JP4406232B2 - Ultraviolet curable polyester resin and method for producing the same, ultraviolet curable resin composition, cured product thereof and printed wiring board - Google Patents

Description

The present invention relates to an ultraviolet curable polyester resin having both an ethylenically unsaturated group and a carboxyl group and a production method thereof, an ultraviolet curable resin composition containing the polyester resin, a cured product of the ultraviolet curable resin composition, and the The present invention relates to a printed wiring board having a layer made of a cured product.

  Conventionally, a printed wiring board in which a permanent protective film made of photo solder resist ink is formed on a base substrate has been used. This photo solder resist ink is a developable liquid photo solder with excellent resolution and dimensional accuracy in order to cope with the fine and high density of the conductor pattern of various printed wiring boards for consumer and industrial use. Resist ink or the like is preferably used.

  Such printed wiring boards have conventionally generated halides such as bromide as a flame retardant component, and thus generate toxic gases during combustion. However, in recent years, there has been concern for environmental problems and human safety. Along with this increase, printed wiring boards that do not generate toxic gas during combustion have been demanded. For example, dehalogenated glass epoxy copper clad laminates have been developed. As such a dehalogenated base substrate, a substrate in which a phosphorus-based flame retardant is used as a flame retardant instead of a halogen-based one has been proposed.

  As the demand for further flame retardancy improvement and halogen content reduction increases, the photo solder resist for forming a permanent protective film is also required to improve flame retardancy and reduce halogen content. It is getting to be. In order to meet such a demand, conventionally, a photo solder resist ink containing a phosphorus compound as a flame retardant component has been proposed.

  Such a photo solder resist needs to have various properties as a photo solder resist such as exposure / development characteristics as well as achieving flame retardance without depending on halogen by containing phosphorus.

  As such a photo solder resist ink, for example, one disclosed in Patent Document 1 has been proposed. This photo solder resist ink comprises an unsaturated group-containing diol compound obtained by reacting an epoxy resin with an unsaturated group-containing monocarboxylic acid, and 2- (9,10-dihydro-9-oxa-10-oxide-10. -Phosphaphenanthrene-10-yl) methylsuccinic acid-bis- (2-hydroxyethyl) -ester or a polycondensate thereof, a polyol compound other than the above as an optional component, and at least two acid anhydride groups in one molecule It contains an unsaturated group-containing polycarboxylic acid resin obtained by reacting a compound having two as a resin component.

  In this photo solder resist ink, exposure curability is imparted mainly by imparting an unsaturated bond by an unsaturated group-containing diol compound obtained by reacting an epoxy resin with an unsaturated group-containing monocarboxylic acid. The solubility in water or dilute alkaline solution is imparted by the basic acid anhydride, and 2- (9,10-dihydro-9-oxa-10-oxide-10-phosphaphenanthren-10-yl) methylsuccinic acid-bis- Flame retardancy is imparted by (2-hydroxyethyl) -ester or a polycondensate thereof.

By the way, the factors that determine the performance of the photo solder resist ink include the acid value, molecular weight, double bond equivalent, etc. of the UV curable resin. If the acid value is too low, developability will be poor, and if it is too high, the electrical characteristics and anticorrosion resistance will be. May cause problems such as deterioration in water resistance and water resistance. On the other hand, if the molecular weight is too low, the sensitivity tends to be insufficient, and if it is too high, there is a possibility of causing a problem of deterioration in developability. In addition, if the double bond equivalent is too high, the sensitivity tends to be insufficient. For these reasons, when designing an ultraviolet curable resin, it is necessary to have an appropriate acid value, molecular weight, double bond equivalent, etc. according to the intended use.
JP 2000-327758 A

  In the unsaturated group-containing polycarboxylic acid resin as disclosed in Patent Document 1, the unsaturated group-containing diol compound and 2- (9,10-dihydro-9-oxa-10-oxide-10-phos Faphenanthrene-10-yl) methylsuccinic acid-bis- (2-hydroxyethyl) -ester or a polycondensate thereof reacts only with a compound having at least two acid anhydride groups in one molecule. Therefore, when an attempt is made to increase the ratio of the unsaturated group-containing polyol compound in order to improve the double bond amount in the resulting resin, 2- (9,10-dihydro-9-oxa-10-oxide-10- The ratio of phosphaphenanthrene-10-yl) methylsuccinic acid-bis- (2-hydroxyethyl) -ester or its polycondensate decreases, flame retardancy decreases, and When you try to improve the flame retardancy by increasing the proportion of the phosphorus compound, it is necessary to lower the proportion of unsaturated group-containing polycarboxylic acid resin was achieved, double bond equivalent decreases. Further, by changing the use ratio of these compounds, the acid value and the molecular weight also fluctuate at the same time, and it was difficult to obtain a resin having a desired acid value.

  From the above, in the method as disclosed in Patent Document 1 above, the combination of raw materials for obtaining a resin having desired characteristics is limited, and the resin obtained if the raw materials to be used are the same Therefore, it is difficult to appropriately control the characteristics to desired ones, and the degree of freedom in material design is reduced. For this reason, when changing the design of a material, it is necessary to first reexamine the selection of raw materials, which is very troublesome and makes it difficult to procure stable raw materials. It was a thing.

The present invention has been made in view of the above points, and is excellent in various properties such as resolution, sensitivity, solder heat resistance, substrate adhesion, chemical resistance, and corrosion resistance, and particularly excellent flame retardancy. Can be formed, and the acid value, molecular weight, double bond equivalent, etc. and phosphorus content can be easily designed independently, and the degree of freedom in material design is high. UV curable polyester resin capable of preparing an ultraviolet curable resin composition developable with a dilute alkaline aqueous solution that can be suitably used as a photo solder resist ink, an interlayer insulating material for a printed wiring board, and a resist ink for a color filter, and The object is to provide a manufacturing method thereof.

Furthermore, the present invention is prepared with the above ultraviolet curable polyester resin, and can be used for a photo solder resist ink, an interlayer insulating material for a printed wiring board, a resist ink for a color filter, and the like. UV curable resin composition developable with dilute alkaline aqueous solution that can be suitably used as a photo solder resist ink that can improve flame retardancy when used as a printed wiring board in combination with the UV curable resin composition It is an object of the present invention to provide a cured product formed in this manner and a printed wiring board on which a layer of the cured product is formed.

The method for producing a polyester resin according to the present invention comprises reacting a polyol compound (a) having a structure represented by the following structural formula (1) with a compound (c) having at least two acid anhydride groups in one molecule. Then, a monoepoxy compound (d) having one or more ethylenically unsaturated groups in one molecule is reacted with some of the carboxyl groups in the compound obtained by this reaction. Compound (c) having at least two acid anhydride groups in one molecule is pyromellitic anhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1, Selected from 2-dicarboxylic anhydride. The monoepoxy compound (d) having one or more ethylenically unsaturated groups in one molecule is glycidyl methacrylate.

The polyester resin according to the present invention is obtained by reacting a polyol compound (a) having the structure represented by the structural formula (1) with a compound (c) having at least two acid anhydride groups in one molecule. It is obtained by reacting a monoepoxy compound (d) having one or more ethylenically unsaturated groups in one molecule with some of the carboxyl groups in the obtained compound. Compound (c) having at least two acid anhydride groups in one molecule is pyromellitic anhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1, Selected from 2-dicarboxylic anhydride. The monoepoxy compound (d) having one or more ethylenically unsaturated groups in one molecule is glycidyl methacrylate.

Moreover, the ultraviolet curable resin composition which concerns on this invention contains each component of said ultraviolet curable polyester resin A, the photoinitiator D, and the diluent E, It is characterized by the above-mentioned.

  Moreover, the said ultraviolet curable resin composition may contain the ultraviolet curable resin B which has an ethylenically unsaturated bond.

  The ultraviolet curable resin composition may contain a polyfunctional epoxy compound C.

  Moreover, the said ultraviolet curable resin composition may be prepared as a photo soldering resist ink for printed wiring boards.

  The cured product according to the present invention is obtained by curing and molding the ultraviolet curable resin composition as described above.

  Moreover, the printed wiring board according to the present invention is characterized by having a layer made of the cured product as described above.

In the ultraviolet curable polyester resin and the method for producing the same according to the present invention, the polyol compound (a) having the structure represented by the structural formula (1) and the compound (c) having at least two acid anhydride groups in one molecule ) And then reacting with a monoepoxy compound (d) having one or more ethylenically unsaturated groups in one molecule with a part of the carboxyl groups in the compound obtained by this reaction . to obtain the polyester resin, thereby imparting an ultraviolet-curable and an alkali soluble in the ultraviolet-curing polyester resin, good resolution in the cured product, sensitivity, solder heat resistance, substrate adhesion, chemical resistance, withstanding Various properties such as corrosion can be imparted, and further, a cured product exhibiting excellent flame retardancy can be formed without containing halogen.

  In addition, it becomes easy to design the acid content, molecular weight, double bond equivalent, etc. and phosphorus content independently, and the degree of freedom in material design is increased.

Therefore, this ultraviolet curable polyester resin can be suitably used for preparing an ultraviolet curable resin composition particularly suitable as a photo solder resist ink, an interlayer insulating material for printed wiring boards, and a resist ink for color filters. It is.

Moreover, since the ultraviolet curable resin composition according to the present invention contains the components of the ultraviolet curable polyester resin A, the photopolymerization initiator D, and the diluent E, the ultraviolet curable and alkali-soluble components are included. In addition, the cured product has excellent hardness, heat resistance, and adhesion to the substrate, and the cured product particularly has excellent flame retardancy without containing halogen. In particular, it can be suitably used for a solder resist forming application of a printed wiring board.

Moreover, at the time of synthesis of the ultraviolet curable polyester resin A, it becomes easy to independently design the acid value, molecular weight, double bond equivalent and the phosphorus content, and the degree of freedom in material design is increased.

  Further, the ultraviolet curable resin composition can contain an ultraviolet curable resin B having an ethylenically unsaturated bond, thereby adjusting the ultraviolet curable property and the physical properties of the cured product. It is something that can be done.

  In addition, the ultraviolet curable resin composition may contain a polyfunctional epoxy compound C, whereby thermosetting can be imparted to the ultraviolet curable resin, and further heat-cured after ultraviolet curing. Thus, the cured product properties such as strength, hardness and chemical resistance of the cured product can be further improved.

  Further, the ultraviolet curable resin composition may be prepared as a photo solder resist ink for a printed wiring board. In this case, the ultraviolet curable resin composition has excellent characteristics as a solder resist forming application for a printed wiring board, particularly in flame retardancy. An excellent solder resist can be formed.

  Further, the cured product according to the present invention is obtained by curing and molding the ultraviolet curable resin composition as described above, and thereby has excellent characteristics as a solder resist application for a printed wiring board, particularly flame retardant. It is excellent.

  Moreover, the printed wiring board according to the present invention has a layer made of the cured product as described above, and the layer made of the cured product has excellent flame retardancy on the printed wiring board. The solder resist which has can be formed.

  Embodiments of the present invention will be described below. In this specification, (meth) acrylic is a generic term for acrylic and methacrylic. For example, (meth) acrylic acid is a generic term for acrylic acid and methacrylic acid. is there.

[A. (UV curable polyester resin)
The polyester resin A according to the present invention is obtained by reacting a polyol compound (a) having a structure represented by the following structural formula (1) with a compound (c) having at least two acid anhydride groups in one molecule. It can be obtained by reacting some of the carboxyl groups in the resulting compound with a monoepoxy compound (d) having one or more ethylenically unsaturated groups in one molecule.

  As each of the above components (a) to (d), an appropriate one can be selected and used so that desired performance can be imparted to the polyester resin. Such a thing can be used.

  In the above reaction, when the polyol compound (a) and the compound (c) are reacted, the polyol compound (b) other than the polyol compound (a) may be reacted together.

When the monoepoxy compound (d) is reacted with the compound of the polyol compound (a) and the compound (c) or the compound of the polyol compound (a), the polyol compound (b) and the compound (c), In addition, a monoepoxy compound (e) other than the monoepoxy compound (d) may be reacted.

<Polyol compound (a)>
The polyol compound (a) having the structure represented by the above structural formula (1) is 2- (9,10-dihydro-9-oxa-10-oxide-10-phosphaphenanthrene-10-yl) methylsuccinic acid or its A polycondensation product of an acid anhydride and ethylene glycol, or 2- (9,10-dihydro-9-oxa-10-oxide-10-phosphaphenanthren-10-yl) methylsuccinic acid-bis- (2-hydroxy) Ethyl) -ester, or a polymer obtained by polycondensation thereof.

  The polycondensation reaction will be specifically described. For example, 2- (9,10-dihydro-9-oxa-10-oxide-10-phosphaphenanthrene-10-yl) methylsuccinic acid-bis- (2-hydroxyethyl) ) -Ester is added to the reaction vessel, and the temperature is gradually raised and heated. 2- (9,10-dihydro-9-oxa-10-oxide-10-phosphaphenanthrene-10-yl) methylsuccinic acid-bis- (2-hydroxyethyl) by heating within the temperature range of ° C. An ester copolymer is obtained.

  In this reaction, conventionally known titanium, antimony, lead, zinc, magnesium, calcium, manganese, alkali metal, or the like may be added as a catalyst at any time.

<Polyol compound (b)>
The polyol compound (b) other than the polyol compound (a) is appropriately used arbitrarily in order to improve various properties such as heat resistance and flexibility. As such a polyol compound (b), an appropriate one can be used and is not particularly limited. For example, a compound (s) having two epoxy groups in one molecule and one in one molecule An unsaturated group-containing polyol compound (b ₁ ) obtained by reacting the above monocarboxylic acid (t) having an ethylenically unsaturated group and a polyol compound other than the unsaturated group-containing polyol compound (b ₁ ) ( b ₂ ).

  As the compound (s) having two epoxy groups in one molecule, diglycidyl ethers, diglycidyl esters, diglycidyl amines and the like can be used. Diglycidyl ethers are diglycidyl ethers of polyol compounds, and can be obtained, for example, by reacting a polyol compound with epichlorohydrin. As the polyol compound, an appropriate one can be selected and used. For example, bisphenols such as bisphenol A, bisphenol F, bisphenol S, and tetrabromobisphenol A; hydrogenated products of the bisphenols, ethylene oxide modified products, polyethylene oxide modified products Products, propylene oxide modified products, polypropylene oxide modified products, caprolactone modified products, polycaprolactone modified products, etc .; biphenols such as biphenol, tetramethylbisphenol, tetraalkylbiphenol; ethylene glycol, propylene glycol, tetraethylene glycol, polyethylene glycol, polypropylene (Poly) alkylene glycols such as glycol and polytetramethylene glycol; neopentyl glycol, 1,6- Hexanediol, 3-methyl-1,5-pentanediol, 1,9-nonanediol may be mentioned 1,4-cyclohexanedimethanol, naphthalene diol and the like.

  Glycidyl esters are diglycidyl esters of polycarboxyl compounds, and can be obtained, for example, by reacting polycarboxylic acid with epichlorohydrin. As the polycarboxyl compound, an appropriate one is used, and examples thereof include phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, endomethylenetetrahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, succinic acid, maleic acid and the like. .

  Diglycidylamines can be obtained, for example, by reacting a polyamino compound and epichlorohydrin. Examples of the polyamino compound include aniline and o-toluidine.

  As the monocarboxylic acid (t) having one or more ethylenically unsaturated groups in one molecule, suitable ones are used. For example, (meth) acrylic acid, dibasic acid anhydride and hydroxyl group-containing (meth) Examples include half esters obtained by reacting acrylates, half esters obtained by reacting dibasic acids and monoglycidyl (meth) acrylates, and the like.

  Examples of (meth) acrylic acids include (meth) acrylic acid, dimers of acrylic acid, β-styrylacrylic acid, β-furfurylacrylic acid, and the like.

  As a dibasic acid anhydride used for the preparation of half esters obtained by reacting a dibasic acid anhydride with a hydroxyl group-containing (meth) acrylate, an appropriate saturated or unsaturated dibasic acid anhydride is used. For example, succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, itaconic anhydride, methylendomethylenetetrahydroanhydride Examples include phthalic acid. Further, suitable hydroxyl group-containing (meth) acrylates can be used. For example, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, glycerin di ( Examples thereof include (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and (meth) acrylate of phenylglycidyl ether.

  Moreover, as a dibasic acid used for the preparation of half esters obtained by reacting a dibasic acid with monoglycidyl (meth) acrylates, an appropriate saturated or unsaturated dibasic acid can be used, Examples include succinic acid, maleic acid, adipic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, itaconic acid, fumaric acid and the like. Monoglycidyl (meth) acrylates can also be used as appropriate. For example, glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, 2-methylglycidyl (meth) acrylate, (3,4 -Epoxycyclohexyl) methyl (meth) acrylate and the like. Other examples include crotonic acid and cinnamic acid.

  Of these monocarboxylic acids (t), it is particularly preferable to use (meth) acrylic acid.

A compound (s) having two epoxy groups in one molecule as described above and a monocarboxylic acid (t) having one or more ethylenically unsaturated groups in one molecule are reacted to produce an unsaturated group. In obtaining the contained polyol compound (b ₁ ), the reaction ratio between the (s) component and the (t) component is not particularly limited, but in particular, the chemical equivalent of the (t) component with respect to 1 epoxy equivalent of the (s) component. Is preferably in the range of 0.7 to 1.2.

An example of the chemical reaction formula at this time is shown below. In addition, R < ₄ > -R < ₈ > in a formula shows arbitrary substituents.

  At the time of reaction of this (s) component and (t) component, one or both of a photopolymerizable monomer and an organic solvent can be used as a diluent.

  When a photopolymerizable monomer is used as such a diluent, an appropriate one is used. For example, N-vinylpyrrolidone, (meth) acryloylmorpholine, methoxytetraethylene glycol (meth) acrylate, methoxypolyethylene glycol (Meth) acrylate, polyethylene glycol di (meth) acrylate, N, N-dimethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, melamine (meth) acrylate, and diethylene glycol di (meth) acrylate, tri Ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, phenoxyethyl (meth) acrylate, tetrahydrofurfuryl ) Acrylate, cyclohexyl (meth) acrylate, trimethylolpropane tri (meth) acrylate, isobornyl (meth) acrylate, cyclopentenyl mono (meth) acrylate, cyclopentanyl di (meth) acrylate, cyclopentenyl di (meth) acrylate, and Examples thereof include polyester (meth) acrylate and urethane (meth) acrylate.

  In addition, when an organic solvent is used as a diluent, appropriate ones are used. For example, ketones such as methyl ethyl ketone and cyclohexanone; aliphatic hydrocarbons such as octane and decane; aromatic hydrocarbons such as toluene and xylene Petroleum-based aromatic mixed solvents such as Swazol series (manufactured by Maruzen Petrochemical Co., Ltd.) and Solvesso series (manufactured by Exxon Chemical Co.); propylene glycol dimethyl ether, propylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol Glycol ethers such as diethyl ether; Acetic esters such as ethyl acetate, butyl acetate, butyl cellosolve acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate; Dialkyl glycol Ether, and the like can be exemplified, and these used alone or may be used in combination of two or more.

  Furthermore, it is preferable to use a catalyst to accelerate the reaction. Examples of the catalyst include tertiary amines such as benzyldimethylamine and trimethylamine; quaternary ammonium salts with trimethylbenzylammonium chloride and methyltriethylammonium chloride; triphenylphosphine and triphenylstibine.

  The amount of such a catalyst used is preferably 0.1 to 10% by weight based on the reaction raw material mixture.

  It is also preferable to use a polymerization inhibitor for the purpose of preventing polymerization during the reaction. Examples of the polymerization inhibitor include hydroquinone and hydroquinone monomethyl ether. The amount of the polymerization inhibitor used is preferably 0.01 to 1% by weight based on the reaction raw material mixture.

In obtaining the unsaturated group-containing polyol compound (b ₁ ) by reacting the component (s) with the component (t), the reaction temperature is preferably 60 to 150 ° C., particularly preferably 80 to 120 ° C., by a conventional method. React. The reaction time is preferably 5 to 60 hours.

Examples of the polyol compound (b ₂ ) other than the unsaturated group-containing polyol compound (b ₁ ) include alkyl polyols, polyester polyols, polyether polyols, polybutadiene polyols, phenolic polyols, silicone polyols and urethane polyols. One of these can be used, or two or more can be used in combination.

  Examples of the alkyl polyol include 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, 3-methyl 1,5-pentanediol, 1,9-nonanediol, and 1,4-cyclohexanedimethanol. Dimethylolpropionic acid, dimethylolbutanoic acid and the like.

  Polyester polyols include ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, tetramethylene glycol, polytetramethylene glycol, etc .; bisphenols such as bisphenol A, hydrogenated bisphenol A, bisphenol F, hydrogenated bisphenol F, and the like. Examples thereof include oxide-modified products and propylene oxide-modified products.

  The polybutadiene polyol is a butadiene homo- or copolymer having a hydroxyl group at the terminal, the phenolic polyol is a polyol containing a phenol molecule in the molecule, and the silicone polyol is a siloxane compound having a hydroxyl group at the terminal.

  Moreover, as a urethane polyol, the reaction material of a polyol compound as enumerated above and a polyisocyanate compound can be mentioned. Examples of the polyisocyanate compound to be reacted with the polyol include 2,4- and / or 2,6-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate (MDI), polymeric MDI, 1,5-naphthylene diisocyanate, tolidine diisocyanate, Examples include 1,6-hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate (IPDI), xylylene diisocyanate (XDI), hydrogenated XDI, hydrogenated MDI, and lysine diisocyanate. These polyisocyanate compounds can be used alone or in combination of two or more.

  When preparing urethane polyol by reaction, it is preferable to react so that the equivalent of the isocyanate group of the polyisocyanate compound is 0.5 equivalent or more and less than 1.0 equivalent with respect to 1 equivalent of the hydroxyl group of the polyol compound. . This urethanization reaction is carried out by a conventional method, and the reaction temperature is preferably 50 to 90 ° C. for 1 to 20 hours. At this time, a catalyst such as triethylamine, dibutyltin laurate or dibutyltin diacetate may be added.

  Other examples include glycerol mono (meth) acrylate.

<Compound (c) having at least two acid anhydride groups in one molecule>
As the compound (c) having at least two acid anhydride groups in one molecule, suitable compounds can be used. For example, pyromellitic anhydride, biphenyltetracarboxylic dianhydride, diphenylsulfonetetracarboxylic dianhydride , Benzophenone tetracarboxylic dianhydride, diphenylmethane tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, ethylene glycol bis (anhydrotrimellitate), 5- (2,5-dioxotetrahydro-3-furanyl ) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride (manufactured by Dainippon Ink and Chemicals, product number "EPICLON B-4400"), New Japan Chemical Co., Ltd. No. "likasi head TDA -100 "and product number" TMTA-C ".

<Mono epoxy compound (d)>
The monoepoxy compound having one or more ethylenically unsaturated groups in one molecule (d), although those suitable are used, for example, glycidyl (meth) acrylate, (3,4-epoxy Shishi Kurohekishiru) methyl ( (Meth) acrylate, β-methylglycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, allyl glycidyl ether, epoxidized stearyl acrylate (manufactured by Shin Nippon Rika Co., Ltd .; product number “Rikaresin ESA”) Can do.

<Mono epoxy compound (e)>
As the monoepoxy compound (e) other than the monoepoxy compound (d) having one or more ethylenically unsaturated groups in one molecule, that is, the monoepoxy compound (e) having no ethylenically unsaturated groups, For example, methyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, decyl glycidyl ether, stearyl glycidyl ether, phenyl glycidyl ether, sec-butyl glycidyl ether p-tertiary butyl phenyl glycidyl Alkyl glycidyl ethers such as ether, cresyl glycidyl ether, higher alcohol glycidyl ether (manufactured by Sakamoto Pharmaceutical Co., Ltd .; product numbers “SY-35M” and “SY-25L”); ethylene oxide-modified phenyl glycy Ethylene oxide-modified alkyl glycidyl ethers such as Ruether (manufactured by Nagase Kasei Kogyo Co., Ltd .; product number “Denacol EX-145”), ethylene oxide-modified lauryl glycidyl ether (manufactured by Nagase Kasei Kogyo Co., Ltd .; product number “Denacol EX-171”); Monoepoxy compounds having a long-chain alkyl group such as part number AOE series (manufactured by Daicel Chemical Industries, Ltd.); monoglycidyl esters obtained by reaction of monocarboxylic acid and epichlorohydrin; other glycidol, styrene oxide, glycidyl phthalimide, etc. These can be used alone or in combination.

<Synthesis>
An example of a chemical reaction formula in the case of reacting the above polyol compound (a) with the compound (c) having at least two acid anhydride groups in one molecule is shown below. In the formula, R ₁ and R ₂ are arbitrary substituents.

  Said reaction has shown the case where polyol compound (b) other than the said polyol compound (a) is made to react together, when making a polyol compound (a) and a compound (c) react.

  Here, (a ′), (b ′) and (c ′) in the above formula are structural units of the compound to be produced, and x, y and z represent the number of each structural unit in the compound, The above formula is convenient, and in this compound, only (c ′) is bound to (a ′), only (c ′) is bound to (b ′), (C ') is combined with (a') and (b ').

  In the case of such a reaction, the component (c) per equivalent of hydroxyl groups with respect to the total of hydroxyl groups of the component (a) (when the component (b) is used in combination, the component (a) and the component (b)) It is preferable to react the acid anhydride group of at least 0.1 and less than 1.0 equivalent. The reaction temperature at this time is preferably 60 to 150 ° C., particularly preferably 80 to 120 ° C., and the reaction time is preferably 1 to 10 hours. During this reaction, a catalyst such as triethylamine may be added in the range of 0.1 to 10% by weight.

And with respect to the compound obtained by making said (a) component and (c) component ((b) component use together, (a) component, (b) component, and (c) component) react), the above-mentioned

The polyester resin A is obtained by reacting the component (d) (when the component (e) is used in combination, the component (d) and the component (e)). This reaction is carried out by adding component (d) (or component (d) or component (e) when component (e) is used in combination) to part of the carboxyl group in the compound. The amount of carboxyl groups remaining in the polyester resin A is adjusted by adjusting the reaction amount of the component (and component (e)), and the polyester resin A having a desired acid value can be easily obtained.

An example of the chemical reaction formula at this time is shown below. In addition, R < ₁ > -R < ₃ > in a formula is arbitrary substituents. Moreover, (d) component and (e) component may be an alicyclic epoxy resin.

  Here, (a ′), (b ′) and (c ″) in the above formula are structural units of the produced polyester resin A, and x, y and z represent the number of each structural unit in the compound. However, the above formula is convenient, and in this compound, only (c ″) is bonded to (a ′), and only (c ″) is bonded to (b ′). (A ′) and (b ′) are coupled to (c ″). In addition, the structural unit (c ″) contains two carboxyl groups. As described above, the monoepoxy compound (d) or the monoepoxy compound (e) reacts with one of the carboxyl groups as described above. When the monoepoxy compound (d) or the monoepoxy compound (e) is reacted with each of the two carboxyl groups, both of the carboxyl groups do not react with the monoepoxy compound (d) and the monoepoxy compound (e). It may remain.

  Since the amount of the component (d) and the component (e) used is adjusted so that the polyester resin A obtained by the reaction has a desired acid value as described above, the components (a) to (c) Is determined based on the content of the carboxyl group in the compound obtained by reacting and the acid value of the desired polyester resin A. At this time, in order for the ultraviolet curable resin composition prepared using the polyester resin A to have good developability (alkali solubility), the acid value of the polyester resin A is in the range of 20 to 200 mgKOH / g. It is preferable to do so. If the acid value is less than 20, developability is poor, and if it is greater than 200, the electrical characteristics and electric resistance of the cured film to be formed due to residual carboxyl groups in the cured UV curable resin composition. There is a risk of causing problems such as corrosion and water resistance. In particular, when the acid value is in the range of 30 to 150 mgKOH / g, the optimum effect can be obtained.

  Thus, since the acid value of the polyester resin A can be adjusted by adjusting the reaction amount of the component (d) (when the component (e) is used in combination, the component (d) and the component (e)), The range of selection of the above-described components (a) to (c) used for synthesizing the polyester resin A will be widened.

  Moreover, the molecular weight design of the polyester resin A can be easily performed by appropriately selecting the components (a) to (c) by expanding the selection range of the components (a) to (c). Thus, further excellent developability (alkali solubility) can be imparted to the ultraviolet curable resin composition prepared using the polyester resin A. At this time, the polyester resin A is preferably prepared such that the weight average molecular weight is in the range of 800 to 100,000.

  Moreover, the polyester resin A which has a desired double bond equivalent can also be easily adjusted by selecting suitably the kind of (d) component which has an ethylenically unsaturated group, and its reaction amount. Here, the double bond equivalent of the polyester resin affects the reactivity at the time of curing molding of the ultraviolet curable resin composition containing the polyester resin A and the film strength of the cured film obtained by the curing molding. Therefore, by appropriately selecting the component (d) and the reaction amount thereof, the ultraviolet curable resin composition containing the polyester resin A is imparted with excellent reactivity and formed from the ultraviolet curable resin composition. It is possible to impart excellent strength to the cured film. At this time, the double bond equivalent of the polyester resin A is preferably in the range of 250 to 10,000.

  In reacting the compound obtained by reacting the components (a) to (c) with the component (d) (the component (d) and the component (e) when the component (e) is used in combination), the conventional method is used. The reaction is preferably carried out at a reaction temperature of 60 to 150 ° C., particularly preferably 80 to 120 ° C. for 1 to 30 hours. At this time, a tertiary amine such as triethylamine, a quaternary ammonium salt such as triethylammonium chloride, and a catalyst such as triphenylphosphine may be added in an amount of 0.1 to 10% by weight.

[B. (UV curable resin)
The ultraviolet curable resin B having an ethylenically unsaturated bond is not particularly limited, and appropriate ones including conventionally known ultraviolet curable resins can be used. For example, the following (1) to ( 4) can be mentioned.

(1) glycidyl (meth) acrylate, 2-methyl glycidyl (meth) acrylate, (3,4-epoxy Kurohekishiru) methyl (meth) polymerized units ethylenically unsaturated monomer having an epoxy group such as acrylate As a polymer or copolymer containing as an ethylenically unsaturated monocarboxylic acid such as (meth) acrylic acid, and the like, succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, etc. An ultraviolet curable resin obtained by adding an unsaturated or saturated polybasic acid anhydride.

  (2) at least two such as phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol A-novolak type epoxy resin, tris (hydroxydiphenyl) methane based polyfunctional epoxy resin, etc. Unsaturated or saturated polyfunctional epoxy compound having epoxy group, ethylenically unsaturated monocarboxylic acid such as (meth) acrylic acid, succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, etc. An ultraviolet curable resin obtained by adding a polybasic acid anhydride.

  (3) 2-hydroxyethyl (meth) acrylate, a copolymer of an unsaturated polybasic acid anhydride such as maleic anhydride and an aromatic hydrocarbon or vinyl alkyl ether having a vinyl group such as styrene; -One in a molecule such as hydroxypropyl (meth) acrylate, 2-hydroxydibutyl (meth) acrylate, diethylene glycol mono (meth) acrylate, dipropylene glycol mono (meth) acrylate, dibutylene glycol mono (meth) acrylate, etc. An ultraviolet curable resin obtained by reacting a compound having a hydroxyl group and one photoreactive ethylenically unsaturated group.

(4) an ethylenically unsaturated monomer having no carboxyl group, such as an ethylene glycol ester (meth) acrylate such as alkyl (meth) acrylate, hydroxyethyl (meth) acrylate, methoxyethyl (meth) acrylate, and the like; Glycidyl (meth) acrylate in a part of the carboxyl group in the copolymer composed of an ethylenically unsaturated monomer having a carboxyl group such as (meth) acrylic acid, maleic acid, crotonic acid, itaconic acid, etc. , 2-methyl glycidyl (meth) acrylate, (3,4-epoxy Kurohekishiru) methyl (meth) ethylenically unsaturated compounds are reacted with an ultraviolet curable resin obtained having an epoxy group only one such as acrylate.

  Here, the above-mentioned polyester resin A and ultraviolet curable resin B are resin components of the ultraviolet curable resin composition of the present invention. As this resin component, only polyester resin A may be contained, The polyester resin A and the ultraviolet curable resin B may be used in combination.

  Here, the content of the resin component in the ultraviolet curable resin composition is to ensure good photosensitivity and workability of the ultraviolet curable resin composition, and good physical properties of the finally formed cured film. The total amount of the ultraviolet curable resin composition (when the organic solvent is contained as the diluent E in the ultraviolet curable resin composition, the total amount of the ultraviolet curable resin composition excluding the organic solvent) On the other hand, it is preferable to be in the range of 10 to 80% by weight. The blending weight ratio of the polyester resin A and the ultraviolet curable resin B is desirably in the range of (weight of component A) :( weight of component B) = 100: 0 to 1:99.

[C. Multifunctional epoxy compound)
When the polyfunctional epoxy compound C is blended in the ultraviolet curable resin composition, as the polyfunctional epoxy compound C, a solvent-insoluble epoxy compound, a general-purpose solvent-soluble epoxy compound, or the like can be used.

  Specifically, for example, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol A-novolac type epoxy resin, bisphenol F type epoxy resin, triglycidyl isocyanurate, product number “YX4000” (Japan) Epoxy Resin Co., Ltd.), sorbitol polyglycidyl ether, N-glycidyl type epoxy resin, alicyclic epoxy resin (for example, product number “EHPE-3150” manufactured by Daicel Chemical Industries, Ltd.), polyol polyglycidyl ether compound, glycidyl Ester compound, N-glycidyl type epoxy resin, tris (hydroxydiphenyl) methane based polyfunctional epoxy resin (for example, product number “EPPN-502H” manufactured by Nippon Kayaku Co., Ltd., product number “ ACTIX-742 ”,“ XD-9053 ”, etc.), hydrogenated bisphenol A type epoxy resin, dicyclopentadiene-phenol type epoxy resin, naphthalene type epoxy resin, vinyl polymer having epoxy group, polyisocyanate modification of polyfunctional glycidyl compound The thing etc. are mentioned, These can be used individually or in combination.

  Of these, triglycidyl isocyanurate, product number “YX4000”, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol A-novolak type epoxy resin, and the like are particularly desirable.

  When such a polyfunctional epoxy compound C is blended in the ultraviolet curable resin composition, the blending amount is the total amount of the ultraviolet curable resin composition (the organic solvent as the diluent E in the ultraviolet curable resin composition). Is preferably 0.1 to 50% by weight, particularly in the range of 0.1 to 30% by weight, based on the total amount of the ultraviolet curable resin composition excluding the organic solvent) The optimal effect can be obtained.

[D. Photopolymerization initiator)
The photopolymerization initiator D is not particularly limited, and examples thereof include benzoin such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether and alkyl ethers thereof; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, Acetophenones such as 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone and 1-hydroxycyclohexyl phenyl ketone; anthraquinones such as 2-methylanthraquinone and 2-amylanthraquinone; 2,4-dimethylthioxanthone, Thioxanthones such as 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone, 1-chloro-4-propoxythioxanthone; Ketals such as dimethyl ketal and benzyl dimethyl ketal; benzophenone, 3,3-dimethyl-4-methoxybenzophenone, 3,3 ′, 4,4′-tetra- (t-butylperoxylcarbonyl) benzophenone, 4-benzoyl- Benzophenones or xanthones such as 4′-methyldiphenyl sulfide; 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- ( 4-morpholinophenyl) -butanone-1,4,4′-bis-diethylaminobenzophenone and the like containing nitrogen atoms; 2,4,6-trimethylbenzoyldiphenylphosphine oxide and the like.

  These photopolymerization initiators D can be blended in the ultraviolet curable resin composition alone or in combination with each other as appropriate.

  In addition to these photopolymerization initiators D, known benzoic acids or tertiary amines such as p-dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid isoamyl ester, 2-dimethylaminoethylbenzoate, etc. These photopolymerization accelerators and sensitizers may be used in combination.

  Further, for example, as a sensitizer for laser exposure method, coumarin derivatives such as 7-diethylamino-4-methylcoumarin, 4,6-diethyl-7-ethylaminocoumarin, other carbocyanine dyes, xanthene dyes, etc. are appropriately selected. The ultraviolet curable resin composition of the present invention can be made visible or near infrared curable by adding a photopolymerization initiator for visible light, near infrared exposure, etc. As long as it has sclerosis | hardenability, what used these is also contained in the ultraviolet curable resin composition of this invention.

  The blending amount of the photopolymerization initiator D in the ultraviolet curable resin composition is appropriately set. However, a good balance between the photosensitivity of the ultraviolet curable resin composition and the physical properties of the resulting cured film is obtained. To obtain the total amount of the ultraviolet curable resin composition (when the organic solvent is contained as the diluent E in the ultraviolet curable resin composition, the total amount of the ultraviolet curable resin composition excluding the organic solvent) ) To 0.1 to 30% by weight.

[E. Diluent)
As the diluent E, one of a photopolymerizable monomer and an organic solvent can be used, or both can be used in combination.

  Examples of the photopolymerizable monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, N-vinylpyrrolidone, (meth) acryloylmorpholine, methoxytetraethylene glycol (meth) acrylate, Methoxypolyethylene glycol (meth) acrylate, polyethylene glycol di (meth) acrylate, N, N-dimethyl (meth) acrylamide, N-methylol (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, N- Dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, melamine (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) Acrylate, propylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, phenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, cyclohexyl (meth) acrylate, trimethylolpropane di (meth) acrylate, tri Methylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, isobornyl (meth) acrylate, cyclopenta Nyl mono (meth) acrylate, cyclopentenyl mono (meth) acrylate, cyclopentanyl di (meth) acrylate , Cyclopentenyl di (meth) acrylate, mono-, di-, tri- or higher polyesters of polybasic acid and hydroxyalkyl (meth) acrylate, polyester (meth) acrylate, urethane (meth) acrylate, etc. ( And a (meth) acrylate monomer.

  Such photopolymerizable monomers may be used alone or in combination of two or more as appropriate.

  Examples of the organic solvent include linear, branched, secondary or polyhydric alcohols such as ethanol, propyl alcohol, isopropyl alcohol, butyl alcohol, isobutyl alcohol, 2-butyl alcohol, hexanol and ethylene glycol; methyl ethyl ketone and cyclohexanone. Ketones such as toluene; aromatic hydrocarbons such as toluene and xylene; petroleum-based aromatic mixed solvents such as swazil series (manufactured by Maruzen Petrochemical Co., Ltd.) and solvesso series (manufactured by Exxon Chemical Co., Ltd.); cellosolve, butyl cellosolve Cellosolvs such as carbitol, carbitol such as butyl carbitol; propylene glycol alkyl ethers such as propylene glycol methyl ether; polypropylene glycol such as dipropylene glycol methyl ether Lumpur alkyl ethers; ethyl acetate, butyl acetate, cellosolve acetate, butyl cellosolve sol blanking acetate, butyl carbitol acetate, acetic acid esters such as propylene glycol monomethyl ether acetate; dialkyl glycol ethers, and the like.

  Such organic solvents can be used alone or in combination of two or more.

  The photopolymerizable monomer has a function of diluting the resin component of the ultraviolet curable resin composition so that it can be easily applied and adjusting the acid value of the ultraviolet curable resin composition. It also has a function of imparting further photopolymerization to the functional resin composition. The organic solvent dissolves and dilutes the resin component of the ultraviolet curable resin composition so that the ultraviolet curable resin composition can be applied as a liquid, and the ultraviolet curable resin composition is applied. Later, it evaporates by drying to form a dry coating film.

  In addition, although the component which has photopolymerizability, such as a photopolymerizable monomer mix | blended as the said diluent E, does not necessarily need to be mix | blended in an ultraviolet curable resin composition, the compounding quantity in the case of mix | blending is , With respect to the total amount of the ultraviolet curable resin composition (when the organic solvent is contained as the diluent E in the ultraviolet curable resin composition, the total amount of the ultraviolet curable resin composition excluding the organic solvent) 50% by weight or less is desirable. When blended in excess of 50% by weight, the surface tackiness of the dried coating film becomes too strong, and when the negative mask on which the pattern is drawn is directly applied to the surface of the dried coating film and exposed, Prone to problems.

  On the other hand, the organic solvent blended as the diluent E is an essential component particularly when the ultraviolet curable resin composition is prepared as a photo solder resist ink that can be developed with a dilute alkaline solution, and is promptly used during preliminary drying. It is necessary to select and mix appropriately so as not to volatilize and remain in the dry coating film. Since the suitable compounding quantity of the organic solvent in an ultraviolet curable resin composition changes with coating methods, it is preferable to adjust suitably according to the coating method selected.

[Other ingredients]
In the ultraviolet curable resin composition, particularly when prepared as a photo solder resist ink, in addition to the above components, for example, tolylene diisocyanate, morpholine diisocyanate, isophorone blocked with caprolactam, oxime, malonic acid ester, etc. Thermal curing of diisocyanates, hexamethylene diisocyanate-based blocked isocyanates, and amino resins such as n-butylated melamine resins, isobutylated melamine resins, butylated urea resins, butylated melamine urea cocondensation resins, and benzoguatemine cocondensation resins Ingredients and UV curable epoxy acrylate or UV curable epoxy methacrylate such as bisphenol A type, phenol novolac type, cresol novolak type, alicyclic type epoxy resin, acrylic acid or High additions such as those with added crylic acid, styrene- (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid resin, diallyl phthalate resin, phenoxy resin, melamine resin, urethane resin, fluorine resin, etc. Molecular compounds can be added.

  In addition, if necessary, the above-mentioned photo solder resist ink further includes epoxy resins such as imidazole derivatives, polyamines, guanamines, tertiary amines, quaternary ammonium salts, polyphenols, polybasic acid anhydrides, melamine, dicyandiamide and the like. Curing agents and curing accelerators; fillers and colorants such as barium sulfate, silicon oxide, talc, clay, calcium carbonate; leveling agents such as silicon, acrylate copolymers, fluorosurfactants; silane coupling agents, etc. Adhesion-imparting agent; thixotropic agent such as aerosil; polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, pyrogallol, t-butylcatechol, phenothiazine; various additions such as antihalation agent, flame retardant, antifoaming agent, antioxidant Agent; for improving dispersion stability Surface active agent and a polymer dispersant may be added.

[Preparation of UV curable resin composition]
The ultraviolet curable resin composition of the present invention is prepared by mixing the above-described components by an appropriate technique. For example, each compounding component and additive can be prepared by a known kneading method using a three-roll, ball mill, sand mill or the like.

[Preparation of cured product of UV curable resin composition and printed wiring board]
The ultraviolet curable resin composition of the present invention can be used for various applications such as a photoresist ink, an interlayer insulating material for a printed wiring board, a resist for a color filter, and the like. In order to form a resist pattern, it is preferably used.

  A method for forming a resist pattern on a substrate using an ultraviolet curable resin composition is not particularly limited, and the most general method is exemplified as follows.

  For example, an ultraviolet curable resin composition prepared as a photo solder resist ink is applied on a substrate by dipping, spraying, spin coater, roll coater, curtain coater, screen printing or the like, and then an organic solvent which is diluent E In order to volatilize, for example, preliminary drying is performed at 60 to 120 ° C. to form a preliminary drying film.

  Next, apply a negative mask with a pattern drawn directly or indirectly to the surface of the pre-dried film, using a chemical lamp, low-pressure mercury lamp, medium-pressure mercury lamp, high-pressure mercury lamp, ultra-high-pressure mercury lamp, xenon lamp, metal halide lamp, etc. After irradiation with ultraviolet rays, a pattern is formed by development. And when the polyfunctional epoxy compound C is mix | blended, various characteristics, such as the film strength of a resist, hardness, and chemical resistance, are further thermoset by heating for about 30 to 90 minutes at 120-180 degreeC, for example. Can be improved.

  Examples of the alkaline solution used in the development step include a sodium carbonate aqueous solution and a potassium carbonate aqueous solution. As the solvent of the alkaline solution, water or a mixture of water and an alcoholic organic solvent such as alcohol can be used.

  Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. Note that “parts” and “%” used below are all based on weight unless otherwise specified.

  The “weight average molecular weight” is measured by GPC (gel permeation chromatography) based on the following measurement conditions.

  A THF (tetrahydrofuran) solution was prepared so that each sample had a solid content of 10 mg / ml, and each sample was measured with an injection amount of 100 μl.

(Measurement condition)
GPC measuring device: SHODEX SYSTEM 11 manufactured by Showa Denko KK
Column: Four series of SHODEX KF-800P, KF-805, KF-803 and KF-801. Moving layer: THF
・ Flow rate: 1 ml / min
-Column temperature: 45 ° C
・ Detector: RI
Conversion: Polystyrene [Synthesis Example 1]
To a four-necked flask equipped with a thermometer, a vacuum pump, and a stirrer was added 2- (9,10-dihydro-9-oxa-10-oxide-10-phosphaphenone-10-yl) -methylsuccinic acid-bis-. 688.9 parts of a 63% ethylene glycol solution of (2-hydroxyethyl) ester (manufactured by Sanko Co., Ltd .; product number “M-ester”) was added, and the temperature was increased while mixing.

  Subsequently, the pressure was gradually reduced at 200 ° C., and ethylene glycol was distilled out of the system under conditions of 200 ° C. and 0.5 mmHg (66.8 Pa).

  Subsequently, the inside of the reactor was returned to normal pressure, a reflux condenser was attached to the reactor, 196.2 parts pyromellitic anhydride (Mitsubishi Gas Chemical Co., Ltd., product number “PMDA”), 515 parts carbitol acetate, hydroquinone 0.5 part and 0.5 part of dimethylbenzylamine were added and reacted at 80 ° C. for 8 hours. Then, 142 parts of glycidyl methacrylate was further added and reacted at 100 ° C. for 10 hours to obtain a 60% polyester resin solution ( A 60% polyester resin (A-1) solution) was obtained.

[Synthesis Example 2]
A four-necked flask equipped with a thermometer, vacuum pump and stirrer was charged with 2- (9,10-dihydro-9-oxa-10-oxide-10-phosphaphenanthrene-10-yl) methylsuccinic acid-bis- (2 -Hydroxyethyl) -ester 63% ethylene glycol solution (manufactured by Sanko Co., Ltd., product number “M-ester”) 1737 parts and 0.3 parts of potassium titanium oxalate as a catalyst were added, and the temperature was increased while stirring and mixing.

  Subsequently, the pressure was gradually reduced at 250 ° C., and a polycondensation reaction was performed for 15 minutes under the conditions of 250 ° C. and 0.5 mmHg (66.7 Pa), the number average molecular weight was 1000, and the average value of n in formula (1). 5, 2- (9,10-dihydro-9-oxa-10-oxide-10-phosphaphenanthrene-10-yl) methylsuccinic acid-bis- (2-hydroxyethyl) -ester polymer was obtained.

  Subsequently, the inside of the reactor was returned to normal pressure, a reflux condenser was attached to the reactor, 218 parts of pyromellitic anhydride (product number “PMDA” manufactured by Mitsubishi Gas Chemical Co., Ltd.), 845 parts of carbitol acetate, 5 parts and 0.5 parts of dimethylbenzylamine were added and reacted at 80 ° C. for 8 hours. Then, 142 parts of glycidyl methacrylate was further added and reacted at 100 ° C. for 10 hours to obtain a 60% solution of polyester resin (60 % Polyester resin (A-2) solution).

[Synthesis Example 3]
A four-necked flask equipped with a thermometer, a vacuum pump and a stirrer was charged with 2- (9,10-dihydro-9-oxa-10-oxide-10-phosphaphenanthren-10-yl) methylsuccinic acid-bis- (2- 688.9 parts of a 63% ethylene glycol solution of hydroxyethyl) -ester (manufactured by Sanko Co., Ltd., product number “M-ester”) was added, and the temperature was increased while mixing.

  Subsequently, the pressure was gradually reduced at 200 ° C., and ethylene glycol was distilled out of the system under conditions of 200 ° C. and 0.5 mmHg (66.7 Pa).

  Subsequently, the reactor was returned to normal pressure, a reflux condenser was attached to the reactor, and 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid was attached. Add 237.6 parts of anhydride (Dainippon Ink Chemical Co., Ltd .; product number “Epiclon B-4400”), 542 parts of carbitol acetate, 0.5 part of hydroquinone, 0.5 part of dimethylbenzylamine, and add 80 ° C. Then, 142 parts of glycidyl methacrylate was further added and reacted at 100 ° C. for 10 hours to obtain a 60% polyester resin solution (60% polyester resin (A-3) solution).

[Synthesis Example 4]
A four-necked flask equipped with a thermometer, vacuum pump and stirrer was charged with 2- (9,10-dihydro-9-oxa-10-oxide-10-phosphaphenanthrene-10-yl) methylsuccinic acid-bis- (2 -Hydroxyethyl) -ester 63% ethylene glycol solution (manufactured by Sanko Co., Ltd., product number “M-ester”) 482.2 parts was added, and the temperature was raised while mixing.

  Subsequently, the pressure was gradually reduced at 200 ° C., and ethylene glycol was distilled out of the system under the conditions of 200 ° C. and 0.5 mmHg (66.7 Pa).

  Subsequently, the inside of the reactor was returned to normal pressure, a reflux condenser was attached to the reactor, ethylene oxide-modified bisphenol A (manufactured by Sanyo Chemical Industries, Ltd .; product number “New Pole BP-3P”) 120.67 parts, anhydrous pyromerit 196.2 parts of acid (Mitsubishi Gas Chemical Co., Ltd .; product number “PMDA”), 510 parts of carbitol acetate, 0.5 part of hydroquinone and 0.5 part of dimethylbenzylamine were added and reacted at 80 ° C. for 8 hours. Further, 142 parts of glycidyl methacrylate was added and the plate was indented at 100 ° C. for 10 hours to obtain a 60% polyester resin solution (60% polyester resin (A-4) solution).

[Synthesis Example 5]
A four-necked flask equipped with a thermometer, vacuum pump and stirrer was charged with 2- (9,10-dihydro-9-oxa-10-oxide-10-phosphaphenanthrene-10-yl) methylsuccinic acid-bis- (2 -Hydroxyethyl) -ester 63% ethylene glycol solution (manufactured by Sanko Co., Ltd., product number “M-ester”) 688.9 parts was added, and the temperature was increased while mixing. Subsequently, the pressure was gradually reduced at 200 ° C., and ethylene glycol was distilled out of the system under the conditions of 200 ° C. and 0.5 mmHg (66.7 Pa).

  Subsequently, the inside of the reactor was returned to normal pressure, a reflux condenser was attached to the reactor, pyromellitic anhydride (Mitsubishi Gas Chemical Co., Ltd .; product number “PMDA”) 196.2 parts, carbitol acetate 518 parts, hydroquinone 0.5 part and 0.5 part of dimethylbenzylamine were added and reacted at 80 ° C. for 8 hours. Then, 113.6 parts of glycidyl methacrylate and phenyl glycidyl ether (manufactured by Nagase Chemical Industries Ltd .; product number “Denacol EX- 141 ") 30.8 parts was added and reacted at 100 ° C for 10 hours to obtain a 60% polyester resin solution (60% polyester resin (A-5) solution).

[Synthesis Example 6]
In a four-necked flask equipped with a reflux condenser, a thermometer, a glass tube for introducing nitrogen and a stirrer, 70 parts of glycidyl methacrylate, 10 parts of methyl methacrylate, 20 parts of t-butyl methacrylate, 100 parts of carbitol acetate, lauryl mercaptan 3 parts and 3 parts of azobisisobutyronitrile were added, heated under a nitrogen stream, and polymerized at 75 ° C. for 5 hours to obtain a 50% copolymer solution.

  To the above 50% copolymer solution, 0.05 part of hydroquinone, 37 parts of acrylic acid and 0.2 part of dimethylbenzylamine were added, followed by addition reaction at 105 ° C. for 24 hours, followed by 38 parts of tetrahydrophthalic anhydride and 72 parts of tall acetate was added and reacted at 100 ° C. for 3 hours to obtain a 50% UV curable resin (B) solution having a polymerization average molecular weight of 22,000. Moreover, the acid value of this was 80 mgKOH / g.

[Comparative Synthesis Example 1]
A four-necked flask equipped with a reflux condenser, a thermometer, a vacuum pump, and a stirrer is equipped with 402.2 parts of ethylene oxide-modified bisphenol A (manufactured by Sanyo Chemical Industries, Ltd .; product number “New Pole BP-3P”), anhydrous pyromerit 196.2 parts of acid (Mitsubishi Gas Chemical Co., Ltd .; product number “PMDA”), 495 parts of carbitol acetate, 0.5 part of hydroquinone and 0.5 part of dimethylbenzylamine were added and reacted at 80 ° C. for 8 hours. Thereafter, 142 parts of glycidyl methacrylate was further added and reacted at 100 ° C. for 10 hours to obtain a 60% polyester resin solution (60% polyester resin (F-1) solution).

[Comparative Synthesis Example 2]
A four-necked flask equipped with a thermometer, vacuum pump and stirrer was charged with 2- (9,10-dihydro-9-oxa-10-oxide-10-phosphaphenanthrene-10-yl) methylsuccinic acid-bis- (2 -Hydroxyethyl) -ester 63% ethylene glycol solution (manufactured by Sanko Co., Ltd., product number “M-ester”) 688.9 parts was added, and the temperature was increased while mixing.

  Subsequently, the pressure was gradually reduced at 200 ° C., and ethylene glycol was distilled out of the system under the conditions of 200 ° C. and 0.5 mmHg (66.7 Pa).

  Subsequently, the inside of the reactor was returned to normal pressure, a reflux condenser was attached to the reactor, pyromellitic anhydride (Mitsubishi Gas Chemical Co., Ltd .; product number “PMDA”) 196.2 parts, carbitol acetate 524 parts, hydroquinone After adding 0.5 part and 0.5 part of dimethylbenzylamine and reacting at 80 ° C. for 8 hours, 154 parts of phenylglycidyl ether (manufactured by Nagase Chemicals Co., Ltd .; product number “Denacol EX-141”) is further added. The mixture was reacted at 100 ° C. for 100 hours to obtain a 60% polyester resin solution (60% polyester resin (F-2) solution).

[Comparative Synthesis Example 3]
In a four-necked flask equipped with a reflux condenser, a thermometer, and a stirrer, 370 parts of bisphenol A type epoxy resin (manufactured by Dainippon Ink & Chemicals, Inc .; product number “Epiclon 850”), 144 parts of acrylic acid, 0.5 of hydroquinone And 0.5 part of dimethylbenzylamine were added and reacted at 100 ° C. for 15 hours to obtain an unsaturated group-containing polyol compound (b ₁ -1).

[Comparative Synthesis Example 4]
A four-necked flask equipped with a thermometer, a vacuum pump, and a stirrer was charged with 2- (9,10-dihydro-9-oxa-10-oxide-10-phosphaphenanthrene-10-yl) methylsuccinic acid-bis- ( 2-hydroxyethyl) -ester 63% ethylene glycol solution (manufactured by Sanko Co., Ltd., product number “M-ester”) 127.3 parts and 0.3 parts of potassium titanium oxalate as a catalyst were added, and the temperature was increased while stirring and mixing. did.

  Subsequently, the pressure was gradually reduced at 250 ° C., and a polycondensation reaction was performed for 25 minutes under the conditions of 250 ° C. and 0.5 mmHg (66.7 Pa). 6- (9,10-dihydro-9-oxa-10-oxide 10-phosphaphenanthrene-10-yl) methylsuccinic acid-bis- (2-hydroxyethyl) -ester polymer was obtained.

Subsequently, the inside of the reactor was returned to normal pressure, a reflux condenser was attached to the reactor, 514 parts of the unsaturated group-containing polyol compound (b ₁ -1) obtained in Comparative Synthesis Example 3, pyromellitic anhydride (Mitsubishi Gas) Chemical Co., Ltd., product number “PMDA”) 150 parts, carbitol acetate 490 parts, hydroquinone 0.5 parts, dimethylbenzylamine 0.5 parts, and reacted at 80 ° C. for 8 hours, 60% of the polyester resin A solution (60% polyester resin (F-3) solution) was obtained.

[Examples 1-7, Comparative Examples 1-3]
Using the polyester resin (A-1) to (A-5) solution, the ultraviolet curable resin (B) solution, and the polyester resin (F-1) to (F-3) solution obtained as described above, A photosensitive resin composition (photo solder resist ink) of each example and comparative example was prepared according to the composition shown in Table 1 below.

  In Table 1, “Epiclon N-695” (trade name) is a cresol novolac type epoxy resin manufactured by Dainippon Ink and Chemicals, Inc., and “Irgacure 907” (trade name) is manufactured by Ciba Specialty Chemicals. “Kayacure” (trade name) is a photopolymerization initiator manufactured by Nippon Kayaku Co., Ltd., and “Modaflow” (trade name) is a leveling agent manufactured by Monsanto. “DPHA” represents dipentaerythritol hexaacrylate.

  The “blue pigment” is a non-halogen blue pigment “CI Pigment Blue 15: 3”, the “yellow pigment” is a non-halogen blue pigment “CI Pigment Yellow 147”, and the “green pigment” is a halogen-containing green color. The pigment “CI Pigment Green 7” is shown respectively.

[Evaluation of resist ink performance]
-Remaining step stage-
The photoresist inks of the examples and comparative examples were applied by screen printing on the entire surface of a copper clad laminate comprising a 35 μm thick copper foil glass epoxy substrate, and a drying time of 20 at 80 ° C. in order to volatilize the solvent. Preliminary drying was performed under a drying condition of minutes, and a test piece having a preliminary drying coating film having a thickness of 20 μm was produced.

Next, with a reduced pressure contact type double-side exposure machine “ORC HMW680GW” manufactured by Oak Manufacturing Co., Ltd., an exposure test mask “Step Tablet PHOTEC 21 steps” manufactured by Hitachi Chemical Co., Ltd. was directly applied to the pre-dried coating film and adhered under reduced pressure. The remaining step was determined for those developed by irradiation with 150 mJ / cm ² of ultraviolet light and subsequently developed using a 1% aqueous sodium carbonate solution as a developer.

[Performance evaluation of printed wiring board]
In order to confirm the performance of the printed wiring board manufactured with each photosensitive resin composition, the test piece was created by passing through the process of following IV sequentially.

<I. Application process>
The photo solder resist ink of each example and comparative example was screened on the entire surface of a copper-clad laminate composed of a 35 μm-thick copper foil glass epoxy substrate and a printed wiring board on which a pattern was formed in advance by etching. It was applied by printing to form a resist ink layer on the substrate surface.

<II. Pre-drying process>
After the coating step, preliminary drying was performed at 80 ° C. for 20 minutes in order to volatilize the solvent in the resist ink layer on the substrate surface to obtain a dry coating film having a thickness of 20 μm.

<III. Exposure process>
Thereafter, the mask on which the pattern was drawn was directly applied to the surface of the dried coating film, and the optimal exposure amount of each photo solder resist ink was irradiated with ultraviolet rays to selectively expose the dried coating film on the substrate surface.

<IV. Development process>
In the dried coating film after the exposure process, the selectively unexposed portion is removed by developing with a 1% aqueous sodium carbonate solution as a developing solution, and the pattern of the dried coating film exposed and cured on the substrate is removed. Formed.

<V. Post-bake process>
The substrate on which the pattern of the exposure-cured dry coating film formed in the development process was formed was heated at 150 ° C. for 30 minutes to cure the dry coating film, thereby obtaining a test piece.

  The following evaluation was performed about the test piece obtained at the said process. The results are shown in Table 1.

-Resolution-
The formation state of the resist pattern formed by a mask pattern composed of concentric circles having a line width and a line spacing of 40 μm was observed.

The evaluation method of resolution is as follows.
X: A pattern was not formed.
(Triangle | delta): Although the pattern was formed, the one part was missing.
○: A sharp pattern could be obtained.

-Pencil hardness-
Pencil hardness was measured and evaluated according to JIS K 5400 using Mitsubishi High Uni (manufactured by Mitsubishi Pencil Co., Ltd.).

-Surface gloss-
For each test piece, the specular gloss at an incident angle of 60 ° according to JIS Z8741 was measured using “GLOSS CHECKER” manufactured by Horiba, Ltd., and evaluated according to the following evaluation criteria.
○: Gloss value of 100 or more Δ: Gloss value of 50 or more and less than 100 ×: Gloss value of less than 50 —Adhesion—
According to the test method of JIS D-0202, the test piece was cross-cut in a checkered pattern, and then peeled after the peeling test using the cellophane adhesive tape was visually determined according to the following criteria.
○: No peeling of the crosscut portion occurred.
(Triangle | delta): A part of crosscut part peeled.
X: All cross-cut portions were peeled off.

-Solder heat resistance-
LONCO 3355-11 (water-soluble flux manufactured by London Chemical Co., Ltd.) was used as a flux. First, the flux was applied to the test piece, and then immersed in a molten solder bath at 260 ° C. for 15 seconds, and then washed with water. The degree of surface whitening after one or six cycles of this cycle was observed. Moreover, the cellophane adhesive tape peeling test by the cross cut was done based on JISD0202, and the change of the adhesion state was observed.

The evaluation method of surface whitening is as follows.
X: Remarkably whitened.
Δ: Slight whitening was observed.
○: No abnormality occurred.

Moreover, the evaluation method of adhesiveness is as follows.
X: Resist swelling or peeling occurred without performing a cross-cut test.
(Triangle | delta): Partial peeling occurred in the crosscut part at the time of tape peeling.
○: No peeling of the crosscut portion occurred.

-Solvent resistance-
It was immersed in 2-propanol and 1,1,1-trichloroethane at room temperature for 1 hour, and the substrate was observed and evaluated.

The evaluation method of solvent resistance is as follows.
○: No abnormality occurs.
Δ: Slight change is observed.
X: The film is peeled off.

-Acid resistance-
The substrate was immersed in 10% hydrochloric acid for 1 hour at room temperature, and the substrate was observed and evaluated.

The acid resistance evaluation method is as follows.
○: No abnormality occurs.
Δ: Slight change is observed.
X: The film is peeled off.

-Resistance to electric corrosion-
In place of the test piece, an IPC B-25 comb-type electrode B coupon was used to produce an evaluation substrate under the above conditions, a bias voltage of DC 100 V was applied to the comb electrode, and 40 ° C., 90% R.D. H. Under the above conditions, the presence or absence of migration after 500 hours was confirmed and evaluated.

The evaluation method of the electric corrosion resistance is as follows.
○: Migration cannot be confirmed at all.
Δ: A slight migration can be confirmed.
×: Migration has occurred.

-Flame resistance-
A coating film was formed on a non-halogen base material having a thickness of 0.4 mm under the same conditions as in the test piece formation, and tests and evaluations were performed in accordance with the UL94 combustion test method.

Claims (8)

Polymellitic anhydride, which is a polyol compound (a) having a structure represented by the following structural formula (1), and a compound (c) having at least two acid anhydride groups in one molecule , 5- (2,5- After reacting with dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, some of the carboxyl groups in the compound obtained by this reaction A method for producing an ultraviolet curable polyester resin, comprising reacting glycidyl methacrylate which is a monoepoxy compound (d) having one or more ethylenically unsaturated groups in one molecule.

5- (2,5-pyromellitic anhydride, which is a polyol compound (a) having the structure represented by the structural formula (1), and a compound (c) having at least two acid anhydride groups in one molecule; Dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride is reacted with a compound selected from a portion of the carboxyl groups in a compound obtained by reacting 1 in 1 molecule. An ultraviolet curable polyester resin obtained by reacting glycidyl methacrylate which is a monoepoxy compound (d) having at least one ethylenically unsaturated group. A. The ultraviolet curable polyester resin according to claim 2. Photoinitiator E.E. An ultraviolet curable resin composition comprising each component of a diluent. B. The ultraviolet curable resin composition according to claim 3, comprising an ultraviolet curable resin having an ethylenically unsaturated bond. C. The ultraviolet curable resin composition according to claim 3, comprising a polyfunctional epoxy compound.   6. The ultraviolet curable resin composition according to claim 3, wherein the ultraviolet curable resin composition is prepared as a photo solder resist ink for a printed wiring board.   A cured product obtained by curing and molding the ultraviolet curable resin composition according to claim 3.   A printed wiring board comprising a layer made of the cured product according to claim 7.