JP2009298991A - Photocurable and thermosetting resin composition, photocurable and thermosetting layer, ink, adhesive and printed circuit board - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photocurable and thermosetting resin composition excellent in latent thermosetting properties, preservation stability for a long period of time, flame retardancy, adhesiveness and flowability required on adhesion, and an ink, an adhesive, a printed wiring board, obtained using these, used for automobile components, electric appliances and the like, and the like. <P>SOLUTION: The photocurable and thermosetting resin composition comprises a modified polyester resin D obtained by causing a polyester resin C, comprised of a segment based on an oxetane ring-containing diol oligomer A<SB>1</SB>bearing at least two oxetane rings and a hydroxy group on both ends, a segment based on an ester bond-containing diol oligomer A<SB>2</SB>bearing at least two ester bonds and a hydroxy group on both ends, and a segment B bearing a residual carboxy group based on an acid dianhydride, to react with a (meth)acrylic monomer bearing a functional group reactive with the residual carboxy group of the polyester resin C. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention includes a modified polyester resin having a carboxyl group based on an oxetane ring and an acid dianhydride in the main chain and an ethylenically unsaturated double bond contributing to photocuring in the side chain, and flame retardancy A photocurable / thermosetting resin composition containing a phosphorus-containing (meth) acrylic monomer and / or a phosphorus-containing allyl group-containing monomer, 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 general, a liquid or film solder resist agent is used in FPCs and printed wiring boards in order to protect circuits and prevent solder adhesion during mounting. As the solder resist agent, the development film type that forms a pattern by photolithography can obtain high accuracy, and therefore, the demand is increasing. These solder resist agents are required to have an adhesive that does not react during heating or storage during solvent evaporation, exhibits the required fluidity during adhesion, and cures rapidly by light or heat. ing.

  In particular, a latent thermosetting adhesive that dramatically changes from thermoplastic to thermosetting at a certain temperature or higher has been put into practical use using an epoxy resin.

  However, when the epoxy resin is the main component, the obtained cured product is inferior in flexibility, needs to be stored at low temperature, distributed at low temperature, and needs to be cured at high temperature for a long time. Have problems.

  In recent years, the use of photocuring and thermosetting materials of oxetane compounds has been studied (Non-patent Document 1, Patent Documents 1 to 3). These documents describe that oxetane, which is a 4-membered cyclic ether, does not react at about 100 ° C., and the reaction starts when the temperature exceeds 150 ° C.

  However, what is described in these is that an oxetane compound is used as a curing agent, and the dependence of the performance on the blending ratio is large, so that precise blending is required.

  In addition, since a low molecular weight compound such as an oxetane compound is used, the oxetane compound itself may ooze out due to heating during bonding, contaminating the adherend, and may accumulate at the interface between the adhesive and the adherend. There is a problem that causes a decrease in adhesive strength.

  Furthermore, oxetane compounds are also a cause of reducing flame retardancy.

Network polymer, vol. 27, 38 (2006) JP 2004-168921 A WO01 / 073510 JP-A-2005-307101

  Therefore, the present invention provides a modified polyester resin having a carboxyl group based on an oxetane ring and an acid dianhydride in the main chain and an ethylenically unsaturated double bond contributing to photocurability in the side chain, and a difficulty. An object is to provide a photocurable thermosetting resin composition containing a phosphorus-containing (meth) acrylic monomer and / or a phosphorus-containing allyl group-containing monomer that contributes to flammability. Furthermore, by using the photocurable / thermosetting resin composition, it is excellent in latent thermosetting, long-term storage stability, flame retardancy, adhesiveness, and fluidity required during bonding. An object of the present invention is to provide inks and adhesives, automobile parts using these, printed circuit boards used for electrical appliances, and the like.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found the following photocurable / thermosetting resin composition and completed the present invention.

That is, the photocurable and thermosetting resin composition of the present invention, the oxetane ring-containing segment based on the oxetane ring-containing diol oligomer A ₁ having at least two oxetane rings and hydroxyl groups at both ends, at least two A polyester resin C comprising the above ester bond and an ester bond-containing segment based on the ester bond-containing diol oligomer A ₂ having hydroxyl groups at both ends, and a residual carboxyl group-containing segment B based on an acid dianhydride,
The oxetane ring-containing segment and the ester bond-containing segment are combined with a residual carboxyl group-containing segment B based on the acid dianhydride,
The glass transition temperature of the ester bond-containing diol oligomer _{A 2} is, is at 0 ℃ or less and a number average molecular weight is 1000 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 1000 to 10000,
A modified polyester resin D obtained by reacting a residual carboxyl group in the polyester resin C with a (meth) acrylic monomer having a functional group that reacts with the residual carboxyl group, a phosphorus-containing (meth) acrylic monomer, and Containing phosphorus-containing allyl group-containing monomers,
In the main chain of the modified polyester resin D, a part of the residual carboxyl group remains, and in the side chain of the modified polyester resin D, it has an ethylenically unsaturated double bond,
The acid value of the modified polyester resin D is 350 to 2000 equivalent / 10 ⁶ g, and the number average molecular weight is 2500 to 10,000.

  The photocurable / thermosetting resin composition of the present invention preferably contains 0.5 to 7% by weight of phosphorus atoms in the polyester resin C.

Photocurable and thermosetting resin composition of the present invention, which the oxetane ring-containing diol oligomer A _1, and the hydroxyl groups of the oxetane ring-containing diol compound, obtained by reacting the isocyanate groups in the diisocyanate compound Preferably there is.

Photocurable and thermosetting resin composition of the present invention, the ester bond-containing diol oligomer A _2, and hydroxyl groups in the diol compound, be a carboxyl group in the dicarboxylic acid is obtained by reacting preferable.

Photocurable and thermosetting resin composition of the present invention, at least a part of the diol compound and / or dicarboxylic acid, containing phosphorus atoms, said ester bond-containing diol oligomer A _2, a phosphorus-containing diol oligomer Preferably there is.

  In the photocurable / thermosetting resin composition 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 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 includes a modified polyester resin having a carboxyl group based on an oxetane ring and an acid dianhydride in the main chain and an ethylenically unsaturated double bond contributing to photocuring in the side chain, and flame retardancy It is possible to obtain a photocurable thermosetting resin composition containing a phosphorus-containing (meth) acrylic monomer and / or a phosphorus-containing allyl group-containing monomer, and further, the photocurable thermosetting resin. By using the composition, latent thermosetting, long-term storage stability, flame retardancy, adhesiveness, fluidity required at the time of bonding, alkali developability, sensitivity, solder heat resistance, flexibility, etc. Excellent inks, adhesives, and the like can be obtained, and further, automobile parts using these, printed circuit boards used for electrical appliances, and the like can be obtained, which is effective.

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

<Polyester resin>
Polyester resin used in the present invention (polyester resin C) is a oxetane ring-containing segment based on the oxetane ring-containing diol oligomer A ₁ having at least two oxetane rings and hydroxyl groups at both ends, at least two or more ester a bond and ester bond-containing segments based on an ester bond-containing diol oligomer a ₂ having both ends hydroxyl groups, a polyester resin C containing a residual carboxyl group-containing segment B based on dianhydride, and the oxetane ring-containing The segment and the ester bond-containing segment are combined with the residual carboxyl group-containing segment B based on the acid dianhydride to constitute the polyester resin C.

  By having an oxetane ring in the main chain of the polyester resin (polyester resin C), latent thermosetting can be imparted to a photo-curable / thermosetting resin using this resin. Moreover, alkali-solubility (alkali developability in a photoresist manufacturing process) is realizable by a carboxyl group remaining in the principal chain of a polyester resin (polyester resin C). The ester bond is effective without causing a resin decomposition reaction called so-called copper damage using copper used for a printed circuit board as a catalyst, like an ether bond. When the oxetane ring-containing segment is a hard segment, the ester bond-containing segment can be defined as a soft segment. By having this soft segment, bending resistance and low warpage are imparted. can do.

Further, in the present invention, the glass transition temperature of the ester bond-containing diol oligomer A ₂ is, is at 0 ℃ or less, preferably -5 ° C. or less, more preferably -10 ° C. or less. If the temperature exceeds 0 ° C., the flexibility is inferior, and when bent, cracks are generated, which is not preferable.

In the present invention, the ester bond-containing diol A _{2 has} a number average molecular weight of 1000 to 4000, preferably 1200 to 3000. If it is less than 1000, the flexibility is inferior, and if bent, cracks occur, which is a problem. On the other hand, if it exceeds 4000, the solubility in an alkali developer becomes insufficient and development becomes impossible, which is not preferable. .

In the present invention, the oxetane ring-containing diol oligomer A ₁ is preferably obtained by reacting a hydroxyl group in the oxetane ring-containing diol compound with an isocyanate group in the diisocyanate compound. The hydroxyl group and the isocyanate group react to form a urethane bond. Since the oxetane ring-containing diol oligomer A ₁ containing a plurality of urethane bonds has an oxetane ring, it can have latent thermosetting properties. Furthermore, the oxetane ring-containing segment based on the oxetane ring-containing diol oligomer A ₁ is a portion serves as a so-called hard segment.

In the present invention, the ester bond-containing diol oligomer A _2, and hydroxyl groups 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 plurality of ester bond-containing diol oligomers A ₂ having an ester bond has an ester bond, and thus has superior heat resistance compared to ether oligomers such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol. Have. Further, ester bond-containing segment based on the ester bond-containing diol oligomer A ₂ becomes a moiety serves as a so-called soft segment, thereby contributing to such flexibility.

Furthermore, at least a part of the diol compound and / or dicarboxylic acid, containing phosphorus atoms, the ester bond-containing diol oligomer A ₂ is preferably a phosphorus-containing diol oligomer. 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.

Examples of the oxetane ring-containing diol oligomer A oxetane ring-containing diol compound used in the _1, containing an oxetane ring in the molecule, as long as it is a compound having two or more hydroxyl groups is not particularly limited, for example, 3,3-bis (hydroxymethyl) oxetane, di [1-hydroxymethyl (3-oxetanyl)] methyl ether, etc. are mentioned, among which 3,3-bis (hydroxymethyl) oxetane (BHO) is particularly in the molecular chain. In addition, the oxetane ring can be introduced relatively easily at a desired ratio, which is preferable.

The diisocyanate compound to be used in the oxetane ring-containing diol oligomer _{A 1,} is not particularly limited, for example, 2,4-toluene diisocyanate (2,4-TDI), 2,6- toluene diisocyanate (2, 6-TDI ), 2,2′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, p-phenylene diisocyanate, m-phenylene diisocyanate, p-xylylene diisocyanate, m -Aliphatic diisocyanates such as xylylene diisocyanate, aliphatics such as ethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 1,6-hexamethylene diisocyanate Diisocyanates, 1,4-cyclohexane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, alicyclic diisocyanates such as isophorone diisocyanate, norbornane diisocyanate, Crude-MDI, etc., and trade names include Cosmonate T series, Cosmo Nate TM series and Cosmonate M series (both manufactured by Mitsui Takeda Chemical Co., Ltd.). These compounds may be used alone or in combination of two or more.

The oxetane ring-containing diol compound A ₁ having at least an oxetane ring and hydroxyl groups at both ends can be produced by reacting the oxetane ring-containing diol compound with a diisocyanate compound. The hydroxyl group in the diol compound reacts with the isocyanate group in the diisocyanate compound to form a urethane bond. In addition, when the compounding quantity of both components is represented by an equivalent ratio, hydroxyl group / isocyanate group = 8 / 7-2 / 1 is preferable, More preferably, it is 5 / 4-2 / 1. When it exceeds 8/7 of the said range, there exists a difficulty in solvent solubility. On the other hand, if it is less than 2/1 of the above range, the amount of oxetane ring reacting with the carboxyl group is insufficient, and the solder heat resistance after thermosetting deteriorates, which is not preferable. Polyester resin used in the present invention (polyester resin C) is, by using an oxetane ring-containing diol oligomer A _1, it is possible to impart latent thermosetting.

The oxetane ring-containing diol oligomer A ₁ having hydroxyl groups at both ends can be obtained by using a known method. For example, in the presence of a solvent in a reaction vessel equipped with a stirrer and a thermometer. It is produced in a reaction time of 2 to 10 hours at a reaction temperature of -100 ° C in the presence or absence of a catalyst. As the solvent used in this case, for example, ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and cyclopentanone, aromatic hydrocarbons such as toluene and xylene, and esters such as ethyl acetate and butyl acetate can be used.

When manufacturing the oxetane ring-containing diol oligomer A ₁ may be a catalyst as described above. Examples of the catalyst include dibutyltin dilaurate, dibutyltin diacetate, ethylenediaminetetraacetate, and triethylamine. It is preferable to use a urethanization catalyst such as dibutyltin dilaurate.

The diol compound used in the ester bond-containing diol oligomer A ₂ 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, and 1,3-propanediol. 2,4-dimethyl-2-ethylhexane-1,3-diol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 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-cyclohexane dimethyl 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 1,9-nonanediol, dimer diol, hydrogenated dimer diol , Tricyclodecandiol, tricyclodecane dimethylol, spiroglycol, hydrogenated bisphenol A, ethylene oxide adduct and propylene oxide adduct of hydrogenated bisphenol A, and the like. 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. From the viewpoint of imparting flexibility, it is preferable to use a mixture of long-chain glycols such as 1,9-nonanediol, dimer diol, hydrogenated dimer diol and the like.

  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.

The dicarboxylic acid compounds used in the ester bond-containing diol oligomer A _2, 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 or 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.

  Moreover, as the dicarboxylic acid compound, a phosphorus-containing dicarboxylic acid containing a phosphorus atom can be used. Specific examples include 2- (10H-9-oxa-10-phospha-10-phenanthrylmethyl) succinic acid.

The ester bond-containing diol oligomer A ₂ is a diol compound (or polyhydric alcohol) and is reacted with 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. The molar ratio (diol compound / dicarboxylic acid) is preferably 2.2 / 1 to 1.8 / 1, and more preferably 2/1 to 1.9 / 1. 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 glycols. When the range is less than 1.8 / 1, in addition to the terminal 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 and the hydroxyl group of the present invention 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. in polymerized reaction, it is possible to obtain an ester bond-containing diol oligomer a ₂ having a number average molecular weight of interest.

When polymerizing the ester bond-containing diol oligomer A _2, 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.

Polyester resin C used in the present invention, and the oxetane ring-containing diol oligomer A _1, and the ester bond-containing diol oligomer A _2, obtained by reacting an acid dianhydride. 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 bis trimellitate Dianhydride, 2,2 ′, 3,3′-diphenyltetracarboxylic dianhydride, thiophene-2,3,4,5-tetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenone Tracarboxylic 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-dicarboxy) Phenyl) 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).

A polyester resin having at least an oxetane ring, a carboxyl group, and an ester bond in the main chain by reacting the oxetane ring-containing diol oligomer A ₁ , the ester bond-containing diol oligomer A ₂ and an acid dianhydride. Can be manufactured. By reacting the hydroxyl group in the oxetane ring-containing diol oligomer A ₁ and the ester bond-containing diol oligomer A ₂ with the acid dianhydride, the acid dianhydride ring-opening reaction proceeds, while the ester bond is changed. 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. Further, by using a diol oligomer containing an oxetane ring, an oxetane ring can be introduced into the main chain, and this oxetane ring hardly causes a ring-opening reaction at about 100 ° C. In the present invention, by using the polyester resin, latent thermosetting can be imparted, it has excellent storage stability, and is effective from the viewpoint of workability and convenience. . Moreover, since it is excellent in storage stability as mentioned above, it can be used effectively as a one-component ink or adhesive.

In the polyester resin C, the molar ratio of the oxetane ring-containing diol oligomer A ₁ to the ester bond-containing diol oligomer A ₂ (hereinafter sometimes referred to as A ₁ / A ₂ ) is 1/9 to 9/1. It is. 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 oxetane ring-containing diol oligomer A ₁ is too high, the content of the ester bond-containing diol, which is a flexible component, becomes too low, and flexibility and warpage tend to be inferior. Conversely, if the ratio of the ester bond-containing diol oligomer A ₂ is too high, an oxetane ring concentration can not be sufficiently reactive carboxyl groups becomes low, it tends to soldering heat is poor because crosslinking density is not sufficient.

In order for the acid dianhydride to react with the hydroxyl group to cause a chain extension reaction, the amount of the acid dianhydride is important in controlling the molecular weight of the polyester resin C. Molar ratio of acid dianhydride / (the oligomer A ₁ + the oligomer A ₂ ) (hereinafter sometimes referred to as B / (A ₁ + A ₂ )) = 65/100 to 98/100, or 135 / Polymerization can be performed in the range of 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 smaller than 65/100 or larger than 135/100, the molecular weight of the polyester resin is not increased, 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. .

  The number average molecular weight of the polyester resin C is 1000 to 10000, preferably 1200 to 9000, and more preferably 1600 to 8500. If the number average molecular weight is less than 1000, the physical and chemical strength and durability of the coating film tend not to be ensured. On the other hand, if it 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 oxetane ring-containing diol oligomer A ₁ , an ester bond-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.

  Furthermore, it is preferable that the polyester resin C used in the present invention contains a phosphorus atom, and the phosphorus atom content (as a solid content ratio of the polyester resin) is preferably 0.5 to 7% by weight, More preferably, it is 1-6 weight%, More preferably, it is 2-5 weight%. If it is less than 0.5% by weight, it is necessary to add a large amount of a flame retardant in order to fully exert the flame retardancy, which tends to adversely affect the physical properties of the coating film other than the flame retardant, If it exceeds 7% by weight, the heat resistance tends to be deteriorated, which is not preferable.

<Modified polyester resin>
The modified polyester resin (modified polyester resin D) used in the present invention is obtained by reacting a residual carboxyl group in the polyester resin C before modification with a (meth) acrylic monomer having a functional group that reacts with the carboxyl group. Thus, the modified polyester resin D can be produced. At this time, part of the carboxyl group remains in the main chain of the modified polyester resin D, and further has an ethylenically unsaturated double bond in the side chain. 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.

The acid value of the modified polyester resin D used in the present invention is from 350 to 2000 was equivalent / 10 ⁶ g, preferably 400 to 1,500 equivalents / 10 ⁶ g, more preferably 400 to 1,000 equivalents / 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 in that the adhesion becomes poor and the film peels off from the substrate during development, which is not preferable. The acid value is derived from a carboxyl group (corresponding to a carboxyl group equivalent).

  The number average molecular weight of the modified polyester resin D used in the present invention is 2500 to 10,000, preferably 2500 to 8000, more preferably 2500 to 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.

The modified polyester resin D used in the present invention preferably has an oxetane ring, a carboxyl group, and an ester bond in the main chain, and the oxetane ring is preferably 350 to 1500 equivalents / 10 ⁶ g. More preferably, it is 500-1000 equivalent / 10 < ⁶ > g. Moreover, it is preferable that the said carboxyl group is 350-2000 equivalent / 10 < ⁶ > g (acid value), More preferably, it is 400-1500 equivalent / 10 < ⁶ > g. When the oxetane ring and the carboxyl group are smaller than the above ranges, the crosslinkability and alkali developability tend to deteriorate. Further, when the oxetane ring exceeds the above range, it becomes difficult to stably produce a polyester resin, and when the carboxyl group exceeds the above range, the alkali resistance of the cured film (curable layer) is deteriorated, and the electrical properties are reduced. This is not preferable because it causes problems such as reduction.

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 oxetane ring concentration can be calculated as an equivalent of 10 ⁶ g by dividing the equivalent of the oxetane ring-containing compound subjected to polymerization by the weight of the raw material provided for the modified polyester.

  Moreover, in this invention, a characteristic can be set to a desired range by adjusting the oxetane ring and carboxyl group in connection with thermosetting. Specifically, the ratio between the oxetane ring and the carboxyl group is preferably oxetane ring / carboxyl group (molar ratio) = 3/1 to 1/3, more preferably 2/1 to 1/2. Exceeding the above range is not preferable because the crosslinkability deteriorates.

  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 capable of reacting with the carboxyl group remaining in the polyester resin before modification. For example, glycidyl A (meth) acrylic monomer containing a group or a hydroxyl group is preferred. Specific examples include 3,4-epoxycyclohexyl methacrylate, 4-hydroxybutyl acrylate glycidyl ether, and glycidyl (meth) acrylate.

  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 to 30%, based on the residual carboxyl group in the polyester resin. 70 equivalent%. When 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.

Moreover, it is preferable that the ethylenically unsaturated double bond in the photocurable / thermosetting resin of the present invention has 500 to 2000 equivalent / 10 ⁶ g in the side chain of the resin, and more preferably 600 to 1500 equivalent. / 10 ⁶ g. If it is less than the above range, the photocuring property becomes insufficient, and if it exceeds the above range, the crosslink density increases, and if 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 an 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 (modified polyester resin D) used in 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. Although not particularly limited, for example, in a reaction can equipped with a stirrer and a thermometer, a reaction catalyst and a radical polymerization inhibitor were appropriately added to the polyester resin C dissolved in a solvent to obtain a uniform solution. After confirming this, a predetermined amount of 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, the oxetane ring may react with a carboxyl group to cause gelation. Therefore, a preferable polymerization temperature is 65 to 90 ° C., and a preferable polymerization time is 4 to 10 hours. It is.

  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, a phosphine such as triphenylphosphine is preferably used. 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 and a phosphorus-containing (meth) acrylic monomer and / or a phosphorus-containing allyl group-containing monomer which is a reactive diluent. Moreover, it is a preferable aspect to use together the (meth) acrylic-type monomer and / or allyl group containing monomer which do not contain phosphorus as said reactive diluent.

  Since the phosphorus-containing (meth) acrylic monomer and the phosphorus-containing allyl group-containing monomer can impart flame retardancy, the amount of the flame retardant added separately can be reduced, or the flame retardant The addition itself can be omitted, and deterioration of alkali developability, sensitivity, flexibility and warpage mechanical properties due to the addition of an excessive flame retardant can be prevented. Moreover, since the said modified polyester resin (modified polyester resin D) and ultraviolet curing are possible, it is hard to produce a bleed-out and can provide a flame retardance for a long period of time.

  Examples of the phosphorus-containing (meth) acrylic monomer include phosphoric acid triacrylate ethylene oxide adduct (trade name: Biscoat 3PA, manufactured by Osaka Organic Chemical Co., Ltd.), triacryloyloxyethyl phosphate, and the like. Examples of phosphorus-containing allyl group-containing monomers include 4,4′-bis (N, N, N ′, N′-tetraallyldiaminophosphoryl) biphenyl and 4,4′-bis (N, N, N ′). , N′-tetraallyldiaminophosphoryl) bisphenol and the like. In addition, since the phosphorus-containing (meth) acrylic monomer is superior in the ultraviolet curing reaction to the phosphorus-containing allyl group-containing monomer, it is more preferable to use a phosphorus-containing (meth) acrylic monomer. It is more preferable to use an acrylate ethylene oxide adduct.

  Further, as the reactive diluent, in addition to the phosphorus-containing (meth) acrylic monomer and / or phosphorus-containing allyl group-containing monomer, a (meth) acrylic monomer and / or allyl group-containing monomer not containing phosphorus is particularly used. Without limitation, it can be used. For example, monofunctional or polyfunctional acrylate monomers or oligomers 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) ) Acrylate, tetratrimethylolpropane tri (meth) acrylate, 1,4-butanediol diacrylate, pentaerythritol triacrylate , Trimethylolpropane triacrylate, tris (acryloxyethyl) isocyanurate, pentaerythritol (meth) acrylate, dipentaerythritol hexa (meth) acrylate, carbitol (meth) acrylate, phenoxyethyl (meth) acrylate, etc. Can do. These (meth) acrylic monomers may be used alone or in combination of two or more.

  The reactive diluent is usually contained in the photocurable / thermosetting resin composition in a solid content ratio of 5 to 40% by weight, preferably 7 to 30% by weight. When the addition amount of the reactive diluent is less than 5% by weight, the curing reaction does not proceed, and the remaining film ratio, heat resistance, chemical resistance and the like tend to decrease. If this amount exceeds 40% by weight, the solubility in the base resin reaches saturation, and the film surface homogeneity, for example, crystals of the polymerization initiator used during the spin coating or coating leveling, are deposited. May not be held, and there is a risk that a film roughness will occur.

  Moreover, the photocurable thermosetting resin composition of the present invention can contain a polymerization initiator in addition to the modified polyester resin and the reactive diluent. 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 are compounds that generate free radicals by the energy of ultraviolet rays, for example, benzophenone derivatives such as benzoin and benzophenone, or derivatives thereof such as xanthone and thioxanthone derivatives; chlorosulfonyl, chloromethyl polynuclear Halogen-containing compounds such as aromatic compounds, chloromethyl heterocyclic compounds and chloromethylbenzophenones; triazines; fluorenones; haloalkanes; redox couples of photoreductive dyes and reducing agents; organic sulfur compounds; peroxides and so on. Preferably, Irgacure 184, Irgacure 369, Irgacure 651, Irgacure 907 (all manufactured by Ciba Specialty Chemicals), Darocur (Merck), Adeka 1717 (Asahi Denka Kogyo Co., Ltd.), 2 , 2′-bis (o-chlorophenyl) -4,5,4′-tetraphenyl-1,2′-biimidazole (manufactured by Kurokin Kasei Co., Ltd.) it can. 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, hydroperoxides of t-butyl hydroperoxide, and dialkyl peroxides.

  In preparing the photocurable / thermosetting resin composition, the photoradical polymerization initiator or the polymerization initiator of the thermal radical polymerization initiator is the photocurable / thermosetting resin composition according to the present invention. It may be added 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.

  A photocurable / thermosetting resin composition containing the modified polyester resin (modified polyester resin D), a phosphorus-containing (meth) acrylic monomer and / or a phosphorus-containing allyl group-containing monomer, and a radical photopolymerization initiator. By reacting, specifically, by irradiating with light in the presence of a photoradical polymerization initiator, radicals are generated, a crosslinking reaction occurs, a rapid curing reaction is promoted, sensitivity is improved, and energy efficiency is increased. Therefore, since the photocuring reaction is completed in a short time, a photocurable / thermosetting resin can be obtained and workability 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. For example, 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 Inorganic flame retardants such as 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, zinc barium stannate Silicone flame retardant such as 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.

  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 is a compounding component such as a polyester resin (polyester resin C), a modified polyester resin (modified polyester resin D), a photocurable / thermosetting resin composition, or a polymerization initiator. It is possible to use a solvent having a good solubility in and having a relatively high boiling point. 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 adhesive film or the like is produced, it is necessary to remove (evaporate) the solvent. Therefore, it is preferable to use a solvent having a relatively low boiling point. Examples thereof include cyclopentanone having a boiling point of about 130 ° C. On the other hand, when manufacturing ink or adhesives, it is preferable to use a solvent having a relatively high boiling point. This is because the ring-opening reaction of the oxetane ring proceeds sufficiently. Examples thereof include γ-butyrolactone having a boiling point of about 200 ° C.

  Furthermore, the photocurable / thermosetting resin composition of the present invention has an epoxy group in the molecule as necessary for the purpose of improving heat resistance, adhesion and chemical resistance (particularly alkali resistance). One or more compounds (epoxy resin) can be blended. Examples of the compound having two or more epoxy groups in the molecule include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolak type epoxy resin and the like. Furthermore, cycloaliphatic epoxy resin and aliphatic polyglycidyl ether can also be illustrated. An acrylic copolymer containing glycidyl (meth) acrylate, alicyclic epoxy (meth) acrylate, etc. in the resin skeleton is also effective.

  Such an epoxy resin is usually contained in the photocurable / thermosetting resin composition in a solid content ratio of 5 to 30% by weight, preferably 10 to 20% by weight. When the content of the epoxy resin is less than 5% by weight, sufficient alkali resistance may not be imparted to the cured resin. On the other hand, when the content of the epoxy resin exceeds 30% by weight, the amount of the epoxy resin is excessively increased, so that the storage stability, flexibility, and development suitability of the photocurable / thermosetting resin composition are decreased. It is not preferable. The epoxy resin is also effective for removing the tack of the dried coating film of the photocurable / thermosetting resin composition, and a sufficient effect is exhibited when the addition amount is about 5% by weight. The epoxy resin reacts with the acidic group remaining in the coating film without reacting even after exposure and alkali development, and imparts excellent alkali resistance to the coating film.

  In addition to the above components, the photocurable / thermosetting composition of the present invention includes various types of surfactants, silane coupling agents, pigments, fillers (fillers), antifoaming agents, and the like as necessary. Additives can be blended.

<Ink etc.>
An ink can be obtained by using the photocurable / thermosetting resin composition of the present invention. Since the photocurable / thermosetting resin composition has latent curability, it can be cured by applying light or heat when necessary, and is excellent in workability and the like.

  When producing an ink using the photocurable / thermosetting resin composition, an inorganic or organic filler may be added in order to improve workability during coating and printing and film properties before and after film formation. This is a preferred embodiment.

  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.

  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, when a photoresist shape is produced 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, 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).

  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 the evaluation result, it showed in the following Tables 1-5.

<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 Table 2.

<Phosphorus concentration (phosphorus content): Determination of phosphorus by wet decomposition and molybdenum blue colorimetric method>
The sample was weighed into 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 thermally decomposed with an electric heater over a half day. After the solution becomes clear, 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 the boiling water bath, the volumetric flask is heated and colored, then cooled to room temperature, degassed with ultrasonic waves, 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 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

<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. The flame retardancy is UL94 standard, HB burns, worst, VTM-2 or more is preferable, VTM-1 is more preferable, and VTM-0 is most preferable.

<Synthesis example 1 of oxetane ring-containing diol oligomer>
In a reaction vessel equipped with a stirrer and a thermometer, 177 parts by weight of 3,3-bis (hydroxymethyl) oxetane (BHO) was dissolved in 642 parts by weight of cyclopentanone as a solvent, and dibutyltin as a catalyst. 0.1 part by weight of dilaurate was added and stirred and dissolved at 65 ° C. Then, 251 parts by weight of 4,4′-diphenylmethane diisocyanate (MDI) was added and stirred, and reacted at 80 ° C. for 6 hours. Thereby, the solid content concentration of the obtained oxetane ring-containing diol oligomer was 40% by weight, and the number average molecular weight was 880.

<Synthesis Example 2 of Oxetane Ring-Containing Diol Oligomer>
In a reaction vessel equipped with a stirrer and a thermometer, 177 parts by weight of 3,3-bis (hydroxymethyl) oxetane (BHO) was dissolved in 542 parts by weight of cyclopentanone as a solvent, and dibutyltin as a catalyst. 0.1 part by weight of dilaurate was added and stirred and dissolved at 65 ° C. Then, 184 parts by weight of 1,3-xylylene diisocyanate (XDI) was added and stirred, and reacted at 80 ° C. for 6 hours. Thereby, the solid content concentration of the obtained oxetane ring-containing diol oligomer was 40% by weight, and the number average molecular weight was 750.

<Synthesis example 1 of ester bond-containing diol oligomer>
166 parts by weight of terephthalic acid, 249 parts by weight of isophthalic acid, 865 parts by weight of 2- (10H-9-oxa-10-phospha-10-phenanthrylmethyl) succinic acid (PPMS) (trade name M-Ester, manufactured by Sanko) , 649 parts by weight of 3-methylpentanediol, 1008 parts by weight of hydrogenated dimer diol (trade name: Pripol 2033, manufactured by Claude Japan), 480 parts by weight of 1,9-nonanediol, and tetra-n-butyl titanate as a catalyst. 2 parts by weight were charged into an autoclave and an esterification reaction was performed at 220 to 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 60 minutes. Table 1 shows the composition, phosphorus content, number average molecular weight, and glass transition temperature (Tg) of the ester bond-containing diol oligomer (phosphorus-containing diol oligomer) thus obtained.

<Synthesis examples 2-3 of ester bond-containing diol oligomers and comparative synthesis examples 1-2>
In the same manner as in Synthesis Example 1, the raw materials shown in Table 1 were charged and polymerized to obtain an ester bond-containing diol oligomer. Table 1 shows the composition, phosphorus content, number average molecular weight, and glass transition temperature (Tg) of the resulting ester bond-containing diol oligomer.

注）ＰＰＭＳ：２−（１０Ｈ−９−オキサー１０−フォスファー１０−フェナンスリルメチル）
コハク酸、商品名Ｍ−Ｅｓｔｅｒ、三光製
水添ダイマージオール：商品名プリポール２０３３、クローダジャパン製
１，９−ノナンジオール：商品名ＮＤ、クラレ製
３−メチル−１，５−ペンタンジオール：商品名ＭＰＤ、クラレ製

Note) PPMS: 2- (10H-9-oxa-10-phosphor 10-phenanthrylmethyl)
Succinic acid, trade name M-Ester, Sanko hydrogenated dimer diol: trade name Pripol 2033, Croda Japan 1,9-nonanediol: trade name ND, Kuraray 3-methyl-1,5-pentanediol: trade name MPD, Kuraray

<Characteristics of modified polyester resin>
[Production Example 1]
In a reaction vessel equipped with a stirrer and a thermometer, 605 parts by weight of the solution obtained in Oxetane group-containing diol oligomer synthesis example 1, 338 parts by weight of ester bond-containing diol oligomer synthesis example 1, and cyclopentanone as a solvent 300 parts by weight and 2 parts by weight of 4-dimethylaminopyridine as a catalyst were added and stirred and dissolved at 65 ° C. Subsequently, 82 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 methylhydroquinone as a polymerization inhibitor and 2 parts by weight of triphenylphosphine as a reaction catalyst were added, and 3,4-epoxycyclohexyl methacrylate (functional group that reacts with residual carboxyl group) (Meth) acrylic monomer having cyclohexane M100, manufactured by Daicel Chemical Industries, Ltd.) 135 parts by weight 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 containing an oxetane ring, a carboxyl group, an ester bond, and a phosphorus atom. The solid content concentration of the obtained modified polyester resin was adjusted with cyclopentanone as a solvent so as to be 40% by weight. The characteristic results of this resin are shown in Table 2.

[Production Examples 2 to 6 and Comparative Production Examples 1 to 5]
Various modified polyester resins were obtained in the same manner as in Production Example 1 except that the composition of the 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>
[Example 1]
For 100 parts by weight of the modified polyester resin solution obtained in Production Example 1 of the modified polyester resin, 0.3 part by weight of “Irgacure 907” manufactured by Ciba Specialty Chemicals as the polymerization initiator and FA731A as the (meth) acrylic monomer 2 parts by weight (manufactured by Hitachi Chemical Co., Ltd.), 7 parts by weight of biscoat 3PA (manufactured by Osaka Organic Chemicals) which is ethylene oxide (EO) modified phosphoric triacrylate as phosphorus-containing (meth) acrylic monomer and 10H-9-oxa as flame retardant -10-phospha-10-phenanthrylmethylbenzene (trade name BCA, manufactured by Sanko Co., Ltd.), a photocurable thermosetting resin composition mixed with 4 parts by weight, a glossy surface of an electrolytic copper foil having a thickness of 18 μm, and The film thickness after drying on polyimide film (Kaneka Apical NPI) with a thickness of 25μm is 20μm. Coating and drying (80 ° C., 5 minutes) to obtain a dry coating film. 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. 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 to 6 and Comparative Examples 1 to 8]
Various photocurable / resin curable compositions and coating films were obtained in the same manner as in Example 1 except that the composition of the raw materials was changed as shown in Tables 4 and 5. Tables 4 and 5 show the composition of these compositions and the evaluation results of the coating film properties.

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
３ＰＡ：エチレンオキサイド（ＥＯ）変性リン酸トリアクリレート、
商品名ビスコート３ＰＡ、大阪有機化学製
ＢＣＡ：１０Ｈ−９−オキサ−１０−フォスファ−１０−フェナンスリルメチルベン ゼン、三光製

Note) FA731A: Tris (acryloxyethyl) isocyanurate, Hitachi Chemical 3PA: ethylene oxide (EO) modified phosphoric acid triacrylate,
Product name Biscoat 3PA, Osaka Organic Chemical BCA: 10H-9-oxa-10-phospha-10-phenanthrylmethylbenzene, Sanko

  In Examples 1 to 6, it can be confirmed that good evaluation results can be obtained in all evaluation items such as chemical characteristics such as alkali developability, mechanical characteristics such as warpage and flexibility, and flame retardancy. It was.

  Comparative Example 1 was inferior in sensitivity, solder heat resistance, flexibility, warpage, adhesion, and incombustibility. This is probably because the modified polyester used here has a low number average molecular weight, which makes the coating film brittle. Moreover, since the phosphorus containing reactive diluent is not used, it is considered that the phosphorus concentration is low and the flame retardancy is insufficient.

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

  Comparative Example 3 was inferior in alkali developability, sensitivity and flexibility, and had insufficient solder heat resistance. The modified polyester resin used here has a low acid value. For this reason, it is considered that the solubility of the modified polyester resin in an alkaline developer is reduced. In addition, since the number of carboxyl groups that react with the oxetane ring during the thermosetting reaction is extremely small, it is considered that the crosslink density during thermosetting becomes insufficient and the mechanical properties are lowered.

  In Comparative Example 4, the alkali developability and sensitivity were inferior, and the solder heat resistance was insufficient. The ester bond-containing diol oligomer used here has a high number average molecular weight, and the ester bond-containing segment obtained by using this is hydrophobic, and this segment is long, so the solubility in an alkaline developer is reduced. This is thought to be due to this.

  Comparative Example 5 was inferior to solder heat resistance, flexibility and warpage. The ester bond-containing diol oligomer used here has a high glass transition temperature. For this reason, it is thought that the obtained cured coating film becomes brittle and deteriorates mechanical properties. Further, since the acid value of the modified polyester resin is high and the residual amount of carboxyl groups after the curing reaction is large, it is considered that the water absorption is high and the solder heat resistance is poor.

  In Comparative Example 6, flame retardancy was good, but other alkali developability, sensitivity, solder heat resistance, flexibility, warpage, and adhesion were inferior. In this comparative example, neither a modified polyester resin nor a reactive diluent containing phosphorus was used, and an additive type phosphorus-containing flame retardant was blended in a large amount. For this reason, although flame retardance was ensured, other photoresist characteristics are considered to have deteriorated.

  Comparative Example 7 resulted in poor flame retardancy. Compared to Comparative Example 6, it was possible to obtain good alkali developability, sensitivity, solder heat resistance, flexibility, warpage, and adhesion by reducing the blending concentration of the additive-type phosphorus-containing flame retardant. However, the flame retardancy has deteriorated.

Comparative Example 8 resulted in poor flame retardancy. The reason for this is that neither phosphorus-containing polyesters nor reactive diluents containing phosphorus are used, and additive-type phosphorus-containing flame retardants are not included. It is thought that it is not.

Claims (11)

Ester bond-containing diol oligomer having an oxetane ring-containing segment based on the oxetane ring-containing diol oligomer A ₁ having at least two oxetane rings and hydroxyl groups at both ends, at least two or more ester bonds at both ends to hydroxyl groups A polyester resin C comprising an ester bond-containing segment based on A ₂ and a residual carboxyl group-containing segment B based on acid dianhydride,
The oxetane ring-containing segment and the ester bond-containing segment are combined with a residual carboxyl group-containing segment B based on the acid dianhydride,
The glass transition temperature of the ester bond-containing diol oligomer _{A 2} is, is at 0 ℃ or less and a number average molecular weight is 1000 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 1000 to 10000,
A modified polyester resin D obtained by reacting a residual carboxyl group in the polyester resin C with a (meth) acrylic monomer having a functional group that reacts with the residual carboxyl group, a phosphorus-containing (meth) acrylic monomer, and Containing phosphorus-containing allyl group-containing monomers,
In the main chain of the modified polyester resin D, a part of the residual carboxyl group remains, and in the side chain of the modified polyester resin D, it has an ethylenically unsaturated double bond,
The acid value of the modified polyester resin D is 350 to 2000 equivalents / 10 ⁶ g, and the number average molecular weight is 2500 to 10,000, A photocurable thermosetting resin composition.   The photocurable thermosetting resin composition according to claim 1, wherein the polyester resin C contains 0.5 to 7 wt% of phosphorus atoms. 3. The photocuring according to claim 1, wherein the oxetane ring-containing diol oligomer A ₁ is obtained by reacting a hydroxyl group in an oxetane ring-containing diol compound with an isocyanate group in a diisocyanate compound. And thermosetting resin composition. The ester bond-containing diol oligomer A _2, and hydroxyl groups in the diol compound, light according to claim 1, characterized in that is obtained by reacting a carboxyl group in the dicarboxylic acid Curable and thermosetting resin composition. At least a part of the diol compound and / or dicarboxylic acid contains a phosphorus atom,
The ester bond-containing diol oligomer A ₂ are, claim 4 photocurable and thermosetting resin composition, wherein the phosphorus containing diol oligomer.   The photocurable / thermosetting resin composition according to claim 1, wherein the functional group of the (meth) acrylic monomer is a glycidyl group and / or a hydroxyl group.   Furthermore, a flame retardant is contained, The photocurable thermosetting resin composition in any one of Claims 1-6 characterized by the above-mentioned.   A photocurable / thermosetting layer obtained by reacting the photocurable / thermosetting resin composition according to claim 1.   An ink comprising the photocurable / thermosetting resin composition according to claim 1.   An adhesive comprising the photocurable / thermosetting resin composition according to claim 1. A printed circuit board comprising the photocurable thermosetting layer according to claim 8 on the surface of the circuit board.