WO2001067178A1 - Encre epargne pour soudures - Google Patents

Encre epargne pour soudures Download PDF

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Publication number
WO2001067178A1
WO2001067178A1 PCT/JP2001/001715 JP0101715W WO0167178A1 WO 2001067178 A1 WO2001067178 A1 WO 2001067178A1 JP 0101715 W JP0101715 W JP 0101715W WO 0167178 A1 WO0167178 A1 WO 0167178A1
Authority
WO
WIPO (PCT)
Prior art keywords
solder resist
resist ink
pigment
halogen
component
Prior art date
Application number
PCT/JP2001/001715
Other languages
English (en)
Japanese (ja)
Inventor
Teruo Furukawa
Soichi Hashimoto
Noriaki Watanabe
Toshikazu Oda
Original Assignee
Goo Chemical Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Goo Chemical Co., Ltd. filed Critical Goo Chemical Co., Ltd.
Priority to AU2001236098A priority Critical patent/AU2001236098A1/en
Publication of WO2001067178A1 publication Critical patent/WO2001067178A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • H05K3/285—Permanent coating compositions
    • H05K3/287—Photosensitive compositions
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/0266—Marks, test patterns or identification means
    • H05K1/0269—Marks, test patterns or identification means for visual or optical inspection
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/16—Inspection; Monitoring; Aligning
    • H05K2203/161—Using chemical substances, e.g. colored or fluorescent, for facilitating optical or visual inspection

Definitions

  • the present invention relates to a solder resist ink for forming a permanent protective film for a printed wiring board. More specifically, the present invention relates to a solder resist ink which is cured by ultraviolet irradiation.
  • the present invention relates to a photo solder-resist ink that can be developed with a dilute aqueous solution of an aqueous solution, and a non-developable ultraviolet-curable solder resist.
  • This solder resist stonk has significantly reduced toxic gas generation during combustion.
  • a printed wiring board used in an electric product has a predetermined wiring formed on a substrate such as a copper-clad laminate.
  • the printed circuit board is designed to prevent solder from sticking to unnecessary parts during soldering, to avoid electrical shorts, and to shorten the life of the printed circuit board. After the wiring is formed, it is general that a permanent protective film made of a cured product of solder resist ink is formed in a predetermined pattern.
  • boards and solder resist inks constituting such printed wiring boards contain halides such as bromide, and toxic gases may be generated during combustion, which has been a problem.
  • solder resist ink a permanent protective film of solder resist ink formed on a printed wiring board is required to have good visibility at the time of visual inspection and to be easy on the eyes. Is required to be present. For this reason, the conventional solder resist ink has been mixed with a coloring pigment such as a phthalocyanine line and has become green.
  • this phthalocyanine green contains a high proportion of chlorine and bromine in its chemical formula. More specifically, for example, phthalocyanine green whose pigment is Pigment Green 7 contains about 47% by weight of chlorine in one molecule, and phthalocyanine green whose pigment is 36 is one in each molecule. Contains about 5% by weight of chlorine and about 60% by weight of bromine.
  • a conventional solder resist ink containing a coloring pigment containing a high ratio of halogen such as phthalocyanine green generates a large amount of toxic gas when burned.
  • an object of the present invention is to provide a solder resist ink containing no halogen or having a significantly reduced halogen content.
  • the first invention of the present application is
  • (C) A solder characterized by containing a coloring pigment comprising an orange pigment containing no halogen in the chemical structural formula and a blue pigment containing no halogen in the chemical structural formula and blended to give a green color.
  • a coloring pigment comprising an orange pigment containing no halogen in the chemical structural formula and a blue pigment containing no halogen in the chemical structural formula and blended to give a green color.
  • One resist ink One resist ink.
  • (A-1) an ultraviolet curable resin having an ethylenically unsaturated group and a carboxyl group in a side chain
  • solder resist comprising a color pigment comprising an orange pigment containing no halogen in the chemical structural formula and a blue pigment containing no halogen in the chemical structural formula and blended to give a green color.
  • This solder resist ink has a use especially as a photo solder resist ink.
  • (A-4) an ethylenically unsaturated monomer be contained as an ultraviolet curable component of the photo solder resist ink of the second invention of the present application.
  • solder resist ink further contains (D) an organic solvent.
  • solder resist ink further contains (E) a polyfunctional epoxy compound.
  • the halogen content in the cured product of the solder resist ink is preferably 500 ppm or less.
  • the ultraviolet curable resin as the component (A-1) and the polyfunctional epoxy compound as the component (E), which are compounded in the solder resist kink are, for example, halogens synthesized by the peracid method. It was prepared from an epoxy compound that did not contain, or an epoxy compound that had been treated to reduce the haegen content, and the (A— :!) component and / or (E ) Component, the halogen content in the cured product of the photo solder resist ink of the present invention can be reduced to 150 ppm or less.
  • the color pigment as the component (C) is preferably a blue pigment and the above-mentioned blue pigment compounded in a weight ratio of 1:10 to 10: 1.
  • solder comprising a color pigment comprising an orange pigment having no halogen in the chemical structural formula and an L or blue pigment having no halogen in the chemical structural formula and having a green color.
  • Resist ink This solder resist ink is used particularly as an ultraviolet curing type solder resist ink.
  • the halogen content in the cured product of the ultraviolet-curable solder resist ink of the third invention of the present application is preferably 500 ppm or less.
  • the color pigment is a combination of an orange color pigment containing no halogen in the chemical structural formula and a blue color pigment containing no halogen in the chemical structural formula in a weight ratio of 1:10 to 10: 1. Preferably, there is.
  • the solder resist ink of the present invention comprises (A) an ultraviolet curing component, (B) a photopolymerization initiator, and (C) an orange pigment containing no halogen in the chemical structural formula, and containing a halogen in the chemical structural formula. Contains no blue pigment.
  • the solder resist ink of the present invention contains an ultraviolet curable component as the component (A).
  • This ultraviolet-curable component is a component having an ultraviolet-curable function, and contains the ultraviolet-curable component together with a photopolymerization initiator as a component (C) described below. , To cure.
  • the ultraviolet curable component (A) in all the components of the solder resist ink of the present invention excluding the organic solvent is preferably 20 to 80% by weight. %include.
  • the ultraviolet curable component (A) blended in the present invention is not particularly limited as long as it can be cured by irradiation with ultraviolet light.
  • examples thereof include an ultraviolet curable resin having a photoreactive double bond and a photopolymerizable resin. It is arbitrarily selected from conventionally known ultraviolet-curable components such as a monomer having a property.
  • the solder resist ink of the present invention contains a photopolymerization initiator as the component (B) in addition to the (A) ultraviolet curable component.
  • the photopolymerization initiator included in the present invention is not particularly limited.
  • the photopolymerization initiator suitable for the present invention include benzoin; benzoin methyl ether, benzoinethyl ether and benzoin.
  • Alkyl ethers of benzoin such as isopropyl ether; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, and 1-hydroxycyclohexylphenylketone such as Acetofphenones; anthraquinones such as 2-methylanthraquinone, 2-ethylanthraquinone and 2-amylanthraquinone; thioxanthones such as 2,4-dimethylthioxanthone, 2,4-getylthioxanthone and 2,4-diisopropylthioxanthone; Ketals such as tyl ketal and benzyl dimethyl ket
  • photopolymerization initiators are benzoic acid-based, p-dimethylaminobenzoic acid It may be used in combination with a known photopolymerization accelerator or sensitizer such as tertiary amines such as tyl ester, isoamyl p-dimethylaminobenzoate, and 2-dimethylaminoethylbenzoate.
  • a known photopolymerization accelerator or sensitizer such as tertiary amines such as tyl ester, isoamyl p-dimethylaminobenzoate, and 2-dimethylaminoethylbenzoate.
  • the photopolymerization initiator as the component (B) is preferably contained in all the components of the solder resist ink of the present invention except for the organic solvent described later (D) when the organic solvent is contained. -30% by weight, more preferably 0.1-10% by weight, and most preferably 0.1-7% by weight.
  • the photopolymerization initiator is contained in the compounding amount in the above range, the solder resist ink of the present invention exhibits excellent photohardening properties, and the physical properties of the obtained permanent protective film are also improved.
  • the solder resist ink of the present invention contains a coloring pigment as the component (C).
  • the coloring pigment to be blended in the present invention is composed of an L orange pigment containing no halogen in the chemical structural formula and a blue pigment containing no halogen in the chemical structural formula.
  • the pigment and the blue pigment are blended in such a ratio that the obtained solder resist ink of the present invention and its hard coating film exhibit a substantially green color.
  • the ratio that is substantially green means that the solder resist ink and its hard coating are sufficiently green so that a viewer can recognize it as green when observed by the naked eye.
  • the pattern of the printed wiring board manufactured using the solder resist ink of the present invention is excellent in visibility at the time of visual inspection and is easy on the eyes.
  • orange coloring pigment containing no halogen in the chemical structural formula constituting the component (C) those which are classified as C.I. .
  • Disazo pigments represented by Color Index (I.) Pigment Orange 14, 15, 16, 50 and 63, etc.
  • Perinone pigments such as Color Index (C.I.) Pigment Orange 43 etc.
  • Quinacridone pigments represented by Color Index (C.I.) Pigment Orange 48, 49, etc., and
  • Pigment Orange 65, 68, 17: 1, etc., and the like are used alone or in appropriate combination.
  • Color index (C.I.) Pigmentable 1-5 The chemical structure represented by 1-5 Copper phthalocyanine blue without halogen in the formula
  • Condensed polycyclic pigment represented by Color Index (I.)
  • Anthraquinone pigments represented by Color Index (C.I.)
  • the color index (I.) can be exemplified by ultramarine strength indicated by pigment blue 29. These pigments are used alone or in an appropriate combination. Among the suitable pigments exemplified above, copper phthalocyanine blue is particularly preferred.
  • the orange pigment and the blue pigment are preferably combined in a weight ratio of 1:10 to; L0: 1, more preferably 1: 5 to 5: 1, and most preferably 2: 5 to 5: 2. It is preferable that By combining the orange pigment and the blue pigment in the above range, the obtained solder resist ink or its hardened film becomes substantially green. Even when the color of the solder resist ink of the present invention is not necessarily green, the cured product of the solder resist ink of the present invention may be green on the bronze copper-clad laminate.
  • the (C) color pigment comprising the orange pigment and the blue pigment blended in the above range has good dispersibility in other components of the solder resist ink of the present invention, and has a bright green color with little color unevenness. Thus, a solder resist ink that forms a permanent protective film can be obtained.
  • the amount of the (C) coloring pigment in the solder resist ink of the present invention is not particularly limited. However, when the (C) coloring pigment contains (D) an organic solvent, the coloring solvent is excluded. Preferably, 0.1 to 20% by weight, more preferably, 0.1 to 10% by weight, and most preferably, 0.2 to 5% by weight in all components of the solder resist ink of the present invention. % Included. When the amount of the coloring pigment is within the above range, it is possible to form a permanent protective film having good visibility at the time of visual inspection while suppressing a decrease in resin hardness due to a decrease in ultraviolet transmittance.
  • the phthalocyanine green pigment conventionally used has a difficulty in making the particles finer and has relatively poor dispersibility. Therefore, a long kneading process was required when formulating the solder resist ink so as not to adversely affect the surface condition of the coating film, electrical characteristics, moisture resistance, and the like.
  • the coloring pigment (C) has a better dispersibility in other components than phthalocyanine green and is relatively easily kneaded and blended, so that the solder resist ink of the present invention can be easily prepared. Can be prepared.
  • the ink When the solder resist ink of the present invention is used as a photo solder resist ink, the ink should be one that can be developed with an organic solvent or a dilute aqueous solution, and should preferably include an ultraviolet curable resin.
  • the ultraviolet-curable component as the component (A) contains (A-1) an ethylenically unsaturated group and a carboxyl group in the side chain.
  • the ultraviolet hardening resin having the resin can be suitably used.
  • (A-1) an ultraviolet curable resin having an ethylenically unsaturated group and a carboxyl group in a side chain
  • (B) a photopolymerization initiator
  • (C) a color pigment
  • the force is comprised of
  • photo solder resist ink refers to a so-called image-type solder resist ink.
  • the solder resist ink applied on a substrate is selectively exposed to ultraviolet light to be exposed to light.
  • Ink power applicable. (A-1) UV curable resin having an ethylenically unsaturated group and a carboxyl group in the side chain !
  • the photo solder resist ink of the present invention contains, as the component (A-1), an ultraviolet curable resin having an ethylenically unsaturated group and a carboxyl group in a side chain.
  • This component (A-1) has a photohardening ethylenically unsaturated group and a carboxylic acid group in its structural formula, so that a predetermined energy can be obtained by exposure to ultraviolet light or the like.
  • the photo solder resist ink of the present invention containing the component (A-1) applied to the substrate is selectively exposed to light to cure the exposed portion of the photo solder resist ink.
  • the uncured photo solder resist ink in the unexposed portion is dissolved and removed with a dilute aqueous solution after washing with an aqueous solution, the prescribed value is obtained. It is formed on a plate in the evening.
  • the ultraviolet curable resin of the component (A-1) has a photopolymerizable ethylenically unsaturated group in its chemical structural formula.
  • a photopolymerizable ethylenically unsaturated group include unsaturated groups such as a (meth) acryloyl group and a vinyl group.
  • the content of the photopolymerizable ethylenically unsaturated group is not particularly limited, the content of unsaturated groups ultraviolet curable planted ⁇ in butter 0.0 1-1 0 mol / £ (UV-curable resin ), Particularly preferably, 0.:!-5 mol / Kg.
  • a photo solder-resist ink having particularly excellent exposure sensitivity and developability can be prepared.
  • the ultraviolet curing resin as the component (A-1) has an acid value of 30 to 20 OmgKOH / g, preferably 40 to 16 OmgKOH / g.
  • the acid value of the UV-hardening resin is in the above range, it becomes compatible with other components and has a particularly good exposure sensitivity, developability and resolution. Can be prepared.
  • the weight-average molecular weight of the ultraviolet-curable resin as the component (A-1) is not particularly limited, but is preferably 3,000 to 400,000, particularly 5,000. It is preferable that the value be 100,000, and most preferably, 5,500 to 500,000. When the weight average molecular weight of the ultraviolet curable resin is in the above range, the balance between the resolution and the exposure sensitivity of the photo solder resist ink of the present invention is particularly excellent.
  • Examples of the component (A-1) include “an ethylenically unsaturated conjugate having a carboxyl group” in the “polymer having an epoxy group in a side chain” and “polycarboxylic anhydride” in the “polymer having an epoxy group in a side chain”. And the like.
  • the “polymer (skeleton polymer) having an epoxy group in a side chain” for preparing the ultraviolet curable resin exemplified as the component (A-1) the following epoxy compound and ethylenic polymer are used. Copolymers with a saturated monomer are exemplified.
  • epoxy compound glycidyl (meth) acrylate, glycidyl (meth) acrylate such as 2-methylglycidyl (meth) acrylate, and (3,4-epoxycyclohexyl) methyl
  • epoxycyclohexyl derivatives of (meth) acrylic acid such as (meth) acrylates.
  • ethylenically unsaturated monomer an aliphatic or alicyclic alkyl
  • (Meth) acrylate aromatic (meth) acrylate such as benzyl (meth) acrylate; ethylene glycol ester (meth) acrylate, polyethylene such as hydroxyethyl (meth) acrylate ⁇ methoxethyl (meth) acrylate Glycol ester (meth) acrylate and propylene glycol (meth) acrylate; (meth) acrylamide compound; N-substituted maleimide compound; bulpyrrolidone; (meth) acrylonitrile; vinyl acetate; styrene; Styrene; and vinyl ether.
  • aromatic (meth) acrylate such as benzyl (meth) acrylate
  • ethylene glycol ester (meth) acrylate polyethylene such as hydroxyethyl (meth) acrylate ⁇ methoxethyl (meth) acrylate
  • (meth) acrylic acid is a generic term for acrylolic acid and methacrylic acid
  • (meth) acrylate is a generic term for acrylate and methacrylate.
  • the “polymer having an epoxy group in the side chain (skeleton polymer)” for preparing the ultraviolet-curable resin exemplified as the component (A-1) includes the epoxy compound described above and the ethylenically unsaturated compound.
  • phenol novolak epoxy resin cresol novolak epoxy resin, bisphenol A epoxy resin sealant, bisphenol F epoxy resin, bisphenol A epoxy resin, alicyclic ring Formula epoxy resin (eg, Daikin Chemical Industry Co., Ltd., ⁇ - 3-315), and polyfunctional epoxy resin that is a derivative of tris (hydroxyphenyl) methane (eg, EPPN- manufactured by Nippon Kayaku Co., Ltd.) Epoxy resin such as 502H and Dow Chemical Co., Ltd. evening tex — 742 and XD — 9553).
  • Rukoto can.
  • Examples of the “ethylenically unsaturated monomer having a carboxyl group” for preparing the ultraviolet-curable resin exemplified as the component (A-1) include, for example, (meth) acrylinoleic acid, crotonic acid, and cinnamic acid.
  • Those having a plurality of ethylenically unsaturated groups such as those obtained by reacting a difunctional anhydride with a polyfunctional acrylate having a hydroxyl group such as acrylate.
  • those having one carboxyl group are preferable, and it is particularly preferable to use (meth) acrylic acid or to use (meth) acrylic acid as a main component.
  • (meth) acrylic acid or to use (meth) acrylic acid as a main component.
  • Examples of the “polyhydric carboxylic anhydride” for preparing the ultraviolet-curable resin exemplified as the component (A-1) include, for example, conodic anhydride, methylsuccinic anhydride, maleic anhydride, and maleic anhydride.
  • Dibasic acids such as citraconic anhydride, glutaric anhydride, itaconic anhydride, phthalenoic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride and methylhexahydrohydrophthalic anhydride
  • Anhydrides, and acid anhydrides of three or more basic acids such as trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, and methylcyclohexene tetracarboxylic acid are exemplified.
  • the above-mentioned epoxy group of the polymer having an epoxy group in the side chain is added with an ethylenically unsaturated compound having a carboxyl group and a polycarboxylic acid anhydride to exemplify the component (A-1).
  • the addition reaction for preparing the ultraviolet curable resin is carried out, for example, by heating to about 60 to 150 ° C. in the presence of a thermal polymerization inhibitor and an addition catalyst.
  • the above addition reaction may be performed by adding a ⁇ polycarboxylic acid anhydride '' after adding a ⁇ ethylenically unsaturated compound having a carboxyl group '' to a ⁇ polymer having an epoxy group in a side chain ''. It is also possible to add a “polyhydric carboxylic anhydride” to a “polymer having an epoxy group in the side chain” and then add a “ethylenically unsaturated compound having a carboxyl group”. Is preferred.
  • the amount of the component (A-1) in all components of the photo solder resist ink of the present invention except for the organic solvent described below is not particularly limited, but is preferably from 10 to 80% by weight, and more preferably from 2 to 10% by weight. 0 to 70% by weight, optimally 25 to 60% by weight. When the amount of the component (A-1) is within the above range, a photo solder resist ink having good alkali developability, sensitivity, and resolution can be obtained.
  • the photo solder resist ink of the present invention further comprises (A) an ethylenically unsaturated monomer (A-4) as an ultraviolet curable component, in addition to the above (A-1). Properties such as applicability, heat resistance and insulation properties may be improved.
  • the (A-4) photopolymerizable ethylenically unsaturated monomer serves not only as a diluent but also for adjusting the exposure sensitivity.
  • Examples of such ethylenically unsaturated monomers include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, N-vinylpyrrolidone, (meth) acryloylmorpholine, Toxitetraethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, polyethylene glycol di (meth) acrylate, N, N-dimethyl (meth) acrylamide, N-methylol (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylate, melamine (meth) acrylate, diethylene glycol di (methyl) acrylate, triethylene glycol di (meth) acrylate , Propyle N-glycol di (meth) acrylic acid, phenoxyshetyl (meth) acrylic acid, te
  • ethylenically unsaturated monomers are used alone or in appropriate combination to prepare the photo solder resist ink of the present invention, and are contained in all components of the photo solder resist ink excluding the organic solvent contained therein.
  • the amount of the (A-4) ethylenically unsaturated monomer described above is not particularly limited, but is preferably 1 to 50% by weight, more preferably 1 to 40% by weight, and most preferably 1 to 3% by weight. 0 weight.
  • the photo solder resist ink of the present invention may further comprise, if necessary, an ultraviolet-curable polymer such as epoxy (meth) acrylate, a (meth) acrylate copolymer, and a styrene-maleic acid resin. Or a UV-curable polymer obtained by further introducing an ethylenically unsaturated group, or the like.
  • an ultraviolet-curable polymer such as epoxy (meth) acrylate, a (meth) acrylate copolymer, and a styrene-maleic acid resin.
  • a UV-curable polymer obtained by further introducing an ethylenically unsaturated group, or the like.
  • the photo solder resist ink of the present invention further contains a photopolymerization initiator as the component (B).
  • the photopolymerization initiators listed above are preferably used. Further, the photopolymerization initiator as the component (B) in all the components of the photo solder resist ink of the present invention except for the organic solvent is preferably 0.1 to 30% by weight, more preferably 1 to 10% by weight. %, Optimally 1-7% by weight. When the photopolymerization initiator is contained in the compounding amount in the above range, the photo solder resist ink of the present invention exhibits excellent photocurability, and the physical properties of the obtained permanent protective film are also improved.
  • the photo solder resist ink of the present invention contains a colored pigment as a component (C).
  • the coloring pigment compounded in the present invention is composed of an orange pigment having no halogen in the chemical structural formula and a blue pigment having no halogen in the chemical structural formula. These orange pigments and blue pigments are blended in such a ratio that the obtained photo solder resist ink of the present invention and its hardened film exhibit a substantially green color.
  • the pattern of the printed wiring board manufactured using the photoresist ink of the present invention has excellent visibility at the time of visual inspection and is easy on the eyes.
  • Suitable orange pigments and blue pigments are the same as those listed above.
  • the weight ratio of the orange pigment to the blue pigment is also preferably 1:10 to: L0: 1, more preferably 1: 5 to 5: 1, and most preferably 2: 5. ⁇ 5: 2.
  • the orange pigment and the blue pigment blended in the above range have good dispersibility in each component of the photo solder resist ink of the present invention, and have L with little color unevenness and a vivid green permanent. It is possible to obtain a photo solder resist ink for forming a protective film.
  • the amount of the (C) coloring pigment is not particularly limited, the (C) coloring pigment is contained in all components of the photo solder resist ink of the present invention except for an organic solvent described below.
  • 0.1 to 20% by weight Preferably 0.1 to 20% by weight, more preferably 0.1 to: 10% by weight, and most preferably 0.2 to 1.5% by weight.
  • amount of the color pigment is in the above range, a permanent protective film having good visibility at the time of visual inspection can be formed while suppressing a decrease in resin curability due to a decrease in ultraviolet transmittance.
  • the photo solder resist ink of the present invention may further contain an organic solvent as the component (D).
  • organic solvent suitable for the present invention include a linear or branched carbon chain such as ethanol, propyl alcohol, isopropyl alcohol, butyl alcohol, isobutyl alcohol, 2-butyl alcohol, hexanol and ethylene glycol.
  • the organic solvent as the component (D) is preferably used in the photo solder resist ink of the present invention in an amount of 1 to 95% by weight, more preferably 5 to 95% by weight, and most preferably 20 to 95% by weight. %. By mixing the organic solvent in the above range, the obtained photo solder resist ink of the present invention has excellent coatability on a substrate.
  • the photo solder resist ink of the present invention may contain (E) a polyfunctional epoxy compound as an optional component in addition to the (A-1) ultraviolet curable resin.
  • the above-mentioned polyfunctional epoxy compound is not particularly limited.
  • bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novola Epoxy resin, cresol novolak type epoxy resin, bisphenol A-novolak type epoxy resin, N-glycidyl type epoxy resin or alicyclic epoxy resin for example, “EHPE-3 15 0 "),” YX-40000 "(epoxy resin manufactured by Yuka Shidori Epoxy Co., Ltd.), hydrogenated bisphenol II type epoxy resin and triglycidyl isocyanurate, and tris (hydroxyphenyl) methane.
  • Polyfunctional epoxy resins (Nippon Kayaku Co., Ltd., 5- ⁇ ⁇ —502 2, Dow Chemical Co., Ltd., Tactex-174, XD—9053, etc.) ⁇ .
  • the polyfunctional epoxy compound of the present invention a homopolymer or a copolymer of an ethylenically unsaturated monomer having an epoxy group may be used.
  • the copolymer shown on the left it is preferable that the monomer constituting the copolymer contains 40 mol% or more of an ethylenically unsaturated monomer having an epoxy group. Thereby, good thermosetting properties can be obtained.
  • the above polyfunctional epoxy compound is a homopolymer or copolymer of an ethylenically unsaturated monomer having an epoxy group
  • its weight average It is preferable that the molecular weight is from 2,000 to 20,000, 000. This makes it possible to prepare a photo solder resist ink that forms a cured film having excellent thermosetting properties.
  • the above polyfunctional epoxy compound as the component (II) is preferably 0.1 to 50% by weight, more preferably 0.1 to 50% by weight in all components of the photo solder resist ink of the present invention except for the organic solvent described below. -40% by weight, optimally 5-40% by weight.
  • amount of the solid content of the polyfunctional epoxy compound is in the above range, a photo solder resist ink having a good balance between developability and thermosetting properties can be obtained.
  • the photo-solder-resist ink of the present invention further provides coatability, heat resistance and Further optional components may be blended in order to improve properties such as edge properties.
  • Such optional components include, for example, extender pigments such as talc, silica, barium sulfate, alumina, calcium carbonate, and my strength, inorganic pigments, adhesion-imparting agents, leveling agents, silane coupling agents, thixotropic agents , A polymerization inhibitor, an antihalation agent, an antifoaming agent, an antioxidant, a surfactant, and a polymer dispersant.
  • extender pigments such as talc, silica, barium sulfate, alumina, calcium carbonate, and my strength
  • inorganic pigments adhesion-imparting agents, leveling agents, silane coupling agents, thixotropic agents , A polymerization inhibitor, an antihalation agent, an antifoaming agent, an antioxidant, a surfactant, and a polymer dispersant.
  • the photo solder resist ink of the present invention is prepared by a known kneading method using a three-roll, ball mill, sand mill and the like.
  • the components need not be completely and uniformly mixed in advance.
  • a mixture 1 composed of the components (E) and (D) and a mixture 2 composed of the components (A-1), (B), (C) and (D) are separately prepared. Then, the mixed liquid 1 and the mixed liquid 2 may be mixed and used immediately before use.
  • the photo solder resist ink of the present invention is applied on a substrate such as a copper-clad laminate and dried, and a predetermined portion on the obtained dried coating film is irradiated with ultraviolet rays to remove the photo solder resist ink in this portion. To cure. Thereafter, the photo-solder resist ink developed by removing the non-exposed portion in a dilute alkaline solution and remaining without being removed by the subsequent post-baking becomes a permanent protective film.
  • the dilute solution used as the developer is preferably an aqueous solution, but may be an aqueous solution containing a hydrophilic organic solvent such as an alcohol.
  • the permanent protective film obtained as described above has a halogen content of preferably 500 ppm or less (actually 0.1 to 500 ppm), and more preferably 300 ppm or less (actually 0 ppm or less). 1 to 300 ppm), optimally less than 150 ppm (actually 0.1 to 150 ppm). This significantly reduces the generation of toxic halogen gas during combustion.
  • a halogen-free color pigment (A -1)
  • the ethylenically unsaturated monomer having an epoxy group is not particularly limited, and by using an industrially available monomer, the halogen content in the cured film is reduced to 500 ppm or less as described above. Specifically, it can be set to 0.1 to 500 ⁇ ⁇ m).
  • the above-mentioned epoxy compound for preparing a photo solder resist ink includes, in particular, an epoxy resin derived from a polycyclic phenol-based compound, an ethylenically unsaturated compound having a daricidyl group such as glycidyl methacrylate.
  • an epoxy resin derived from a polycyclic phenol-based compound an ethylenically unsaturated compound having a daricidyl group such as glycidyl methacrylate.
  • the halogen content in the hard coating film formed on the substrate cannot be reduced to 150 ppm or less. It was difficult.
  • the epoxy compound used for producing the component (A-1) and the epoxy compound used for producing the component (E) or the component (E) have a halogen content of 5 ppm or less. It is preferable to use some.
  • the halogen content in the permanent protective film formed from the photo-solder resist ink of the present invention is significantly reduced as compared with the conventional case. And can be reduced to less than 150 ppm.
  • Examples of the epoxy compound having a halogen content of 50 ppm or less for preparing the photo solder resist ink of the present invention include, for example, epoxy with peracid (eg, formic acid, peracetic acid, perbenzoic acid, etc.).
  • the epoxy resin synthesized by the polymerization reaction and the ethylenically unsaturated monomer containing an epoxy group can be named ⁇ .
  • an epoxyne sealant is “3- ⁇ -150” (a cycloaliphatic epoxy resin manufactured by Daicel Chemical Industries, Ltd.).
  • an ethylenically unsaturated unit containing an epoxy group can be used.
  • the monomer include Cyclomer A-200 (manufactured by Daicel Chemical Industries, Ltd., an ethylenically unsaturated monomer containing an alicyclic epoxy group), Cyclomer M-100, M-1 01 (manufactured by Daicel Chemical Industries, Ltd., an ethylenically unsaturated monomer containing an alicyclic epoxy group).
  • the ultraviolet-curable component as the component (A) is not particularly limited. It may be composed of an esterified product of (meth) acrylate and Z or a polyphenol of polyhydric phenol and (meth) acrylic acid, and (A-4) an ethylenically unsaturated compound other than the A-3 component. Preferred ⁇
  • this UV-hardened solder resist ink comprises (A-3) an epoxy (meth) acrylate and / or an esterified product of a polyether of polyhydric phenol and (meth) acrylic acid, and (A-3) ) It comprises (A-4) an ethylenically unsaturated compound other than the component, (B) a photopolymerization initiator, and (C) a color pigment.
  • the term “ultraviolet-curable solder resist ink” refers to a desired color obtained by a printing method.
  • a solder resist ink printed on a substrate by using a conventionally known printing method such as screen printing is entirely exposed to ultraviolet rays.
  • the ultraviolet hardening type solder resist ink of the present invention contains, as the component (A-3), an epoxy (meth) acrylate and / or an esterified product of a polyether phenol and a (meth) acrylic acid with a polyhydric phenol.
  • component (A-3) an epoxy (meth) acrylate and / or an esterified product of a polyether phenol and a (meth) acrylic acid with a polyhydric phenol.
  • the above-mentioned epoxy (meth) acrylate as the component (A-3) refers to a total esterified product or a partial ester of an epoxy group that can be generated by an esterification reaction between an epoxy compound and (meth) acrylic acid.
  • a compound refers to a total esterified product or a partial ester of an epoxy group that can be generated by an esterification reaction between an epoxy compound and (meth) acrylic acid.
  • epoxy compound which produces the above-mentioned epoxy (meth) acrylate specifically, bisphenol A, bisphenol F, bisphenol A sealing oil, bisphenol F vegetable oil, cresol novolac resin, and phenol ethanol Those obtained by reacting polyhydric phenols such as volakne sealant with epichlorohydrin, and alicyclic epoxy resins (for example, a substantially halogen-free peracetic acid method manufactured by Daicel Chemical Industries, Ltd.) Epoxy resin ⁇ ⁇ ⁇ ⁇ 3 — 3150 J).
  • esterified product of the polyether of polyhydric phenol and (meth) acrylic acid as the component ( ⁇ ⁇ -3) is obtained by the esterification reaction of the polyether of polyhydric phenol and (meth) acrylic acid. It is an all-esterified or partially esterified product that can be produced.
  • the polyether of the above-mentioned polyhydric phenol can be obtained by, for example, adding ethylene oxide, propylene oxide, butylenoxide or ⁇ -force prolactone to the polyhydric phenol.
  • the distribution of the component (III-3) in the ultraviolet hard solder type solder resist ink of the present invention is not particularly limited, preferably, the component (A-3) is present in the ultraviolet-curable solder resist ink of the present invention in an amount of 10 to 70% by weight, more preferably 15 to 65% by weight. , 'Optimally contains 15-60% by weight.
  • the ultraviolet-curable solder resist ink of the present invention containing the component (A-3) in the above range can be cured by irradiation with ultraviolet rays to obtain a cured product having a desired strength.
  • an ethylenically unsaturated compound other than the component (A-3) may be used as the component (A-4) in addition to the component (A-3).
  • Examples of the ethylenically unsaturated compound other than the component (A-3) include those exemplified in the description of the photo solder resist described above.
  • the blending amount of the component (A-4) in the ultraviolet hardening type solder resist ink of the present invention is not particularly limited, but the component (A-4) is preferably contained in the ink of the present invention in an amount of preferably 10 to 70% by weight. %, More preferably 15 to 65% by weight, and most preferably 20 to 60% by weight.
  • the ultraviolet-curable solder resist ink of the present invention containing the component (A-4) in the above range can be hardened by irradiation with ultraviolet rays to obtain a hardened product having a desired strength.
  • the composition ratio of the component (A-3) and the component (A-4) constituting the ultraviolet curable component is not particularly limited.
  • the compounding power of the component (A-3) in the total 100 parts by weight of the component (A-3) and the component (A-4) is preferably 10 to 70% by weight, more preferably 10 to 60% by weight. % By weight, optimally 15 to 50% by weight.
  • the UV-curable solder resist ink forms a permanent protective film having excellent printability and excellent curability and heat resistance.
  • the solder resist ink of the present invention contains a photopolymerization initiator as the component (B) in addition to the components (A-3) and (A-4).
  • Suitable photopolymerization initiators included in the present invention are the same as those listed above.
  • the amount of the photoinitiator (B) of the present invention is preferably 0.1 to 30% by weight, more preferably 1 to 30% by weight, in the ultraviolet-curable solder resist ink of the present invention. -10% by weight, optimally 1-7% by weight.
  • the photopolymerization initiator is contained in the compounding amount in the above range, the solder resist ink of the present invention exhibits excellent photocurability, and the physical properties of the obtained permanent protective film are also improved.
  • the photo solder resist ink of the present invention is blended with a colored pigment as a component (C).
  • the coloring pigment compounded in the present invention is composed of an orange pigment having no halogen in the chemical structural formula and a blue pigment having no halogen in the chemical structural formula. These orange pigments and blue pigments are blended in such a ratio that the obtained photo solder-resist ink of the present invention and its cured film exhibit a substantially green color.
  • the pattern of the printed wiring board manufactured using the photoresist ink of the present invention has excellent visibility at the time of visual inspection and is easy on the eyes.
  • the weight ratio between the orange pigment and the blue pigment is preferably 1:10 to: L0: 1, more preferably 1: 5 to 5: 1, and most preferably 2: 5 to 5: 5. 5: 2 for 2
  • the obtained photo solder resist ink or the cured film thereof becomes substantially green.
  • the orange and blue pigments blended in the above ranges have good dispersibility in other components, and form a vivid green permanent protective film with little force, color, and color unevenness. Ink can be obtained.
  • the amount of the coloring pigment as the component (C) in the ultraviolet hardening type solder resist ink of the present invention is not particularly limited. However, the coloring pigment is contained in the ultraviolet curing solder resist ink of the present invention. It contains 0.1 to 20% by weight, more preferably 0.1 to 10% by weight, and most preferably 0.2 to 5% by weight.
  • the ultraviolet hardening type solder resist ink of the present invention containing the coloring pigment in the above-mentioned compounding amount has a good permanent protection with good visibility at the time of visual inspection while suppressing a reduction in resin hardening due to a decrease in ultraviolet transmittance. A film can be formed.
  • the ultraviolet-curable solder resist ink of the present invention contains the above-mentioned components (A-3), (A-4), (B) and (C) as essential components, but has printability, heat resistance and insulation properties. Other components may be included as long as they do not adversely affect the properties such as.
  • Such components include, for example, extender pigments such as talc, silica, barium sulfate, alumina, calcium carbonate and myritsu, inorganic pigments, adhesion improvers ⁇ reppelling agents, thixotropic agents, defoamers, polymerization inhibitors, etc. Is mentioned.
  • the ultraviolet curing type solder resist ink of the present invention is printed on a substrate such as a copper-clad laminate by employing a conventionally known printing method such as a screen printing method or an offset printing method.
  • the ultraviolet curable solder resist ink of the present invention can significantly reduce the halogen content in the ultraviolet curable solder resist ink by using a halogen-free colored pigment (C). .
  • the ultraviolet curable solder resist ink of the present invention has a halogen content of 50 ppm or less (actually 0.1 to 50 ppm), preferably 40 ppm or less (realistic). 0.1 to 400 ppm), and even less than 300 ppm (actually 0.1 to 300 ppm). Therefore, in the permanent protective film formed from the ultraviolet-curable solder resist ink of the present invention, the amount of halogen gas generated during combustion is significantly reduced.
  • the halogen content in the permanent protective film formed from the solder resist ink of the present invention can be significantly reduced as compared with the conventional case, and can be reduced to 150 ppm or less. This is the same as the case of the described photo solder resist ink.
  • Blemmer GS manufactured by NOF CORPORATION, chlorinated glycidyl methacrylate, halogen content is 1 ppin or less
  • a reflux condenser thermometer
  • glass tube for nitrogen replacement
  • a stirrer 70 parts 30 parts of methyl methacrylate, 100 parts of carbitol acetate and 3 parts of azobisisobutyronitrile were added, and the mixture was polymerized by heating at 80 ° C. for 5 hours under a nitrogen stream with stirring. % Copolymer solution was obtained.
  • EHPE 315 Alicyclic epoxy resin, manufactured by Daicel Chemical Industries, Ltd., epoxy equivalent: 179, halogen-free (halogen was not detected)
  • 179 parts of carbitol acetate 60 Then, 74 parts of acrylic acid, 0.1 part of hydroquinone and 7 parts of dimethylbenzylamine were added with stirring, and the mixture was reacted at 90 to 100 ° C. for 24 hours by a conventional method. To this reaction solution, 95 parts of carbitol acetate was added and stirred to obtain an epoxy acrylate solution. Then, 76 parts of tetrahydrophthalic anhydride and 64 parts of carbitol acetate were added and reacted at 100 for 3 hours to obtain a 60% solution of an ultraviolet-curable resin (A-112). ) was obtained.
  • EHPE 315 used as a polyfunctional epoxy compound described in Table 1 is an epoxy resin manufactured by Daicel Chemical Industries, Ltd., and Epiclone N-680 is a large epoxy resin. It is a cresol nopolak type epoxy resin manufactured by Nippon Ink and Chemicals, Inc. TEPICS is triglycidyl isocyanurate (halogen content 800 ppm) manufactured by Nissan Chemical Industries, Ltd.
  • (E-1) described in Table 1 was prepared as follows. That is, in a four-necked flask equipped with a reflux condenser, a thermometer, a glass tube for purging nitrogen, and a stirrer, 80 parts of Bremma-GS (manufactured by NOF CORPORATION, glycidyl methacrylate with reduced chlorine), 6 parts of carbitol acetate and 3 parts of azobisisoptyronitrile were added, and the mixture was polymerized for 5 hours at 85 ° C under a nitrogen stream with stirring to obtain 60% of the polyfunctional epoxy compound. Obtained solution (E-1) o
  • orange pigment having no halogen in the structural formula of the present invention examples include Seika-1 First Orange 3064 (Color Index (CI) Pigmento Range 5) (Monazo orange pigment manufactured by Dainichi Seirido Co., Ltd.), And 2900 Peri-First Orange GR (Color Index (CI) Pigment Orange 16) (Disazo orange pigment manufactured by Dainichi Seirani Co., Ltd.), CROMOPHTAL DDP Orange TR (Color Index (CI) Pigment Orange 71) (Ciba 'Specialty Chemicals Co., Ltd., diketopiro mouth pyrrole orange pigment), IRGAZ IN DDP Or ange RA (Color Index (CI) Pigment Orange 73) (Ciba Specialty * Chemicals Co., Ltd.'s Diketopiro (A pyrrole-based orange pigment).
  • Examples of the blue pigment having no halogen in the structural formula of the present invention include Chromo Fine Blue 5008 (Color Index (CI) Pigmentable 15) (phthalocyanine blue pigment manufactured by Dainichi Seichi Co., Ltd.), Chromo Fineble I 4927 (Color Index (I.) Pigment Blue 15) (Phthalocyanine pigments manufactured by Dainichi Seika Co., Ltd.) and D-7565 (Color Index) (C.I.) Pigmentable 16) (metal-free phthalocyanine pigment from BASF) was used.
  • Chromo Fine Blue 5008 Color Index (CI) Pigmentable 15)
  • Chromo Fineble I 4927 Color Index (I.) Pigment Blue 15)
  • D-7565 Color Index
  • C.I. Color Index
  • Green 7 (a phthalocyanine green pigment manufactured by Dainichi Seirido Co., Ltd.) and D-8605 (Color Index (I.) Pigment).
  • Green 7) phthalocyanine green pigment manufactured by BASF was used.
  • Irgacure-1907 used as a photopolymerization initiator was manufactured by Ciba-Geigy Corporation, and Kaacure DETX-S was manufactured by Nippon Kayaku Co., Ltd.
  • Modaf Kuchiichi is a leveling agent made of monsanthone earth.
  • a pattern is formed by pre-etching the photo solder-resist inks I-11 to I-11 and I-11 to 12 obtained as described above on a copper-clad laminate made of glass epoxy base material with a copper foil of 35 zm.
  • the resultant was applied by screen printing to the entire surface of the printed wiring board, and precure was performed at 80 ° C. for 20 minutes to volatilize the solvent, thereby obtaining a dry coating film having a thickness of 20 m.
  • epoxy acrylates (A-3-1) to (A-3-6) were prepared in order to prepare the ultraviolet hard solder type resist ink as an example.
  • EPPN-201 a phenol nopolak-type epoxy resin manufactured by Nippon Kayaku Co., Ltd.
  • acrylinoleic acid This is the all esterified epoxy group.
  • 2-Acryloyloxyshethyl acid phosphate used was light ester pA manufactured by Kyoeisha Chemical Co., Ltd.
  • Light ester PM manufactured by Kyoeisha Chemical Co., Ltd. was used for 2-methacryloyloxyshetil acid phosphate.
  • Example 1 the same orange pigments and blue pigments as those of Example 1 were used as the orange pigment and the blue pigment which did not contain hachigen in the structural formula.
  • the same green organic pigment as that used in Example 1 was also used as a conventional green organic pigment used as a comparative example.
  • the components prepared as described above are uniformly mixed in the mixing ratio shown in Table 2, and sufficiently kneaded with a three-roll roll manufactured by Inoue Seisakusho Co., Ltd. to cure the ultraviolet-curable solder resist ink according to the present invention. II I obtained 1 to 7.
  • ultraviolet hard-solder-type solder-resist inks II-11 to 12 out of the scope of the present invention were similarly prepared.
  • the ultraviolet hard solder type solder resist inks obtained as described above were printed and applied on the printed wiring lines formed by the screen printing method using a 225 mesh screen. After that, it is hardened by irradiating with a light of 100 mJ / cm2 using a metal halide lamp (or high pressure mercury lamp) of 12 OW / cm (or 8 OW / cm).
  • a metal halide lamp or high pressure mercury lamp
  • 12 OW / cm or 8 OW / cm
  • test pieces prepared from the (I) photo solder resist ink and the (II) UV hardened type solder resist ink obtained as described above were subjected to a pencil hardness test, a grid adhesion test, and a solder heat resistance. Tests, solvent resistance tests, chemical resistance tests, insulation resistance tests, and property evaluation tests for halogen content were performed. The obtained results are also shown in Table 1.
  • the pencil hardness test was performed according to JIS K-540, 8.4. Using a pencil (Mitsubishi Uji), the highest hardness that does not hurt was measured.
  • the cross-cut adhesion test was performed in accordance with jis K—540, 8.5. Using a Ericssen cross-cut tester, the hard film was cut vertically and horizontally one by one, and a cerote-pull-off test was performed. The remaining number in the 100 grid was counted.
  • the solder heat resistance test was performed in accordance with JISC-6481, 5.5. Using L 0 NC 0 ⁇ CF-350 (water-soluble flux made by London Chemical) as a flux, first apply the flux to the test piece, and then apply it to a molten solder bath at 260 ° C. It was immersed for 10 seconds and then immediately poured into cooling water. By observing the substrate surface immediately after this test, the presence or absence of blisters or peeling was confirmed.
  • the substrate was immersed in 2-propanol and 1,1,1-trichloroethane for 1 hour at room temperature, and the surface of the substrate was observed to check for blisters or peeling.
  • the substrate was immersed in a 10 wt% hydrochloric acid and a 10 wt% sodium hydroxide aqueous solution at room temperature for 1 hour, and the substrate surface was observed to check for blisters or peeling. did.
  • the resistance between opposing electrodes of an IPC-B-25 comb-shaped pattern having the cured coating film of the present invention was measured.
  • the residue obtained by volatilizing and removing the organic solvent from the ink and the cured coating film were weighed as samples, and these samples were burned into a combustion flask.
  • the contents of chlorine, bromine and fluorine in the absorbing solution that absorbed the gas generated by combustion in the furnace were quantified by ion chromatography single analysis measurement.
  • the ink before stiffening and the stiffened coating film were each weighed as a sample, and the halogen-containing solder resist was used in the same manner as in Example 1 above. The amount was quantified.
  • the coatings formed from the photo solder resist ink and the ultraviolet hard solder type solder resist of the present invention show the conventional photo solder resist ink and the ultraviolet hard solder type solder which are out of the scope of the present invention. It had hardness, release resistance, heat resistance, and insulation properties almost equivalent to those of the coating film formed from the resist.
  • the photo-photo solder resist ink of the present invention and an ultraviolet curing type Coatings formed from rudder resist have significantly lower halogen content than films formed from conventional inks. Therefore, the amount of halogen gas generated during the burning of this coating film is considered to be significantly lower than before.
  • the color pigment used in the present invention has good dispersibility, and thus could be easily prepared by mixing and mixing the components.
  • UV curable resin solution (A-1-2) UV curable resin solution (A-1-2)
  • UV curable resin solution (A- 1-3)
  • Cured coating 90 100 90 300 400 400 90 90 4000 4000

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  • Chemical & Material Sciences (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Structural Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Architecture (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Materials For Photolithography (AREA)

Abstract

L'invention porte sur une encre épargne résistant à la soudure formant un film protecteur permanent à faible teneur en halogène. Ladite encre comporte: (A) un ingrédient durcissant sous l'effet des UV, (B) un amorceur de photopolymérisation, et (C) un colorant comportant un pigment orange et un pigment bleu dont les structures chimiques respectives sont exemptes d'halogènes, et qui sont mélangés pour donner une couleur verte.
PCT/JP2001/001715 2000-03-06 2001-03-06 Encre epargne pour soudures WO2001067178A1 (fr)

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AU2001236098A AU2001236098A1 (en) 2000-03-06 2001-03-06 Solder resist ink

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JP2000-60988 2000-03-06
JP2000061036 2000-03-06
JP2000060988 2000-03-06
JP2000-61036 2000-03-06
JP2000069376 2000-03-13
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Cited By (4)

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Publication number Priority date Publication date Assignee Title
JP2007003807A (ja) * 2005-06-23 2007-01-11 Sumitomo Bakelite Co Ltd 感光性樹脂組成物および該組成物を用いたソルダーレジスト
WO2015033880A1 (fr) * 2013-09-04 2015-03-12 富士フイルム株式会社 Composition de résine, procédé de production d'un film durci, film durci, dispositif d'affichage à cristaux liquides et dispositif d'affichage el organique
WO2016208187A1 (fr) * 2015-06-24 2016-12-29 互応化学工業株式会社 Composition de réserve de soudure, revêtement, carte de câblage imprimée revêtue, procédé de fabrication de revêtement, et procédé de fabrication de carte de câblage imprimée revêtue
CN115197632A (zh) * 2021-09-16 2022-10-18 广东硕成科技股份有限公司 一种高铜厚线路板用膜层及其应用

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JPH1164619A (ja) * 1997-08-12 1999-03-05 Toray Ind Inc カラーフィルター用カラーペーストおよびその製造方法並びにカラーフィルター
JPH11194213A (ja) * 1997-10-31 1999-07-21 Toray Ind Inc カラーフィルター用カラーペーストおよびその製造方法並びにカラーフィルター
JPH11258790A (ja) * 1998-03-10 1999-09-24 Sumitomo Chem Co Ltd 着色感光性樹脂組成物
JP2000007974A (ja) * 1998-06-22 2000-01-11 Taiyo Ink Mfg Ltd ハロゲンフリーの着色顔料を用いたプリント配線板用緑色インキ組成物
JP2000232264A (ja) * 1998-12-09 2000-08-22 Goo Chemical Co Ltd フォトソルダーレジストインク

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JPH1164619A (ja) * 1997-08-12 1999-03-05 Toray Ind Inc カラーフィルター用カラーペーストおよびその製造方法並びにカラーフィルター
JPH11194213A (ja) * 1997-10-31 1999-07-21 Toray Ind Inc カラーフィルター用カラーペーストおよびその製造方法並びにカラーフィルター
JPH11258790A (ja) * 1998-03-10 1999-09-24 Sumitomo Chem Co Ltd 着色感光性樹脂組成物
JP2000007974A (ja) * 1998-06-22 2000-01-11 Taiyo Ink Mfg Ltd ハロゲンフリーの着色顔料を用いたプリント配線板用緑色インキ組成物
JP2000232264A (ja) * 1998-12-09 2000-08-22 Goo Chemical Co Ltd フォトソルダーレジストインク

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007003807A (ja) * 2005-06-23 2007-01-11 Sumitomo Bakelite Co Ltd 感光性樹脂組成物および該組成物を用いたソルダーレジスト
WO2015033880A1 (fr) * 2013-09-04 2015-03-12 富士フイルム株式会社 Composition de résine, procédé de production d'un film durci, film durci, dispositif d'affichage à cristaux liquides et dispositif d'affichage el organique
WO2016208187A1 (fr) * 2015-06-24 2016-12-29 互応化学工業株式会社 Composition de réserve de soudure, revêtement, carte de câblage imprimée revêtue, procédé de fabrication de revêtement, et procédé de fabrication de carte de câblage imprimée revêtue
JPWO2016208187A1 (ja) * 2015-06-24 2017-11-02 互応化学工業株式会社 ソルダーレジスト組成物、被膜、被覆プリント配線板、被膜の製造方法、及び被覆プリント配線板の製造方法
CN115197632A (zh) * 2021-09-16 2022-10-18 广东硕成科技股份有限公司 一种高铜厚线路板用膜层及其应用

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