,3,5,6-tetracarboxylic dianhydride, 1-propyl Cyclohexane-1- (2,3), 3,4-tetracarboxylic dianhydride, 1,3-dipropylcyclohexane-1- (2,3), 3- (2,3) -tetracarboxylic dianhydride , Dicyclohexyl-3,4,3 ′, 4′-tetracarboxylic dianhydride, bicyclo [2.2.1] heptane-2,3,5,6-tetracarboxylic dianhydride, bicyclo [2. 2.2] Octane-2,3,5,6-tetraca Bon dianhydride, bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, and the like.

  The trivalent or tetravalent polycarboxylic acid may be used alone or in combination of two or more. Considering heat resistance, transparency, adhesion, solubility, cost, etc., pyromellitic dianhydride, trimellitic anhydride, ethylene glycol bisanhydro trimellitate, 3,3 ', 4,4 '-Benzophenone tetracarboxylic dianhydride and 3,3', 4,4'-biphenyltetracarboxylic dianhydride are preferable, and trimellitic anhydride and ethylene glycol bisahydrohydrotrimellitate are more preferable.

  Examples of the diamine that can be used as a raw material for the polyesterimide diol oligomer include aromatic diamines, aliphatic diamines, and alicyclic diamines.

  The aromatic diamine is not particularly limited, but p-phenylenediamine, m-phenylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene, 2,4-diaminoxylene, 2,4-diaminodurene, 4,4′-diaminodiphenylmethane, 4,4′-methylenebis (2-methylaniline), 4,4′-methylenebis (2-ethylaniline), 4,4′-methylenebis (2,6-dimethylaniline), 4 , 4′-methylenebis (2,6-diethylaniline), 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether, 2,4′-diaminodiphenyl ether, 4,4 ′ -Diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4 -Diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminobenzanilide, 4-aminophenyl-4'-aminobenzoate, 4-amino-2-methylphenyl-4'-aminobenzoate, bis (4 -Aminophenyl) terephthalate, bis (4-amino-2-methylphenyl) terephthalate, benzidine, 3,3'-dihydroxybenzidine, 3,3'-dimethoxybenzidine, o-tolidine, m-tolidine, 2,2'- Bis (trifluoromethyl) benzidine, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 4,4 '-Bis (4-aminophenoxy) biphenyl, bis (4- (3-aminophenoxy) ) Phenyl) sulfone, bis (4- (4-aminophenoxy) phenyl) sulfone, 2,2-bis (4- (4-aminophenoxy) phenyl) propane, 2,2-bis (4- (4-aminophenoxy) ) Phenyl) hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, p-terphenylenediamine, bis (4-aminophenyl) terephthalate, bis (4-amino-2-methylphenyl) terephthalate, Etc. Two or more of these may be used in combination.

  Examples of the aliphatic diamine and alicyclic diamine include, but are not limited to, for example, 4,4′-methylenebis (cyclohexylamine), isophorone diamine, trans-1,4-diaminocyclohexane, cis-1,4-diamino. Cyclohexane, 1,4-cyclohexanebis (methylamine), 2,5-bis (aminomethyl) bicyclo [2.2.1] heptane, 2,6-bis (aminomethyl) bicyclo [2.2.1] heptane 3,8-bis (aminomethyl) tricyclo [5.2.1.0] decane, 1,3-diaminoadamantane, 2,2-bis (4-aminocyclohexyl) propane, 2,2-bis (4- Aminocyclohexyl) hexafluoropropane, 1,3-propanediamine, 1,4-tetramethylenediamine, 1,5-pentamethene Diamine, 1,6-hexamethylene diamine, 1,7-heptamethylene diamine, 1,8-octamethylene diamine, 1,9-nonamethylenediamine, and the like. Two or more of these may be used in combination.

  Solvents used in the synthesis of the polyesterimide diol oligomer include amide solvents such as N-methyl-2-pyrrolidone, dimethylacetamide and dimethylformamide; sulfur solvents such as dimethyl sulfoxide and sulfolane; nitromethane, nitroethane and the like Nitrogen solvents such as diglyme and tetrahydrofuran; ketone solvents such as cyclohexanone and methyl ethyl ketone; nitrile solvents such as acetonitrile and propionitrile; and relatively dielectric constants such as γ-butyrolactone and tetramethylurea A high solvent etc. are mentioned, Preferably it is (gamma) -butyrolactone. These can be used alone or as a mixed solvent (for example, N-methyl-2-pyrrolidone and diglyme, etc.), and a solvent having a relatively low dielectric constant such as xylene or toluene may be used as a mixture. Absent. In addition, a diol compound may be used if the reaction temperature is appropriately set.

  The diol compound that can be used as a raw material for the polyesterimide diol oligomer is not particularly limited as long as it is a compound having hydroxyl groups at both ends. For example, ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 2,4-dimethyl-2-ethylhexane-1,3-diol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 2-methyl-1,3-propanediol, 2-ethyl-2 -Butyl-1,3-propanediol, 2-ethyl-2-isobutyl-1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6- Hexanediol, 3-methyl-1,5-pentanediol, 2,2,4-trimethyl-1,6 Hexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 1,9-nonane Diol, dimer diol, hydrogenated dimer diol, tricyclodecandiol, tricyclodecane dimethylol, spiroglycol, hydrogenated bisphenol A, hydrogenated bisphenol A ethylene oxide adduct and propylene oxide adduct Etc. The diol compound may be used as a solvent during the synthesis of the polyimide precursor oligomer.

Polyester resin of the present invention, the carbonate group-containing diol oligomer A ₂ is preferably a polycarbonate diol. Since the polycarbonate diol contains a plurality of carbonate groups, the polycarbonate diol is characterized by excellent heat resistance as compared with ether-based oligomers such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol. Also, carbonate group-containing segments based on the carbonate group-containing diol oligomer A ₂ becomes a moiety serves as a so-called soft segment, thereby contributing to such flexibility. Further, in order to lower the glass transition temperature of the carbonate group-containing diol oligomer A _2, it is preferable to use a polycarbonate diol which does not contain an aromatic ring.

Further, the carbonate group-containing diol oligomer A ₂ is preferably a phosphorus-containing polycarbonate diol. Since the phosphorus-containing polycarbonate diol contains a plurality of carbonate groups, the phosphorus-containing polycarbonate diol is characterized by excellent heat resistance as compared with ether-based oligomers such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol. Also, carbonate group-containing segments based on the carbonate group-containing diol oligomer A ₂ becomes a moiety serves as a so-called soft segment contributes to such flexibility, since it contains a phosphorus atom, contributes to flame retardance can do.

  The said polycarbonate diol can be manufactured by a well-known method, for example, can be obtained by transesterification of a diol compound and carbonate ester (carbonate).

  The mixing ratio of the diol compound and the carbonate (carbonate) can be obtained by charging the autoclave at a diol compound / carbonate (for example, diphenyl carbonate) = 100/80 to 100/98 (molar ratio). Since the number average molecular weight of the polycarbonate diol used in the present invention can be controlled by the transesterification reaction, this charging ratio is important for determining the molecular weight. Specifically, in the transesterification reaction, a catalyst is added, and the reaction temperature is preferably set to 180 ° C to 240 ° C under normal pressure or vacuum, and more preferably set to 190 ° C to 230 ° C. Then, by distilling phenol out of the reaction system, the polymerization reaction proceeds to obtain a polycarbonate diol having the desired number average molecular weight and having hydroxyl groups at both ends.

  In addition, it is preferable that the said diol compound and / or carbonate ester (carbonate) contain a phosphorus atom. In addition, as a method of introducing a phosphorus atom into a polyester resin, a method of copolymerizing a monomer having a phosphorus atom, a method of modifying, etc. can be mentioned, and in the molecule (regardless of main chain or side chain). It only has to be included.

  As the diol compound, an aliphatic diol or an alicyclic diol is preferably used, and examples thereof include linear and side chain diols having 2 to 10 carbon atoms. For example, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9 -Aliphatic diols such as nonanediol, 1,10-decanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 2-methyl-1,8-octanediol, 1,4-cyclohexanedimethanol, etc. And alicyclic diols. Among these diols, 1,6-hexanediol and 1,4-cyclohexanedimethanol, which are less volatile at high temperatures and under vacuum during polymerization of polycarbonate diol, are preferred.

  Further, as the diol compound, a phosphorus-containing diol compound containing a phosphorus atom can be used. Specifically, 2-phosphaphenanthrene-10-oxide-1,4-bis (2-hydroxyethoxy) benzene, 2-phosphaphenanthrene-10-oxide-1,4-bis (2- Hydroxyethoxy) benzene ethylene oxide adduct, n-butylbis (3-hydroxypropyl) phosphine oxide, and the like.

  Examples of the carbonate ester include alkylene carbonate, dialkyl carbonate, and diaryl carbonate. Examples of the alkylene carbonate include ethylene carbonate, trimethylene carbonate, 1,2-propylene carbonate, 1,2-butylene carbonate, 1,3-butylene carbonate, and 1,2-pentylene carbonate. Examples of the dialkyl carbonate include dimethyl carbonate, diethyl carbonate, and di-n-butyl carbonate, and examples of the dialkylene carbonate include diphenyl carbonate. Among these, diphenyl carbonate having a high boiling point and capable of reacting under high temperature conditions is particularly preferable.

  Moreover, a catalyst can be used when it is desired to speed up the reaction during the transesterification reaction. Examples of the catalyst include tin compounds such as di-n-butyltin dilaurate, di-n-butyltin oxide, and dibutyltin diacetate, tetra-n-propyl titanate, tetraisopropyl titanate, tetra-n-butyl titanate, tetraisobutyl titanate, tetra Examples thereof include titanium compounds such as -tert-butyl titanate, tetracyclohexyl titanate, tetraphenyl titanate, and tetrabenzyl titanate. There are metal salts of acetic acid such as magnesium acetate, calcium acetate, zinc acetate and lead acetate. Of these, titanium compounds and lead acetate are preferably used.

  The catalyst is preferably contained in an amount of 0.0001 to 0.1% by weight, more preferably 0.0001 to 0.05% by weight, based on the total charge of raw materials. In order to further accelerate the transesterification reaction, after the transesterification reaction in the autograve, it is possible to increase the molecular weight by maintaining the temperature at 190 to 230 ° C. and distilling alcohol or phenol out of the system in a vacuum. .

Polyester resin of the present invention, and the ester bond-containing diol oligomer A _1, and the carbonate group-containing diol oligomer A _2, obtained by reacting an acid dianhydride. Here, the acid dianhydride is not particularly limited, and examples thereof include the tetracarboxylic dianhydride. Specifically, pyromellitic dianhydride, oxydiphthalic dianhydride, 1, 2 , 4,5-benzenetetracarboxylic dianhydride, 1,2,3,4-pentanetetracarboxylic dianhydride, 5- (2,5-dioxotetrahydrofurfuryl) -3-methyl-3-cyclohexene -1,2-dicarboxylic dianhydride, 5- (2,5-dioxotetrahydrofurfuryl) -3-cyclohexene-1,2-dicarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, ethylene glycol Bistrimellitate dianhydride, 2,2 ', 3,3'-diphenyltetracarboxylic dianhydride, thiophene-2,3,4,5-tetracarboxylic dianhydride, 3,3', 4,4 ' -Benzo Enone tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4-biphenyltetracarboxylic dianhydride, 2,3,6 7-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,2′-bis (3 , 4-Dicarboxyphenyl) propane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, perylene-3,4,9,10-tetracarboxylic dianhydride, bis (3,4- Dicarboxyphenyl) ether dianhydride, ethylenetetracarboxylic dianhydride and the like. In addition, these compounds may be used independently and may mix and use 2 or more types. Particularly preferred are pyromellitic dianhydride (PMDA) and oxydiphthalic dianhydride (ODPA).

The ester group-containing diol oligomer A ₁ , the carbonate group-containing diol oligomer A ₂ and an acid dianhydride are reacted to form a hard segment and a soft segment in the main chain, and further a carboxyl group based on an acid dianhydride. Or the polyester resin which has an ester bond and a carbonate group can be manufactured. Specifically, a ring-opening reaction of the acid dianhydride proceeds by reacting the hydroxyl group in the ester bond-containing diol oligomer A ₁ and the carbonate group-containing diol oligomer A ₂ with an acid dianhydride, On the other hand, an ester bond can be formed, and on the other hand, two carboxyl groups (residual carboxyl groups) can be formed in the main chain of the polyester resin. The presence of this carboxyl group can impart alkali solubility to the polyester resin.

In the polyester resin C of the present invention, the molar ratio of the ester bond-containing diol oligomer A ₁ to the carbonate group-containing diol oligomer A ₂ (hereinafter sometimes referred to as A ₁ / A ₂ ) is 1/9 to 9 / 1. A ₁ / A ₂ is preferably 2/8 to 8/2, more preferably 3/7 to 7/3, and still more preferably 4/6 to 6/4. When the ratio of the ester bond-containing diol oligomer A ₁ is too high, the content of the carbonate group-containing diol oligomer A ₂ that is a flexible component becomes too low, and the flexibility and warpage tend to be inferior. On the contrary, when the ratio of carbonate groups-containing diol oligomer A ₂ is too high, there is a tendency that the solder heat resistance is poor.

In order to carry out a chain extension reaction between the acid dianhydride, the oligomer A ₁ having a hydroxyl group, and the oligomer A ₂ , the amount of the acid dianhydride is important in controlling the molecular weight of the polyester resin C. It is. Residual carboxyl group-containing segment B / (Oligomer A ₁ + Oligomer A ₂ ) molar ratio based on acid dianhydride (hereinafter sometimes referred to as B / (A ₁ + A ₂ )) = 65 / 100˜ Polymerization can be performed in the range of 98/100 or 135/100 to 102/100. B / (A ₁ + A ₂ ) is preferably 65/100 to 95/100, or 135/100 to 105/100, and is 65/100 to 90/100 or 135/100 to 110/100. Is more preferable, and 65/100 to 85/100 or 135/100 to 115/100 is more preferable. When B / (A ₁ + A ₂ ) is less than 65/100 or greater than 135/100, the molecular weight of the polyester resin does not increase, and the physical and chemical strength and durability of the coating film are increased. There is a tendency not to secure. Conversely, if B / (A ₁ + A ₂ ) exceeds 98/100 and is less than 102/100, the molecular weight of the polyester resin becomes too high, the solubility in alkali tends to be low, and the alkali developability tends to be lowered. .

And the terminal hydroxyl group of the oligomer A ₁ and the oligomer A _2, by acid dianhydride are reacted, the acid dianhydride is ring-opened to produce a carboxyl group, by the reaction, and the hard segment, Residual carboxyl group-containing segment B based on the soft segment and acid dianhydride is formed. Note that the hard segment based on the ester bond-containing diol oligomer A _1, of the soft segment based on the carbonate group-containing diol oligomer A _2, coupled to the remaining carboxyl group-containing segment B, may be linked to alternately However, they may be combined randomly.

  The number average molecular weight of the polyester resin C is 2000 to 10000, preferably 2500 to 9000, and more preferably 3000 to 8500. If the number average molecular weight is less than 2,000, the physical and chemical strength and durability of the coating film tend not to be secured. On the other hand, if the number average molecular weight exceeds 10,000, the molecular weight of the polyester resin becomes too high and the solubility in alkali is high. The alkali developability tends to decrease.

Specifically, in the chain extension reaction, a solvent, an ester bond-containing diol oligomer A ₁ , a carbonate group-containing diol oligomer A ₂ and a catalyst are dissolved in a reaction vessel equipped with a stirrer and a thermometer. An anhydride is added to conduct the polymerization reaction. By setting the polymerization temperature to 60 to 100 ° C. and the polymerization time to 2 to 10 hours, a polyester resin having a predetermined molecular weight can be obtained.

  Examples of the reaction catalyst used in the production of the polyester resin C include amines such as triethylamine and benzyldimethylamine; quaternary ammonium salts such as tetramethylammonium chloride and triethylbenzylammonium chloride; imidazoles such as 2-ethyl 4-imidazole. Amides; pyridines such as 4-dimethylaminopyridine; phosphines such as triphenylphosphine; phosphonium salts such as tetraphenylphosphonium bromide; sulfonium salts; sulfonic acids; organometallic salts such as zinc octylate Are more preferably amines, pyridines, and phosphines.

  Further, in the present invention, the polyester resin C contains a phosphorus atom, and the phosphorus atom content (as a solid content ratio of the polyester resin) is 0.5 to 7% by weight, preferably 1 to 6% by weight. %, More preferably 2 to 5% by weight. When the amount is less than 0.5% by weight, the flame retardancy cannot be sufficiently exhibited. For example, even when a large amount of a flame retardant is added, it is difficult to obtain the flame retardancy. If it exceeds%, the heat resistance and the like tend to deteriorate, which is not preferable. In addition, since the phosphorus skeleton is contained in the resin skeleton, it is effective in that flame retardancy is obtained even if the phosphorus content is set lower than in the case where only the phosphorus-based flame retardant is added.

<Modified polyester resin>
The modified polyester resin D of the present invention is obtained by reacting the residual carboxyl group in the polyester resin C before the modification with a (meth) acrylic monomer having a functional group that reacts with the residual carboxyl group. Can be manufactured. At this time, it is preferable that a part of the carboxyl group remains in the main chain of the modified polyester resin D, and it is preferable that the side chain has an ethylenically unsaturated double bond. Alkali solubility can be imparted when a carboxyl group partially remains in the main chain, and photocurability can be imparted by having a double bond in the side chain. In the present invention, (meth) acryl means either an acryl group or a methacryl group.

Moreover, it is preferable that the acid value of the modified polyester resin D of this invention is 350-2000 equivalent / 10 < ⁶ > g, More preferably, it is 400-1500 equivalent / 10 < ⁶ > g, More preferably, it is 400-1000 equivalent / 10 ⁶ g. If it is less than 350 equivalents / 10 ⁶ g, the solubility in an alkali developer is insufficient, and development is impossible, and if it exceeds 2000 equivalents / 10 ⁶ g, the photocured part swells in the alkali developer. However, there is a problem that the adhesiveness becomes poor and peels off from the substrate at the time of development, which is not preferable. The acid value is derived from a carboxyl group (corresponding to a carboxyl group equivalent).

  Moreover, it is preferable that the number average molecular weights of the modified polyester resin D of this invention are 2500-10000, More preferably, it is 2500-8000, More preferably, it is 2500-7000. If it is less than 2500, the photocured portion swells in the alkaline developer, resulting in poor adhesion, and peeling from the substrate during development makes development impossible. On the other hand, if it exceeds 10,000, the solubility in an alkali developer becomes insufficient, and development becomes impossible, which is not preferable.

Moreover, the modified polyester resin D of the present invention preferably has a carboxyl group and an ester bond in the main chain, and the carboxyl group is preferably 350 to 2000 equivalents / 10 ⁶ g (acid value). Preferably, it is 400-1500 equivalent / 10 < ⁶ > g. When the said carboxyl group is smaller than the said range, it exists in the tendency for a crosslinking property and alkali developability to worsen. On the other hand, if the carboxyl group exceeds the above range, problems such as a decrease in alkali resistance of the cured film (curable layer) and a decrease in electrical characteristics occur, which is not preferable.

  The acid value in this invention is calculated | required by melt | dissolving a polyester resin in chloroform and titrating with a 0.1N potassium hydroxide ethanol solution.

  The (meth) acrylic monomer having a functional group that reacts with the carboxyl group is not particularly limited as long as it has a functional group that can react with the carboxyl group remaining in the polyester resin C before modification. A (meth) acrylic monomer containing a glycidyl group or a hydroxyl group is preferred. Specific examples include 3,4-epoxycyclohexyl (meth) acrylate, 4-hydroxybutyl acrylate glycidyl ether, glycidyl (meth) acrylate, and the like, and particularly preferably an acrylic monomer from the viewpoint of reactivity (sensitivity). 4-hydroxybutyl acrylate glycidyl ether.

  Moreover, as said (meth) acrylic-type monomer, what contains a phosphorus atom can also be used. Specific examples of the (meth) acrylic monomer containing a phosphorus atom include triacryloyloxyethyl phosphate, 4,4′-bis (N, N, N ′, N′-tetraallyldiaminophosphoryl) bisphenol. 4,4′-bis (N, N, N ′, N′-tetraallyldiaminophosphoryl) biphenyl and the like.

  The blending amount of the (meth) acrylic monomer having a functional group that reacts with the carboxyl group is preferably 20 to 80 equivalent%, more preferably 30% with respect to the residual carboxyl group in the polyester resin C. -70 equivalent%. If the blending amount of the (meth) acrylic monomer is less than the above range, the photocurability is insufficient and the developability is deteriorated. On the other hand, when the amount exceeds the above range, the amount of carboxyl groups contributing to alkali solubility is small, resulting in poor development.

In addition, the ethylenically unsaturated double bond in the photocurable / thermosetting resin obtained by the photocurable / thermosetting resin composition of the present invention is 500 to 2000 equivalent / 10 ⁶ g in the side chain of the resin. It is preferable to have, More preferably, it is 600-1500 equivalent / 10 < ⁶ > g. When the amount is less than the above range, the photocurability becomes insufficient. When the range is exceeded, the crosslink density becomes high, and when the coating film is formed on one side of the substrate, the warpage is large. The problem of becoming may arise. Photocurability can be imparted by introducing the double bond into the molecule. In addition, the said range is a value obtained by the segment of equivalent / 10 < ⁶ > g by dividing the compounding equivalent of the said (meth) acrylic-type monomer by the weight of a polyester resin.

  The modified polyester resin D of the present invention is obtained by a reaction between a residual carboxyl group in the polyester resin C before modification and a (meth) acrylic monomer having a functional group that reacts with the carboxyl group, and is not particularly limited. For example, in a reaction vessel equipped with a stirrer and a thermometer, a reaction catalyst and a radical polymerization inhibitor are appropriately added to the polyester resin dissolved in a solvent, and after confirming that a uniform solution is obtained, a predetermined amount The (meth) acrylic monomer is added. The progress of the reaction and the end point can be determined by measuring the carboxyl group (acid value) of the modified polyester resin at a polymerization temperature of 60 to 100 ° C. and a polymerization time of 4 to 12 hours. If the polymerization temperature is too high or the polymerization time is too long, gelation may occur. Therefore, the preferable polymerization temperature is 65 to 90 ° C., and the preferable polymerization time is 4 to 10 hours.

  As the catalyst used for the production of the modified polyester resin D, a catalyst equivalent to that for the production of the polyester resin C before the modification can be used. In particular, it is preferable to use phosphines such as triphenylphosphine. is there.

  As said catalyst, 0.01-2 weight% is normally contained as a solid content ratio in a photocurable thermosetting resin composition, Preferably it is 0.05-0.5 weight%. If the amount of the catalyst added is less than 0.01% by weight, the catalytic effect tends to be insufficient, which is not preferable. On the other hand, if it exceeds 2% by weight, adhesion failure with the substrate may occur, which is not preferable.

  Examples of the radical polymerization inhibitor include p-benzoquinone, naphthoquinone, phenanthraquinone, p-xyloquinone, p-toluquinone, 2,6-dichloroquinone, 2,5-diphenyl-p-benzoquinone, 2,5- Quinones such as diacetoxy-p-benzoquinone; hydroquinone, pt-butylcatechol, 2,5-di-t-butylhydroquinone; hydroquinones such as mono-t-butylhydroquinone and hydroquinone monomethyl ether; di-t-butyl Phenols such as paracresol; amidines such as acetamidine acetate and acetamidine sulfate; hydrazines such as phenylhydrazine hydrochloride and hydrazine hydrochloride; trimethylbenzylammonium chloride, trimethylbenzylammonium chloride, laur Thiazine such as phenothiazine; Lupi lysine chloride, quaternary ammonium salts such as trimethylbenzylammonium oxalate The rate quinone dioxime can be used oximes such as cyclohexanone oxime.

  The radical polymerization inhibitor is usually contained in the photocurable / thermosetting resin composition in a solid content ratio of 0.01 to 0.5% by weight, preferably 0.02 to 0.2% by weight. . When the addition amount of the polymerization inhibitor is less than 0.01% by weight, the effect of the polymerization inhibitor is insufficient, and gelation may occur during the reaction and storage, which is not preferable. On the other hand, if it exceeds 0.5% by weight, it is difficult to obtain sufficient photosensitivity during the photocuring process, which causes deterioration of developability, which is not preferable.

<Photocurable / thermosetting resin composition>
The photocurable / thermosetting resin composition of the present invention contains the modified polyester resin D, the (meth) acrylic monomer E, and the epoxy resin F, and the (( It is preferable that 5-30 parts by weight of the (meth) acrylic monomer E and 5-50 parts by weight of the epoxy resin F are contained.

  The (meth) acrylic monomer E (hereinafter sometimes referred to as E component) is used as a reactive diluent, and is not particularly limited. Are preferably used. For example, ethylene glycol (meth) acrylate, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, Polypropylene glycol di (meth) acrylate, hexane di (meth) acrylate, neopentyl glycol di (meth) acrylate, glycerin di (meth) acrylate, glycerin tri (meth) acrylate, glycerin tetra (meth) Chlorate, tetratrimethylolpropane tri (meth) acrylate, 1,4-butanediol diacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, tris (acryloxyethyl) isocyanurate, pentaerythritol (meth) acrylate, dipenta Examples include erythritol hexa (meth) acrylate, carbitol (meth) acrylate, and phenoxyethyl (meth) acrylate. These (meth) acrylic monomers may be used alone or in combination of two or more.

  The said (meth) acrylic-type monomer E (E component) is 5-30 weight part normally as solid content ratio with respect to 100 weight part of modified polyester resins D, Preferably it is 7-25 weight part, More preferably, it is 10-20. Contained in parts by weight. When the addition amount of the (meth) acrylic monomer E is less than 5 parts by weight, the curing reaction does not proceed, and the remaining film ratio, heat resistance, chemical resistance and the like tend to decrease. Further, when the added amount exceeds 30 parts by weight, the solubility in the base resin reaches saturation, and, for example, crystals of the polymerization initiator to be used are precipitated during spin coating or coating leveling. May not be able to be retained, and there is a risk of film failure.

  Examples of the epoxy resin F (hereinafter sometimes referred to as F component) used in the present invention include, for example, bisphenol A type epoxy resins such as trade names jER828 and 1001 manufactured by Japan Epoxy Resins Co., Ltd., manufactured by Toto Kasei Co., Ltd. Hydrogenated bisphenol A type epoxy resins such as ST-2004 and 2007, bisphenol F type epoxy resins such as YDF-170 and 2004 made by Toto Kasei Co., Ltd., and YDB made by Toto Kasei Co., Ltd. -Brominated bisphenol A type epoxy resins such as -400, 600, brand name Epicoat 152, 154 manufactured by Yuka Shell Epoxy Co., Ltd., brand name EPPN-201 manufactured by Nippon Kayaku Co., Ltd., BREN, manufactured by Dow Chemical Product name DEN-438 phenol novolac type epoxy resin, Toto Kasei Co., Ltd. product name YDCN-702, 703, Nippon Kayaku ( Product name EOCN-125S, 103S, 104S, etc. o-cresol novolac type epoxy resin, Toto Kasei Co., Ltd. product name YD-171, etc., flexible epoxy resin, Yuka Shell Epoxy Co., Ltd. Product name Epon1031S, product name Araldite 0163 manufactured by Ciba Specialty Chemicals Co., Ltd., product name Denacol EX-611, EX-614, EX-622, EX-512, EX-521 manufactured by Nagase Chemtech Co., Ltd. , EX-421, EX-411, EX-321 and other polyfunctional epoxy resins, Yuka Shell Epoxy Co., Ltd. trade name Epicoat 604, Toto Kasei Co., Ltd. trade name YH-434, Mitsubishi Gas Chemical ( Amine types such as trade names TETRAD-X, TETRAD-C, trade name GAN, manufactured by Nippon Kayaku Co., Ltd., trade name ELM-120, manufactured by Sumitomo Chemical Co., Ltd. Poxy resin, heterocycle-containing epoxy resin such as trade name Araldite PT810 manufactured by Ciba Specialty Chemicals Co., Ltd., alicyclic such as product name Celoxide 2021, EHPE3150 manufactured by Daicel Chemical Industries, Ltd., ERL4234 manufactured by UCC, etc. Epoxy resins, bisphenol S-type epoxy resins such as Epicron EXA-1514 manufactured by Dainippon Ink & Chemicals, Inc., triglycidyl isocyanurates such as TEPIC manufactured by Nissan Chemical Industries, and Yuka Shell Epoxy Co., Ltd. Bixylenol type epoxy resin such as YX-4000 manufactured by KK, and bisphenol type epoxy resin such as YL-6056 manufactured by Yuka Shell Epoxy Co., Ltd. may be used alone or in combination of two or more. You may use.

  Among the epoxy resins, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin having more than two epoxy groups in one molecule, o-cresol novolac type epoxy resin, amine type epoxy resin are: It is a non-halogen epoxy resin, and is preferable in terms of compatibility with the modified polyester resin D, solvent resistance, chemical resistance, and moisture resistance.

  The amount of the epoxy resin F (component F) used in the present invention is preferably 5 to 50 parts by weight, more preferably 10 to 40 parts by weight, and particularly preferably 15 to 30 parts by weight with respect to 100 parts by weight of the modified polyester resin D. Part. If the amount of the epoxy resin is less than 5 parts by weight, the solder heat resistance, solvent resistance, and chemical resistance tend to decrease. If the amount exceeds 50 parts by weight, low warpage, mechanical properties, heat resistance, and modified polyester resin. The compatibility with D tends to decrease.

  The epoxy resin F (F component) used in the present invention may further contain an epoxy compound having only one epoxy group in one molecule as a diluent.

  As a method for adding the epoxy resin, the epoxy resin may be dissolved in the same solvent as the solvent contained in the modified polyester resin D, or may be added directly to the modified polyester resin D. .

  In order to further improve properties such as adhesion, chemical resistance, heat resistance, etc., an epoxy curing accelerator (thermosetting accelerator) is added to the photocurable / thermosetting resin composition of the present invention. Also good. The curing accelerator used in the present invention is not particularly limited as long as it can accelerate the curing reaction between the modified polyester resin D and the epoxy resin.

Specific examples of the epoxy curing accelerator, for example, Shikoku Chemicals _{Corp., 2MZ, 2E4MZ, C 11 Z} , C 17 Z, 2PZ, 1B2MZ, 2MZ-CN, 2E4MZ-CN, C 11 Z-CN , 2PZ-CN, 2PHZ-CN , 2MZ-CNS, 2E4MZ-CNS, 2PZ-CNS, 2MZ-AZINE, 2E4MZ-AZINE, C 11 Z -AZINE, 2MA-OK, 2P4MHZ, 2PHZ, imidazole derivatives such 2P4BHZ, aceto Guanamines such as guanamine and benzoguanamine, diaminodiphenylmethane, m-phenylenediamine, m-xylenediamine, diaminodiphenylsulfone, dicyandiamide, urea, urea derivatives, polyamines such as melamine and polybasic hydrazide, organic acid salts thereof and / or Epoxy Ducts, amine complexes of boron trifluoride, triazine derivatives such as ethyldiamino-S-triazine, 2,4-diamino-S-triazine, 2,4-diamino-6-xylyl-S-triazine, trimethylamine, triethanol Amine, N, N-dimethyloctylamine, N-benzyldimethylamine, pyridine, N-methylmorpholine, hexa (N-methyl) melamine, 2,4,6-tris (dimethylaminophenol), tetramethylguanidine, DBU ( 1,8-diazabicyclo [5,4,0] -7-undecene), tertiary amines such as DBN (1,5-diazabicyclo [4,3,0] -5-nonene), organic acid salts thereof and // Tetraphenylborate, polyvinylphenol, polyvinylphenol bromide, tributylphosphite , Quaternary compounds such as triphosphine, tris-2-cyanoethylphosphine, organic phosphines, tri-n-butyl (2,5-dihydroxyphenyl) phosphonium bromide, hexadecyltributylphosphonium chloride, tetraphenylphosphonium tetraphenylborate Quaternary ammonium salts such as phosphonium salts, benzyltrimethylammonium chloride, phenyltributylammonium chloride, trimellitic anhydride, pyromellitic dianhydride, aromatic polycarboxylic acid anhydrides such as ethylene glycol bisanhydro trimellitate, Aliphatic polycarboxylic anhydrides such as butane-1,2,3,4-tetracarboxylic dianhydride, hexahydropyromellitic dianhydride, bicyclo [2.2.1] heptane-2,3,5 Alicyclic polycarboxylic acid anhydrides such as 6-tetracarboxylic dianhydride, diphenyliodonium tetrafluoroborate, triphenylsulfonium hexafluoroantimonate, 2,4,6-triphenylthiopyrylium hexafluorophosphate, Irgacure 261 (manufactured by Ciba Specialty Chemicals Co., Ltd.), photocation polymerization catalyst such as Optoma-SP-170 (manufactured by ADEKA Co., Ltd.), styrene-maleic anhydride resin, equimolar reaction product of phenyl isocyanate and dimethylamine, And an equimolar reaction product of organic polyisocyanate such as tolylene diisocyanate and isophorone diisocyanate and dimethylamine. You may use these individually or in combination of 2 or more types. Preferably, a curing accelerator having excellent liquid or solvent solubility at room temperature is used. For example, tertiary amines such as trimethylamine, triethanolamine, DBU, DBN and their organic acid salts, tributylphosphine, triphenylphosphine, etc. These organic phosphophones can be preferably used.

  As for the compounding quantity of the said epoxy hardening accelerator, 0-30 mass parts is preferable with respect to 100 mass parts of said epoxy resins. When it exceeds 30 parts by mass, mechanical properties such as heat resistance, flexibility and low warpage of the cured coating film are deteriorated, which is not preferable.

  In addition to the modified polyester resin D, the (meth) acrylic monomer E, and the epoxy resin F, the photocurable / thermosetting resin composition of the present invention can contain a polymerization initiator. Although it does not specifically limit as said polymerization initiator, The photoradical polymerization initiator etc. which generate | occur | produce a radical by irradiation of ultraviolet rays, ionizing radiation, visible light, or each other wavelength, especially an active energy ray below 365 nm are used. be able to.

  Examples of the photo radical polymerization initiator include compounds that generate free radicals by the energy of ultraviolet rays, and derivatives such as benzophenone derivatives such as benzoin and benzophenone or esters thereof; xanthone and thioxanthone derivatives; chlorosulfonyl, chloromethyl Halogenated compounds such as polynuclear aromatic compounds, chloromethyl heterocyclic compounds, chloromethylbenzophenones; triazines; fluorenones; haloalkanes; redox couples of photoreducing dyes and reducing agents; organic sulfur compounds; There are things. Preferably, IRGACURE 184, IRGACURE 369, IRGACURE 651, IRGACURE 907 (Ciba Specialty Chemicals), DaroCure (Merck), Adeka 1717 (Asahi Denka Kogyo Co., Ltd.), 2, 2 Examples include ketone-based and biimidazole-based compounds such as' -bis (o-chlorophenyl) -4,5,4'-tetraphenyl-1,2'-biimidazole (manufactured by Kurokin Kasei Co., Ltd.). These initiators can be used alone or in combination of two or more.

  The radical photopolymerization initiator is usually contained in the photocurable / thermosetting resin composition in a solid content ratio of 0.1 to 5% by weight, preferably 0.2 to 2% by weight. When the addition amount of the polymerization initiator is less than 0.1% by weight, the curing reaction does not proceed and the remaining film ratio, heat resistance, chemical resistance and the like tend to decrease. Moreover, when this addition amount exceeds 5 weight%, there exists a possibility that the malfunction that the contact | adherence defect with a base material and solder heat resistance may deteriorate may arise.

  A thermal radical polymerization initiator may be used in combination as a polymerization initiator other than the photo radical polymerization initiator. You may use the thermal radical initiator which does not react at the temperature which dries a photocurable thermosetting resin composition, and generate | occur | produces a thermal radical at the temperature at the time of thermosetting. Examples thereof include 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide hydroperoxides, and dialkyl peroxides.

  In preparing the photocurable / thermosetting resin composition, the photoinitiator such as the photoradical polymerization initiator or the thermoradical polymerization initiator is the photocurable / thermosetting resin composition according to the present invention. It may be added to the product from the beginning, but when stored for a relatively long period of time, it is preferably dispersed or dissolved in the photocurable / thermosetting resin composition immediately before use.

  By reacting the modified polyester resin D with a (meth) acrylic monomer E, an epoxy resin F, and a photocurable / thermosetting resin composition containing a radical photopolymerization initiator, specifically, When light irradiation is performed in the presence of a photo-radical polymerization initiator, radicals are generated, a crosslinking reaction occurs, a rapid curing reaction is promoted, sensitivity is improved, and energy efficiency is improved, so that a photo-curing reaction can be performed in a short time. Is completed. Thereby, workability | operativity can be improved.

  Furthermore, the photocurable / thermosetting resin composition of the present invention preferably contains a flame retardant. By adding a flame retardant, flame retardancy can be improved, which is effective. The flame retardant is not particularly limited, and examples thereof include triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, triethyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, cresyl bis (2 , 6-Xylenyl) phosphate, 2-ethylhexyl phosphate, dimethylmethyl phosphate, resorcinol bis (diphenyl) phosphate, bisphenol A bis (diphenyl) phosphate, bisphenol A bis (dicresyl) phosphate, diethyl-N, N -Phosphorus flame retardants such as bis (2-hydroxyethyl) aminomethyl phosphate, phosphoric acid amide, organic phosphine oxide, red phosphorus, ammonium polyphosphate, phosphatase , Cyclophosphazene, 9,10-dihydro-9-oxa-10-phosphahenanthrene-10-oxide, 9,10-dihydro-9-oxa-10-phosphahenanthrene-10-oxide derivative, triazine , Melamine cyanurate, succinoguanamine, ethylene dimelamine, triguanamine, cyanuric acid triazinyl salt, melem, melam, tris (β-cyanoethyl) isocyanurate, acetoguanamine, guanylmelamine sulfate, melem sulfate, melam sulfate, etc. Flame retardant, metal salt flame retardant such as potassium diphenylsulfone-3-sulfonate, aromatic sulfonimide metal salt, alkali metal polystyrene sulfonate, aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, barium hydroxide , Hydrated metal flame retardants such as basic magnesium carbonate, zirconium hydroxide, tin oxide, silica, aluminum oxide, iron oxide, titanium oxide, manganese oxide, magnesium oxide, zirconium oxide, zinc oxide, molybdenum oxide, cobalt oxide, oxidation Bismuth, chromium oxide, tin oxide, antimony oxide, nickel oxide, copper oxide, tungsten oxide, zinc borate, zinc metaborate, barium metaborate, zinc carbonate, magnesium carbonate, calcium carbonate, barium carbonate, zinc stannate, etc. Silicone flame retardants such as flame retardant and silicone powder. These flame retardants may be used alone or in combination of two or more. In particular, phosphorus-based flame retardants are preferable because they are easily available and can easily impart flame retardancy. More preferred are phosphazene and phosphinic acid derivatives in terms of hydrolysis resistance, heat resistance and surface bleeding. You may use these individually or in combination of 2 or more types.

  Examples of the phosphazenes include, for example, cyclic phenoxyphosphazenes such as trade name SPE-100 manufactured by Otsuka Chemical Co., Ltd., cyclic cyanophenoxyphosphazenes such as trade name FP-300 manufactured by Fushimi Pharmaceutical Co., Ltd., and Otsuka Chemical Co., Ltd. Cyclic hydroxyphenoxyphosphazenes such as trade name SPH-100 manufactured by the manufacturer, chain phenoxyphosphazenes, cross-linked phenoxyphosphazenes, etc. are mentioned, but since chain phosphazenes have a substituent at the molecular end, they are generally compared to cyclic phosphazenes. Phosphorus content decreases. Accordingly, in the present invention, cyclic phosphazenes are preferable, and cyclic trimers and / or tetrameric phosphazenes are more preferable.

  In addition, non-reactive phosphazenes may cause bleeding on the surface over time, elute free phosphorus under the influence of hydrolysis under severe use conditions, or the insulating properties may be degraded by decomposition products. Therefore, most preferably, a reactive phosphazene having a functional group that reacts with the epoxy resin is selected. Specific examples thereof include cyclic hydroxyphenoxyphosphazene having a hydroxyl group.

  Examples of the phosphinic acid derivative include HCA (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) and HCA-HQ (10- (2,5-dihydroxy) from Sanko Co., Ltd. Phenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide), 10- (2,5-dihydroxynaphthyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide , BCA (10-benzyl-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide), phenylphosphinic acid, diphenylphosphinic acid and the like. Among the phosphinic acid derivatives, HCA and HCA-HQ have reactivity with epoxy resins, but may cause bleed on the surface or may be inferior in solubility in non-nitrogen solvents, so performance such as low warpage is also considered. And select as appropriate.

  In addition to the above non-halogen flame retardants, other non-halogen flame retardants may be used in combination as required as long as the low warpage, heat resistance, and bleeding are not impaired. Examples include phosphorus-containing epoxy resins copolymerized with HCA and condensed phosphate esters such as resorcyl diphenyl phosphate, but are not limited to these, and two or more types may be used in combination.

  In the photocurable / thermosetting resin composition of the present invention, the phosphorus atom content is 0.1-7 wt% of phosphorus atoms as the solid content ratio of the photocurable / thermosetting resin composition. It is preferably 0.5 to 5% by weight, more preferably 0.9 to 4% by weight. If it is less than 0.1% by weight, the flame retardancy is lowered. On the other hand, if it exceeds 7% by weight, alkali developability, flexibility, solder heat resistance and the like are deteriorated, which is not preferable.

  The solvent used in the present invention is not particularly limited, but has good solubility in compounding components such as polyester resin C, modified polyester resin D, photocurable / thermosetting resin composition, polymerization initiator, and boiling point. A relatively high solvent can be used. For example, alcohol solvents such as methyl alcohol, ethyl alcohol, N-propyl alcohol and isopropyl alcohol; cellosolv solvents such as methoxy alcohol and ethoxy alcohol; carbitol solvents such as methoxy ethoxy ethanol and ethoxy ethoxy ethanol; ethyl acetate and acetic acid Ester solvents such as butyl, methyl methoxypropionate, ethyl ethoxypropionate, ethyl lactate; ketone solvents such as acetone, methyl isobutyl ketone, cyclohexanone, cyclopentanone; methoxyethyl acetate, ethoxyethyl acetate, ethyl cellosolve acetate, etc. Cellosolve acetate solvents; carbitol acetate solvents such as methoxyethoxyethyl acetate and ethoxyethoxyethyl acetate Ether solvents such as diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether and tetrahydrofuran; aprotic amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone; lactones such as γ-butyrolactone; Examples of the solvent include organic solvents such as unsaturated hydrocarbon solvents such as benzene, toluene, xylene, and naphthalene; saturated hydrocarbon solvents such as N-heptane, N-hexane, and N-octane. As the solvent, for example, when an ink or an adhesive is produced, it is preferable to use a solvent having a relatively high boiling point.

  In addition to the above-described components, the photocurable / thermosetting resin composition of the present invention may include a surfactant, a silane coupling agent, a pigment, a colorant, a filler (filler), and an antifoaming agent. Various additives such as can be blended.

<Ink etc.>
By using the photocurable / thermosetting resin composition of the present invention, an ink, an adhesive, or the like can be obtained. The photocurable / thermosetting resin composition can be cured by applying light to a necessary part by using a light-shielding pattern mask, and has high accuracy and excellent workability. .

  For example, when manufacturing ink (photosensitive solder resist ink) using the photocurable / thermosetting resin composition, in order to improve workability during coating and printing and film properties before and after film formation, It is a preferred embodiment that an inorganic or organic filler is added.

  The inorganic or organic filler is not particularly limited as long as it can be dispersed in the above-described photocurable / thermosetting resin composition to form a paste and can impart thixotropy to the paste.

Examples of the inorganic filler include silica (SiO ₂ ), alumina (Al ₂ O ₃ ), titania (TiO ₂ ), tantalum oxide (Ta ₂ O ₅ ), zirconia (ZrO ₂ ), silicon nitride (Si ₃ N _4). ), Barium titanate (BaO · TiO ₂ ), barium carbonate (BaCO ₃ ), lead titanate (PbO · TiO ₂ ), lead zirconate titanate (PZT), lead lanthanum zirconate titanate (PLZT), gallium oxide (Ga ₂ O ₃ ), spinel (MgO.Al ₂ O ₃ ), mullite (3Al ₂ O ₃ .2SiO ₂ ), cordierite (2MgO.2Al ₂ O ₃ .5SiO ₂ ), talc (3MgO.4SiO _2. H ₂ O), aluminum titanate _{(TiO 2 -Al 2 O 3)} , yttria-containing zirconia _{(Y 2 O 3 -ZrO 2)} , silicate barium (BaO · 8SiO ₂ , Boron nitride (BN), calcium carbonate (CaCO _3), calcium sulfate (CaSO _4), zinc oxide (ZnO), magnesium titanate (MgO · TiO _2), barium sulfate (BaSO _4), organic bentonite, carbon (C ) Etc., and these may be used alone or in combination of two or more. From the viewpoint of imparting color tone, transparency, mechanical properties and thixotropy of the obtained paste, silica fine particles (product name Aerogel, manufactured by Nippon Aerosil Co., Ltd.) are preferred.

  The average particle size of the inorganic filler is preferably 20 μm or less, and the maximum particle size is preferably 40 μm or less. More preferably, the average particle size is 10 μm or less, and still more preferably the average particle size is 5 μm or less. When the average particle diameter exceeds 20 μm, it becomes difficult to obtain a paste having sufficient thixotropy, and the flexibility of the coating film is lowered. When the maximum particle diameter exceeds 40 μm, the appearance and adhesion of the coating film tend to be insufficient.

  The organic filler is not particularly limited as long as it can disperse in the above-mentioned photocurable / thermosetting resin composition solution to form a paste, and can impart thixotropic properties to the paste. Polyimide resin particles, benzoguanamine Examples thereof include resin particles and epoxy resin particles.

  The amount of the inorganic or organic filler used is preferably 1 to 25% by mass, more preferably 2 when the total nonvolatile content of the paste of the photocurable / thermosetting resin composition is 100% by mass. -15% by mass, more preferably 3-12% by mass. If the blending amount of the inorganic or organic filler is less than 1% by mass, the printability tends to decrease, and if it exceeds 25% by mass, the mechanical properties such as the flexibility of the coating film and the transparency tend to decrease.

  Further, the photocurable / thermosetting resin composition of the present invention, and further the ink (photosensitive solder ink) obtained by using the composition may contain a colorant, if necessary. Examples of the colorant include known and commonly used colorants such as phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, crystal violet, titanium oxide, carbon black, and naphthalene black.

  The photocurable / thermosetting resin composition of the present invention can be prepared in the form of a solution, and as a liquid coating composition, it can be applied and immersed in a substrate or the like to produce an adhesive, a sheet, a film, or the like. it can. Specifically, it can be applied on a substrate or a support using a general method including screen printing, flow coating, roller coating, slot coating, spin coating, curtain coating, spray coating, and dip coating. . After coating on the substrate or support, the liquid coating layer is dried to remove the solvent.

  The photosensitive layer can be obtained by, for example, applying the photocurable / thermosetting resin composition of the present invention on a support and then drying. As the support, a polymer film can be used. Specifically, a film made of polyethylene terephthalate, polypropylene, polyethylene or the like is used. Among these, a particularly preferable film is polyethylene terephthalate. These polymer films can be removed from the photosensitive layer later, and it is necessary that the polymer film be subjected to a surface treatment that cannot be removed or be a material.

  The thickness of the polymer film is usually 5 to 100 μm, preferably 10 to 30 μm. The polymer film can be used by being laminated on both sides of the photosensitive layer. Specifically, one polymer film is used as a support, and the other is used as a protective film for the photosensitive layer. Moreover, after apply | coating the photocurable thermosetting resin composition of this invention on the said support body, the photosensitive layer was formed by drying, and the flexible printed wiring board by which wiring was formed in this photosensitive layer ( FPC) can be pressure-bonded to obtain a laminate. Furthermore, the said laminated body can also be wound up and stored in roll shape.

  In the present invention, in the case of producing a photoresist shape using a photocurable / thermosetting resin composition, when the protective film is present, the protective layer is removed and then the photosensitive layer is heated. It can be laminated by pressure bonding to the substrate.

When a flexible printed wiring board (FPC) is manufactured, the surface to be laminated is usually an FPC in which wiring is formed by etching or the like, but is not particularly limited. Heating and pressure bonding of the photosensitive layer is usually performed at a temperature of 90 to 130 ° C. and a pressure pressure of 3.0 × 10 ⁵ Pa. To further improve the followability of the photosensitive layer to FPC, 4 × 10 ³ It is preferable to perform thermocompression bonding under the above conditions under a reduced pressure of Pa or less. When thermocompression bonding is performed under reduced pressure, it is preferable to use a vacuum laminator having a structure capable of thermocompression bonding the photosensitive layer in a vacuum chamber. Further, if the photosensitive layer is heated as described above, it is not necessary to preheat the substrate in advance, but the substrate can be preheated in order to further improve the followability.

In addition, the roll-shaped FPC sheet is continuously drawn out, and the photosensitive layer is continuously laminated by applying heat and pressure to the FPC sheet. You can also. In the step of continuously laminating the photosensitive layer, in order to further improve the followability of the photosensitive layer to the FPC, it is preferable to perform heat-pressure bonding using a vacuum laminator under a reduced pressure of 4 × 10 ³ Pa or less.

  The photosensitive layer thus laminated is then imagewise exposed with actinic light using a negative film or a positive film. At this time, if the polymer film present on the photosensitive layer is transparent, it may be exposed as it is, but if it is opaque, it must be removed as a matter of course. From the viewpoint of protecting the photosensitive layer, the polymer film is transparent, and it is preferable to expose the polymer film while leaving the polymer film remaining. As the active light, light generated from a known active light source such as a carbon arc, a mercury vapor arc, a xenon arc, or the like is used. As the light source, a photographic flood light bulb, a solar lamp and the like are used in addition to the above.

  After exposure, if a polymer film is present on the photocurable / thermosetting layer, after removing this, using a known developer such as an alkaline aqueous solution, a surfactant aqueous solution, for example, The unexposed portion is removed and developed by a known method such as spraying, rocking dipping, brushing or scraping. Examples of the base of the alkaline aqueous solution include alkali hydroxides such as lithium, sodium or potassium hydroxide, alkali carbonates such as lithium, sodium or potassium carbonate or bicarbonate, alkali metals such as potassium phosphate and sodium phosphate. Alkali metal pyrophosphates such as phosphate, sodium pyrophosphate and potassium pyrophosphate are used, and an aqueous solution of sodium carbonate is particularly preferable. The pH of the alkaline aqueous solution used for development is preferably in the range of 9 to 11, and the temperature is adjusted according to the developability of the photocurable / thermosetting layer. In this alkaline aqueous solution, a surfactant, an antifoaming agent, an organic solvent, or the like may be added.

  The surfactant is not particularly limited, and any of an anionic surfactant, a cationic surfactant, and a nonionic surfactant (nonionic surfactant) can be used.

  Examples of the anionic surfactant include sodium lauryl alcohol sulfate, sodium oleyl alcohol sulfate, sodium lauryl sulfate, ammonium lauryl sulfate, and sodium dodecylbenzenesulfonate.

  Examples of the cationic surfactant include stearylamine hydrochloride, lauryltrimethylammonium chloride, and alkylbenzenedimethylammonium chloride.

  Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene derivative, oxyethylene / oxypropylene block copolymer, sorbitan fatty acid ester, and glycerin fatty acid. Examples include esters, polyoxyethylene fatty acid esters, polyoxyethylene alkylamines, and the like, and nonionic surfactants such as polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, and polyoxyethylene derivatives are particularly preferable.

  The concentration of the surfactant is preferably 0.01 to 15% by weight, more preferably 0.1 to 10% by weight, and more preferably 0.5 to 5% by weight in the alkali developer. Is particularly preferred. If it is less than 0.01% by weight, there is an inconvenience that the desired resist shape cannot be obtained due to insufficient cleaning. If it exceeds 15% by weight, the surfactant cannot be sufficiently washed in the pure water washing step after development, and is taken into the resist film, thereby causing poor electrical insulation, which is not preferable.

  The ink (including the resist agent) using the photocurable / thermosetting resin composition of the present invention can obtain a rapid curing reaction by applying light (active light) or heat energy, Excellent in properties. The same applies to the adhesive of the present invention (including an adhesive sheet and a film).

<Photosensitive solder resist ink>
In addition, as a method for producing a photosensitive solder resist ink using the photocurable / thermosetting resin composition of the present invention, the photocurable / thermosetting resin composition may further include other methods as necessary. The method is not particularly limited as long as it is a method obtained by blending raw materials and uniformly mixing with a roll mill, a mixer, etc., and sufficient dispersion can be obtained, but kneading a plurality of times with three rolls is preferable.

  The photosensitive solder resist ink has a viscosity with a B-type viscometer of preferably 50 dPa · s to 1000 dPa · s at 25 ° C., more preferably 100 dPa · s to 800 dPa · s. When the viscosity is less than 50 dPa · s, the flow of the paste after printing increases, and the film thickness tends to be reduced. When the viscosity exceeds 1000 dPa · s, the paste is applied to the base material during printing. This is not preferable because the transferability is reduced and blurring occurs, and voids and pinholes in the printed film tend to increase.

  In the photosensitive solder resist ink, the degree of variability (thixotropic property) is also important, and in the measurement method described later, the lower limit of the degree of paste change is preferably 1.3 or more, and preferably 2.0 or more. More preferred. The upper limit is preferably 7.0 or less, and more preferably 6.0 or less. If the degree of change is less than 1.3, the flow of paste after printing becomes large and the film thickness tends to be reduced, which is not preferable. Moreover, when it exceeds 7.0, it exists in the tendency for a paste to stop flowing, and is unpreferable.

  For example, as a solder resist, the paste made of the photocurable / thermosetting resin composition can be cured as follows to obtain a cured product. That is, the composition of the present invention is applied to a flexible printed wiring board with a film thickness of 5 to 80 μm by a screen printing method, a spray method, a roll coating method, an electrostatic coating method, a curtain coating method, etc. After preliminary drying at 60 to 120 ° C., the film is finally dried at 120 to 200 ° C. Drying may be in air or in an inert atmosphere.

  The paste is useful as a film-forming material for semiconductor elements and overcoat inks for various electronic components, solder resist inks, interlayer insulating films, and can also be used as paints, coating agents, adhesives, and the like.

  The ink (including the resist agent) using the photocurable / thermosetting resin composition of the present invention can obtain a rapid curing reaction by applying light (active light) or heat energy, Because it contains phosphorus atoms that contribute to flame retardancy, it is halogen-free and effective for environmental conservation. The same applies to the adhesive of the present invention (including an adhesive sheet and a film).

<Printed circuit board>
Further, the printed circuit board of the present invention can form a photocurable / thermosetting layer obtained by reacting the photocurable / thermosetting composition on the circuit board surface in a short time, and has a crosslinking density. The highly photocurable / thermosetting layer (cured product) can protect the surface of the circuit board and can provide an excellent printed circuit board that also achieves flame retardancy.

  EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. The evaluation items in the following examples were carried out by the following methods. In addition, about the mixing | blending content and evaluation result, it showed in the following Tables 1-7.

<Number average molecular weight>
A sample such as polyester resin is dissolved and / or diluted with tetrahydrofuran so that the resin concentration is about 0.5%, and filtered through a polytetrafluoroethylene membrane filter having a pore diameter of 0.5 μm as a measurement sample. The molecular weight was measured by gel permeation chromatography (GPC) using tetrahydrofuran as a mobile phase and a differential refractometer as a detector. The flow rate was 1 mL / min and the column temperature was 30 ° C. Showa Denko KF-802, 804L and 806L were used for the column. Monodisperse polystyrene was used as the molecular weight standard.

<Resin composition>
The polyester resin was dissolved in deuterated chloroform, ¹ H-NMR analysis was performed using a nuclear magnetic resonance analyzer (NMR) Gemini-200 manufactured by Varian, and the molar ratio was determined from the integral ratio.

<Glass transition temperature>
Using a differential scanning calorimeter (DSC) DSC-220 manufactured by Seiko Instruments Inc., put 5 mg of a measurement sample in an aluminum pan, seal with a lid, and increase the temperature from 20 ° C / min to 260 ° C. Warm up. Next, after rapidly cooling from 250 ° C. to −100 ° C. at a temperature decrease rate of 50 ° C./min, the temperature was immediately increased to 200 ° C. again at a temperature increase rate of 20 ° C./min. The glass transition temperature (Tg) was defined as the temperature at the intersection of the extended line of the base line below the glass transition temperature and the tangent indicating the maximum slope at the transition.

<Acid value>
The polyester resin 0.2g was melt | dissolved in 20 ml chloroform, and it titrated with the 0.1N potassium hydroxide ethanol solution, and calculated | required the equivalent (equivalent / 10 ⁶ g) per 10 ⁶ g of polyester resins. The evaluation results are shown in Tables 1 and 2.

<Phosphorus atom concentration (phosphorus content): Determination of phosphorus by wet decomposition and molybdenum blue colorimetric method>
The sample was weighed in an Erlenmeyer flask in accordance with the phosphorus concentration in the sample, 3 ml of sulfuric acid, 0.5 ml of perchloric acid and 3.5 ml of nitric acid were added, and the mixture was gradually decomposed by heating with an electric heater over a half day. After the solution becomes transparent, it is further heated to produce white sulfuric acid smoke, allowed to cool to room temperature, this decomposition solution is transferred to a 50 ml volumetric flask, 5 ml of 2% ammonium molybdate solution and 0.2% hydrazine sulfate solution. 2 ml was added, and the volume was made up with pure water, and the contents were mixed well. After 10 minutes in a boiling water bath, the volumetric flask is heated and colored, and then cooled to room temperature, degassed with ultrasound, the solution is taken into an absorption cell 10 mm, and a blank test is performed with a spectrophotometer (wavelength 830 nm). Absorbance was measured using the solution as a control. The phosphorus content (% by weight) was determined from the calibration curve prepared previously, and the phosphorus atom concentration (phosphorus content) in the sample was calculated.

<Alkali developability>
After applying the photocurable / thermosetting resin composition to the electrolytic copper foil, it was dried at 80 ° C. for 5 minutes to prepare a dried coating film having a thickness of 20 μm. Next, a 1% by weight sodium carbonate aqueous solution (trade name: APACLIN KA, manufactured by Nippon Surface Chemicals Co., Ltd.) adjusted to 30 ° C. is sprayed onto the dry coating film (thickness 20 μm) on a micro development device (Ninomiya System Co., Ltd.). A nozzle (full-scale pyramid: manufactured by Ikeuchi Co., Ltd.) was attached, development was performed for 60 seconds under the condition of a spray pressure of 0.1 MPa, and the presence or absence of the development residue of the dried coating film was visually confirmed. The judgment criteria are as follows.
○: Completely developed △: Part of the coating film remains ×: The coating film remains completely

<Sensitivity>
After applying the photocurable / thermosetting resin composition to the electrolytic copper foil, it was dried at 80 ° C. for 5 minutes to prepare a dry coating film. Next, the dried coating film (thickness 20 μm) was mounted on a step tablet (manufactured by Kodak Co., No. 2, total 21 stages) and adhered under reduced pressure under vacuum, and a jet printer JP-2000 (manufactured by Oak Manufacturing Co., Ltd.) And a light source with a UV integrated light amount of 600 mJ / cm ^{2. After} exposure and removal of the step tablet, the dried coating film was coated with a 1 wt% aqueous sodium carbonate solution adjusted to 30 ° C. (trade name: Apacrine KA, Nippon Surface Chemical Co., Ltd.) was developed for 60 seconds under the condition of a spray pressure of 0.1 MPa, and the sensitivity to ultraviolet rays was evaluated by visually measuring the number of steps of the remaining coating film. In addition, it means that the sensitivity to an ultraviolet-ray is so high that the number of steps is large. If there are 8 or more stages, the sensitivity is good.
○: 8 steps or more △: 4 to 7 steps ×: 3 steps or less

<Solder heat resistance>
After applying the photocurable / thermosetting resin composition to the electrolytic copper foil, it was dried at 80 ° C. for 5 minutes to prepare a dry coating film. Next, the dried coating film (thickness 20 μm) is exposed under the condition of 1000 mJ / cm ² of UV integrated light quantity and thermally cured at 150 ° C. for 1 hour to prepare a resist film. Further, a rosin flux is added to the resist film. After applying MH-820V (manufactured by Tamura Kaken), it was immersed in a solder bath at 260 ° C. for 30 seconds in accordance with JIS-C6481, and the presence or absence of appearance abnormality such as peeling or swelling was observed.
○: No appearance abnormality △: Slight appearance abnormality ×: Overall appearance abnormality

<Flexibility>
After applying the photocurable / thermosetting resin composition to the electrolytic copper foil, it was dried at 80 ° C. for 5 minutes to prepare a dry coating film. Next, the dried coating film (thickness 20 μm) is exposed under the conditions of 1000 mJ / cm ² of UV integrated light quantity, and a heat-cured resist film is prepared at 150 ° C. for 1 hour. This resist film conforms to JIS-K5400. And evaluated. The diameter of the mandrel was 2 mm, and the presence or absence of cracks was confirmed.
○: No crack occurred ×: Crack occurred

<Sleigh>
A photocurable thermosetting resin composition was applied to a 25 μm-thick polyimide film (Akane NPI manufactured by Kaneka Corporation), and then dried at 80 ° C. for 5 minutes to prepare a dry coating film (thickness 20 μm). Subsequently, the dried coating film was exposed using a jet printer JP-2000 (manufactured by Oak Manufacturing Co., Ltd.) as a light source under the condition of an integrated ultraviolet light quantity of 1000 mJ / cm ² , and further subjected to heat treatment at 150 ° C. for 1 hour. The obtained laminated film was cut out to 10 cm × 10 cm. Next, the laminated film was conditioned at 25 ° C. and a relative humidity of 65% for 24 hours to obtain a measurement sample. The sample was placed on a horizontal glass plate in a convex downward state, and the average height of the four corners was evaluated.
○: Less than 2 mm in height Δ: Less than 10 mm in height ×: More than 10 mm in height

<Adhesion>
After applying the photocurable / thermosetting resin composition to the electrolytic copper foil, it was dried at 80 ° C. for 5 minutes to prepare a dry coating film (thickness 20 μm). Next, the dried coating film was exposed under the conditions of 1000 mJ / cm ² of UV accumulated light amount, and a resist film that was thermally cured at 150 ° C. for 1 hr was made in 100 locations of 1 mm grids in accordance with JIS-K5600, A peel test with cello tape (registered trademark) was performed, and the peeled state of the grid was observed. Moreover, it carried out similarly about the case where a 25-micrometer-thick polyimide film was used as the base material.
○: No peeling at 100/100 Δ: 70 to 99/100
X: 0-70 / 100

<Chemical resistance>
After applying the photocurable / thermosetting resin composition to the electrolytic copper foil, it was dried at 80 ° C. for 5 minutes to prepare a dry coating film. Subsequently, the dried coating film (thickness: 20 μm) was exposed under the condition of 1000 mJ / cm ² of UV integrated light quantity and thermally cured at 150 ° C. for 1 hour. After being immersed in an aqueous sodium solution at 20 ° C. for 30 minutes, the test substrate was taken out and the state of the cured film was evaluated according to the following criteria.
○: No change is observed Δ: Only a slight change ×: The cured film has blisters or swelling and falling off

<Flame retardance evaluation>
A photocurable thermosetting resin composition was applied to a 25 μm-thick polyimide film (Akane NPI manufactured by Kaneka Corporation), and then dried at 80 ° C. for 5 minutes to prepare a dry coating film (thickness 20 μm). Subsequently, the dried coating film was exposed using a jet printer JP-2000 (manufactured by Oak Manufacturing Co., Ltd.) as a light source under the condition of an integrated ultraviolet light quantity of 1000 mJ / cm ² , and further subjected to heat treatment at 150 ° C. for 1 hour. About the obtained laminated | multilayer film (thickness 15 micrometers), the flame retardance was evaluated according to UL94 specification. In terms of flame retardancy, in UL94 standard, HB burns and is the worst, VTM-2 or higher is preferable, VTM-1 is more preferable, and VTM-0 is most preferable.

<Synthesis example 1 of ester bond-containing diol oligomer>
The autoclave was charged with 540 parts by weight of terephthalic acid, 290 parts by weight of isophthalic acid, 410 parts by weight of ethylene glycol, 460 parts by weight of neopentyl glycol, and 0.2 parts by weight of tetra-n-butyl titanate as a catalyst at 220 to 235 ° C. The esterification reaction was carried out for 3 hours. The reaction system was depressurized to 5 mmHg over 20 minutes, during which the temperature was raised to 250 ° C., and a polycondensation reaction was carried out at 250 ° C. for 45 minutes. The composition of the ester bond-containing diol oligomer thus obtained is such that the acid component is terephthalic acid / isophthalic acid = 65/35 (mol%) and the glycol component is ethylene glycol / neopentyl glycol = 52/48 (mol%). The number average molecular weight was 1600, and the glass transition temperature was 52 ° C.

<Synthesis example 2 of ester bond-containing diol oligomer (polyesterimide diol oligomer)>
744 parts by weight of 3,3′-diaminodiphenylsulfone and 2160 parts by weight of 2-methyl-1,3-propanediol were charged in an autoclave and mixed. 1152 parts by weight of trimellitic anhydride was added over 10 minutes. Stirring was continued and the temperature was kept at 50 ° C. to confirm that the trimellitic anhydride was dissolved and the solution became transparent. Thereafter, a dehydration reaction was performed at 145 ° C. for 4 hours, and after confirming that a theoretical amount of water for imide ring closure was distilled out of the system, 0.2 part by weight of tetra-n-butyl titanate as a catalyst was charged, 220 The esterification reaction was carried out at ˜235 ° C. for 3 hours. The reaction system was depressurized to 5 mmHg over 20 minutes, during which the temperature was raised to 250 ° C., and a polycondensation reaction was carried out at 250 ° C. for 45 minutes. The composition of the polyesterimide diol oligomer thus obtained is 3,3′-diaminodiphenylsulfone / 2-methyl-1,3-propanediol / trimellitic anhydride = 23/31/46 (mol%), number average molecular weight. 1550 and glass transition temperature 113 ° C.

<Synthesis example 3 of ester bond-containing diol oligomer (polyesterimide diol oligomer)>
744 parts by weight of 3,3′-diaminodiphenylsulfone and 2800 parts by weight of 3-methyl-1,5-pentanediol were charged in an autoclave and stirred and mixed. 1152 parts by weight of trimellitic anhydride was added over 10 minutes. Stirring was continued and the temperature was kept at 50 ° C. to confirm that the trimellitic anhydride was dissolved and the solution became transparent. Thereafter, a dehydration reaction was performed at 145 ° C. for 4 hours, and after confirming that a theoretical amount of water for imide ring closure was distilled out of the system, 0.2 part by weight of tetra-n-butyl titanate as a catalyst was charged, 220 The esterification reaction was carried out at ˜235 ° C. for 3 hours. The reaction system was depressurized to 5 mmHg over 20 minutes, during which the temperature was raised to 250 ° C., and a polycondensation reaction was carried out at 250 ° C. for 45 minutes. The composition of the resulting polyesterimide diol oligomer was 3,3′-diaminodiphenylsulfone / 3-methyl-1,5-pentanediol / trimellitic anhydride = 22/34/44 (mol%), number average molecular weight. 1300 and glass transition temperature 95 ° C.

<Synthesis example 1 of carbonate group-containing diol oligomer>
354 parts by weight of 1,6-hexanediol (HD), 444 parts by weight of n-butyl-bis (3-hydroxypropyl) phosphine oxide (PO-4500, phosphorus-containing diol, manufactured by Nippon Chemical Industry), 1017 parts by weight of diphenyl carbonate, After charging 0.5 parts by weight of tetra-n-butyl titanate as a catalyst into an autoclave, heating up to 220 ° C. and confirming the distillation of phenol, the reaction system was reduced from normal pressure to 5 mmHg over 20 minutes. did. While maintaining the reaction system at 200 ° C. under a reduced pressure of 5 mmHg, phenol was distilled out of the reaction system, and a polycondensation reaction was carried out for 80 minutes. Table 1 shows the composition, phosphorus content, number average molecular weight, and glass transition temperature (Tg) of the carbonate group-containing diol oligomer thus obtained.

<Synthesis example 2 and comparative synthesis examples 1 to 3 of carbonate group-containing diol oligomer>
In the same manner as in Synthesis Example 1, the raw materials shown in Table 1 were charged and polymerized to obtain a carbonate group-containing diol oligomer. Table 1 shows the composition, number average molecular weight, and glass transition temperature (Tg) of the resulting carbonate group-containing diol oligomer. In the table, [Chemical Formula 1] is a compound represented by the following formula.

注）ＣＨＤＭ：シクロヘキサンジメタノール

Note) CHDM: cyclohexanedimethanol

<Characteristics of modified polyester resin>
[Example 1-1]
In a reaction vessel equipped with a stirrer and a thermometer, 400 parts by weight of the ester bond-containing oligomer obtained in Synthesis Example 1 of an ester bond-containing diol oligomer and a carbonate bond obtained in Synthesis Example 1 of a carbonate group-containing diol oligomer 465 parts by weight of the oligomer, 650 parts by weight of γ-butyrolactone as a solvent, and 2 parts by weight of 4-dimethylaminopyridine as a catalyst were added and stirred and dissolved at 65 ° C. Subsequently, 87 parts by weight of pyromellitic anhydride was added and stirred, and reacted at 70 ° C. for 6 hours. To the obtained solution, 0.2 part by weight of hydroquinone monomethyl ether as a radical polymerization inhibitor and 2 parts by weight of triphenylphosphine as a reaction catalyst are added, and 3,4-epoxycyclohexyl methacrylate (reacts with the remaining carboxyl group). 142 parts by weight of (meth) acrylic monomer having a functional group, Cyclomer M100, manufactured by Daicel Chemical Industries) was further added, and reacted at 80 ° C. for 10 hours. Then, it cooled to room temperature and obtained the solution. The resulting solution contained a modified polyester resin having a carboxyl group, an ester bond, a carbonate group and an ethylenically unsaturated double bond. The obtained modified polyester resin was prepared with γ-butyrolactone as a solvent so that the solid content concentration was 55% by weight. The characteristic results of this resin are shown in Table 2.

[Examples 1-2 to 1-10, Comparative Examples 1-1 to 1-9]
Various modified polyester resins were obtained in the same manner as in Example 1-1 except that the blending of raw materials was changed as shown in Tables 2 and 3. Tables 2 and 3 show the blending and property evaluation results of these resins.

注）ＰＭＤＡ：ダイセル化学工業製、無水ピロメリット酸
ＯＤＰＡ：マナック製、ＯＤＰＡ−Ｍ、オキシジフタルジフタル酸二無水物
４ＨＢＡＧＥ：ブチルアクリレートグリシジルエーテル、日本化成製

Note) PMDA: Daicel Chemical Industries, pyromellitic anhydride ODPA: Manac, ODPA-M, oxydiphthaldiphthalic dianhydride 4HBAGE: Butyl acrylate glycidyl ether, Nippon Kasei

<Characteristics of solder resist ink>
[Example 2-1]
With respect to 50 parts by weight of the modified polyester resin solution obtained in Example 1-1, 0.2 part by weight of “Irgacure 907” manufactured by Ciba Specialty Chemicals as photo radical polymerization initiator, and FA731A ((meth) acrylic monomer) Hitachi Chemical Co., Ltd. (4 parts by weight) and epoxy resin jER152 (Japan Epoxy Resin Co., Ltd., phenol novolac type epoxy resin product name) (6.6 parts by weight) were added, and Ucat5002 (San Apro Co., Ltd.) was added as a thermosetting accelerator. 0.2 parts by weight of DBU tetraphenylborate) and 6 parts by weight of 10H-9-oxa-10-phospha-10-phenanthrylmethylbenzene (trade name BCA, manufactured by Sanko) as a flame retardant and Aerogel as a filler # 300 (Nippon Aerosil Co., Ltd. hydrophilic silica fine particles) 3 2 parts by weight, 0.5 part by weight of Floren AC-326F (manufactured by Kyoeisha Chemical Co., Ltd.) as an antifoaming agent, 0.5 part by weight of BYK-358 (manufactured by BYK Chemie) as a leveling agent, and as a solvent Then, γ-butyrolactone was added so that the solid content concentration was 50% by weight, then coarsely kneaded, and then kneaded three times using a high-speed three roll. An ink made of the photo-curing / thermosetting resin composition of the present invention having a thixotropic property in which the filler was uniformly dispersed and the variation was 2.8 was obtained. Coating and drying (85 ° C., 60 minutes) to a glossy surface of 18 μm thick electrolytic copper foil and 25 μm thick polyimide film (Kaneka Apical NPI) to a dry film thickness of 20 μm. A membrane was obtained. The blending contents are shown in Table 4.

The obtained dried coating film was placed on a step tablet (No. 2 manufactured by Kodak Co., Ltd., 21 stages) and vacuum-adhered under reduced pressure. For the dried coating film with surface tack, a 15 μm thick polypropylene film (Pyrene P2282, manufactured by Toyobo Co., Ltd.) was sandwiched between the dried coating film and the step tablet as a release film. Using a jet printer JP-2000 (manufactured by Oak Manufacturing Co., Ltd.) as a light source, exposure was performed under the condition of 1000 mJ / cm ² of UV integrated light quantity, and after removing the step tablet, a 30 ° C. sodium carbonate aqueous solution (trade name: trade name: Apaclin KA (manufactured by Nihon Surface Chemical Co., Ltd.) is mounted on a micro development device (manufactured by Ninomiya System Co., Ltd.) with a spray nozzle (manufactured prism: manufactured by Ikeuchi) and developed for 60 seconds under a spray pressure of 0.1 MPa. The developability and sensitivity were evaluated. Further, heat treatment was performed at 150 ° C. for 1 hour, and the solder resist characteristics were evaluated using the heat treatment. The evaluation results are shown in Table 4.

<Examples 2-2 to 2-12 and Comparative Examples 2-1 to 2-12>
Tables 4 to 7 show the blending contents and the evaluation results, which were evaluated in the same manner as in Example 2-1.

注）ＦＡ７３１Ａ：トリス（アクリロキシエチル）イソシアヌレート、日立化成製
ＤＰＥ−６Ａ：ジペンタエリスリトールヘキサ（メタ）アクリレート、共栄社化学製

Note) FA731A: Tris (acryloxyethyl) isocyanurate, manufactured by Hitachi Chemical DPE-6A: Dipentaerythritol hexa (meth) acrylate, manufactured by Kyoeisha Chemical Co., Ltd.

  In Examples 2-1 to 2-12, good evaluation results can be obtained in all evaluation items of chemical characteristics such as alkali developability, mechanical characteristics such as warpage and flexibility, and flame retardancy. It could be confirmed.

  Comparative Example 2-1 resulted in poor sensitivity, solder heat resistance, flexibility, warpage, and adhesion. This is probably because the modified polyester used here has a low number average molecular weight and thus the coating film becomes brittle.

  Comparative Example 2-2 resulted in poor alkali developability and sensitivity. Since the modified polyester resin used here has a high number average molecular weight, it is considered that the solubility of the modified polyester resin in an alkaline developer is lowered.

  Comparative Example 2-3 resulted in poor alkali developability and sensitivity. Since the modified polyester resin used here has a low acid value, it can be considered that the solubility of the modified polyester resin in an alkaline developer is lowered.

Comparative Example 2-4 was inferior in alkali developability and sensitivity. Carbonate groups-containing diol oligomer A ₂ constituting the modified polyester resin used herein has a high number average molecular weight, because it is hydrophobic, it is believed to decrease the solubility in an alkali developer.

Comparative Example 2-5 resulted in poor flexibility, warpage, and flame retardancy. The carbonate group-containing diol oligomer A ₂ constituting the modified polyester resin used here is a soft segment because it has a low number average molecular weight, but the number average molecular weight is too low. It is thought that the film did not function as a segment and the coating film became brittle. Moreover, since the content of phosphorus atoms effective for imparting flame retardancy is low, the effect is small and it is considered that the product burned.

  Comparative Example 2-6 was inferior in sensitivity and solder heat resistance. The modified polyester resin used here has a high acid value and an excessive amount of carboxyl groups, so that it easily swells in an alkali developer even after photocuring, and is considered to have deteriorated sensitivity. Moreover, since there are many residual carboxyl groups after thermosetting reaction, water absorption is high, Therefore It is thought that solder heat resistance is inferior.

Comparative Example 2-7 resulted in inferior flexibility, warpage, and flame retardancy. The 90 wt% or more ester bond-containing diol oligomer A ₁ used here has a high glass transition temperature and corresponds to a hard segment. For this reason, it is thought that the obtained cured coating film became brittle and the flexibility and mechanical properties of the warp deteriorated. Moreover, since the content of the phosphorus atom effective for imparting flame retardancy is low, the effect is small and it is considered that the product burned.

Comparative Example 2-8 was inferior in solder heat resistance. Here of which 90 wt% or more using carbonate group-containing diol oligomer A ₂ are those having a glass transition temperature is low, corresponding to the soft segment. For this reason, it is thought that heat resistance is inferior.

  Comparative Example 2-9 resulted in inferior alkali developability, sensitivity, flexibility, warpage, and adhesion. The photocurable / thermosetting resin composition used here has many acrylic monomers. Since the acrylic monomer is hydrophobic, it is considered that the solubility in an alkaline developer is lowered. Further, it is considered that a large amount of acrylic monomer is blended, and the obtained cured coating film becomes brittle and deteriorates mechanical properties.

  Comparative Example 2-10 resulted in inferior alkali developability, sensitivity, flexibility, warpage, and adhesion. The photocurable / thermosetting resin composition used here has a large amount of epoxy resin. Since the epoxy resin is hydrophobic, it is considered that the solubility in an alkali developer is lowered. Further, it is considered that a large amount of epoxy resin is blended, and the obtained cured coating film becomes brittle and deteriorates mechanical properties.

  Comparative Example 2-11 resulted in inferior alkali developability, sensitivity, solder heat resistance, flexibility, warpage, adhesion, and flame retardancy. In the photo-curing / thermosetting resin composition used here, the modified polyester resin does not contain phosphorus atoms, so a large amount of flame retardant is blended, but the effect is small and flame retardancy can be imparted. Not only that, but also alkali developability, sensitivity, solder heat resistance, flexibility, warpage, and adhesion deteriorated. Since the flame retardant is hydrophobic, it is considered that the solubility in an alkali developer is lowered. Moreover, it is thought that heat resistance and mechanical characteristics deteriorated due to the blending of a large amount of flame retardant.

  Comparative Example 2-12 was inferior in flame retardancy. In the photocurable thermosetting resin composition used here, the modified polyester resin does not contain a phosphorus atom. Therefore, the maximum amount of the flame retardant BCA was blended within the range where the chemical property evaluation of the ink such as alkali developability (solder resist ink) can be maintained at ◯. It is thought that it was insufficient to grant.

Claims (13)

A hard segment based on an ester bond-containing diol oligomer A ₁ having at least two ester bonds and hydroxyl groups at both ends, and a carbonate group-containing diol oligomer A ₂ having at least two carbonate groups and hydroxyl groups at both ends A polyester resin C comprising a soft segment based on the above and a residual carboxyl group-containing segment B based on an acid dianhydride,
The hard segment and the soft segment are combined with a residual carboxyl group-containing segment B based on the acid dianhydride to constitute a polyester resin C,
The glass transition temperature of the ester bond-containing diol oligomer _{A 1} is, exceed 0 ° C., and a number average molecular weight is 600 to 4000,
Glass transition temperature of the carbonate group-containing diol oligomer _{A 2} is, is at 0 ℃ or less and a number average molecular weight is 800 to 4000,
The molar ratio of the oligomer _{A 1} and the oligomer _{A 2 (A 1 / A 2} ) is 1 / 9-9 / 1,
The molar ratio B / (A ₁ + A ₂ ) of the acid dianhydride B, the oligomer A ₁ and the oligomer A ₂ is 65/100 to 98/100 or 135/100 to 102/100,
The number average molecular weight of the polyester resin C is 2000 to 10,000.
A polyester resin containing 0.5 to 7% by weight of phosphorus atoms in the polyester resin C. The ester bond-containing diol oligomer A ₁ is a hydroxyl group in the diol compound of claim 1, wherein the polyester resin characterized in that it is obtained by reacting a carboxyl group of the dicarboxylic acid compound.   The polyester resin according to claim 2, wherein the dicarboxylic acid compound is an imide group-containing dicarboxylic acid oligomer. The carbonate group-containing diol oligomer A ₂ is a polyester resin according to claim 1, characterized in that it is a polycarbonate diol. The carbonate group-containing diol oligomer A ₂ is a polyester resin according to any one of claims 1 to 4, characterized in that a phosphorus-containing polycarbonate diol. A modified polyester resin D obtained by reacting a residual carboxyl group in the polyester resin according to claim 1 with a (meth) acrylic monomer having a functional group that reacts with the residual carboxyl group, ,
In the main chain of the modified polyester resin D, the residual carboxyl group partially remains,
In the side chain of the modified polyester resin D, it has an ethylenically unsaturated double bond,
The modified polyester resin, wherein the modified polyester resin D has an acid value of 350 to 2000 equivalent / 10 ⁶ g and a number average molecular weight of 2500 to 10,000.   The modified polyester resin according to claim 6, wherein the functional group of the (meth) acrylic monomer is a glycidyl group and / or a hydroxyl group. The modified polyester resin D, the (meth) acrylic monomer E, and the epoxy resin F according to claim 6 or 7,
The photo-curing / thermosetting characterized by containing 5-30 parts by weight of the (meth) acrylic monomer E and 5-50 parts by weight of the epoxy resin F with respect to 100 parts by weight of the modified polyester resin D. Resin composition.   Furthermore, a flame retardant is contained, The photocurable thermosetting resin composition of Claim 8 characterized by the above-mentioned.   A photocurable / thermosetting layer obtained by reacting the photocurable / thermosetting resin composition according to claim 8 or 9.   An ink comprising the photocurable / thermosetting resin composition according to claim 8 or 9.   An adhesive comprising the photocurable / thermosetting resin composition according to claim 8 or 9. A printed circuit board comprising the photocurable thermosetting layer according to claim 10 on the surface of the circuit board.