WO2002023275A1

WO2002023275A1 - Ultraviolet-curing resin composition and photo solder resist ink containing the same

Info

Publication number: WO2002023275A1
Application number: PCT/JP2001/007944
Authority: WO
Inventors: Hiroko Daido; Soichi Hashimoto
Original assignee: Goo Chemical Co., Ltd.
Priority date: 2000-09-14
Filing date: 2001-09-13
Publication date: 2002-03-21
Also published as: JP4705311B2; JPWO2002023275A1; CN1455889A; TW583510B; AU2001286219A1; CN1231815C

Abstract

An ultraviolet-curing resin composition which comprises (A) an ultraviolet-curing resin prepared by reacting an epoxy component comprising (a) an epoxy polymer prepared by polymerizing an ethylenically unsaturated monomer component containing (i) an epoxy-bearing ethylenically unsaturated monomer and (b) an epoxy-bearing isocyanurate derivative with (c) a carboxyl-bearing ethylenically unsaturated monomer, and then reacting the obtained intermediate with (d) a saturated or unsaturated polybasic acid anhydride; (B) an epoxy compound having two or more epoxy groups in the molecule; (C) a photopolymerization initiator; and (D) a diluent. A photo solder resist ink containing the composition can be developed with a dilute aqueous solution of an alkali and can form on a substrate a solder resist excellent in resistances to soldering heat and gold plating.

Description

Specification .

UV curable resin composition Photo solder resist ink containing the same

TECHNICAL FIELD The present invention relates to an ultraviolet-curable resin composition used for a photo solder resist ink, a protective film for a color filter, an image element, and the like, which has an ultraviolet-curing property and a thermosetting property and can be developed with a dilute alkaline aqueous solution. . Background art

Conventionally, developable liquid photoresist inks have been used in order to cope with finer and higher density conductive patterns on printed wiring boards. For example, the liquid photo solder resist ink disclosed in Japanese Patent Publication No. 61-2436969 can be imaged with a dilute alkaline aqueous solution, and is an ultraviolet-curable, soluble in dilute alkaline aqueous solution. It consists of a resin, a photopolymerization initiator and an epoxy compound. A sufficient amount of lipoxyl groups is introduced into the ultraviolet curable resin to enable development with a dilute aqueous alkali solution.

However, since the above resist ink contains an epoxy compound, thermal curing due to the reaction with the lipoxyl group present in the ultraviolet curable resin or the like is likely to occur in the predrying step, and the development failure And poor resolution were likely to occur. As a result, the amount of epoxy compound used is limited to a range that does not cause these problems, and the effects of the epoxy compound combination, such as the improvement in solder heat resistance and resistance to electrolytic corrosion of the resist coating, can be fully demonstrated. Nakata. Disclosure of the invention The present invention has been made in view of the above problems, and an object of the present invention is to provide an ultraviolet-curable resin yarn composition excellent in developability, resolution, development width, and heat resistance. . That is, the ultraviolet-curable resin composition of the present invention:

(A) an epoxy group-containing polymer (a) obtained by polymerizing an ethylenically unsaturated monomer component containing an epoxy group-containing ethylenically unsaturated monomer (i), and an epoxy group-containing isocyanurate An epoxy compound component containing the derivative (b) is reacted with an ethylenically unsaturated monomer (c) having a carboxyl group, and the resulting intermediate product is added to a saturated or unsaturated polybasic anhydride. UV-curable resin obtained by reacting (d);

(B) an epoxy compound having two or more epoxy groups in the molecule;

(C) a photopolymerization initiator; and

(D) Diluent

The ultraviolet curable resin as the component (A) can improve the heat resistance, the developability and the softening point of the resin composition.

A further object of the present invention is to provide a photosolder resist ink containing the above resin composition. This photo solder resist ink can be developed with a dilute alkaline aqueous solution and provides a solder resist on a substrate that exhibits excellent substrate adhesion and electrolytic corrosion resistance, and excellent solder heat resistance and gold plating resistance. Can be. Here, the development width means a range of predrying conditions that can maintain the developability, and is also referred to as a predrying control width or a predrying allowable range.

Another object of the present invention is to provide a substrate and a printed wiring board having a cured film formed of the resin composition or the photo solder resist ink described above. Still another object of the present invention is to provide a dry film obtained by forming a film obtained by drying the above-mentioned ultraviolet curable resin composition or photo solder resist ink on the surface of a support. is there. By using this dry film, a solder resist composed of the resin composition or the photo solder resist ink described above can be easily provided on a substrate.

Further features of the present invention and the effects provided by the same will be more clearly understood based on the best mode for carrying out the invention described below with reference to the accompanying drawings. BEST MODE FOR CARRYING OUT THE INVENTION

The ultraviolet-curable resin (A) used in the present invention contains an epoxy group-containing monomer obtained by polymerizing an ethylenically unsaturated monomer component containing an ethylenically unsaturated monomer (i) having an epoxy group. The polymer (a) and an epoxy compound component (b) containing an epoxy group-containing disocyanurate derivative are reacted with an ethylenically unsaturated monomer (c) having a carboxyl group to obtain an intermediate product. By reacting the product with a saturated or unsaturated polybasic acid anhydride (d).

Examples of the epoxy group-containing polymer (a) include an ethylenically unsaturated monomer (i) having an epoxy group, and an ethylenically unsaturated monomer copolymerizable with the monomer (i). A copolymer obtained by polymerizing an ethylenically unsaturated monomer component containing (ii) can be used.

Further, as the epoxy group-containing polymer (a), an ethylenically unsaturated monomer (i) having an epoxy group and a compound (iii) having two or more ethylenically unsaturated groups in one molecule are used. Polymerizing the ethylenically unsaturated monomer component contained A copolymer obtained by the above method may be used.

Further, as the epoxy group-containing polymer (a), an ethylenically unsaturated monomer having an epoxy group (i), a compound having two or more ethylenically unsaturated groups in one molecule (iii), A copolymer obtained by polymerizing an ethylenically unsaturated monomer component containing an ethylenically unsaturated monomer (ii) copolymerizable therewith may be used.

The ethylenically unsaturated monomer (i) having an epoxy group introduces an epoxy group into the epoxy group-containing polymer (a). The addition of the ethylenically unsaturated monomer having a carboxyl group imparts photocurability to the epoxy group-containing polymer (a) by an ethylenically unsaturated double bond.

Incidentally, an ethylenically unsaturated monomer having an epoxy group (i), a compound having two or more ethylenically unsaturated groups in one molecule (iii), and an ethylenically unsaturated monomer copolymerizable therewith. When an ethylenically unsaturated monomer component containing the polymer (ii) is used, the content of the ethylenically unsaturated monomer (i) is determined by the amount of ethylene used in the production of the epoxy group-containing polymer (a). It is preferably in the range of 40 to 99.9 mol%, more preferably 55 to 95 mol%, based on the total amount of the unsaturated monomer components. When an ethylenically unsaturated monomer component not containing the compound (iii) and the ethylenically unsaturated monomer (ii) is used, the content of the ethylenically unsaturated monomer (i) should be It is 100 mol% in the total amount of the ethylenically unsaturated monomer component used for producing the group-containing polymer (a).

Within the above range, the ultraviolet curable resin composition of the present invention exhibits particularly excellent photocurability and resolution, and a cured film finally formed using the composition has excellent heat resistance. However, it can be particularly preferably used as a permanent film. When this permanent film is used as a solder resist Shows particularly excellent solder heat resistance and electric corrosion resistance.

Examples of the ethylenically unsaturated monomer (i) include, for example, glycidyl (meth) acrylate, (3,4-epoxycyclohexyl) methinole (meth) acrylate, and the like. Derivatives, alicyclic epoxy derivatives of (meth) acrylate, —methyldaricidyl (meth) acrylate and monoaryldiglycidyl isocyanurate and the like can be used. These can be used alone or in combination. In particular, it is preferable to use glycidyl (meth) acrylate which is easily available. In this specification, (meth) acrylic acid is a general term for acrylic acid and methacrylic acid, and (meth) atari is a general term for atari and methacrylic.

The compound (iii) having two or more ethylenically unsaturated groups in one molecule is an optional component, and is intended to further improve the heat resistance and softening point of the ultraviolet-curable resin composition of the present invention. Used for primary purposes. When this compound (iii) is used, its content should be 0.1 to 1 (3 mol%) in the total amount of the ethylenically unsaturated monomer component used for producing the epoxy group-containing polymer (a). Within this range, the polymerization reaction for producing the epoxy group-containing polymer (a) can proceed in good conditions, and is particularly effective in preventing gelation. The cured film formed by the UV-curable resin composition of the present invention has excellent heat resistance, and particularly when used as a solder resist, exhibits particularly excellent solder heat resistance. %, It is optimal because it has both the effect of improving heat resistance and good polymerizability.

Compounds having two or more ethylenically unsaturated groups in one molecule (iii) include, for example, diethylene glycol di (meth) acrylate, triethylene Polyglycol (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, propylene glycol di-resin (meth) acrylate, polypropylene glycol / resid (meth) acrylate, Ε Ρ Ο Ο Modified dimethacrylate, bisphenol Α Ε Ο Adduct di (meth) acrylate, bisphenol FEO adduct di (meth) acrylate, bisphenol A Ο Ο Adduct di (meth) acrylate, bisphenol AEOPO adduct Di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, cyclo. Compounds having two ethylenically unsaturated groups in one molecule, such as pentanyl di (meth) acrylate, cyclopentenyl di (meth) acrylate, and diaryl monoglycidyl isocyanurate, can be used.

Also, a compound having three or more ethylenically unsaturated groups in one molecule, such as trimethylolpropane tri (meth) acrylate, pentaerythritol noretri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythryl Tonorepenta (meth) acrylate, dipent taerythritol hexa (meth) acrylate, polybasic acid and hydroxy

It is also possible to use di-, tri- or higher polyesters with (meth) alkyl acrylates, and polyester (meth) acrylates. These compounds (iii) can be used alone or in combination.

The compound (iii) contained in the epoxy group-containing polymer (a) reinforces the main chain thereof, and has effects such as improvement of solder heat resistance, adjustment of softening point, and improvement of development width.

Specifically, di (meth) acrylate is used in the above compound (iii). Is preferred. As the di (meth) acrylate, it is particularly preferable to use, for example, those having at least one oxyanolekilen unit such as oxyethylene and oxypropylene in the molecule. The solder heat resistance of the curable resin composition can be improved, and a particularly excellent development width can be provided. Here, the preferred number of oxyalkylene units in one molecule of di (meth) atarylate is 1 to 40, preferably 4 to 30, and more preferably 4 to 10. By doing so, the reactivity during the production of the ultraviolet-curable resin (A) is stabilized, the development range of the ultraviolet-curable resin composition of the present invention is widened, and the cured film has excellent solder heat resistance. It will be shown. -When a di (meth) acrylate having a bisphenol skeleton together with an oxyalkylene unit is used, it is preferable since it has particularly excellent solder heat resistance and particularly excellent development width.

As the di (meth) acrylate having an oxyalkylene unit usable as the compound (iii), ethylene glycol methacrylate or polyethylene glycol dimethacrylate represented by the following general formula (1) can be used. :

CH ₃ CH ₃

|. I

CH ₂ = C-COO- (CH ₂ CH ₂ 0) _n -OCC = CH _z

... (1) Here, the value of n in the formula is an integer of 1 to 40.

Alternatively, propylene glycol dimethacrylate or polypropylene glycol dimethacrylate represented by the following general formula (2) may be used. CH ₃ CH ₃ CH ₃ CH ₃

CH ₂ = C-CO-0-(CH-CH _z O) _m (CH ₂ -CHO) _n -OC-C = CH ₂ (2) where n and m are each an integer of 0 or more. There is a sum of n and m 1-4. It is. '

Further, ethylene glycol diacrylate or polyethylene glycol diacrylate represented by the following general formula (3) can be used:

CH, = CH-CO-0 (CH ₂ -CH ₂ 0) _n OC-CH = CH

(3) The value of n in the expression is an integer of 1 to 40. ,

As the di (meth) acrylate having an oxyalkylene unit and a bisphenol skeleton, a compound represented by the following general formula (4) may be used.

CH CH

Can be.

CH ₂ = C-CO- (OCH ₂ CH ₂ ) _m -0 TV c

CH

O-(CH ₂ CH ₂ 〇> OC— C = CH ₂

'CH ₃ … (4) where the values of n and m in the equation are integers greater than or equal to 0, and + of n + m is

1 to 40. Compounds of this type include, for example, 2,2-bis [4- (methacryloxyethoxy) pheninole] propane, 2,2,1-bis [41- (methacryloxy ethoxy) phenyl] propane, or 2-bis [4- (methacryloxy.polyethoxy) phenyl] propane.

Alternatively, a compound represented by the following general formula (5):

CH ₃

CH ₂ = CH-CO- (OCH ₂ CH ₂ ) _m -0 Vc

C H-.. (5)

^L 0- (CH ₂ CH ₂ 0) _n -OC- CH = CH Here, the values of n and m in the formula are integers of 0 or more, respectively, and the value of n + m is 1 to 40. Compounds of this type include, for example, 2,2-bis [4- (ataryloxyethoxy) pheninole] propane, 2,2-bis [4-1 (a-acryloxy'dietkin) pheninole] propane, or 2 , 2-bis [4- (acryloxy'polyethoxy) phenyl] propane, and dimethacrylate of bisphenol A polyethylene glycol polypropylene glycol adduct.

Specifically, as a di (meth) acrylate having an oxyalkylene unit, for example, NK ester 4G represented by the formula (1) (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd., polyethylene glycol # 200 dimethacrylate) Rate (average value of n: 4)), NK ester 9G represented by the formula (1) (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd., polyethylene dalicol # 400 dimethacrylate (average value of η: 9)) , Ester 9 PG represented by the formula (2) (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd., polypropylene glycol # 400 dimethacrylate (average value of m + n: 7)), NK S represented by the formula (3) Ter A-200 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd., polyethylene glycol # 200 diacrylate (average value of n: 4)), NK ester A-400 represented by formula (3) (trade name, new Nakamura Chemical Co., Ltd. Rie Chi render Recall # 400 Jiakurireto (average of n: 9)), NK ester A- 600 (trade name of the formula (3), Shin-Nakamura Chemical Co., Ltd., average polyethylene glycol # 600 Jiatarireto _(n Value: 14)).

Further, as a di (meth) acrylate having an oxyalkylene unit and a bisphenol skeleton, for example, NK ester mono-BPE-100 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd., 2 , 2-screw [4 Tacryloxyethoxy) phenyl] propane (average value of m + ri: 2.6)), NK ester-one BPE—20◦ (trade name, manufactured by Shin-Nakamura Ihgaku Kogyo Co., Ltd., 2, 2-bis [41- (Methacryloxy 'ethoxy) feninole] propane (average of m + n: 4)), NK ester-one BPE-50 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd., 2,2-bis [4-1 ( Methacryloxy.polyethoxy) phenyl] propane (strictly average value of m + n: 10)), NK ester A—BPE—4 represented by the formula (5) (2,2-—available from Shin-Nakamura Chemical Co., Ltd.) Bis [4-1 (Atari mouth xy. Jetoxy) feninole] propane (average value of m + n: 4)), Blemmer 43DB-40B (Nippon Yushi Co., Ltd. Bisphenol / A polyethylene glycol polypropylene glycol adduct dimethacrylate).

The ethylenically unsaturated monomer (ii) copolymerizable with the ethylenically unsaturated monomer (i) having an epoxy group and the compound (iii) having two or more ethylenically unsaturated groups in one molecule is It is an optional component and is used for adjusting the photocurability of the ultraviolet-curable resin composition of the present invention and adjusting the physical properties of the cured film, if necessary. Such ethylenically unsaturated monomers (ii) are not particularly limited. Examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and ptynole (meth) acrylate. , Isobutyl (meth) acrylate, t-butyl (meth) acrylate, 21-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (Meth) acrylate, lauryl (meth) acrylate, myristinole (meth) acrylate, cetyl (meth) atalylate, stearyl (meth) atalylate, cyclohexyl (meth) acrylate, isoborninole (meta) acrylate Straight-chain, branched or alicyclic such as plate (provided that there are some unsaturated bonds in the ring (Meta) Atari Lulic acid ester and hydroxyxetyl (meth) acrylate, methoxethyl (meth) acrylate, ethoxyxyl (meth) acrylate, ethylenglycol mono (meth) acrylate, triethylene glycol monoacrylate (meth) acrylate, Ethylene glycol ester (meth) acrylates such as methoxydiethylene glycol mono (meth) acrylate, and similar propylene glycol (meth) acrylates, butylene glycol mono (meth) acrylate, glycerol mono (meta) ) Aromatic (meth) acrylates such as acrylate and benzyl (meth) acrylate, and (meth) acrylamide, N-methyl (meth) acrylamide, N-propyl (meth) acrylic Amide, N-t-butyl (meth) acrylamide, N-t-octyl (meth) acrylamide, diacetone (meth) acrylamide, and other (meth) acrylamide compounds, N-phenylmaleimid M, N— (2-Methynolephene) Male, N—Cyclohexinolemate, N— (2,6-Jetinolefe) Maleimide, N—Laulinole Maleimide, N—Benzylmaleide And vinylpyrrolidone, (meth) acrylonitrile, butyl acetate, styrene, _α -methylstyrene, bierether, and the like. These can be used alone or in combination. Among them, linear or branched aliphatic, aromatic, or alicyclic (but may have some unsaturated bonds in the ring) (meth) acrylic acid ester, hydroxyalkyl (meta) The use of acrylates, alkoxyalkyl (meth) atalylates, maleimide compounds, etc. can control the hardness and oiliness of the film of the ultraviolet curable resin composition and the hardness of the finally formed resist. It is suitable because it is easy to adjust.

When using the ethylenically unsaturated monomer (ii) as described above, Is not particularly limited content, ethylenically unsaturated monomer component total amount of 1-6 0 mole ^_0/0, more preferably from 1 'to 5 5 mol%, particularly preferably 1 0-5 The content is preferably 0 mol%, and within this range, the amount of ethylenically unsaturated groups introduced into the ultraviolet-curable resin (A) can be sufficiently ensured. In addition, the hardness, hydrophilicity, and the like of the cured film can be particularly easily adjusted.

The epoxy group-containing polymer (a) can be obtained by a known polymerization method, for example, solution polymerization emulsion polymerization. When solution polymerization is used, for example, an ethylenically unsaturated monomer comprising the above-mentioned ethylenically unsaturated monomer (i) and, if necessary, ethylenically unsaturated monomer (ii) or compound (iii) A polymerization initiator is added to a body component in an appropriate organic solvent, and the mixture is heated and stirred under a stream of water. Further, a polymerization method under reflux may be employed.

Examples of the organic solvent used in the above polymerization method include ketones such as methyl ethyl ketone and cyclohexanone, and aromatic hydrocarbons such as toluene and xylene, and ethyl acetate, butyl acetate, and cellosolve acetate. Acetates such as sorbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, and dialkyl glycol ethers can be used. These can be used alone or in combination.

Examples of the polymerization initiator for the polymerization include t-butylhydronoxide, g-butylinoleoxide, lauroinoleoxide, benzoinolenoside, and diisopropinoleno. Peroxy acids such as peroxydicarbonate and azo compounds such as azobisisobutyronitrile, 2,2,2-methylbisazobisisobutyrate, and azobiscyanovaleronitrile can be used. These are used alone or in combination be able to.

The ultraviolet-curable resin (A) of the present invention comprises, as an epoxy compound component containing the epoxy group-containing polymer (a) obtained as described above and an epoxy group-containing isocyanurate derivative (b), a carboxyl group. It can be produced by reacting a group-containing ethylenically unsaturated monomer (c) with an addition reaction of the resulting intermediate product with a saturated or unsaturated polybasic acid anhydride (d).

The addition of the ethylenically unsaturated monomer (c) having a carboxyl group allows the ethylenically unsaturated monomer to be added to the epoxy compound component containing the epoxy group-containing isocyanate, the rate derivative (b) and the epoxy group-containing polymer (a). Photocurability due to heavy bonds is imparted.

The epoxy group-containing isocyanurate derivative (b) and the epoxy group-containing isocyanurate derivative (b) used for producing the ultraviolet-curable resin (A) were used to remarkably evolve the characteristics of the epoxy group-containing isocyanurate derivative (b). ), The amount of the epoxy group-containing cyanurate derivative (b) is preferably 1 to 50% by weight, more preferably 1 to 35% by weight, and particularly preferably 2 to 20% by weight. % By weight. Further, with respect to the epoxy compound component containing the epoxy group-containing polymer ( _a ) and the epoxy group-containing isocyanurate derivative (b), the amount of the epoxy group-containing polymer ( _a ) is preferably 50 to 9%. It is 9% by weight, more preferably 65 to 99% by weight, particularly preferably 80 to 98% by weight.

In the present invention, the epoxy compound component used for producing the ultraviolet-curable resin (A) may contain another epoxy compound together with the component (a) and the component (b). The epoxy group-containing isocyanuric acid in the epoxy compound component used to produce the ultraviolet-curable resin (A) The preferred amount of the derivative (b) is within the above range.

Examples of the epoxy group-containing isocyanurate derivative (b) include triglycidyl isocyanurate, monoaryldiglycidyl isocyanurate U ^, and diaryl monoglycidyl isocyanurate. These can be used alone or in combination. Specifically, TEP IC (trade name, manufactured by Nissan Chemical Co., Ltd., triglycidyl isocyanurate), monoallyl diglycidyl isocyanuric acid (trade name, manufactured by Shikoku Chemicals Co., Ltd., monoaryl diglycidyl isocyanate) Cyanurate), diaryl monoglycidyl isocyanuric acid (trade name, diaryl monoglycidyl isocyanurate, manufactured by Shikoku Chemicals Co., Ltd.) and the like. In particular, it is preferable to use triglycidyl isocyanate as the epoxy group-containing isocyanurate derivative (b). .

Other epoxy compounds in the epoxy compound component used for producing the ultraviolet-curable resin (A), if necessary, together with the epoxy group-containing polymer ( _a ) and the epoxy group-containing isocyanurate derivative (b) include: For example, phenol novolak epoxy resin, cresol nopolak epoxy resin, bisphenol A epoxy resin, bisphenol A-novolak epoxy resin, bisphenol F epoxy resin, YX4000 (Yuka Shell Epoxy Co., Ltd.) ), Alicyclic epoxy resin (for example, “E HPE-3150” manufactured by Daicel Chemical Industries, Ltd.), and tris (hydroxyphenyl) methane-based multifunctional epoxy resin (EPPN-502H, manufactured by Nippon Kayaku Co., Ltd., and Dow Chemica) Textex-1 742 and XD—9053 manufactured by Le Co., Ltd.), hydrogenated bisphenol A type epoxy resin, Tajen - a phenol type epoxy resin and naphthalene type epoxy resin or the like can be used.

—As a carboxyl-containing ethylenically unsaturated monomer (C) Is, for example, (meth) acrylic acid, crotonic acid, cinnamic acid, 2- (meth) acryloyloxetylsuccinic acid, 2- (meth) acryloyloxetil phthalic acid, —carboxyethyl Atarilate, Atariloyloxyshetti / Resuccinate, 2-Propernoic Acid, 3- (2-Norboxoxytoxy) -13-Oxypropylester, 2- (Meth) 'acryloyloxyshethyltetrahydrophthalic acid, 2- Those having only one ethylenically unsaturated group such as (meth) acryloylonoxetyl hexahydrophtalic acid, and pentaerythritol tri (meth) acrylate, trimethylol lipepandi (meth) acrylate, dipentaerythritol Polyfunctional acrylates having a hydroxyl group such as penta (meth) acrylate Examples thereof include those having a plurality of ethylenically unsaturated groups, such as those obtained by reacting a dibasic acid anhydride with a rate. These can be used alone or in combination. Among them, those having only one carboxyl group are preferable, and those having (meth) acrylic acid or (meth) acrylic acid as a main component are particularly preferable. Since the ethylenically unsaturated group introduced by (meth) atalinoleic acid has excellent photoreactivity, it is preferable to use (meth) acrylic acid as the ethylenically unsaturated monomer (c) having a carboxyl group.

The compounding amount of the carboxyl group-containing ethylenically unsaturated monomer (c) is determined based on the amount of ethylenically unsaturated monomer per mole of epoxy group in the epoxy compound component used for producing the above-mentioned ultraviolet curable resin (樹脂). The amount of the carboxyl group of the compound (c) is 0.7 to 1.2 mol, more preferably 0.9 to 1.1 mol, particularly preferably 0.95 to 1.1 mol. It is preferable to be decided. Within this range, the ultraviolet-curable resin composition (Α) of the present invention exhibits a particularly wide development width, and is less affected by the residual unreacted ethylenically unsaturated monomer (c) having a carboxyl group. As the saturated or unsaturated polybasic anhydride (d), for example, succinic anhydride, methinoresuccinic anhydride, maleic anhydride, citraconic anhydride, gnophthalic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride Dibasic acid anhydrides such as methinoletetrahydrophthalic anhydride, ice-free methylnadic acid, hexahydrohydrous phthalic anhydride, and methylhexahydrophthalic anhydride; and trimellitic anhydride, pyromellitic anhydride, and anhydride Acid anhydrides of three or more basic acids such as benzophenone tetracarboxylic acid, methylcyclohexenetetracarboxylic anhydride and the like can be used. These can be used alone or in combination. ·

The above-mentioned saturated or unsaturated polybasic acid anhydride (d) has a main purpose of giving an acid value to the ultraviolet-curable resin, redispersing with a dilute alkali aqueous solution, providing remelting needles, and providing thermosetting properties. Used as The amount used can be selected so that the acid value of the UV-curable resin obtained by adding the polybasic acid anhydride is in the range of 25 to 15 Omg KOH / g, particularly preferably 45 to: LO Omg KOHZg. preferable. Within this range, the UV-curable resin composition of the present invention exhibits particularly good ¾ developability, and the cured film formed thereby has particularly excellent electrical properties, corrosion resistance or water resistance. . Optimum results are obtained when the acid value is in the range of 50 to 85 mg KOHZg.

The ultraviolet-curable resin (A) of the present invention comprises an epoxy compound containing the epoxy group-containing polymer (a) obtained as described above and an epoxy group-containing isocyanurate derivative (b). The ethylenically unsaturated monomer having a ropoxyl group (c) is reacted, and at least two isocyanate groups are added to the resulting intermediate product in addition to a saturated or unsaturated polybasic anhydride (d). The compound can be produced by reacting the isocyanate compound (e). Examples of the isocyanate compound (e.) Include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, and isophorone diisocyanate. , 4,1-diphenylemethane diisocyanate, tonoleidine diisocyanate, lysine diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, trimethyl to Xamethylene diisocyanate, trifluoromethane triisocyanate, polymethylene polyphenyl polyisocyanate, and the like can be used. These can be used alone or in combination. Among these, those having only two y-cyanate groups in the molecule are preferably used, and in particular, isophorone diisocyanate, hydrogenated xylylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate and the like are preferable. preferable. It is also most suitable to use isophorone diisocyanate or hydrogenated xylylene diisocyanate having only two isocyanate groups in the molecule and having no aromatic ring.

By adding such an isocyanate compound (e), excellent film properties after pre-drying can be obtained, and excellent resist performance such as developability, resolution, and heat resistance can be obtained.

The amount of the isocyanate compound (e) used is a secondary hydroxyl group in a medium product obtained by reacting the above-mentioned epoxy compound component with an ethylenically unsaturated monomer (c) having a propyloxyl group. The amount of the isocyanate group of the isocyanate compound (e) is preferably 0.01 to 0.90 mol, more preferably 0.05 to 0.40 mol, per 1 mol of the hydroxyl group. Is preferably performed. Within this range, the solubility of the ultraviolet curable resin (A) in the diluent (D) is particularly good. The addition reaction of the ethylenically unsaturated monomer (C) having a carboxyl group and the saturated or unsaturated polybasic anhydride (d) can be carried out by using a known method. For example, the addition reaction of an ethylenically unsaturated monomer having a carboxyl group (C) is carried out, for example, by adding an epoxy compound containing an epoxy group-containing polymer (a) and an epoxy group-containing isocyanurate derivative (b) to an epoxy compound component. Addition of an ethylenically unsaturated monomer (c) having a carboxyl group, methoxyhydroquinone as a thermal polymerization inhibitor, tertiary amines, quaternary ammonium salts or triphenylstibine as a catalyst. The mixture is stirred and mixed, and the reaction is carried out by a conventional method at a reaction temperature of preferably 60 to 150 ° C, particularly preferably 80 to 120 ° C. The addition reaction of the saturated or unsaturated polybasic acid anhydride (d) can be carried out in the same manner as described above.

When the optional isocyanate compound (e) is reacted in addition to the above-mentioned saturated or unsaturated polybasic acid anhydride (d), for example, the epoxy group-containing polymer (a) and the epoxy group-containing isocyanurate derivative (b ) Is reacted with a solvent solution of the epoxy compound component containing the carboxyl group-containing ethylenically unsaturated monomer (c), and then a saturated or unsaturated polybase is added to the resulting intermediate product. The isocyanate compound (e) is reacted before, after or at the same time as the reaction of the addition reaction of the acid anhydride (d). 'This reaction can be carried out, for example, by adding an organotin compound such as dibutyltin diallate or a tertiary amine such as benzyldimethylamine as a catalyst by a conventional method, or under a catalyst blended in the previous reaction with or without addition. The reaction may be carried out by heating and stirring at a reaction temperature of 20 to 100 ° C.

The weight average molecular weight of the ultraviolet-curable resin (A) prepared as described above is not particularly limited, but a preferable range is a weight average molecular weight of 3,000 to 400,000. Within this range, the ultraviolet-curable resin composition of the present invention is: Particularly, it has both excellent sensitivity and resolution.

The compounding amount of the ultraviolet-curable resin (A) is simultaneously adjusted so as to ensure good sensitivity and working characteristics of the ultraviolet-curable resin composition of the present invention and good physical properties of the finally formed resist. It is desirably 10 to 80% by weight based on the total amount of the components of the ultraviolet-curable resin composition of the present invention excluding the organic solvent in the diluent (D). Within this range, the ultraviolet-curable resin composition of the present invention has particularly excellent ultraviolet-curability, and the tackiness of the preliminary dried film is particularly reduced.

Examples of the epoxy compound (B) having two or more epoxy groups in one molecule include a poorly solvent-soluble epoxy compound, a solvent-soluble epoxy compound, and the like. A phenol novolak epoxy resin and a cresol novolak epoxy Resin, bisphenol A type epoxy resin, bisphenol A-nopolak type epoxy resin, bisphenol F type epoxy resin, triglycidyl isocyanurate, monolinoleic glycidyl isocyanurate, YX400 (oiled shell epoxy) Sorbitol polyglycidyl ether, N-glycidyl type epoxy resin, alicyclic epoxy resin (for example, "EHPE-3150" manufactured by Daicel Chemical Industries, Ltd.), polyol polyglycidyl ether / le compound, glycidyl ester compound , N-glycidyl type epoxy resin Tris (hydroxyphenyl) methane-based polyfunctional epoxy resin (EPPN-502H manufactured by Nippon Kayaku Co., Ltd. and Tactex-174 and XD-9503 manufactured by Dow Chemical Co., Ltd.), iced bisphenol A A type epoxy resin, a dicyclopentadiene-phenol-type epoxy resin, a naphthalene type epoxy resin, a butyl polymer having an epoxy group, and the like can be used. These can be used alone or in combination, or after cross-linking modification. In particular, phenol nopolak epoxy resin, It is preferable to use cresol novolak type epoxy resin, bisphenol A type epoxy resin, bisphenol A-novolak type epoxy resin, triglycidyl isocyanurate, and YX400.

The compounding amount of the epoxy compound (B) in the ultraviolet-curable resin composition of the present invention is based on the total amount of the components of the ultraviolet-curable resin composition of the present invention excluding the organic solvent in the diluent (D) that is simultaneously mixed. The content is preferably 0.1 to 50% by weight. Within this range, the ultraviolet-curable resin composition of the present invention exhibits particularly excellent thermosetting properties and has a particularly wide development width.

Examples of the photopolymerization initiator (C) include benzoin and its alkyl ethers such as benzoin, benzoin methyl oleate / re, benzoin ethie / leate phenol, benzoin isopropynoleate, and acetophenone, 2,2-dimethoxy. 2-pheninoleacetophenone, 2,2-diethoxy 2-phenienoleacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexylphen-2-acetophenones such as hexylphenic / reketone, and 2-methylanthraquinone, 2-amyl Anthraquinones such as anthraquinone, and 2,4-dimethinorethioxanthone, 2,4-getylthioxanthone,

2 Black port Chiokisanton, 2, 4-di-isopropylidene Bruno Lexan tons, 1-click Lolo one ₄ - Chiokisanton such as propoxy Chio xanthone,及Pi Aseto Fuenonjimechi / Reketaru, Keta / Les such as benzyl dimethyl ketal,及Pi benzophenone , 3,3-Dimethinole-1- 4-methoxybenzophenone, 3,3 ', 4,4'-tetra (t-butylperoxylcarbonyl) benzophenone, 4-benzoinolene 4, methinoresifeninoles / Benzophenones or xanthones such as sulfide, and 2-methyl-1- [4- (methinolethio) phene / re] —2-morpholinopropane-1-one, 2-benzoinole-1-dimethylamine-1 — (4 monorefuorinofeninore) One pig Those containing a nitrogen atom such as non-1,4,4,1-bis-jetylaminobenzophenone, and 2,4,6-trimethylbenzoyldiphenylphosphine oxide can be used. These include known photopolymerization accelerators such as benzoic acid or tertiary amines such as P-dimethylaminobenzoic acid ethyl ester, P-dimethylaminobenzoic acid isoamyl ester, and 2-dimethylaminoethylbenzoate. It may be used in combination with an agent. These photopolymerization initiators are blended alone or in combination with one another as appropriate.

In addition, as sensitizers for laser exposure methods, for example, coumarin derivatives such as 7-ethylamino-4-methyl coumarin, 4,6-ethylamino 7-ethylaminocoumarin, carbocyanine dyes, xanthene dyes, bis ( . eta ⁵ one 2, 4-cyclopentadiene-1 one ^ f le) - bis (2, 6-Jifunore silo one 3- (1 H- pyro one Norre one 1- Inore) Single-phenylene Honoré) titanium, etc. It is also possible to appropriately use meta-methacrylates and the like, and the ultraviolet-curable resin composition of the present invention can be made into a visible or near-infrared curable resin composition.

The amount of the photopolymerization initiator (C) in the ultraviolet-curable resin composition of the present invention may be adjusted so as to obtain a good balance between the photocurability and the physical properties of the obtained solder resist. It is desirable that the content is 0.1 to 30% by weight based on the total amount of the components of the ultraviolet-curable resin composition of the present invention excluding the organic solvent in D). Within this range, the ultraviolet-curable resin composition of the present invention exhibits particularly excellent ultraviolet-curability, and also has particularly excellent heat resistance and electric corrosion resistance of the cured film.

As the diluent (D), a photopolymerizable ethylenically unsaturated monomer or an organic solvent can be used alone or in combination. Examples of the photopolymerizable ethylenically unsaturated monomer include, for example, 2-hydroxyxethyl (meth) acrylate, 2-hydroxypropinole (meth) acrylate, and N-bininolepyro. Ridone, (meth) acryloyl morpholine, methoxy tedolaethylene glycol. Recall (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, polyethylene glycol di (meth) acrylate, N, N-dimethinole (Meth) acrylamide, N-methylol (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (Meth) acrylate, melamine (meth) acrylate, and diethylene glycol di (meth) acrylate, triethylene glycolone resin (meth) acrylate, propylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate , Phenoxyshethyl (meta) acrylate, tetrahydrofurfuryl (meta) acrylate, cyclohexyl (meth) acrylate, trimethylolpropanedi (meth) acrylate, trimethylolpropanetri (meta) acrylate, Pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol tonolehexa (meth) acrylate, isoboninole (meta) acrylate, cyclopentanyl mono ( (Meta) acrylate, cyclopenteninolemono (meth) atalylate, cyclopentaerdi (meth) atalylate, cyclopentenyl di (meth) acrylate, and polybasic acids and hydrides Use mono-, di-, tri- or more polyesters with logisalkyl (meth) acrylate, and (meth) acrylate monomers such as polyester (meth) acrylate, urethane (meth) acrylate, etc. Can be The photopolymerizable ethylenically unsaturated monomers can be used alone or in combination with one another as appropriate.

Organic solvents include, for example, ethanol, pulp alcohol, Linear, branched, secondary or polyhydric alcohols such as isopropyl alcohol, butyl alcohol, isobutyl alcohol, 2-butynoleanol, hexanol, ethylene glycol, etc., and methyl alcohol Ketones such as tyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene and xylene; petroleum oils such as the Suzul series (manufactured by Maruzen Petrochemical) and the Solbesso series (manufactured by Exxon Chemical) Aromatic mixed solvents and cellosolves such as cellosolve and butyl sorbitol, and power rubitols such as carbitol and butyl carbitol; and propylene glycol oleanol quinoleate ethereol such as propylene daricol methyl ether; andポリプロピレン Polypropylene rubbers such as dipropylene glycolone methylone ether Cholealkyl ethers, and acetates such as ethyl acetate, butyl acetate, cellonolebu acetate, sorbose acetate butyl acetate, butino olecanolevitone oleate, propylene glycolone monomethinoleate acetate, and dialkyl glycol. Ethers and the like can be used. These can be used alone or in combination with one another as appropriate.

The photopolymerizable ethylenically unsaturated monomer used as the diluent (D) dilutes the UV-curable resin (A), etc. to make it easy to apply, and adjusts the acid value to improve photopolymerizability. give. The organic solvent used as the diluent (D) is prepared by dissolving and diluting the ultraviolet-curable resin (A), etc., so that it can be applied as a liquid and dried to form a film.

The diluent (D) and the above-mentioned photopolymerizable ethylenically unsaturated monomer and other components having photosensitivity must be added to the ultraviolet-curable resin composition of the present invention. However, the total amount in the case of blending is 50% by weight in the total amount of the components of the ultraviolet-curable resin composition of the present invention excluding the organic solvent similarly blended as the diluent (D). It is desirable that the ratio be less than / ₀ . this If more than 50% by weight of ⁰ / o is added, the pre-dried film will have too high surface tack and the negative mask on which the pattern is drawn will be applied directly to the dried film surface to expose it. This may cause problems such as soiling.

On the other hand, the organic solvent used as the diluent (D) ′ like the above photopolymerizable ethylenically unsaturated monomer is the ultraviolet-curable resin composition of the present invention, particularly, It is an essential component when used as a developable photo solder resist ink. It must be selected so that it volatilizes quickly during pre-drying and does not remain on the pre-dried film. The amount of the organic solvent in the composition is desirably 5% or more of the total components of the ultraviolet-curable resin composition of the present invention. If the amount is less than this, application of the composition tends to be difficult. Note that the preferable amount is different depending on the application method, and it is necessary to appropriately adjust the amount according to the application method. Therefore, the upper limit of the amount is not particularly limited.

The UV-curable resin composition of the present invention includes, in addition to the above-mentioned components, thermosetting components such as block dissociates and amino resins, and UV-curable epoxy (meth) atalylates such as bisphenol A type and phenol novolak. Type, cresol nopolak type, alicyclic epoxy resin to which (meth) acrylic acid is added, or furthermore maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, etc. A product obtained by adding a saturated or unsaturated polybasic acid anhydride to a copolymer of maleic anhydride and another ethylenically unsaturated monomer having a hydroxyalkyl (meth) acrylate or epoxy group UV-curable polymer obtained by reacting (meth) acrylate, and styrene (meth) Copolymers of ethylenically unsaturated compounds, such as mono- (meth) arylate ester copolymers or ethylenically unsaturated compounds, such as styrene- (meth) acrylic acid (meth) acrylate copolymers Copolymers or epoxies UV-curable polymer obtained by reacting an ethylenically unsaturated monomer having a silicone group, and a vinyl copolymer having an ethylenically unsaturated monomer having an epoxy group as one of the monomer units ( (Meth) A high molecular compound such as an ultraviolet curable polymer to which atrial acid is added, a styrene-maleic acid resin, a diaryl phthalate resin, a phenoxy resin, a melamine resin, a urethane resin, and a fluororesin can be mixed.

In addition, the ultraviolet curable resin composition of the present invention may contain an epoxy resin curing agent, a curing accelerator, a filler, a coloring agent, a leveling agent, an adhesion promoter, a thixotropic agent, and a polymerization inhibitor, if necessary. Various additives such as an antihalation agent, a flame retardant, an antifoaming agent, a dispersion stabilizer, a polymer dispersant, and an antioxidant may be added.

The ultraviolet-curable resin composition of the present invention is prepared, for example, by a known kneading method using a three-roll, ball mill, sand mill or the like with respect to each compounding component and additives. In this case, a part of the above components (A) to (D), for example, a part of the component (D) and the component (B) are mixed and dispersed in advance to obtain a first mixture. A), (C) and a part of the components (D) are preliminarily mixed and dispersed to obtain a second mixture. When used, the first and second mixtures are mixed and prepared so as to have the above composition. May be adopted.

The method of using the ultraviolet-curable resin composition of the present invention is not particularly limited. For example, an ultraviolet curable resin composition can be used as a photo solder resist ink suitably used for manufacturing a printed wiring board having a fine and high-density conductor pattern. By using the photo solder resist ink, a resist pattern can be formed on a printed wiring board or a substrate. In this case, this photo solder-resist ink is cured and molded into an appropriate pattern on a printed wiring board or substrate. A film is formed, and a resist pattern is formed by the cured film. An example for forming a resist pattern on a substrate will be described below. First, the photo solder resist ink is immersed on the substrate by spraying, spin coating, roll coating, curtain coating or screen printing.

Apply from 5. Next, in order to volatilize the organic solvent as a diluent, preliminary drying is performed at, for example, 60 to 120 ° C. to form a preliminary dried film.

Next, a negative mask with a pattern is placed directly or indirectly on the surface of the pre-dried film, and a chemical lamp, low-pressure mercury lamp, medium-pressure, mercury lamp, high-pressure mercury lamp, ultra-high-pressure mercury lamp, xenon lamp, or metal halide is applied through the negative mask. 10 After irradiating ultraviolet rays with a lamp, etc., a pattern is formed by development. Further, for example, 120 to 180. By curing the epoxy compound by heating for about 30 to 90 minutes at C, a resist pattern consisting of a cured film having excellent film strength, hardness and chemical resistance can be obtained.

Examples of the alkaline solution used in the above-mentioned developing step include a 15% aqueous solution of sodium carbonate, an aqueous solution of carbonic acid carbonate, an aqueous solution of ammonium carbonate, an aqueous solution of sodium hydrogencarbonate, an aqueous solution of potassium hydrogencarbonate, an aqueous solution of ammonium hydrogencarbonate, an aqueous solution of sodium hydroxide. For example, an aqueous solution of a hydroxide power, an aqueous solution of ammonium hydroxide, or an ice solution of lithium hydroxide can be used. Further, the _alkali: monoethanolamine § Min other than, diethanol § Min, triethanolamine § 20 Min, mono isopropanoyl no Honoré amine, diisopropanolamine § Min, may be used organic amines such as Torii isopropanol § Min. These can be used alone or in combination. As the solvent for the alkaline solution, not only water alone, but also a mixture of water and a hydrophilic organic solvent such as lower alcohols can be used.

25 In addition, the ultraviolet curable resin composition or the photo solder resist of the present invention A so-called dry film resist can be formed by forming a film of the ink on the surface of the support. In this case, the thickness of the film is preferably 10 to 100 / im, and a film having a thickness of 5 to 100 μπι such as polyethylene terephthalate can be used as the support. . The coating film of the ultraviolet curable resin composition or the photo solder resist ink can be formed by applying a purple ray curable resin composition or a photo solder resist ink on a support film and drying it.

The ultraviolet-curable resin composition of the present invention is particularly preferably used for a photo solder resist ink, but is not limited thereto. For example, for forming a color filter protective film, and as a colorant, for example, an azo lake-based resin. , Organic pigments such as insoluble azo and phthalocyanine, and inorganic pigments such as miril blue, iron oxide and cobalt, and appropriate pigments or dyes such as oil-soluble dyes, basic dyes and dispersible dyes. It can also be used as a composition for preparing a color filter element. Example

Example 1

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

(Synthesis example 1)

Glycidyl methacrylate 70 parts, methyl methacrylate 20 parts, t-butyl methacrylate 10 parts, carbitol acetate 1 in a four-neck flask equipped with a reflux condenser, a thermometer, a glass tube for nitrogen replacement and a stirrer 0 parts, lauryl mercaptan 0.2 parts, azobisisobutyronitrile 3 The polymerization was carried out at 80 ° C for ⁵ hours while heating and stirring under a nitrogen stream to obtain a 50% epoxy group-containing copolymer solution.

Subsequently, 10 parts of TEP IC-S (triglycidyl isocyanurate manufactured by Nissan Chemical Co., Ltd.), 0.05 part of hydroquinone, 43 parts of acrylic acid, and 43 parts of dimethylbenzylamine were added to the 50% epoxy group-containing copolymer solution. Addition of 0.2 parts of min, addition reaction at 100 ° C for 24 hours, followed by addition of 45 parts of tetrahydrophthalic anhydride and 98 parts of carbitol acetate, followed by reaction at 100 ° C for 3 hours. % UV-curable resin solution (A-1) was obtained.

(Synthesis example 2)

'' 70 mL of glycidyl methacrylate, NK ester 9G (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd., polyethylene glycol # 400 dimethacrylate) in a four-neck flask equipped with a reflux condenser, thermometer, glass tube for nitrogen replacement, and a stirrer (N = 9) molecular weight = 536) 10 parts, methyl methacrylate 20 parts, carbitol acetate 100 parts, lauryl menolecabbutane 0.2 parts, azobisisobutyronitrile 3 parts, and heated under nitrogen stream While stirring, polymerization was carried out at 80 ° C for 5 hours to obtain a 50% epoxy group-containing copolymer solution.

Subsequently, 20 parts of TEP IC-S (triglycidyl isocyanurate manufactured by Nissan Chemical Industries, Ltd.), 05 parts of hydroquinone, 50 parts of acrylic acid, and 0 parts of dimethylbenzylamine were added to the 50% epoxy group-containing copolymer solution. Add 2 parts, perform addition reaction at 100 ° C for 24 hours, then add 45 parts of tetrahydrophthalic anhydride and 115 parts of carbitol acetate, and react at 100 ° C for 3 hours to obtain 50% An ultraviolet curable resin solution (A-2) was obtained.

(Synthesis Example 3)

4 equipped with a reflux condenser, thermometer, glass tube for nitrogen replacement and a stirrer In a flask, 70 parts of glycidyl methacrylate

9? 0 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd., polypropylene glycol # 400 dimethacrylate (n = 7) molecular weight = 536) 10 parts, methyl methacrylate 15 parts, t-butyl methacrylate 5 parts, carbide Add 100 parts of luacetate and 3 parts of azobisisobutyronitrile, and heat and stir under a nitrogen stream 80. Polymerization was performed for 5 hours at C to obtain a 50% epoxy group-containing copolymer solution. '

Subsequently, 20 parts of TEP IC-S (triglycyliso, cyanate manufactured by Nissan Chemical Industries, Ltd.), 0.05 parts of hydroquinone, 50 parts of acrylic acid, 50 parts of dimethylbenzyl were added to the 50% epoxy group-containing copolymer solution. Addition of 0.2 parts of dimethylamine, add reaction at 100 at 24 hours, add 2.7 parts of isophorone diisocyanate and 0.01 part of dibutyltin dilaurate and react under stirring at 50 ° C for 4 hours I let it. Subsequently, 45 parts of tetrahydrophthalic anhydride and 118 parts of carbitol acetate were added and reacted at 100 ° C for 3 hours to obtain a 50% UV-curable resin solution (A-3).

(Synthesis example 4)

In a four-neck flask equipped with a reflux condenser, a thermometer, a glass tube for purging nitrogen, and a stirrer, 70 parts of glycidyl methacrylate, ΝΚester A—Β ΡΕ-4 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd., 2, 2 —Bis [4- (α-acryloxy'diethoxy) phenyl] propane, molecular weight = 512) 5 parts, methyl methacrylate 15 parts, cyc hexyl maleimide 10 parts, carbitol acetate 100 parts, lauryl mercaptan 0.1 parts, azobisy 3 parts of sobutyronitrile was added, and polymerization was carried out at 80 ° C for 5 hours while heating and stirring under a nitrogen stream to obtain a 50% epoxy group-containing copolymer solution.

Subsequently, TEP IC— was added to the above 50% epoxy group-containing copolymer solution. 50 parts of S (triglycidyl isocyanurate manufactured by Nissan Chemical Co., Ltd.), 0.05 parts of hydroquinone, 72 parts of acrylic acid, and 0.2 parts of dimethylbenzylamine were added, and an addition reaction was performed at 100 ° C for 24 hours. Subsequently, 56 parts of tetrahydrophthalic anhydride and 178 parts of carbitol acetate were added and reacted at 100 ° C. for 3 hours to obtain a 50% UV-curable resin solution (A-4). .

(Synthesis Example 5)

In a flask equipped with a reflux condenser, thermometer, glass tube for nitrogen replacement, and a stirrer, 70 parts of glycidinolemethacrylate, Blemmer 43DB-1 40B (trade name, manufactured by NOF CORPORATION, bisphenol A polyethylene glycol) ^^ Polypropylene glycol adduct dimethacrylate, molecular weight = about 1180) 14 parts, methyl methacrylate 6 parts, t-butyl methacrylate 1 part, canolebitol acetate 100 parts, 0.3 parts of mercaptan and 3 parts of azobisisobutyronitrile were added, and the mixture was heated under a nitrogen stream and polymerized at 80 ° C for 5 hours to obtain a 50% epoxy group-containing copolymer solution.

Subsequently, 20 parts of TEP IC-S (triglycidyl isocyanurate manufactured by Nissan Chemical Co., Ltd.), 0.05 parts of hydroquinone, 50 parts of acrylic acid, and 50 parts of dimethylbenzyla were added to the 50% epoxy group-containing copolymer solution. Add 0.2 parts of min and carry out addition reaction at 105 ° C for 24 hours, then add 38 parts of tetrahydrophthalic anhydride and 108 parts of carbitol acetate, and add 3 parts at 100 ° C. The reaction was allowed to proceed for a time to obtain a 50% externally curable resin solution (A-5).

(Synthesis Example 6)

In a four-neck flask equipped with a reflux condenser, a thermometer, a glass tube for purging nitrogen, and a stirrer, glycidino remethallate 70 parts, NK ester T.MPT (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd., trimethylol Propane trimming (Tacrylate, molecular weight = 338) 10 parts, methyl methacrylate 15 parts, t-butyl methacrylate 5 parts, carbitol acetate 100 parts, lauryl mercaptan 0.2 parts, azobisisobutyronitrile 3 parts, and nitrogen The mixture was heated under a stream of air and polymerized at 80 ° C for 5 hours to obtain a 50% epoxy group-containing copolymer solution.

Subsequently, 10 parts of TEP IC-S (triglycidyl isocyanurate manufactured by Nissan Chemical Industries, Ltd.), 0.05 parts of hydroquinone, 43 parts of acrylic acid, and dimethylbenzylamine were added to the 50% epoxy group-containing copolymer solution. Add 0.2 parts, perform addition reaction at 105 ° C for 24 hours, then add 38 parts of tetrahydrophthalic anhydride and 91 parts of carbitol acetate, react at 100 ° C for 3 hours, and react with 50% An ultraviolet curable resin solution (A-6) was obtained.

(Synthesis Example 7)

In a four-neck flask equipped with a reflux condenser, a thermometer, a glass tube for purging nitrogen and a stirrer, 70 parts of glycidyl methacrylate, 20 parts of methyl methacrylate, 10 parts of t-butyl methacrylate, 100 parts of carbitol acetate, 0.2 parts of lauryl mercaptan and 3 parts of azobisisobutyronitrile were added, and the mixture was polymerized at 80 ° C for 5 hours while heating and stirring under a nitrogen stream to obtain a 50% copolymer solution. Subsequently, 0.05 parts of hydroquinone, 37 parts of acrylic acid, and 0.2 parts of dimethylbenzylamine were added to the above 50% copolymer solution, and 100 was added. C for 24 hours, then add 45 parts of tetrahydrophthalic anhydride and 79 parts of carbitol acetate and react at 100 ° C for 3 hours to obtain a 50% UV-curable resin solution (E-1 ).

(Synthesis Example 8)

Epiclone N-680 (trade name; One lunovolak epoxy resin, epoxy equivalent: 214) 214 parts of carbitol acetate heated and dissolved in 214 parts were stirred and mixed with 74 parts of acryloyl acid, 0.1 part of hydroquinone and 0.1 part of benzyldimethylamine. 7 parts were added, and the reaction was carried out at 90 to 100 ° C for 24 hours by a conventional method. To this reaction solution, 95 parts of carbitol acetate was added, and the mixture was stirred and cooled to obtain an epoxy acrylate solution. Subsequently, 76 parts of tetrahydrophthalic anhydride and 87 parts of carbitol acetate were added and reacted at 100 ° C. for 3 hours to obtain a 60% UV-curable resin solution (E-2).

[Examples 1 to 6 and Comparative Examples 1 to 3]

UV curable resin liquids (A-1) to (A-6) produced in the above synthesis examples,

Using (E-1) to (E-2), the mixture obtained by mixing each composition shown in Table 1 was kneaded in a three-hole mixer, and the mixture was prepared in Examples 1 to 6 and compared. Example 1 A liquid photo solder resist ink that can be developed with a dilute aqueous alkaline solution was prepared.

table 1

Actual so-called comparative example

1 2 3 4 5 6 1 2 3 UV curable resin solution (Α-1) 50

UV curable resin solution (Α-2) 50

UV curable resin solution (Α-3) 50

UV-curable resin solution (Α) 50

UV curable resin solution (A-5) 50

UV curable resin solution (A-6) 50

UV curable resin solution (E-1) 50 50

UV curable resin solution (E- 2) 50 Dipentaerythritol 55 55 55 55 55 55

Epiclone N-695 10 10 10 10 C

YX4000 10 10

TEPIC— S 10 10 10 Irgacure 907 4 4 4 4 4 4 4 4 4 DETX-S 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Modaf mouth 1 1 1 1 1 1 1 1 1 Silica (average grain (Diameter: ¹ / m) 10 10 10 10 10 10 10 10 10 10 Barium sulfate 17 17 17 17 17 17 17 17 17 Melamine 1 1 1 1 1 1 1 1 1 Phthalocyanine green 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Susol 1500 1 1 1 1 1 1 1 1 1

In Table 1, “Epiclone N-695” (trade name) is Cresol novolac epoxy resin manufactured by Dainippon Ink and Chemicals, Inc. “YX4 000” (trade name) has an epoxy equivalent of 195 Epoxy compound manufactured by Yuka Shell Epoxy Co., Ltd., and “TEP IC-S” (trade name) is a triglycidyl isocyanurate manufactured by Nissan Chemical Industries, Ltd. having an epoxy equivalent of 100. “Irgacure I-907” (trade name) is a photopolymerization initiator (2-methyl-11- [4-methylthio (phenyl)] — 2-morpholinopropane 111-one) manufactured by CHIPAGIGI CORPORATION. “Kyakua I DETX-S” (trade name) is a photopolymerization initiator (2,4 getylthioxanthone) manufactured by Nippon Kayaku Co., Ltd. “Modaflow” (trade name) is Monsantone Earth leveling agent. Susol 1 500 (trade name) is a petroleum-based aromatic mixed solvent manufactured by Maruzen Petrochemical Co., Ltd.

The performance of each resist ink and a printed wiring board having a solder resist formed using the same resist ink was evaluated by the following test methods. Table 2 shows the test results.

Table 2

[Performance evaluation of resist ink]

One-side adhesiveness--Apply resist ink on the entire surface of copper-clad laminate consisting of glass epoxy base material of copper foil with a thickness of 35 am by screen printing, and dry at 80 ° C to volatilize the solvent. Pre-drying was performed under the respective drying conditions of 10, 20, and 30 minutes, and three types of test pieces having a pre-dried film having a thickness of 20 μin were prepared for each of the inks. After that, using ORC HMW680GW (Model No., manufactured by Oak Manufacturing Co., Ltd., 'Depressurized contact type double-sided exposure machine'), the mask on which the pattern was drawn was placed directly on the pre-dried film surface and adhered under reduced pressure, and irradiated with 150m jZcni ² ultraviolet rays. The degree of adhesion when the mask was removed under each drying condition was evaluated.

The evaluation method of surface tackiness is as follows.

X: It was difficult to remove the mask, and if it was forcibly removed, the mask was damaged and could not be reused.

Δ: After the mask was removed, traces of sticking of the mask were observed on the preliminarily dried film.

〇: The mask could be easily removed. There were no sticking marks.

-Development width (preliminary drying time allowable range)

A resist ink is applied by screen printing to the entire surface of a copper-clad laminate consisting of a 35-μm-thick copper-foil glass-epoxy base material to volatilize the solvent80. Pre-drying was performed under drying conditions of 10, 20, 30, 40, 50, 60, 70, 80 minutes and 90 minutes at C, and eight types of test specimens having a pre-dried film with a thickness of 20 m were obtained. It was created for each ink. Then, a mask on which the pattern was drawn was directly placed on the surface of the pre-dried film and brought into close contact with each other, and the resist ink was irradiated with an optimal exposure amount of ultraviolet light. Next, develop with 1% aqueous sodium carbonate solution as a developing solution to form developability and pattern The condition was observed. The evaluation method of the development width is as follows.

X: It was difficult to remove unexposed portions by development, and a pattern could not be formed.

Δ: It took a long time to develop the unexposed portion, and no pattern could be formed in a fine pattern portion.

〇: The unexposed area was easy to develop and a sharp pattern could be obtained. Number of remaining steps one

The resist ink is applied by screen printing to the entire surface of a copper-clad laminate made of a 35-μm-thick copper foil glass-epoxy substrate, and dried at 80 ° C for 20 minutes to volatilize the solvent. By performing preliminary drying under drying conditions, test pieces having a preliminary dried film having a thickness of 20 μππ 2 were prepared for each ink. Then, using ORC HMW 680 GW (model number, reduced pressure contact type double-sided exposure machine manufactured by Oak Manufacturing Co., Ltd.), step tablet PHOTEC 2 1-stage (exposure test mask manufactured by Hitachi Chemical Co., Ltd.) was directly placed on the preliminary dried film. vacuum adhesion is thereby arranged and irradiated with each of 5 0 and 1 5 0 mj Z cm ² ultraviolet. Next, the number of steps remaining after the development was determined by developing with an aqueous 1% sodium carbonate solution as a developer, and used as a measure of exposure sensitivity.

[Performance evaluation of printed wiring boards]

In order to confirm the performance of the printed wiring board manufactured with each resist ink, test pieces were prepared by the following steps (1) to (4).

(1) Coating process>

A liquid photo solder resist ink is applied by screen printing to the entire surface of a copper-clad laminate made of a glass epoxy base material of copper foil with a thickness of 35 πι, and a printed wiring board that has been etched and patterned in advance. Thus, a resist ink layer was obtained on the substrate surface. ② Pre-drying process>

After the coating step, predrying was performed at 80 ° C. for 20 minutes to volatilize the solvent in the resist ink layer on the substrate surface, and a predry film having a film thickness of 20 μπι was obtained.

(3) Exposure process>

After that, the mask on which the pattern was drawn was placed directly on the surface of the pre-dried film, and the resist film was irradiated with the optimal exposure amount of ultraviolet light to selectively expose the pre-dried film on the substrate surface. '

Paku development process>

In the pre-dried film after the exposure step, a 1% aqueous solution of sodium carbonate was used as a developing solution to remove unexposed portions by developing, and a pattern of the exposed and cured pre-dried film was formed on the substrate.

Paku Post Beta Process>

The substrate having the pre-dried film was heated at 150 ° C. for 30 minutes, and the pre-dried film was cured to obtain a test piece having a resist composed of the cured film.

The following evaluation was performed about the test piece obtained by the above process.

— Fiber property —.

The formation state of a pattern formed by a mask pattern composed of concentric circles having both a line width and a line interval of 40 μπι was observed. The evaluation method for resolution is as follows.

X: A pattern could not be formed.

Δ: A pattern could be formed, but part of it was missing.

〇: A sharp pattern could be formed.

One solder heat resistance

As flux, LONCO 3 3 5 5-1 1 (trade name, London First, a flux was applied to a test piece using Mical Corporation's water-soluble flux (raw flux), then immersed in a molten solder bath at 260 ° C for 15 seconds, and then washed with water. After this cycle was repeated once or five times, the degree of surface whitening was observed. In addition, a cellophane adhesive tape peeling test using a cross-cut was performed in accordance with JISD 202, and changes in the adhesion state were observed. The evaluation method of surface whitening is as follows.

X: Markedly white.

Δ: Whitening was observed.

〇: Very slight whitening occurred.

A: No whitening occurred.

The method for evaluating the adhesion is as follows.

X: Swelling or peeling of the resist occurred before the cross cut test. C: Partial peeling occurred at the cross-cut portion during tape peeling.

〇: No peeling of the cross cut portion occurred.

A: No change at all.

One pencil hardness

The pencil hardness was measured and evaluated in accordance with JIS 540, and the other items were evaluated by a common method.

— Gold plating resistance —

The test pieces were plated using commercially available electroless nickel plating baths and electroless plating baths, and the adhesion of the coating films was observed. The method for evaluating the gold plating resistance is as follows.

X: Lifting of the coating film was observed, and peeling was observed when the tape was peeled.

Δ: No change in appearance, but partial peeling was observed when the tape was peeled.

〇: No change at all. One electric corrosion resistance

A test printed circuit board was prepared under the above conditions using a coupon electrode B of IPCB-25 instead of the test piece. ° (: The presence of migration after 500 hours under the conditions of 90% R.H. was evaluated. The method for evaluating the corrosion resistance was as follows.

X: Migration was confirmed.

Δ: Slight migration was confirmed.

〇: No migration was confirmed at all.

As is clear from Tables 1 and 2, in Examples 1 to 6, the development width, solder heat resistance, and metallization resistance were improved, and excellent substrate adhesion and electric resistance were obtained as compared with Comparative Examples 1 to 3. It can be seen that it has corrosiveness. Industrial applicability

As described above, according to the present invention, an ultraviolet curable resin composition having excellent developability, resolution, development width, and heat resistance can be provided. A photo solder resist ink containing this composition can be developed with a dilute aqueous solution, and has excellent substrate adhesion and electrolytic corrosion resistance, and excellent solder heat resistance and gold plating resistance. Can be formed on a substrate such as a printed wiring board.

Claims

The scope of the claims.

1. UV curable resin composition comprising the following components:

(A) an epoxy group-containing polymer (a) obtained by polymerizing an ethylenically unsaturated monomer component containing an epoxy group-containing ethylenically unsaturated monomer (i), and an epoxy group-containing isocyanurate A dioxy compound component containing the derivative (b) is reacted with an ethylenically unsaturated monomer (c) having a carboxyl group, and the resulting intermediate product is added to a saturated or unsaturated polybasic anhydride. UV-curable resin obtained by reacting the product (d);

(B) an epoxy compound having two or more epoxy groups in the molecule;

(C) a photopolymerization initiator; and

(D) Diluent.

2. The ethylenically unsaturated monomer component is characterized in that it contains an ethylenically unsaturated monomer (ii) copolymerizable with the ethylenically unsaturated monomer (i). 2. The ultraviolet-curable resin composition according to 1.

3. The ultraviolet curable resin composition according to claim 1, wherein the ethylenically unsaturated monomer component contains a compound (iii) having two or more ethylenically unsaturated groups in one molecule. .

4. The ethylenically unsaturated monomer component contains the ethylenically unsaturated monomer (i) and the ethylenically unsaturated monomer (ii) copolymerizable with the compound (iii). 4. The ultraviolet-curable resin composition according to claim 3, wherein:

5. The ultraviolet curable resin (A) is prepared by reacting the intermediate product with a saturated or unsaturated polybasic acid anhydride (d) and an isocyanate compound (e) having at least two isocyanate groups in the molecule. The ultraviolet-curable resin composition according to claim 1, which is obtained by:

6. The ultraviolet-curable resin composition according to claim 1, comprising the ethylenically unsaturated monomer (i) glycidyl (meth) atarylate.

7. The ultraviolet-curable resin composition according to claim 1, comprising the above isocyanurate derivative (b) I tolidaridyl isocyanurate.

8. The ultraviolet curable resin composition according to claim 3, wherein the compound (iii) contains di (meth) acrylate.

9. The ultraviolet ray curable resin composition according to claim 3, wherein the compound (iii) is a di (meth) acrylate having at least one oxyalkylene unit.

10 The content of the compound (iii) is in the range of 0.1 to 10 mol% in the total amount of the ethylenically unsaturated monomer components used for producing the epoxy group-containing polymer (a). 4. The ultraviolet curable resin composition according to claim 3, wherein:

1. A substrate having a cured film of the ultraviolet-curable resin composition according to claim 1.

12. A photo sonoreta, a resist ink comprising the ultraviolet curable resin composition according to claim 1.

13. A printed wiring board having a cured film of the photo solder resist ink according to claim 12.

14. A film obtained by drying the ultraviolet-curable resin composition according to claim 1 is formed on the surface of a support.

5. A film obtained by drying the photo solder resist ink according to claim 12 is formed on the surface of a support.