JP2012117055A - Insulator ink resin composition, resist pattern, and resist pattern-forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an insulator ink resin composition that can help form a resist pattern by simple printing method, wherein the resist pattern is excellent in storage stability, ionic migration resistance, visibility in a thin film, and insulation reliability; to provide the resist pattern formed by using the insulator ink resin composition; and to provide a method of forming the resist pattern.SOLUTION: The insulator ink resin composition contains: a metal complex salt dye that contains trivalent chromium and amine salt; an insulating resin; and a curing agent.

Description

  The present invention relates to an insulating ink resin composition, a multilayer wiring board having a resist pattern formed using the same, and a method for manufacturing the same.

Conventionally, an etching method and an additive method are known as wiring formation methods.
In recent years, wiring formation by a printing method has been considered promising from advantages such as low energy, low cost, high throughput, and on-demand production. Specifically, it is realized by forming a pattern by a printing method using an ink paste containing a metal element and then imparting metal conductivity to the printed wiring pattern. In addition, after forming a pattern by a printing method using an ink paste containing an insulating resin, a resist pattern can be formed by a curing process.

  Conventionally, a conductive paste in which flaky silver or copper is mixed with a binder of a thermoplastic resin or a thermosetting resin together with an organic solvent, a curing agent, a catalyst, or the like has been used for forming a wiring pattern by a printing method. This conductive paste is used by applying it to an object by dispenser or screen printing and drying at room temperature or by heating to about 150 ° C. to cure the binder resin to form a conductive film. It was.

  Further, as a technique for forming a fine wiring pattern with low resistance by a printing method, a wiring pattern forming method using metal nanoparticles has been studied, and a method using gold or silver nanoparticles has been studied. Specifically, a dispersion liquid containing gold or silver nanoparticles having a diameter of 100 nm or less is applied on a substrate as a very fine circuit pattern by a printing method, and then sintered by performing mutual sintering of metal nanoparticles. A combined wiring layer is obtained.

However, when a high-definition thin film pattern is formed by a printing method, the dispersion containing metal nanoparticles is almost colorless and transparent, so it is printed in the desired location and shape, and it is confirmed whether a resist can be formed. Visibility in doing so was poor, and visual judgment was extremely difficult.
Therefore, in order to improve the fineness of line formation by exposure, in Patent Document 1, a dye is contained in at least one of a blue colorant and a yellow colorant in a green solder resist pattern ink, and an exposure solution of a coating film is exposed. It is noted that image quality and green color tone are excellent. Copper phthalocyanine dyes are used as blue dyes.

JP 2003-124613 A

However, when copper phthalocyanine-based insulator ink is used, there is a problem of ion migration caused by copper.
In addition, since the conventional solder resist pattern ink is mainly copper phthalocyanine, the curing reaction easily proceeds and the storage stability is poor.
Further, when using a dye as a colorant, it has been a problem that the coloring reliability is insufficient or fading, the solubility in the insulator ink, and the dye itself deteriorate the insulation reliability as compared with the pigment.
Moreover, originally, it was not preferable to use a conductive metal complex for an insulating ink, and a metal complex dye was never used for an insulating ink except for a copper phthalocyanine-based material having an excellent vivid green color tone. .
In particular, when a pattern of a high-definition thin film (film thickness of 50 μm or less, particularly 25 μm or less) is formed by a printing method, when a copper phthalocyanine-based colorant is not used, a line and space of about 100 μm in a desired place and shape The resist pattern is printed with high accuracy and the visibility when confirming whether or not the obtained resist pattern can be accurately formed is often poor, and whether or not the desired resist pattern is formed by visual judgment It was often difficult to confirm.

The present invention relates to an insulator ink resin composition capable of forming a resist pattern excellent in storage stability, ion migration resistance, visibility in a thin film, and insulation reliability by a simple printing method, and the insulator ink resin. A resist pattern using the composition and a method for forming the resist pattern are provided.
The insulator ink resin composition of the present invention is suitable for forming a thin-film resist pattern using an inkjet method.

The present inventors have intensively studied an insulating ink resin composition excellent in storage stability and insulation reliability, and the insulating ink resin composition contains a metal complex dye containing trivalent chromium and an amine salt. It has been found that ion migration, storage stability and insulation reliability can be balanced.
That is, the present invention is as follows.

(1) An insulator ink resin composition comprising a metal complex dye containing trivalent chromium and an amine salt, an insulating resin and a curing agent.

(2) The insulator ink resin composition according to the above (1), wherein the content of trivalent chromium is 50 to 2000 ppm with respect to the total solid content of the insulator ink resin composition.

(3) The insulator ink resin composition according to (1) or (2), wherein the content of divalent copper is 150 ppm or less with respect to the total solid content of the insulating ink resin composition.

(4) The insulator ink resin composition according to any one of (1) to (3), wherein the metal complex dye is a monoazo metal complex dye or an azo compound metal complex dye.

(5) The insulator ink resin composition according to any one of (1) to (4), wherein the color tone of the metal complex salt dye is either red or orange.

(6) The insulator ink resin composition according to any one of (1) to (5), wherein the viscosity of the insulator ink resin composition is 0.1 to 50 mPa · s or less.

(7) A resist pattern obtained using the insulator ink resin composition according to any one of (1) to (6).

(8) The insulating ink resin composition according to any one of (1) to (6) above is used for a wiring board having one or more lands and lead-out wiring connected to the one or more lands. A method of forming a resist pattern, comprising a step of forming a resist pattern so that one or more lands are exposed.

According to the present invention, it is possible to form a resist pattern excellent in storage stability, resistance to ion migration, visibility in a thin film, and insulation reliability by a simple printing method.
Further, it is possible to form a circuit layer in which one or more resist patterns and wiring layers are alternately formed by the above method, and the wiring layers are partially electrically connected. Furthermore, by forming a resist pattern on the outermost surface of this circuit layer, it can be used as a resist pattern layer to prevent short circuit between the protective layer of the circuit layer with excellent adhesion, the conductive material for connection such as solder balls, and the circuit layer. it can.

It is a top view which illustrates the wiring board before forming a resist pattern using the insulator ink resin composition of this invention. (A) is a top view of the wiring board which formed the resist pattern using the insulator ink resin composition of this invention, (B) is sectional drawing along the AB line | wire of (A). . It is sectional drawing of the wiring board which formed the resist pattern using the insulator ink resin composition of this invention in the case where wiring is two layers, and mounted the solder ball.

  Hereinafter, preferred embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

<Insulator ink resin composition>
The insulator ink resin composition of the present invention is characterized by comprising a metal complex dye containing trivalent chromium and an amine salt, an insulating resin, and a curing agent.
Below, each component of the insulator ink resin composition of this invention is explained in full detail.

[Metal complex dyes]
In the present invention, the metal complex dye is classified as a solvent color in the color index, and includes trivalent chromium and an amine salt. By containing trivalent chromium, excellent insulation reliability of the resist pattern can be obtained, and by containing an amine salt, the solubility in a water-soluble organic solvent is improved, and a homogeneous insulator ink resin composition and A resist pattern can be obtained. Examples of such metal complex dyes include Kayaset K series from Nippon Kayaku Co., Ltd., Balifast Color series from Orient Chemical Co., Ltd., Eisenspiron series and SOT series from Hodogaya Chemical Co., Ltd. .
In addition, from the viewpoint of obtaining further excellent insulation reliability of the resist pattern, a monoazo metal complex dye or an azo compound metal complex dye in which the coordination metal atom is any one of iron, chromium, and cobalt is preferable. Some of these metal complex dyes can be used in combination. In addition, although it does not specifically limit as a color tone of a metal complex dye, For example, blue, green, red, orange etc. are mentioned, From the point of visibility improvement, red and orange are preferable.

Furthermore, examples of the metal complex dye used in the present invention include Spiro Red BEH special, Spiron Black BH special, and Spiro Orange 2RH special manufactured by Hodogaya Chemical Co., Ltd.
Further, within the range not inhibiting the effect of the present invention, Spiron Blue 2BNH, Spiron Green 3GNH special, Spiron Black GMH special (CI Solvent Black 43), Spiron Yellow C-2GH, Spiron NH C GH, Spiron Red C-BH, Spiron Blue BPNH, S.H. B. N. Blue 701, Spiron Blue C-RH, Spillion Violet C-RH, S.R. P. T.A. Orange-6, S.M. P. T.A. Blue-111, Aizen Spiro Yellow C-2GH, Aizen Spiron Yellow C-GNH, Aizen Spiron SBN Yellow 530, Aizen Spiron SPT Rand A-SPT Red-6, Aizen Spiro Red be able to.

  Examples of dyes classified as solvent colors in the color index include C.I. I. Acid Black 52, C.I. I. Solvent Black 22, C.I. I. Solvent Black 27, C.I. I. Solvent Black 29, C.I. I. Solvent Black 34, C.I. I. Solvent Black 35, C.I. I. Solvent Yellow 16, C.I. I. Solvent Yellow 19, C.I. I. Solvent Yellow 25, C.I. I. Solvent Yellow 32, C.I. I. Solvent Yellow 79, C.I. I. Solvent Yellow 81, C.I. I. Solvent Yellow 82, C.I. I. Solvent Orange 45, C.I. I. Solvent Orange 54, C.I. I. Solvent Orange 56, C.I. I. Solvent Orange 62, C.I. I. Solvent Orange 99, C.I. I. Solvent Brown 42, C.I. I. Solvent Brown 48, C.I. I. Solvent Red 8, C.I. I. Solvent Red 18, C.I. I. Solvent Red 24, C.I. I. Solvent Red 27, C.I. I. Solvent Red 109, C.I. I. Solvent Red 118, C.I. I. Solvent Red 119, C.I. I. Solvent Red 122, C.I. I. Solvent Red 127, C.I. I. Solvent Red 160, C.I. I. Solvent Blue 5, C.I. I. Solvent Blue 35, C.I. I. Solvent Blue 36, Solvent Blue 70, etc. can be used within the range which does not inhibit the effect of this invention.

  The content of the amine salt contained in the metal complex dye is preferably 15 ppm or more with respect to the total solid content of the insulator ink resin composition. For example, the content of the amine salt can be measured by the Kjeldahl method (the nitrogen of the azo compound contained in the dye structure can be excluded) as the amine nitrogen content. In addition, although an upper limit is not specifically limited, 3000 ppm or less is preferable and when it exceeds this, there exists a possibility that storage stability may worsen.

  The metal element contained in the metal complex dye can be used in combination with any number of valent chromium, divalent cobalt, divalent and trivalent iron, and the content is insulated. The amount is preferably 50 to 2000 ppm, more preferably 250 to 1000 ppm, and particularly preferably 500 to 750 ppm with respect to the total solid content of the body ink resin composition. If the trivalent chromium content is less than 50 ppm, the insulation reliability deteriorates, and if it exceeds 2000 ppm, the visibility deteriorates.

  The divalent copper, which is a metal element contained in the metal complex dye, is preferably 150 ppm or less with respect to the total solid content of the insulator ink resin composition. From the viewpoint of protecting the wiring layer from an electrical short circuit by using the resist pattern as a base or protective layer for the wiring layer having a fine pattern, it is more preferably 50 ppm or less. From the viewpoint of long-term insulation reliability, 0 ppm is more preferable, but a small amount may be included for the purpose of obtaining a desired color tone.

[Insulating resin]
The insulating resin is not particularly limited, but is preferably a thermosetting resin. The thermosetting resin refers to a reactive compound that can cause a crosslinking reaction by heat. Examples of such compounds include epoxy resins, cyanate resins, bismaleimide resins, phenol resins, urea resins, melamine resins, alkyd resins, acrylic resins, unsaturated polyester resins, diallyl phthalate resins, silicone resins, resorcinol formaldehyde resins, From xylene resin, furan resin, polyurethane resin, ketone resin, triallyl cyanurate resin, polyisocyanate resin, resin containing tris (2-hydroxyethyl) isocyanurate, resin containing triallyl trimellitate, cyclopentadiene Examples thereof include a thermosetting resin synthesized and a thermosetting resin by trimerization of aromatic dicyanamide. Among these, an epoxy resin, a cyanate resin, and a bismaleimide resin are preferable in that an excellent adhesive force can be imparted at a high temperature, and an epoxy resin is particularly preferable in terms of handling properties and compatibility with polyimide. These thermosetting resins can be used alone or in combination of two or more.

  Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenol type epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin, glycidyl ester type epoxy resin, or Glycidyl etherified products of phenols, cresols, alkylphenols, catechols, bisphenol F, bisphenol A, bisphenol S and other phenols and aldehydes such as formaldehyde and salicylaldehyde, and other glycidyl ethers, bifunctional phenols There are glycidyl etherified products of alcohol, glycidyl etherified products of polyphenols, and hydrogenated products and halides thereof, but there are phenols from the viewpoint of heat resistance and connection reliability. Glycidyl ethers of condensation products of Le and aldehydes are preferred. These epoxy resins may have any molecular weight, and several types can be used in combination.

  The weight average molecular weight of the epoxy resin is preferably 200 or more and 50000 or less because the cross-linking points for the curing treatment are dense and good mechanical properties, heat resistance and environmental reliability can be obtained. For example, when used as an insulating ink resin composition that can be applied to a plateless printing method such as inkjet, the viscosity of the insulating ink is more preferably 200 or more and 35000 or less in order to ensure stable nozzle ejection properties of the inkjet. In order to suppress an increase and to use it stably, 200 or more and 20000 or less are still more preferable.

[Curing agent]
Examples of the curing agent include amines such as diethylenetriamine, triethylenetetramine, metaxylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, m-phenylenediamine, and dicyandiamide, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl Tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl nadic anhydride, pyromellitic anhydride, trimellitic anhydride and other acid anhydrides, imidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2- Phenylimidazole, 2-undecylimidazole, 1-benzyl-2-methylimidazole, 2-heptadecylimidazole, 4,5-diphenylimidazole, 2-methylimidazoline, 2-pheni Imidazoline, 2-undecylimidazoline, 2-heptadecylimidazoline, 2-isopropylimidazole, 2,4-dimethylimidazole, 2-phenyl-4-methylimidazole, 2-ethylimidazoline, 2-isopropylimidazoline, 2,4-dimethyl Imidazoles such as imidazoline and 2-phenyl-4-methylimidazoline, and imidazoles whose imino group is masked with acrylonitrile, phenylene diisocyanate, toluidine isocyanate, naphthalene diisocyanate, methylene bisphenyl isocyanate, melamine acrylate, etc., bisphenol F, bisphenol A , Phenols such as bisphenol S and polyvinylphenol, and phenol, cresol, alkylphenol, catechol There are bisphenol F, bisphenol A, condensation products and halides of these and aldehydes such as phenol with formaldehyde and salicylaldehyde, such as bisphenol S. Some of these compounds can be used in combination.

  Among the curing agents described above, a condensate of a phenol compound having a phenolic hydroxyl group and an aldehyde compound is preferable from the viewpoint of heat resistance and connection reliability. Examples of such condensates are condensates of phenolic compounds such as hydroquinone, resorcinol, catechol, bisphenol A, bisphenol F, bisphenol S, naphthalene diols, biphenols and the like, and phenol novolac resins, resole resins, Examples thereof include bisphenol A novolak resins, cresol novolak resins, and their condensates such as halides, alkyl group-substituted products, and nitrogen-containing group-substituted products. These can be used singly or in combination of two or more.

  When using a combination of the epoxy resin and the condensate of the phenol compound and the aldehyde compound, the blending amount of both is an equivalent ratio of epoxy equivalent and hydroxyl equivalent (epoxy equivalent / hydroxyl equivalent) from the viewpoint of curability. 0.70 / 0.30 to 0.30 / 0.70 is preferable, and from the viewpoint of solvent resistance and mechanical properties, 0.65 / 0.35 to 0.35 / 0.65 is preferable. More preferably, from the viewpoint of connection reliability, 0.60 / 0.40 to 0.40 / 0.60 is still more preferable, and from the viewpoint of heat resistance, 0.55 / 0.45 to 0.45 / A value of 0.55 is particularly preferable. If the blending amount of both is out of the above equivalent ratio range, the curability tends to be insufficient.

[Curing accelerator]
Moreover, when using combining the condensate of the said epoxy resin, the said phenol compound, and an aldehyde compound, a hardening accelerator can be contained for the reaction rate adjustment at the time of hardening. From the viewpoint of curability and storage stability, imidazoles and diamines are more preferable. Examples include 2-undecylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1- Benzyl-2-phenylimidazole, 1-cyano-1-cyanoethyl-2-undecylimidazole, 1-cyano-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole trimellitate, 1-cyanoethyl-2-phenyl Imidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'- Methylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino-6- 2'-methylimidazolyl- (1 ')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl Examples include -5-hydroxymethylimidazole, 3,3'-methylenedianiline, 4,4'-methylenedianiline, adducts of epoxy resin and imidazoles. These may be used alone or in combination of two or more. Moreover, you may use what microencapsulated these and raised the potential. These are solid at normal temperature (25 ° C.) and are excellent in workability.

The amount of the curing accelerator is preferably 0.0001 to 1 part by weight, more preferably 0.001 to 0.5 part by weight, and 0.01 to 0.2 part per 100 parts by weight of the insulating resin. More preferably, it is part by mass. If it exceeds 1 part by mass, there is a problem in terms of storage stability, and if it is less than 0.0001 part by mass, sufficient acceleration of curing cannot be obtained.
The above is a description of a material when a thermosetting system is selected as the curing system and a curing method using the material. However, the present invention is not limited to this and can be used for a photocuring system. A known photocuring material can be used.

[solvent]
The insulator ink resin composition may contain a solvent as necessary. The solvent is preferably a solvent having a vapor pressure at 25 ° C. of less than 1.34 × 10 ³ Pa. With such a solvent, an increase in ink viscosity due to the volatilization of the solvent can be suppressed. For example, when only a solvent having a vapor pressure of 25 ° C. of 1.34 × 10 ³ Pa or higher is used, the ink viscosity is remarkably increased due to the volatilization of the solvent. The ink jet head tends to be clogged.

A solvent having a vapor pressure of less than 1.34 × 10 ³ Pa and a solvent having a vapor pressure of 1.34 × 10 ³ Pa or more may be used in combination. The blending ratio of the solvent of 34 × 10 ³ Pa or more is preferably 60% by mass or less based on the mass of the total amount of the solvent, and is 50% by mass or less from the viewpoint of suppressing an increase in ink viscosity due to the volatilization of the solvent. More preferably, from the viewpoint of ejecting liquid droplets from the nozzles of the inkjet head, it is even more preferable that the content be 40% by mass or less. Various solvents can be used as long as the vapor pressure is in a desired range and the insulating resin is dispersed or dissolved.

The solvent having a vapor pressure at 25 ° C. of less than 1.34 × 10 ³ Pa may be any solvent that can dissolve the curable resin. Specifically, sulfolane, propylene carbonate, γ-butyrolactone, cyclohexanone, N— Methyl-2-pyrrolidone, anisole, ethylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, triethylene glycol monomethyl ether, triethylene glycol dimethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol dimethyl ether, diacetone alcohol, 1,3-butylene glycol di Acetate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, tetradecane, methyl lactate, ethyl lactate, alcohol Tofenon, limonene, and the like.
Specific examples of the solvent having a vapor pressure at 25 ° C. of 1.34 × 10 ³ Pa or more include methyl ethyl ketone, methyl isobutyl ketone, toluene, isopropyl alcohol and the like. These solvents can be used singly or in combination of two or more.

  The content ratio of the solvent is not particularly limited. Usually, it is preferable to set it as 10-99 mass% with respect to an insulator ink resin composition, for example, when applying to an inkjet printing method, it is more preferable to set it as 30-99 mass%.

  The appropriate range of the viscosity of the insulating ink resin composition varies depending on the printing method to be applied.

  When applied to the inkjet printing method, the viscosity of the insulating ink resin composition is preferably 0.1 to 50 mPa · s, more preferably 1 to 30 mPa · s at 25 ° C., and more preferably 5 to 20 mPa. -Particularly preferred is s. If the viscosity of the insulating ink resin composition is 0.1 mPa · s or more, there is no ink flow and the pattern misalignment can be suppressed, and if it is 50 mPa · s or less, the non-ejection nozzle during ink jet printing And nozzle clogging can be prevented. Further, the diameter of the droplet can be reduced, and a finer pattern can be easily formed by further reducing the landing diameter of the insulating ink.

On the other hand, when applied to the screen printing method, the viscosity of the insulating ink resin composition is 0.01 Pa · s (= 10 mPa · s) to 500 Pa · s at 25 ° C. and a shear rate of 100 s ^−1. Preferably, it is 0.1 to 300 Pa · s, more preferably 0.5 to 100 Pa · s. If the viscosity of the insulating ink resin composition is 500 Pa · s or less, the ink can easily be removed during printing, and the occurrence of plate clogging can be more reliably prevented during continuous printing operations. can do. In order to cope with the formation of fine patterns, the viscosity of the insulating ink resin composition is preferably 0.01 Pa · s or more from the viewpoint of preventing abnormal wetting and spreading of the ink after printing.

When applied to a printing method using a dispenser, the viscosity of the insulating ink resin composition is preferably 20 mPa · s to 3000 Pa · s at 25 ° C. If the viscosity is less than 20 mPa · s, liquid sag is likely to occur, and if it exceeds 3000 Pa · s, it is difficult to reduce the diameter of the droplets and form a fine pattern. Moreover, when using a jet-type dispenser, it is more preferable that it is 30mPa * s-500Pa * s, and it is further more preferable that it is 50mPa * s-300Pa * s.
The viscosity at 25 ° C. of the insulating ink resin composition is measured using an E-type viscometer (cone angle 1 degree, rotation speed 5 rpm).

  The appropriate range of the surface tension of the insulating ink resin composition varies depending on the printing method to be applied.

  When applied to the ink jet printing method, the surface tension at 25 ° C. of the insulator ink resin composition is preferably 20 mN / m or more, and the surface tension can be adjusted with a surface conditioner. When the surface tension of the insulating ink resin composition is less than 20 mN / m, the droplets of the insulating ink resin composition spread on the substrate after landing, and there is a tendency that a flat thick film cannot be formed. The surface tension of the insulator ink resin composition is more preferably in the range of 20 to 80 mN / m. This is because when the surface tension of the insulating ink resin composition exceeds 80 mN / m, the inkjet nozzle clogging tends to occur easily. From the viewpoints of flat film formability and stable inkjet ejection properties, it is more preferably 20 to 40 mN / m.

  On the other hand, when applied to the screen printing method, the surface tension of the insulating ink resin composition at 25 ° C. is preferably 10 mN / m or more, and the surface tension can be adjusted by a surface conditioner. When the surface tension of the insulator ink resin composition is less than 10 mN / m, the insulator ink resin composition tends to spread on the base material, and a flat thick film cannot be formed. The surface tension of the insulator ink resin composition is more preferably in the range of 10 to 80 mN / m. This is because when the surface tension of the insulator ink resin composition exceeds 80 mN / m, the substrate tends to be repelled. From the viewpoint of flat film formability and stable fine pattern formation, it is more preferably 20 to 60 mN / m.

  As the surface conditioner to be added to the insulating ink resin composition, for example, one kind selected from silicone, vinyl, acrylic and fluorine can be used alone, or two or more kinds can be used in combination. For example, such commercially available surface conditioners include BYK-051, BYK-054, BYK-057, BYK-A 506, BYK-A 520, BYK-A 530, BYK-A 535, BYK-A. 555, BYK-300, BYK-302, BYK-306, BYK-310, BYK-315, BYK-320, BYK-322, BYK-323, BYK-325, BYK-330, BYK-331, BYK-333, BYK-337, BYK-340, BYK-344, BYK-370, BYK-375, BYK-377, BYK-350, BYK-352, BYK-354, BYK-355, BYK-358N, BYK-361N, BYK- 392, BYK-UV3500, BYK-UV3510, BYK-3570, BY K-Silclean 3700 (above, trade name, manufactured by Big Chemie Japan Co., Ltd.), LF-1922, LF-1927, LF-1930N, LF-1931, LF-1933, LF-1934, LF-1958, P-410EF, P -420, P-425, PD-7, OX-880EF, OX-881, OX-883, OX-883HF, OX-70, OX-77EF, OX-60, OX-710, OX-720, OX-720EF , OX-750HF, LAP-10, LAP-20, LAP-30, 1970, 230, LF-1980, LF-1982, LF-1983, LF-1984, LF-1985, LHP-90, LHP-91, LHP -95, LHP-96, 1711, 1751N, 1761, LS-001, LS-050 As mentioned above, manufactured by Enomoto Kasei Co., Ltd., trade name), SD5591, SH200-100CS, SH7PA, 11ADDITIVE, SH28PA, SH-29PA, SH-30PA, ST80PA, ST83PA, ST86PA, ST90PA, ST97PA, ST105PA (Toray Dow Corning Co., Ltd.) Product name), Polyflow No. 3, Polyflow No. 7, Polyflow No. 50E, Polyflow No. 50EHF, Polyflow No. 54N, Polyflow No. 55, Polyflow No. 64, polyflow no. 75, Polyflow No. 77, Polyflow No. 85, Polyflow No. 85HF, Polyflow No. S, Polyflow No. 90, polyflow no. 90D-50, Polyflow No. 95, Polyflow No. 300, Polyflow No. 460, polyflow WS, polyflow WS-30, polyflow WS-314 (manufactured by Kyoeisha Chemical Co., Ltd., trade name) and the like.

  In addition to the above, additives such as a silane coupling agent and a thixotropic agent can be appropriately added to the insulating ink resin composition. Moreover, a monomer, an oligomer, etc. can also be dissolved and used for a solvent as needed.

<Resist pattern and formation method thereof>
The resist pattern of the present invention is a resist pattern obtained using the above-described insulator ink resin composition of the present invention.
Here, the resist pattern is used, for example, for insulation and protection of a conductor in the wiring board. In other words, the wiring board is composed of a substrate, an insulating layer, a conductor layer that is a conductor connecting portion, and a land, and the land is provided with conductor wiring by solder ball connection, solder lead solder connection, conductor wiring connection, etc. By forming it, a conductor connection function is exhibited, and other regions can be insulated and protected by the resist pattern of the present invention.

  In addition, the method for forming a resist pattern of the present invention uses the above-described insulator ink resin composition of the present invention for a wiring board having one or more lands and lead wirings connected to the one or more lands. It includes a step of forming a resist pattern so that one or more lands are exposed.

  In order to form a resist pattern on the wiring board, for example, the wiring board before forming the resist pattern shown in FIG. 1 can be used as a starting material. The wiring board shown in FIG. 1 has twelve lands 2 formed on the surface of the board 1, and each land 2 is connected to a lead-out wiring 3. Then, when a resist pattern is formed on such a wiring board so that the lands 2 are exposed, the result is as shown in FIG. 2A and 2B are cross-sectional views taken along line A-B in FIGS. 2A and 2A, each showing a state in which a resist pattern is formed on the wiring substrate shown in FIG. In FIG. 2A, since the resist pattern is formed up to the inside of the peripheral edge of each land 2, the peripheral edge of each land 2 is indicated by a broken line.

  The resist pattern is preferably formed by applying the above-described insulator ink resin composition of the present invention onto a wiring board by a printing method. After coating, if necessary, the solvent is removed (for example, heat treatment and / or vacuum deaeration), and the coated insulating ink resin composition is cured (for example, heat treatment or ultraviolet irradiation) to form a resist pattern. be able to.

  As a printing method of the insulator ink resin composition, inkjet printing, super inkjet printing, screen printing, transfer printing, offset printing, jet printing method, dispenser, jet dispenser, needle dispenser, comma coater, slit coater, die coater, gravure coater, Topographic printing, intaglio printing, gravure printing, soft lithography, dip pen lithography, spray coater, spin coater, dip coater, electrodeposition coating, etc. can be used, among them inkjet printing, super inkjet printing, screen printing, transfer printing, offset Selected from the group consisting of printing, jet printing, dispenser, needle dispenser, comma coater, slit coater, die coater, and gravure coater Any one is preferable. Among them, the ink jet printing method or the dispenser method can print a desired amount of ink at a desired position without using a special plate, and has characteristics such as material utilization efficiency and ease of adapting to pattern design changes. More preferred.

  As the inkjet printing method, for example, a commonly-known ejection method such as a piezo method for ejecting a liquid by vibration of a piezo element or a thermal method for ejecting a liquid by utilizing the expansion of the liquid by rapid heating can be used. . Among these, the piezo method is preferable from the viewpoint that the ink is not heated. In order to carry out such an ink jet printing method, for example, a normal ink jet apparatus can be used. The optimum nozzle diameter of the head that ejects ink can be selected depending on the desired droplet size.

  In the screen printing method, first, the surface of the substrate is covered with a mask having an opening of a desired pattern, the opening of the mask is filled with an insulating ink resin composition, and then moved on the mask while pressing the squeegee. Then, the insulating ink resin composition filled in the openings is brought into contact with the surface to be printed, and then the desired pattern can be formed by removing the mask. As the material of the mask, an optimum material can be selected from metal, nylon mesh, and the like according to a desired pattern, and the mesh size of the mask can be appropriately selected.

As a method of removing the solvent after applying the insulating ink resin composition to the substrate, a heat treatment method of heating the substrate or blowing hot air can be employed. Such heat treatment can be performed, for example, at a heating temperature of 60 to 200 ° C. and a heating time of 0.1 second to 2.0 hours. When a thermosetting resin is used as the resin, the resin can be cured after removing the solvent or simultaneously with removing the solvent. For example, in the case of an ultraviolet curable resin, the resin can be cured by irradiating ultraviolet rays after removing the solvent.
In addition, as a method for removing the solvent after applying the insulating ink resin composition to the substrate, a method of treating under a reduced pressure environment or a vacuum environment may be employed. Further, the solvent can be removed by combining such reduced pressure or vacuum drying treatment and heat treatment.

  The resist pattern made of the insulator ink resin composition of the present invention is used as an insulating base layer in the case of forming a wiring layer on a substrate by a printing method and / or after the wiring layer is formed, It is also suitable as a protective layer for physical and physical shielding.

The resist pattern using the insulator ink resin composition of the present invention can be suitably used as a solder resist pattern for a circuit board for a semiconductor package by being combined with another circuit board. The mounting board | substrate shown in FIG. 3 is the one aspect | mode. The embodiment shown in FIG. 3 will be described below.
First, the insulating layer 11 is applied and cured on the substrate 1 shown in FIG. 3A, a hole for a conductor layer is formed by etching using a resist pattern, and a plating layer is embedded as the conductor layer 31 and the land 21 ( FIG. 3 (B)). Depending on the application, the insulating layer 11 and the conductor layer 31 can also be formed by an ink jet method.
Subsequently, as shown in FIG. 3C, a resist pattern 40 is formed using the insulator ink resin composition of the present invention so that the land 21 is exposed.
Finally, as shown in FIG. 3D, the solder ball 7 is placed on the land region 6 composed of the resist pattern 40 and the land 21 and then heated at the solder reflow temperature to be bonded to another substrate 10. A mounting substrate is obtained.

  Although the resist pattern 5 in FIG. 3 is not indispensable, it can be used as a wall for forming a shape in which, for example, a semiconductor chip is embedded in a recess of a wiring board. When the resist pattern 40 is formed at a position lower than the wall constituted by the resist pattern 5, the screen printing method is not suitable, and the ink jet method is suitable. Therefore, the insulator ink resin composition of the present invention is used for the screen printing method. There is an advantage that it can be applied to both the ink jet method and the ink jet method.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to a following example.

[Examples 1 to 6, Comparative Example 1]
(Preparation of insulator ink resin composition)
An insulator ink resin composition was prepared for each of Examples 1 to 6 and Comparative Example 1.

(Preparation of Insulator Ink Resin Composition 1)
1.9 g of dye (trade name “Aizen Spiron Red BEH special”, manufactured by Hodogaya Chemical Co., Ltd.) and bisphenol A novolac type epoxy resin (trade name “N-865”, manufactured by Dainippon Ink & Chemicals, Inc.) 24 .2 g, 13.3 g of bisphenol A novolak resin (trade name “VH-4170”, manufactured by Dainippon Ink and Chemicals, Inc.) as a curing agent, and 2-ethyl-4-methylimidazole (Tokyo) as a curing accelerator 0.02 g of Oka Kogyo Co., Ltd. and 0.05 g of a silicone-based surface conditioner (trade name “BYK307”, manufactured by BYK Chemie) and γ-butyrolactone (vapor pressure at 25 ° C .: 3.4) as a solvent. × 102 Pa) 14.2 g was dissolved to obtain an insulating ink resin composition 1.

(Dilution of Insulator Ink Resin Composition 1)
In order to print by the inkjet method using the insulator ink resin composition 1, the insulator ink resin composition needs to have a viscosity of 50 mPa · s (= 0.05 Pa · s) or less. Therefore, 53.6 g of the insulator ink resin composition 1 prepared above was dissolved in 105.7 g of γ-butyrolactone as a diluent solvent to obtain a diluted insulator ink 1 for ink jet printing having a viscosity of 10 mPa · s. .

(Measurement of viscosity of insulator ink resin composition)
For the viscosity of the insulator ink resin composition, different measurement methods are used depending on the viscosity range. When measuring a viscosity of 300 mPa · s (= 0.3 Pa · s) or more in a low shear rate region (shear rate condition of 0.1 s ⁻¹ or less), a rheometer MCR301 (Anton) is used as a viscosity / viscoelasticity measuring device. Measured by using a cone plate CP50-1 (manufactured by Anton Paar) as a jig, and measured at 25 ° C., a cone angle of 1 degree, a rotation speed of 5 rpm, and a shear rate of 100 s ^−1. It was.
When measuring a viscosity of less than 300 mPa · s in the low shear rate region in the above measurement method, a tuning fork type vibration viscometer SV-10 (manufactured by A & D) was used and obtained at 25 ° C. The value was taken as the measured value.

(Preparation and dilution of insulator ink resin compositions 2-7)
Insulator ink resin compositions 2 to 7 were prepared in the same manner as for the insulator ink resin composition 1, and diluted ink for inkjet printing was prepared. The composition of these insulator ink resin compositions is as summarized in Table 1.
In addition, the unit of the mixing | blending in Table 1 is a mass part. In addition, all the dyes (metal complex dyes) used are the Eisenspiron series from Hodogaya Chemical Co., Ltd.

(Measuring method of metal elements)
The insulating ink resin composition was cured by heat treatment at 180 ° C. for 30 minutes to obtain a cured product having a thickness of 5 μm. A sample obtained by cutting this cured product into a size of about 1 cm square was attached to a measuring jig with a double-sided tape, and the surface thereof was further subjected to platinum vapor deposition to obtain a measurement sample. Using this measurement sample method, EDX (energy dispersive X-ray) analysis by SEM observation was performed, and from the obtained chromium and copper elemental amount measurements, the trivalent chromium content relative to the total amount of insulating resin and curing agent The content of bivalent copper was calculated.

(Calculation method of amine nitrogen)
Amine nitrogen is related to amine salts contained in metal (chromium) complex dyes, and the content of amine nitrogen was measured by Kjeldahl method.

(Storage stability evaluation method)
The insulator ink resin compositions of Examples 1 to 6 and Comparative Example 1 were stored at room temperature (25 ° C.) for 30 days, and the viscosity was measured using the measurement method described above.

(Printability evaluation method)
For evaluation of printability, each of Examples 1 to 6 and Comparative Example 1 was obtained by using the ink-jet printing method and the bar-coater printing material corresponding to the screen printing method. The printability of the obtained film was evaluated.
When producing by the ink jet method, 80 pL of insulating ink is ejected onto a polyimide film (trade name “Upilex 25SX”, manufactured by Ube Industries Co., Ltd.) using a piezo type ink jet device equipped with a 50 μm diameter head. did. After ejecting the ink, it was quickly transferred onto a hot plate heated to 180 ° C. and dried and cured for 30 minutes to obtain a film having a thickness of 5 μm.
On the other hand, when producing by the bar coater method, 3 mL of the insulator ink was applied onto a polyimide film (trade name “Upilex 25SX”, manufactured by Ube Industries, Ltd.) with a dropper. 3 (bar coater gap 6.9 μm corresponding to wet film thickness) was applied by a bar coater and cured by heat treatment at 180 ° C. for 30 minutes to obtain a film having a thickness of 5 μm.
In the obtained film, a film in which no vertical stripes or unevenness was observed was judged as ◯, and a film in which vertical stripes or unevenness was seen was judged as x.

(Visibility evaluation method)
Visibility evaluation films were prepared using 5 μm and 10 μm bar coater coating films, respectively. For a film having a film thickness of 5 μm, when a film having a film thickness of 5 μm in the above-described evaluation method for printability is diverted to produce a film having a film thickness of 10 μm, Lod No. A film was prepared in the same manner as the printability evaluation film using a bar coater of 5 (a bar coater gap of 11.4 μm corresponding to the wet film thickness). The evaluation film having the film thickness of 5 μm and 10 μm produced above is placed on a desk under the condition that commercially available fluorescent lamps are arranged on the ceiling at intervals of about 2 m, and the presence of a resist pattern is visually observed about 30 cm apart. It was observed whether the portion to be clearly visible. When the film thickness is 5 μm, the visibility is good. When the film thickness is 5 μm, the visibility is poor. When the film thickness is 10 μm, the visibility is good. When both the film thickness is 5 μm and 10 μm, the visibility is poor. The case was determined as x.
The ink jet method was also evaluated using films having a film thickness of 5 μm and 10 μm, but the evaluation results with the film produced by the bar coater method were compared with each other. However, there was a difference in each of Examples 1 to 6 and Comparative Example 1. There wasn't.

(Crack resistance evaluation method)
Since crack resistance is difficult to evaluate unless the film is thick, a visibility evaluation film was prepared using a bar coater-coated film having a thickness of 20 μm. When producing a film with a film thickness of 20 μm, Lod No. A film was produced in the same manner as the printability evaluation film using a bar coater having a thickness of 10 (a bar coater gap corresponding to a wet film thickness of 22.9 μm).
The prepared film for evaluation having a thickness of 20 μm is heated on a hot plate at 240 ° C. for 30 seconds, and the state of the resist pattern obtained after heating is visually observed, and there is no crack or peeling from the polyimide film. The crack resistance was evaluated by △ indicating that there was a crack and × indicating that there was peeling from the polyimide film.

(Sample preparation for insulation reliability evaluation)
As the insulation reliability evaluation sample, a comb-shaped test electrode in accordance with the IPC-SM-840B standard was used. Specifically, the wiring width is 25 μm and the space is 95 μm on the copper foil portion of the substrate material with copper foil for wiring board (trade name “MCL-E-679FG (s) t0.1 VLP 12 μm”, manufactured by Hitachi Chemical Co., Ltd.). Twenty comb-shaped electrodes with a copper foil thickness of 9 μm were prepared. The comb-shaped electrodes were arranged so that the anode and the cathode were alternately arranged facing each other with a gap of 35 μm. Insulator ink was applied to the comb-teeth portions of the electrodes opposed to each other with a bar coater and cured by heat treatment at 180 ° C. for 30 minutes to form a comb-tooth copper wiring with a resist pattern having a thickness of 7 μm.

(Insulation reliability evaluation method)
A HAST test was performed according to JIS c 60068-2-66 using an unsaturated pressure cooker HAST device PC-422R8D manufactured by Hirayama Seisakusho. The test conditions were a temperature of 130 ° C., a relative humidity of 85%, the applied voltage between the anode and the cathode was 5 V DC, the test time was 96 hours, and the migration tester made by IMV was used for voltage application and measurement of the insulation resistance value during the test. MIG-8600B was used. Insulation resistance value during the test is always 10 ⁷ Ω or more. After the test, the comb-shaped copper wiring with a resist pattern has a dendrite due to electrochemical mag- lation, blackening of the comb-shaped copper wiring, If there was no phenomenon that the wiring width became thicker than before the test, the evaluation was ○, and the others were evaluated as ×.

As shown in Table 1, the insulator inks of Examples 1 to 6 were excellent in storage stability unlike Comparative Example 1 in which the element contained in the metal complex dye was divalent copper. Moreover, the resist pattern obtained using the insulator ink of Examples 1-6 was excellent in visibility, and unlike Comparative Example 1, it was excellent in insulation reliability and crack resistance.
Further, unlike the comparative example 1, the insulating inks of Examples 1 to 6 could be used as they were without causing any problem in characteristics even when diluted for inkjet.
Moreover, it was also confirmed that the insulator inks of Examples 1 to 6 have a resolution of 100 μm of line and space.
In addition, it was confirmed that the insulator inks of Examples 1 to 6 were excellent in migration resistance even when applied to a substrate having a wiring pattern formed using a paste containing nano-order copper particles.

1 10 Substrate 2 21 Land 3 Lead-out wiring 4 31 Conductor layer 5 40 Resist pattern 6 Land region 7 Solder ball 8 Insulating layer

Claims (8)

  An insulating ink resin composition comprising a metal complex dye containing trivalent chromium and an amine salt, an insulating resin and a curing agent.   The insulator ink resin composition according to claim 1, wherein the content of trivalent chromium is 50 to 2000 ppm with respect to the total amount of solids of the insulator ink resin composition.   The insulating ink resin composition according to claim 1 or 2, wherein the content of divalent copper is 150 ppm or less with respect to the total amount of solid content of the insulating ink resin composition.   The insulator ink resin composition according to any one of claims 1 to 3, wherein the metal complex dye is a monoazo metal complex dye or an azo compound metal complex dye.   The insulator ink resin composition according to any one of claims 1 to 4, wherein the color tone of the metal complex dye is either red or orange.   The insulator ink resin composition according to any one of claims 1 to 5, wherein the viscosity of the insulator ink resin composition is 0.1 to 50 mPa · s or less.   The resist pattern obtained using the insulator ink resin composition of any one of Claims 1-6.   The one or more lands using the insulating ink resin composition according to any one of claims 1 to 6 on a wiring board having one or more lands and lead-out wiring connected to the one or more lands. A method for forming a resist pattern, comprising the step of forming a resist pattern so as to be exposed.

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