JP2011093999A - Carboxy group-containing resin, carboxy group-containing resin composition and cured product of the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a carboxy group-containing resin and a carboxy group-containing resin composition excellent in reliability of a cured film because of no halogen, and a cured product of the composition. <P>SOLUTION: The carboxy group-containing resin (E) is obtained by reacting secondary alcoholic hydroxy groups in a reaction product of a compound (A) having two alicyclic epoxy skeleton structures in one molecule and a compound (B) having two phenolic hydroxy groups in one molecule or a dibasic acid (C) having two carboxy groups in one molecule with a polybasic acid anhydride (D). A carboxy group-containing photosensitive resin (F) is obtained by introducing an unsaturated group into the carboxy group-containing resin (E). The carboxy group-containing resin composition contains the carboxy group-containing resin (E) and/or the carboxy group-containing photosensitive resin (F). The cured product of the composition is also provided. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a novel carboxyl group-containing resin, a carboxyl group-containing resin composition containing the resin, and a cured product thereof.

  Photosensitive resins made from phenol novolac resins with glycidyl ether groups are used in many fields related to electronic materials such as solder resists and etching resists because of their excellent heat resistance, adhesion, and chemical resistance. ing.

  However, in recent years, various electronic materials such as solder resists are increasingly required for reliability under severe use environments, and the presence of halogen (ions) due to the introduction of glycidyl ether groups becomes a problem. It has become like this.

  As a carboxyl group-containing photosensitive resin used in a solder resist, in Patent Document 1, a phenol novolac epoxy resin obtained by introducing a glycidyl ether group is reacted with an unsaturated group-containing monocarboxylic acid, and then a polybasic acid Resins reacted with anhydrides are used.

  Patent Document 2 makes use of the characteristics of novolac type phenolic resins such as heat resistance, toughness, flexibility, and water resistance, and reacts an unsaturated group-containing monocarboxylic acid with a product obtained by reacting a phenolic hydroxyl group with an alkylene oxide. Furthermore, a carboxyl group-containing photosensitive resin obtained by reacting a polybasic acid anhydride is described. However, a special facility such as an autoclave is required for the reaction between the novolak type phenol resin and the alkylene oxide.

  Patent Document 3 discloses a carboxyl group-containing photosensitive resin obtained by reacting a reaction product of a novolak-type phenol resin and a cyclic carbonate with an unsaturated group-containing monocarboxylic acid and further reacting with a polybasic acid anhydride. Is described.

JP-A 61-243869 Japanese Patent No. 3964326 Japanese Patent No. 3974875

  An object of the present invention is to provide a carboxyl group-containing resin, a carboxyl group-containing resin composition, and a cured product thereof, which are excellent in reliability of a cured film because they are halogen-free.

  As a result of intensive studies to solve the above problems, the present inventors have completed the present invention.

That is, the present invention relates to the following (1) to (4).
(1) Compound (A) having two alicyclic epoxy skeleton structures in one molecule and compound (B) having two phenolic hydroxyl groups in one molecule or two carboxyl groups in one molecule Carboxyl group-containing resin (E) obtained by reacting the polybasic acid anhydride (D) with the alcoholic secondary hydroxyl group of the reaction product (G) with the dibasic acid (C) having benzene.

(2) A carboxyl group-containing photosensitive resin (F) obtained by introducing an unsaturated group into the carboxyl group-containing resin (E) described in (1).
(3) A carboxyl group-containing resin composition containing the carboxyl group-containing resin (E) according to (1) and / or the carboxyl group-containing photosensitive resin (F) according to (2).
(4) Hardened | cured material of the carboxyl group-containing resin composition as described in said (3).

  The carboxyl group-containing resin of the present invention and the resin composition containing the resin are excellent in sensitivity, developability, and resolution, and contain no halogen (ion) in the resin. The reliability when used is greatly improved.

  The carboxyl group-containing resin (E) of the present invention comprises a compound (A) having two alicyclic epoxy skeleton structures in one molecule and a compound (B) having two phenolic hydroxyl groups in one molecule or It is obtained by reacting a polybasic acid anhydride (D) with an alcoholic secondary hydroxyl group of a reaction product (G) with a dibasic acid (C) having two carboxyl groups in one molecule.

  The compound (A) having two alicyclic epoxy skeleton structures in one molecule is directly or linked to two 4- to 8-membered aliphatic cyclic alkyl groups having one epoxy group on the ring. A compound bonded through a group. The two aliphatic cyclic alkyl groups may be the same or different. Examples of the aliphatic cyclic alkyl group include an epoxycyclopentyl group, an epoxycyclohexyl group, an epoxycycloheptyl group, and an epoxycyclooctyl group. Examples of the linking group include an alkylene group, an ester group, an ether group, and the like, and a group obtained by combining them may be used. The compound (A) having two alicyclic epoxy skeleton structures in one molecule can be produced by applying a known production method or a known literature method.

  Examples of the compound (A) include compounds represented by the following formulas (A-1) to (A-4). The compounds of (A-1) to (A-4) are disclosed in, for example, JP-A Nos. 62-164675, 2004-99467, U.S. Pat. No. 2,962,469, and JP-B-48-30673. It can be obtained by the production method described.

(A-1)

(A-2)

(A-3)

(A-4)

  The compound (A) having two alicyclic epoxy skeleton structures in one molecule can be used alone or in combination of two or more.

  As the compound (B) having two phenolic hydroxyl groups in one molecule, a conventionally known compound may be used. Examples of the compound (B) include hydroquinone, catechol, resorcinol, bis (4-hydroxyphenyl) ketone, bis (4-hydroxy-3,5-dimethylphenyl) ketone, bis (4-hydroxy-3,5- Dichlorophenyl) ketone, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxy-3,5-dimethylphenyl) sulfone, bis (4-hydroxy-3,5-dichlorophenyl) sulfone, bis (4-hydroxyphenyl) hexa Fluoropropane, bis (4-hydroxy-3,5-dimethylphenyl) hexafluoropropane, bis (4-hydroxy-3,5-dichlorophenyl) hexafluoropropane, bis (4-hydroxyphenyl) dimethylsilane, bis (4- Hydroxy-3,5-dimethylphenol Nyl) dimethylsilane, bis (4-hydroxy-3,5-dichlorophenyl) dimethylsilane, bis (4-hydroxyphenyl) methane, bis (4-hydroxy-3,5-dichlorophenyl) methane, bis (4-hydroxy-3) , 5-Dibromophenyl) methane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-) 3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3-chlorophenyl) propane, bis (4-hydroxyphenyl) ether, Bis (4-hydroxy-3,5-dimethylphenyl) ether, bis (4-hydroxy-3,5- Chlorophenyl) ether, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9,9-bis (4-hydroxy-3-chlorophenyl) fluorene, 9,9-bis (4-hydroxy-3-bromophenyl) fluorene, 9,9-bis (4-hydroxy-3-fluorophenyl) fluorene, 9,9-bis (4-hydroxy-3-methoxyphenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dimethylphenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dichlorophenyl) fluorene, 9,9-bis (4-hydroxy-3,5 -Dibromophenyl) fluorene, 4,4'-biphenol, 3,3'-biphenol and the like. You may use these individually or in combination of 2 or more types.

  As the dibasic acid (C) having two carboxyl groups in one molecule, a conventionally known compound can be used. Examples of the dibasic acid (C) include succinic acid, adipic acid, isophthalic acid, terephthalic acid, biphenyldicarboxylic acid, oxydibenzoic acid, thiodibenzoic acid, dithiodibenzoic acid, carbonyldibenzoic acid, sulfonyldibenzoic acid, Naphthalenedibenzoic acid, methylenedibenzoic acid, isopropylidenedibenzoic acid and the like can be mentioned. You may use these individually or in combination of 2 or more types.

  A compound (A) having two alicyclic epoxy skeleton structures in one molecule and a compound (B) having two phenolic hydroxyl groups in one molecule, or two having two carboxyl groups in one molecule The reaction with the basic acid (C) is preferably carried out in the absence of a solvent, but if necessary, an appropriate solvent that does not participate in the reaction can be used, and the solubility of raw materials, the suppression of side reactions, and the boiling point Ketone solvents such as isobutyl ketone and cyclopentanone are preferred.

  Further, a reaction catalyst can be used. Examples of the catalyst include quaternary ammonium salts such as tetramethylammonium chloride, tetramethylammonium bromide and trimethylbenzylammonium chloride; triphenylethylphosphonium chloride, triphenylphosphonium bromide and the like. Quaternary phosphonium salts; alkali metal salts such as sodium hydroxide, potassium hydroxide, potassium carbonate, cesium carbonate; 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, etc. Imidazoles; Tertiary amines such as 2- (dimethylaminomethyl) phenol, triethylenediamine, triethanolamine, 1,8-diazabicyclo (5,4,0) undecene-7; Organic phosphines such as diphenylphosphine and tributylphosphine; metal compounds such as tin octylate; tetrasubstituted phosphonium tetrasubstituted borates such as tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium ethyltriphenylborate, 2-ethyl- And tetraphenylborate such as 4-methylimidazole / tetraphenylborate and N-methylmorpholine / tetraphenylborate. When the catalyst is used, the amount used depends on the type of the catalyst, but is generally about 10 ppm to 30000 ppm, preferably about 100 ppm to 5000 ppm with respect to the total resin amount.

The reaction temperature and reaction time may be appropriately selected depending on the resin concentration, the presence / absence and use of the solvent, the presence / absence of the catalyst and the amount used, and the reaction time is usually 1 to 100 hours, preferably 1 to It is about 50 hours. The reaction time is preferably short from the viewpoint of productivity.
Moreover, reaction temperature is 50-250 degreeC normally, Preferably it is about 80-180 degreeC.

  At the end of the reaction, the epoxy equivalent (g / eq.) Was 20000 g / eq. It must be above. Epoxy equivalent is 20000 g / eq. In the following cases, the molecular weight of the carboxyl group-containing resin (E) obtained in the subsequent polybasic acid anhydride addition step tends to vary due to the influence of the residual epoxy group.

  A conventionally well-known compound can also be used as this polybasic acid anhydride (D). The polybasic acid anhydride (D) is not particularly limited as long as it is a compound having an acid anhydride structure in one molecule, and is excellent in alkaline aqueous solution developability, heat resistance, hydrolysis resistance, and the like. Preferred are succinic acid, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, itaconic anhydride, 3-methyl-tetrahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride, trimellitic anhydride or maleic anhydride .

  The addition reaction of the polybasic acid anhydride (D) to the reactant (G) can be performed under the same conditions as the reaction of the compound (A) with the compound (B) or dibasic acid (C). A calculated amount of the polybasic acid anhydride (D) for obtaining an acid value according to the purpose may be used.

  The present invention also includes a carboxyl group-containing photosensitive resin (F) obtained by introducing an unsaturated group into the carboxyl group-containing resin (E).

  The introduction of the unsaturated group is the carboxyl group of the carboxyl group-containing resin (E), or the reaction product remaining in the addition reaction of the polybasic acid anhydride (D) during the production of the carboxyl group-containing resin (E) ( It is performed on the alcoholic secondary hydroxyl group of G).

  When an unsaturated group is introduced into the alcoholic secondary hydroxyl group, an unsaturated group-containing monocarboxylic acid, an unsaturated group-containing isocyanate, or the like is used.

  Examples of the unsaturated group-containing monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, and cinnamic acid. As the reaction conditions, ordinary esterification reaction conditions can be applied.

  That is, in the presence of an organic solvent described later, the reaction is usually performed at 50 to 150 ° C. in the presence of a polymerization inhibitor such as hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, catechol, and pyrogallol as necessary. Furthermore, sulfuric acid, hydrochloric acid, phosphoric acid, boron trifluoride, methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, cation exchange resin, and the like can be used as a reaction catalyst as necessary.

  Examples of the organic solvent include benzene, toluene, xylene, tetramethylbenzene, n-hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, octane, methyl isobutyl ketone, diisopropyl ether, and the like.

  Examples of the unsaturated group-containing isocyanate include methacryloyloxyethyl isocyanate and acryloyloxyethyl isocyanate.

  The reaction temperature is usually 30 to 150 ° C, preferably 50 to 100 ° C.

  A catalyst may be added for the purpose of shortening the reaction time. As the catalyst, either a basic catalyst or an acidic catalyst is used. Examples of the basic catalyst include amines such as pyridine, pyrrole, triethylamine, diethylamine, dibutylamine and ammonia, and phosphines such as tributylphosphine and triphenylphosphine. Examples of the acidic catalyst include naphthenic acid metal salts such as copper naphthenate, cobalt naphthenate and zinc naphthenate, metal alkoxides such as tributoxyaluminum, trititanium tetrabutoxide and zirconium tetrabutoxide, and Lewis acids such as aluminum chloride. , Tin compounds such as 2-ethylhexanetin, octyltin trilaurate, dibutyltin dilaurate, and octyltin diacetate. The amount of these catalysts added is usually about 10 ppm to 10000 ppm with respect to the unsaturated group-containing isocyanate.

  When introducing an unsaturated group into the carboxyl group of the carboxyl group-containing resin (E), a compound having an alcoholic hydroxyl group and an unsaturated group in one molecule is used. Examples of the compound include monofunctional and polyfunctional (meth) acrylates such as hydroxyl group-containing (meth) acrylates, (meth) acrylic esters of pentaerythritols, (meth) acrylic esters of methylols, and epoxy acrylates. A compound can be mentioned.

As the reaction conditions, ordinary esterification reaction conditions can be applied.
That is, in the presence of an organic solvent described later, the reaction is usually performed at 50 to 150 ° C. in the presence of a polymerization inhibitor such as hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, catechol, and pyrogallol as necessary. Furthermore, sulfuric acid, hydrochloric acid, phosphoric acid, boron trifluoride, methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, cation exchange resin, and the like can be used as a reaction catalyst as necessary.

  Examples of the organic solvent include benzene, toluene, xylene, tetramethylbenzene, n-hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, octane, methyl isobutyl ketone, diisopropyl ether, and the like.

  Furthermore, the present invention includes a carboxyl group-containing resin composition containing a carboxyl group-containing resin (E) and / or a carboxyl group-containing resin (F). The carboxyl group-containing resin composition is preferably easily cured by active energy rays, and the cured product is also included in the present invention. Examples of the active energy rays include electromagnetic waves such as ultraviolet rays, visible rays, infrared rays, X-rays, gamma rays and laser rays, and particle rays such as alpha rays, beta rays and electron rays. Of these, ultraviolet rays, laser beams, visible rays, or electron beams are preferred in view of suitable applications of the present invention.

  The carboxyl group-containing resin composition of the present invention can be used for molding materials, film-forming materials, resist material compositions and the like, but is not limited thereto.

  As the molding material, for example, a so-called nanoimprint that performs fine molding by pressing a flatly molded sheet, a sealing material for protecting an element, and a “mold” that has been finely processed into an uncured composition. Examples thereof include materials, particularly peripheral sealing materials such as light-emitting diodes and photoelectric conversion elements, which have severe thermal requirements.

  Examples of the film-forming material include ink materials such as gravure ink, flexo ink, silk screen ink, and offset ink, coating materials such as hard coat, top coat, overprint varnish, and clear coat, and laminates and optical disks. Examples thereof include other adhesive materials such as adhesives and pressure-sensitive adhesives, and resist materials such as solder resists, etching resists, and micromachine resists. Furthermore, after the layer of the cured product of the carboxyl group-containing resin composition of the present invention is temporarily formed on a peelable substrate and formed into a film, it is bonded to the originally intended substrate and the peelable substrate is removed. A so-called dry film that forms a film on a substrate also corresponds to the film forming material.

  The resist material composition is formed by forming a film layer of the composition on a base material, and then partially irradiating active energy rays such as ultraviolet rays using a mask or the like to form an irradiated portion and an unirradiated portion. It refers to an active energy ray-sensitive composition drawn using physical differences. That is, the composition is used for the purpose of removing the irradiated or unirradiated part by dissolving the irradiated part or unirradiated part by some method such as a solvent or an alkali solution.

  The resist material composition can be applied to various materials that can be patterned. For example, the resist material composition is useful as a solder resist material and an interlayer insulating material for a build-up method, such as a printed wiring board, an optoelectronic substrate, and an optical substrate. It is also used for various electrical / electronic / optical substrates.

  As a particularly suitable application, a permanent resist such as a solder resist material is preferable taking advantage of the feature of being halogen-free.

  To the carboxyl group-containing resin composition of the present invention, other components can be added up to 90% by weight in the resin composition for the purpose of adapting to various uses. Examples of other components include a photopolymerization initiator, other additives, a coloring material, and a volatile solvent added for viscosity adjustment for the purpose of imparting coating suitability.

  Examples of the photopolymerization initiator include radical photopolymerization initiators and cationic photopolymerization initiators.

  Examples of the radical photopolymerization initiator include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether; acetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2 -Diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxyhexylphenyl ketone, 2-methyl-1- [4 Acetophenones such as-(methylthio) phenyl] -2-morpholino-propan-1-one; acetylphenones such as 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-chloroanthraquinone and 2-amylanthraquinone Traquinones; thioxanthones such as 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyldimethyl ketal; benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide Benzophenones such as 4,4′-bismethylaminobenzophenone; phosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide. .

  Examples of the cationic photopolymerization initiator include Lewis acid diazonium salt, Lewis acid iodonium salt, Lewis acid sulfonium salt, Lewis acid phosphonium salt, other halides, triazine initiator, borate initiator, and others. And a photoacid generator.

  Examples of the diazonium salt of Lewis acid include p-methoxyphenyldiazonium fluorophosphonate, N, N-diethylaminophenyldiazonium hexafluorophosphonate (Sun Shine SI-60L / SI-80L / SI-100L, etc. manufactured by Sanshin Chemical Industry Co., Ltd.) Etc.

  Examples of the Lewis acid iodonium salt include diphenyliodonium hexafluorophosphonate and diphenyliodonium hexafluoroantimonate.

  Examples of the sulfonium salt of Lewis acid include triphenylsulfonium hexafluorophosphonate (such as Cyracure UVI-6990 manufactured by Union Carbide), triphenylsulfonium hexafluoroantimonate (such as Cyracure UVI-6974 manufactured by Union Carbide), and the like. It is done.

  Examples of the phosphonium salt of Lewis acid include triphenylphosphonium hexafluoroantimonate.

  Examples of the other halides include 2,2,2-trichloro- [1-4 ′-(dimethylethyl) phenyl] ethanone (Trigonal PI, etc., manufactured by AKZO), and 2,2-dichloro-1-4. -(Phenoxyphenyl) ethanone (Sandray 1000 manufactured by Sandoz, etc.), α, α, α-tribromomethylphenyl sulfone (manufactured by Steel Manufacturing Chemical Co., Ltd., BMPS, etc.) and the like.

  Examples of the triazine-based initiator include 2,4,6-tris (trichloromethyl) triazine, 2,4- (trichloromethyl)-(4′-methoxyphenyl) -6-triazine (Triazine A manufactured by Panchim), etc. ), 2,4-trichloromethyl- (4′-methoxystyryl) -6-triazine (Triazine PMS, etc., manufactured by Panchim), 2,4- (trichloromethyl)-(pipronyl) -6-triazine (Triazine, manufactured by Panchim) PP, etc.), 2,4- (trichloromethyl)-(4′-methoxynaphthyl) -6-triazine (Trizine B, etc., manufactured by Panchim), 2- [2 ′-(5 ″ -methylfuryl) ethylidene]- 4,6-bis (trichloromethyl) -s-triazine (manufactured by Sanwa Chemical Co., Ltd.), 2- (2′-furylethylidene) -4,6-bis (trichloromethyl) -s-triazine (manufactured by Sanwa Chemical Co., Ltd.) and the like.

  Examples of the baud rate initiator include NK-3876 or NK-3881 manufactured by Nippon Photosensitive Dye.

  Examples of other photoacid generators include 9-phenylacridine, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2-biimidazole. (Kurokin Kasei Biimidazole, etc.), 2,2-azobis (2-amino-propane) dihydrochloride (Wako Pure Chemical Industries, Ltd. V50 etc.), 2,2-azobis [2- (imidazolin-2-yl) propane ] Dihydrochloride (VA044 manufactured by Wako Pure Chemical Industries, Ltd.), [Eta-5-2-4- (cyclopentadecyl) (1,2,3,4,5,6, eta)-(methylethyl) benzene] iron (II) hexafluorophosphonate (Irgacure 261, etc., manufactured by Ciba Geigy), bis (y5-cyclopentadienyl) bis [2,6-difluoro-3- (1H-pyridine-1) -Yl) phenyl] titanium (CGI-784 manufactured by Ciba Geigy) and the like.

  Furthermore, an azo initiator such as azobisisobutyronitrile, a peroxide radical initiator sensitive to heat such as benzoyl peroxide, and the like may be used in combination with the photopolymerization initiator.

  These photopolymerization initiators may be used alone or in combination of two or more. Also, both radical and cationic initiators may be used in combination.

  Other additives include, for example, thermosetting catalysts such as melamine, thixotropy imparting agents such as Aerosil, silicone and fluorine leveling agents and antifoaming agents, polymerization inhibitors such as hydroquinone and hydroquinone monomethyl ether, stabilizers, Antioxidants and the like can be used.

  Other pigment materials may be used, for example, those not intended for coloring, so-called extender pigments such as talc, barium sulfate, calcium carbonate, magnesium carbonate, barium titanate, aluminum hydroxide, silica, clay Etc. can also be used.

  The carboxyl group-containing resin composition of the present invention includes resins that are not reactive to active energy rays (so-called inert polymers) such as other epoxy resins, phenol resins, urethane resins, polyester resins, ketone formaldehyde resins, Cresol resin, xylene resin, diallyl phthalate resin, styrene resin, guanamine resin, natural and synthetic rubber, acrylic resin, polyolefin resin, or modified products thereof can also be used. These are preferably used in the range of up to 40% by weight.

  In particular, when a carboxyl group-containing resin (E) or a carboxyl group-containing photosensitive resin (F) is used for solder resist applications, it is preferable to use an epoxy resin as a resin that does not react with active energy rays. This is because the water resistance and hydrolyzability of the cured product may be inferior due to the carboxyl group remaining after reacting and curing with active energy rays, and reacting with the remaining carboxyl group by using the epoxy resin It is prevented by making it carboxylate, and has an effect of forming a stronger crosslinked structure.

  In order to adjust the viscosity according to the purpose of use, a volatile solvent may be added to the resin composition in a range of 50% by weight, more preferably up to 35% by weight.

  EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to these Examples. Moreover, unless otherwise indicated, a part shows a weight part in an Example.

The epoxy equivalent, acid value, and molecular weight were measured under the following conditions.
1) Epoxy equivalent: measured by a method according to JIS K 7236: 2001 2) Acid value: measured by a method according to JIS K 0070: 1992 3) GPC measurement conditions are as follows Model: TOSOH HLC-8220 GPC
Column: TSKGEL Super HZM-N
Eluent: THF (tetrahydrofuran); 0.35 ml / min, temperature 40 ° C.
Detector: Differential refractometer Molecular weight standard: Polystyrene

Synthesis example 1
In a flask equipped with a stirrer and a reflux tube, Nippon Kayaku SEJ-01R (epoxy equivalent 133 g / eq.) As a compound (A) having two alicyclic epoxy skeleton structures in one molecule is 22. 1 g, 25 g of bisphenol F and 0.14 g of triphenylphosphine were added as a compound (B) having two phenolic hydroxyl groups in one molecule, and reacted at 130 ° C. for 24 hours. The epoxy equivalent after the reaction was 23000 g / eq. Met. Thereafter, 31 g of methyl isobutyl ketone was added for dilution, 25 g of tetrahydrophthalic anhydride was added as the polybasic acid anhydride (D), and the mixture was reacted at 110 ° C. for 6 hours. The acid value of the reaction liquid at this time was 94 mgKOH / g.

  The obtained carboxyl group-containing resin (E-1) solution was dropped into the stirred cyclohexanone to precipitate the resin (E-1). Then, the solvent was removed by decantation, and further dried with a drier, to obtain 70 g (yield 85%) of carboxyl group-containing resin (E-1). The carboxyl group-containing resin (E-1) had a solid content acid value of 132 gKOH / g and a weight average molecular weight of 4400 as measured by GPC.

  Hydroxyethyl acrylate was used for introduction of the unsaturated group into the carboxyl group-containing resin (E-1). In a flask equipped with a stirrer and a Dean-stark tube, 50 g of carboxyl group-containing resin (E-1), 6.34 g of hydroxyethyl acrylate, 35 g of toluene as a reaction solvent, 1.5 g of sulfuric acid, 0.5 g of methoquinone And reacted at 100 ° C. for 6 hours. Thereafter, the reaction solution was transferred to a separatory funnel, washed with water, and then the solvent was removed to obtain 46 g of a carboxyl group-containing photosensitive resin (F-1) having a chlorine content in the resin of 5 ppm or less. The acid value of the carboxyl group-containing photosensitive resin (F-1) was 70 mgKOH / g, and the weight average molecular weight measured by GPC was 3900.

Example 1 and Comparative Example 1
The carboxyl group-containing photosensitive resin (F-1) obtained in Synthesis Example 1 or Nippon Kayaku acid-modified epoxy acrylate KAYARAD CCR-1159H containing several hundred ppm of chlorine in the resin is shown in Table 1. Each component was mixed at a blending ratio and kneaded with a three-roll mill to obtain a photosensitive resin composition. This was applied onto a substrate by a screen printing method, and the coating film was dried with a hot air dryer at 80 ° C. for 30 minutes. Next, in order to estimate the mask or sensitivity on which the circuit pattern was drawn using an ultraviolet exposure apparatus (Oak Manufacturing Co., Ltd., model HMW-680GW), Kodak Step Tablet No. 2 was irradiated with ultraviolet rays of 500 mJ / cm ² . Thereafter, spray development was performed with a 1% sodium carbonate aqueous solution to remove the resin in the non-irradiated part. After washing with water and drying, the printed circuit board was heated with a hot air dryer at 150 ° C. for 60 minutes to be post-cured to obtain a cured film.

Table 1 Composition of photosensitive resin composition for printed wiring board

Irgacure 907: 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one DETX-S manufactured by Ciba Specialty Chemicals 2,4-dimethylthioxanthone DPEA12 manufactured by Nippon Kayaku Multifunctional acrylate RE306: Nippon Kayaku bisphenol A epoxy resin melamine: 2,4,6-triamino-1,3,5-triazine barium sulfate: Sakai Chemical B30
Phthalocyanine Blue: Lionel Green 2YS made by Dainichi Seika
KS-66: KS-66 manufactured by Shin-Etsu Chemical
DPM: Dipropylene glycol monomethyl ether manufactured by Kyowa Hakko Chemical

  Next, the test method is described.

Sensitivity Sensitivity was determined by how many density portions remained in the exposed portion that passed through the step tablet during development. The higher the number of steps (value), the higher the sensitivity of the tablet. (Unit: Step)

Developability After exposure, development was performed at a spray pressure of 0.2 MPa for 60 seconds using a 1 wt% aqueous sodium carbonate solution at a liquid temperature of 30 ° C., and the time until the resin composition in the unexposed area was removed visually was measured. .

◎: Less than 25 seconds ○: More than 25 seconds, less than 45 seconds ×: More than 45 seconds

After applying the tack, the substrate was dried for 30 minutes with a hot air dryer at 80 ° C., and it was judged whether or not a mark touching the coating film was made.
◎: No mark on the coating film ○: Stickiness when touched ×: Mark on touching the coating film

Resolution The film was exposed through a photomask, and the resolution was confirmed with a 1/1 line and space line size obtained.
◎: 80 μm or less ○: 80 μm or more, 150 μm or less ×: 150 μm or more

HAST
As a reliability evaluation for temperature and humidity, electrical characteristics under high temperature and high humidity were evaluated. The evaluation board | substrate produced on the comb-type electrode board | substrate (a line and space is 100 micrometers / 100 micrometers) on the said conditions is 120 degreeC, 85% R. H. A bias voltage of DC 100 V was applied in a high-temperature and high-humidity tank (relative humidity), and the presence or absence of migration after 120 hours and 240 hours was confirmed.
○: No change △: Slight change is observed ×: Migration occurs

Table 2

    From the results of Table 2 above, it was found that Composition 1 was excellent in sensitivity, developability, tack, and resolution, and was excellent in a reliability test by HAST, which is most important as a photosensitive resin composition for printed wiring boards. .

Claims (4)

A compound (A) having two alicyclic epoxy skeleton structures in one molecule and a compound (B) having two phenolic hydroxyl groups in one molecule, or two having two carboxyl groups in one molecule A carboxyl group-containing resin (E) obtained by reacting a polybasic acid anhydride (D) with a secondary alcoholic hydroxyl group of a reaction product with a basic acid (C). A carboxyl group-containing photosensitive resin (F) obtained by introducing an unsaturated group into the carboxyl group-containing resin (E) according to claim 1. A carboxyl group-containing resin composition comprising the carboxyl group-containing resin (E) according to claim 1 and / or the carboxyl group-containing photosensitive resin (F) according to claim 2. Hardened | cured material of the carboxyl group-containing resin composition of Claim 3.