WO2002048794A1

WO2002048794A1 - Solder resist ink

Info

Publication number: WO2002048794A1
Application number: PCT/JP2001/010288
Authority: WO
Inventors: Hiroko Daido; Soichi Hashimoto; Tatsuya Kubo; Akiyuki Nakata; Teruo Furukawa
Original assignee: Goo Chemical Co., Ltd.
Priority date: 2000-12-13
Filing date: 2001-11-26
Publication date: 2002-06-20
Also published as: JP3805745B2; TWI237531B; AU2002221042A1; JPWO2002048794A1

Abstract

A solder resist ink characterized by comprising (A) a ultraviolet-curing component, (B) a photopolymerization initiator, and (C) a copper-phthalocyanine pigment containing at least one halogen atom in the chemical structure and having a halogen content of 25 % or below based on the molecular weight. This ink can efficiently form a permanent protective film reduced in halogen content. When an ultraviolet-curing resin (A-1) having in side chains ethylenically unsaturated groups and carboxyl groups is used as the component (A), products useful as photo solder resist ink can be obtained.

Description

TECHNICAL FIELD The present invention relates to a solder resist ink for forming a permanent protective film of a printed wiring board. More specifically, the present invention relates to a solder resist ink that is cured by irradiation with ultraviolet rays, and includes both a developable photo solder resist ink and a non-developable ultraviolet curing solder resist.

The amount of toxic gas generated during combustion of this solder resist is significantly reduced. 2. Description of the Related Art Printed wiring boards used in electrical products are formed by forming a predetermined wiring force on a substrate such as a copper-clad laminate. This printed wiring board has conductor wiring on the board to prevent solder from adhering to unnecessary parts during soldering, to avoid electrical shorts, and to shorten the life of the printed wiring board. After the formation, a permanent protective film made of a cured product of solder resist ink is generally formed in a predetermined pattern. Conventionally, the board and the solder resist ink constituting such a printed wiring board contain a halide power such as bromide, and may generate a toxic gas power when burned, which has been a problem. However, with the growing concern over environmental issues and human safety in recent years, there is a need for the development of printed wiring boards that do not generate toxic gases during combustion. In response to such demands, for example, in the case of force solder resist inks in which substrates such as dehalogenated glass epoxy copper-clad laminates have been developed, it is necessary to achieve a sufficient reduction in halogen content. Not reached. In general, a permanent protective film of solder resist ink formed on a printed wiring board needs to be excellent in visibility at the time of visual inspection and also be easy on the eyes. It is strongly required to be green or blue. Therefore, conventionally, there has been a green solder resist ink containing a coloring pigment such as phthalocyanine green. However, this phthalocyanine green contains a high proportion of chlorine and bromine in its structural formula. More specifically, for example, phthalocyanine green, whose color index (C.I.) is pigment green 7, contains about 47% by weight of chlorine in one molecule, and pigment green 36. Some lid mouth cyaning lines contain about 5% by weight of chlorine and about 60% by weight of bromine in one molecule. Therefore, 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. On the other hand, there has been proposed a solder resist ink in which a halogen-free coloring pigment is blended to reduce the halogen content of the permanent protective film.

As an example, the blue color containing L ゝ blue pigment containing no halogen in the chemical structural formula There is solder resist ink. Among the blue pigments incorporated herein, for example, those represented by C.I. Pigmentable 15 include copper phthalocyanine bleeding containing no halogen in its chemical structural formula, C.I. Among the compounds represented by G.I.ment Blue 16, there are, in its chemical formula, L, L that does not contain a logen, and metal-free phthalocyanine blue. In addition, a solder that forms a green permanent protective film by combining a combination of a blue pigment without L and a halogen and a yellow pigment without a halogen in the chemical structural formula. One resist ink has also been proposed. However, coloring pigments having no halogen in these structural formulas, particularly blue pigments, are not only poor in the pulverizability and dispersibility of particles, but also in a solder resist ink containing this pigment. The permanent protective film tends to fade when subjected to heat treatment such as soldering. Therefore, an object of the present invention is to provide a solder resist ink that can be efficiently prepared by using a blue pigment having excellent pulverizability and dispersibility. In particular, an object of the present invention is to provide a solder resist ink capable of forming a permanent protective film that is less likely to generate fading even when subjected to a heat treatment such as soldering while generating less halogen gas during combustion. DISCLOSURE OF THE INVENTION

(A) UV-curable component,

(B) a photopolymerization initiator, and (C) A solder resist comprising a copper phthalocyanine pigment having at least one halogen atom in the structural formula and having a halogen content of 25% or less in the molecular weight. Ink. When a UV curable resin having an ethylenically unsaturated group and a carboxyl group in the side chain is used as the component (A), a product useful as a photo solder resist ink can be obtained. it can. Further, the component (A) preferably contains (A-4) an ethylenically unsaturated monomer. Usually, the solder resist ink preferably further contains (D) an organic solvent.

It is preferable that the solder resist ink using the ultraviolet-curable resin (A-1) as the component (A) further contains (E) a polyfunctional epoxy compound.

Further, it is preferable that the halogen content of the solder resist ink is 500 ppm or less. Further, the ultraviolet curable resin as the component (A-1) and the polyfunctional epoxy compound as the component (E), which are blended in the above-mentioned solder resist ink, are, for example, halogens synthesized by a peracid method. It is preferably prepared from an epoxy conjugate which does not contain, or an epoxy compound which has been subjected to a treatment for reducing the content of lipogen. The component (A-1) thus prepared and the component (A-1) / Ma When the component (E) is used, 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. It is preferable that the solder resist ink further includes a second color pigment having a halogen content of 25% or less in the molecular weight. Further, as the component (A), an esterified product of (A-3) an epoxy (meth) acrylate and / or a polyether of polyhydric phenol and (meth) acrylic acid; An (A-4) ethylenically unsaturated compound other than the component may be used. In this case, a product useful as an ultraviolet-curable solder resist ink can be obtained. Also in this case, it is preferable that the halogen content in the cured product of the solder resist ink be 500 ppm or less. The component (A-3) contained in the solder resist ink is a halogen-free epoxy conjugate synthesized by a peracid method or an epoxy conjugate treated to reduce halogen. It is preferred that the compound is prepared from the compound. In this case, the halogen content in the cured product of the solder resist ink is preferably 150 ppm or less. Further, it is preferable that the solder resist ink further includes a second color pigment having a halogen content of 25% or less in the molecular weight. (A) an ultraviolet-curable component, (B) a photopolymerization initiator, and (C) at least one halogen atom in the chemical structural formula contained in the solder resist ink of the present invention. The copper phthalocyanine pigment having a halogen content of 25% or less in the molecular weight of the copper phthalocyanine pigment is described below.

(A) UV curable component

The component (A) is a component having an ultraviolet curable function. By using the component (C) in combination with the photopolymerization initiator 1, the solder resist ink can be cured by irradiation with ultraviolet rays. The solder resist ink may contain the component (D) and the organic solvent. However, excluding this organic solvent, the amount of the component (A) contained in the solder resist ink of the present invention is 20%. It is preferably about 80% by weight. The component (A) blended in the present invention is not particularly limited as long as it can be cured by ultraviolet irradiation, and examples thereof include an ultraviolet-curable resin having a photoreactive double bond and a photopolymerizable monomer. Arbitrarily selected from conventionally known UV-curable components o

(B) Photopolymerization initiator

The photopolymerization initiator used in the present invention is not particularly limited, but is preferably, for example, benzoin; benzoin methyl ether, benzoine ethyl ether, benzoin isopropyl ether and the like. Alkyl ethers of benzoin; acetofphenone, 2,2-dimethoxy-1-2-phenylacetophenone, 2,2,1-ethoxy-1,2-phenylacetophenone, and 1-hydroxycyclohexylphenyl Acetophenones such as ketones; anthraquinones such as 2-methylanthraquinone, 2-ethylanthraquinone and 2-amylanthraquinone; 2,4-dimethylthioxanthone, 2,4-getylthioxanthone and 2-isoprop Thioxanthones such as propylthioxanthone, 4-isopropylthioxanthone and 2,4-diisopropylthioxanthone; ketals such as benzyldimethylketal; benzophenone, 3,3-dimethyl-14-methoxybenzophenone, 3, Benzophenones such as 3 ', 4,4, -tetra (t-butylperoxylcarbonyl) benzophenone and 4-benzoyl-1-methyldiphenyl sulfide; and xanthonones such as 2,4-diisopropylxanthone Α-hydroxy ketones such as 2-hydroxy-2-methyl-1-phenylpropane-one-one and hydroxy-1-hydroxyhexyl-2-ene; 2-methyl-1-1 [ 4- (Methylthio) phenyl] 1-2-morpholino 1-propanone, 2-benzyl-1-2-dimethylamine I 1 _ (4-morpholinofinyl) 1-butanone 1, 4,4, -Bis (getylamino) benzophenone and other nitrogen-containing compounds; (2,4,6-trimethylbenzoyl) diphenyl Nylphosphoxide and the like. These photopolymerization initiators may be used alone or in combination of two or more. These photopolymerization initiators include known photopolymerization accelerators such as tertiary amines such as ρ-dimethylaminobenzoic acid ester, ρ-dimethylaminobenzoic acid isoamyl ester, and 2-dimethylaminoethyl benzoate. Good in combination with sensitizers etc. In addition, a photopolymerization initiator for visible light, near-infrared light exposure and the like can be used. The component (1) photopolymerization initiator 1 may be contained in an amount of about 0.1 to 30% by weight in all the components of the solder resist ink except for the organic solvent optionally contained. 1 to 10% by weight, preferably 0.1 to 7% by weight. When the photopolymerization initiator power is contained in the compounding amount in the above range, the solder resist Shows excellent photocurability, and the physical properties of the obtained permanent protective film are also improved.

(C) Color pigment

The component (C) contained in the solder resist ink of the present invention in addition to the components (A) and (B) has at least one halogen atom in the structural formula, and has a molecular weight of at least one. It is a copper phthalocyanine pigment having an amount of halogen of 25% or less. Examples of such copper phthalocyanine pigments include, among those represented by I. Pigmentable 15 (including 15: 1), those containing 1 to 3 chlorine atoms as halogen in the chemical structural formula. . Such a copper phthalocyanine pigment has better pulverizability and dispersibility at the time of kneading and higher heat resistance than a halogen-free phthalocyanine pigment. In addition, even if the permanent protective film of the photo solder resist ink of the present invention containing the above-mentioned coloring pigment is burned, the amount of halogen gas generated is small, and heat treatment such as soldering is applied. In the event of exposure to light or prolonged exposure to light, the permanent protective coating is less likely to fade. In the solder resist ink of the present invention, other coloring pigments (hereinafter, referred to as “second pigments”) may be blended in addition to the copper phthalocyanine pigment. Such a second pigment is not particularly limited, but the amount of halogen occupying in the molecular weight is 25% or less, or the second pigment does not contain a halogen atom in the structural formula. Therefore, it is possible to sufficiently reduce the kerogen content of the permanent protective film to be formed. The following are examples of the second pigment which can be blended with the ink of the present invention. O.

(Blue pigment)

As blue pigments not containing a halogen atom in the structural formula, c. I. Among the pigments represented by Igmentable Table 15, copper phthalocyanine blue containing no halogen in the chemical structural formula,

C. Pigmentable 1-6 metal-free phthalocyanine

C. Indigo designated by Pigmentable 63 and 66,

C. condensed polycyclic pigments represented by Pigmentable 65, etc.,

C. anthraquinone pigments represented by CI Pigmentable 60, etc .;

C. Pigment Benoray 1, 2, 3, 10, 14, 18, 19, 24, 56,

57 and 6 Alkaline tablets indicated by 1 etc.,

C.I.Navy blue, indicated by Pigment Blue 27,

C. I. Pigmented Bulletin 28, and

C. I. Pigment Blue 29 can be exemplified. These pigments

Can be used alone or in appropriate combination.

(Yellow pigment)

As the yellow pigment not containing a halogen atom in the chemical structural formula, pigments classified as C.I.P.:menthero in the color index are exemplified and preferred. As such a yellow pigment, in particular,

Isoindoline pigments represented by C.I.

C. I. pigment yellow 120, 151, 175, 180, 181 and 194, etc., a benzimidazolone-based pigment,

Condensed polycyclic pigments represented by CI Pigment Yellow 148, 182 and 192, etc. Bisazomethine pigments represented by C.I.

C. I. Pigment yellow 1,4,5,7,9,65,74,150,154 and 167, etc.

C. I. pigment anthraquinone pigments represented by 24, 108, 123, 147 and 193;

Bisazo pigments represented by C.I.

C. I. pigment yellow 1 17, 129, 153, 177 and 1 79

Flavantrone Yellow, designated C.I.

Iron oxide pigments such as C.I.

C. I. Pigment Yellows 61, 62, 100, 104, 133, 168 and 169, etc., azo lake pigments and the like can be exemplified.

In addition, a yellow pigment having at least one halogen atom in the chemical structural formula is exemplified as having a halogen content of 25% or less in the molecular weight.

A monoazo pigment represented by C.I.

C. I. Pigment yellows represented by 12, 13, 14 and 17;

Others Examples include the pigments and the like shown in I. Pigment Yellow 55.

These yellow pigments can be used alone or in combination as appropriate. Chopsticks :)

As the orange pigment having no hachigen atom in the structural formula of the danigami, those which are classified as C.I. Pigment Orange in the color index are preferred as well as exemplified. As such an orange pigment, in particular,

CI Pigment Orange 1, 2, 3, 5, 6, 17, 17, 62 and 64, etc. Monoazo pigments,

C.I.Pyrantrone pigments such as Pigment Orange 40 and 41 etc.

C.I. pigment orange Disazo pigments represented by 14, 15, 15, 16, 50 and 63, etc.

Cerium sulfide represented by C.I.

C.I.perinone pigments represented by Pigment Orange 43, etc.

C. I. Pigment Oranges 71 and 73 etc.

C.I. pigment orange Quinacridone pigments such as 48 and 49

C. I. Pigment Orange 65, 68, 17: 1, etc. can be exemplified.

On the other hand, orange pigments having at least one halogen atom in the chemical structural formula are exemplified as having an amount of halogen of 25% or less in the molecular weight, and preferable examples thereof include:

C.I. pigment orange 36, a monoazo pigment represented by 6,

The pigments are monoazo pigments represented by C.I. Pigment Orange 13 and 34.

These orange pigments can be used alone or in combination as appropriate. In general, the solder resist ink that forms the permanent protective film is such that the permanent protective film formed thereby is colored green so that it is excellent in visual inspection and easy on the eyes. Power preferred. As described above, the ink of the present invention has at least one halogen in the chemical formula. A copper phthalocyanine pigment as a component (C) having atoms and having a halogen content of 25% or less in the molecular weight is blended as an essential component. In addition to the copper phthalocyanine pigment, By further blending at least one pigment selected from the above blue pigments, yellow pigments and orange pigments, a green or blue, especially green, permanent protective film can be obtained. Moreover, such a green permanent protective film is low in nitrogen. Although the invention described in Japanese Patent Application Laid-Open No. 2000-2323264 is excellent in that it is low in nitrogen, the pulverizability and dispersibility of the pigment used are indispensable. Although not good, the pigments blended in the present invention also have good pulverizability and dispersibility, and can reduce the amount of coloring pigment used. In addition, such a permanent protective film of the solder resist ink of the present invention generates a small amount of halogen gas at the time of combustion, and hardly fades even when subjected to heat treatment such as soldering. The weight ratio of the copper phthalocyanine pigment as the component (C) to the second pigment is required to obtain a photo solder resist ink that forms a vivid green permanent protective film with little color unevenness. : The second pigment is preferably in a ratio of 1:10 to L0: 1, and more preferably in a ratio of 1: 5 to 5: 1. In the present invention, the compounding amount of the copper phthalocyanine pigment as the component (C), which has at least one halogen atom in the chemical structural formula and has a halogen content of 25% or less in the molecular weight, is particularly limited. However, it is preferably contained in an amount of about 0.1 to 20% by weight, more preferably about 0.1 to 10% by weight, and especially about 0.1 to 10% by weight in all components of the ink of the present invention except for an organic solvent optionally contained. The power of 2-5% by weight is preferred. When the amount of the copper phthalocyanine pigment is within the above range, the UV transmittance is reduced. A permanent protective film with good visibility during visual inspection can be formed while suppressing a decrease in photoreactivity.

The total amount of the copper phthalocyanine pigment and the second pigment is not particularly limited, but is 0.1 to 2 in all components of the ink of the present invention except for an organic solvent optionally contained. It is preferably contained in an amount of about 0% by weight, and 0.1 to: 0% by weight of L, particularly preferably 0.2 to 5% by weight. When the total compounding power of the copper phthalocyanine pigment and the second pigment is in the above range, permanent protection with good visibility at the time of visual inspection while suppressing a decrease in photoreactivity due to a decrease in ultraviolet transmittance. Can form a film o

(I) Photo solder resist ink

When the solder resist ink of the present invention is used as a photo solder resist ink, it is preferable that the ink can be developed with an organic solvent or a dilute alkaline aqueous solution, and the ultraviolet curable resin is used as the component (A). It is better to use In particular, in order to make the ink developable with a dilute aqueous alkaline solution, ultraviolet curing using the component (A-1) as the component (A), ie, having an ethylenically unsaturated group and a carboxyl group in the side chain, is required. It is preferable to use a conductive resin. In the present invention, the “photo solder resist ink” refers to a so-called image-type solder resist ink, for example, by selectively exposing a solder resist ink applied on a substrate to ultraviolet rays. The solder resist ink of the exposed portion is cured, and then the solder resist ink of the unexposed portion is washed and removed in, for example, an aqueous alkaline solution to obtain a permanent protective film of a predetermined pattern. Applicable to solder resist ink. Since the component (A-1) has a photocurable ethylenically unsaturated group and a carboxylic group in its chemical structural formula, it absorbs predetermined energy by exposure to ultraviolet rays or the like. However, the exposed portion is hardened, and the dispersibility and solubility in a dilute aqueous solution are reduced. Therefore, the photo solder resist ink of the present invention containing the component (A-1) is applied to a substrate, selectively exposed, and the exposed portion of the photo solder resist ink is hardened. A predetermined pattern can be formed on the substrate by washing the substrate with a dilute alkaline aqueous solution and dissolving and removing the uncured photo solder resist ink in the non-exposed area with a dilute aqueous solution. . The ultraviolet curable resin as the component (A-1) has a photopolymerizable ethylenically unsaturated group in the chemical structural formula. Examples of such a photopolymerizable ethylenically unsaturated group include unsaturated groups such as a (meth) acryloyl group and a vinyl group. Although the content of the photopolymerizable ethylenically unsaturated group is not particularly limited, the content of the unsaturated group in the ultraviolet curable resin is 0.01 to 10 mol / Kg (ultraviolet curable resin), particularly Preferably, it is 0.1 to 5 mol / Kg. When the content of unsaturated groups in the ultraviolet curable resin falls within the above range, a photo solder-resist ink having particularly excellent exposure sensitivity and image developability can be prepared. The ultraviolet-curable resin as the component (A-1) preferably has an acid value of 30 to 20 OmgKOH / g, particularly 40 to 160 mgKOHZg. When the acid value of the ultraviolet-curable resin is in the above range, the compatibility with other components becomes good, and the photo solder resist ink has particularly good exposure sensitivity, developability and resolution. Can be prepared. Furthermore, the weight-average molecular weight of the UV-curable resin as the component (A-1) is particularly limited. Although not specified, 3, 000 to 400, 000, especially 5, 000 to 100, 0000, and optimally 5, 000 to 50, 0 It is preferably 0. When the weight-average molecular weight of the ultraviolet-curable resin is in the above range, the balance between resolution and exposure sensitivity of the photo solder resist ink of the present invention is particularly excellent.

As the component (A-1), for example, “an ethylenically unsaturated compound having a carboxyl group” and “a polyvalent ruponic anhydride” in the epoxy group in the “polymer having an epoxy group in a side chain” may be used. An ultraviolet curable resin formed by addition is exemplified. As 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 polyethylene-based polymer are used. Copolymer strength with a saturated monomer. That is, epoxy conjugates include glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylic acid and other daricidyl (meth) acrylic acids, and (3,4-epoxycyclo). (Methoxy) hexyl derivatives of (meth) acrylic acid such as methyl (meth) acrylate. Examples of the ethylenically unsaturated monomer include aliphatic or alicyclic alkyl (meth) acrylate; aromatic (meth) acrylate such as benzyl (meth) acrylate; hydroxyethyl (meth) acrylate. Ethylene glycol ester (meth) acrylate such as dimethyl oxethyl (meth) acrylate, polyethylene glycol ester (meth) acrylate and propylene glycol (meth) acrylate; (meth) acrylamide compound; N —Substituted maleimide compounds; vinylpyrrolidone; (methyl) acrylonitrile; vinyl sulphate; styrene; —methylstyrene; In the present specification, (meth) acrylinoleic acid is a general term for acryloline acid and methacrylic acid, and (meth) acrylate is a general term for acrylate and methacrylate. The “polymer having an epoxy group in a side chain (skeleton polymer)” for preparing an ultraviolet-curable resin exemplified as the component (A-1) includes the above epoxy compound and ethylenically unsaturated polymer. In addition to copolymers with monomers, for example, phenol novolak epoxy resin, cresol novolak epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol A-nopolak epoxy resin, Alicyclic epoxy resin (for example, “EHPE—310” manufactured by Daicel Chemical Industries, Ltd.) and polyfunctional epoxy resin that is a derivative of tris (hydroxyphenyl) methane (for example, EPPN—produced by Nippon Kayaku Co., Ltd.) Epoxy resins such as 502 H and Dow Chemical Tactex-742 and XD-9503). You. Examples of the “ethylenically unsaturated monomer having a carboxyl group” for preparing an ultraviolet-curable resin exemplified as the component (A-1) include, for example, (meth) acrylic acid, crotonic acid, and cinnamic acid. , 2-(meth) acryloyloxetyl succinic acid, 2 _ (meth) acryloyloxetyl phthalic acid, ^ -carboxyethyl acrylate, acryloyloxetyl succinate , 2-Prodinoic acid, 3- (2-Carboxyethoxy) _3-oxypropyl ester, 2- (Meth) acryloyloxhetyltetrahydrophthalic acid and 2- (Meth) acryloyl Those having one ethylenically unsaturated group such as xicetylhexahydrophthalic acid, pentaerythritol tri (meth) acrylate, trimethylethylpropane Meta) Acrylate, Dipentaerythritol Penta (Meta) Examples include those having a plurality of ethylenic unsaturated groups, such as those obtained by reacting a difunctional acid anhydride with a polyfunctional acrylate having a hydroxy group such as acrylate. Among them, 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. Whether the ethylenically unsaturated group introduced by (meth) acrylic acid has excellent photoreactivity. These “ethylenically unsaturated monomers having a carboxyl group” can be used alone or in an appropriate combination. Examples of the "polycarboxylic anhydride" for preparing an ultraviolet-curable resin exemplified as the component (A-1) include, for example, succinic anhydride, methylsuccinic anhydride, maleic anhydride, and citracon anhydride. Dibasic acids such as acid, glutaric anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride and methylhexahydrophthalic anhydride Anhydrides and acid anhydrides of three or more basic acids such as trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride and methylcyclohexenetetracarbonic anhydride are exemplified.

Each of these “polycarboxylic anhydrides” can be used alone or in combination as appropriate. As described above, the epoxy group of the polymer having an epoxy group in the side chain is heated with an ethylenically unsaturated compound having a carboxyl group and a polyvalent sulfonic acid anhydride as a component (A-1). Addition reaction for preparing exemplified UV curable resins The heating is performed, for example, by heating to about 60 to about 50 ° C. in the presence of a thermal polymerization inhibitor and an addition catalyst. In addition, 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 '' followed by a `` ethylenically unsaturated compound having a carboxyl group ''. Is more 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 10 to 80% by weight. It is 20 to 70% by weight, optimally 25 to 60% by weight. When the compounding power 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.

(A— 4) Ethylenically unsaturated monomer

The photo solder resist ink of the present invention may further comprise (A-4) an ethylenically unsaturated monomer as component (A) in addition to component (A-1). Properties such as heat resistance, heat resistance and insulation properties may be improved. Further, the (A-4) photopolymerizable ethylenically unsaturated monomer plays a role as a diluent and also plays a role in adjusting exposure sensitivity. Examples of such ethylenically unsaturated monomers include 2-hydroxyethyl (methyl) acrylate, 2-hydroxypropyl (meth) acrylate, N-vinylpyrrolidone, (meth) acryloylmorpholin, Methoxytetraethylene glycol (methyl) acrylate, methoxypolyethylene glycol (methyl) 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, diethyleneglycol di (meth) acrylate, triethyleneglycoldi (meth) acrylate, propyleneglycoldi (meth) acrylate, phenyloxethyl (meta) ) Acrylate, tetrahydrofurfuryl (meth) acrylate, cyclohexyl (meth) acrylate, trimethylolpropanedi (meta) acrylate, trimethylolpu, mouth pantry (meta) acrylate, penyu erythritol Meta) Acrylate, pentaerythritol tetra (methy) acrylate, dipentaerythritol-lepene (meta) acrylate, dipentyerythritol hexa (meta) acrylate, isobonyl (meta) acrylate, cyclopenyl mono (meta) Acrylates and cyclopentenyl mono (meth) acrylates; monoesters, diesters, triesters or polyesters of polybasic acids with hydroxyalkyl (meth) acrylates; polyester (meth) acrylates, urethane (meth) acrylates, etc. (Meth) Acrylate monomer and the like.

These ethylenically unsaturated monomers can be blended alone or in an appropriate combination to prepare the photo solder resist ink of the present invention.

The amount of the (A-4) ethylenically unsaturated monomer in the photo solder resist ink excluding the organic solvent is not particularly limited, but is preferably 1 to 50% by weight, and more preferably 1 to 40% by weight. %, Optimally between 1 and 30% by weight. By blending the photopolymerizable ethylenically unsaturated monomer in the above range, the dried coating film has an appropriate surface tackiness and is exposed by applying a negative mask on which the pattern is drawn to the dried coating film. In this case, the problem of contamination of the negative mask can be prevented. The photo solder resist ink of the present invention may further include, if necessary, an ultraviolet-curable polymer such as epoxy (meth) acrylate, a (meth) acrylate copolymer, and a styrene copolymer. A polymer of an ethylenically unsaturated compound such as a maleic acid resin, or a UV-curable polymer obtained by further introducing an ethylenically unsaturated group into these may be blended. The photo solder resist ink of the present invention contains the component (B) and the component (C) described above in addition to the component (A), and contains a copper phthalocyanine pigment of the component (C). As described above, the permanent protective film of the photo solder resist ink is substantially green or blue as described above, so that the printed wiring board manufactured using the photo solder-resist ink of the present invention is used. The pattern is excellent in visual recognition f during visual inspection and easy on the eyes. Also, as described above, the photo solder resist ink of the present invention may contain another coloring pigment “second pigment” in addition to the copper phthalocyanine pigment. The mixing ratio of the copper phthalocyanine pigment and the second pigment is the same as described above.

(D) Organic solvent

The solder resist ink of the present invention may further contain an organic solvent as the component (D). In the case of a photo solder resist ink, it is particularly preferable to add an organic solvent.

Examples of the organic solvent suitable for the present invention include linear or branched organic solvents such as ethanol, propyl alcohol, isopropyl alcohol, butyl alcohol, isobutyl alcohol, 2-butyl alcohol, hexanol and ethylene glycol. Primary, secondary or polyhydric alcohols having a carbon chain in the form of a chain; ketones such as methylethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene and xylene; sulfur series (Maruzen Petrochemical Mixed solvents such as petroleum-based aromatic solvents such as Solbeso series (manufactured by Exxon Chemical Co.); cellosolves such as cellosolve and butylse-carbosolve; carbitols such as carbitol and butyl carbitol; propylene Propylene glycol alkyl ethers such as Daricol methyl ether; Polypropylene glycol alkyl ethers such as dipropylene glycol methyl ether; Ethyl acetate, butyl acetate, cellosolve acetate, butylacetate solve acetate, butyl carbitol acetate and propylene Acetic esters such as recall monomethyl ether § cetearyl one DOO; as well as dialkyl glycoside one Rue one ethers such force. These organic solvents are used alone or in an appropriate combination in order to prepare the photo solder resist ink of the present invention. These organic solvents may be incorporated in the solder resist ink of the present invention at an arbitrary ratio, for example, 1 to 95% by weight, preferably 5 to 95% by weight, particularly 20 to 95% by weight. % Harmful to be combined with IJ. The photo solder resist ink of the present invention obtained by blending an organic solvent has excellent coatability on a substrate.

(E) Multifunctional epoxy compound

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 multi-state epoxy compound is not particularly limited, but for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, cresol nopolak type epoxy resin, bisphenol A Novolak type epoxy resin, N-glycidyl type epoxy resin or alicyclic epoxy resin (for example, "EHPE-3150" manufactured by Daicel Chemical Industries, Ltd.), "YX-40000" (epoxy manufactured by Yuka Seil Epoxy) Resin), hydrogenated bisphenol II type epoxy resin, triglycidyl isocyanurate, and polyfunctional epoxy resin derived from tris (hydroxyphenyl) methane (EPPN-502H, manufactured by Nippon Kayaku Co., Ltd. Chemical Tactex-社 42 and XD-903 3 etc.)

Further, as the polyfunctional epoxy compound, a homopolymer or a copolymer of an ethylenically unsaturated monomer having an epoxy group may be used. When the copolymer shown on the left is used, it is preferred that the monomer constituting the copolymer contains at least 40 mol% of an ethylenically unsaturated monomer having an epoxy group. Thereby, good thermosetting properties can be obtained. Although not particularly limited, when the above polyfunctional epoxy compound is a homopolymer or a copolymer of an ethylenically unsaturated monomer having an epoxy group, its weight average molecular weight is 2%. , 000 to 200, 000. This makes it possible to prepare a photo solder resist ink that forms a cured film having excellent thermosetting properties. The polyfunctional epoxy compound as the component (E) is present in an amount of about 0.1 to 50% by weight, preferably 0.1 to 50% by weight, based on all components of the photo solder resist ink of the present invention except for the organic solvent. 40% by weight, more preferably 5 to 40% by weight. When the amount of the solid content of the polyfunctional epoxy compound is within the above range, a photo solder resist ink having a good balance between image developability and thermosetting properties can be obtained. Further optional ingredients

The photo solder resist ink of the present invention may further contain further optional components in order to improve properties such as applicability, heat resistance and insulation.

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, Examples include polymerization inhibitors, antihalation agents, defoamers, antioxidants, surfactants, and polymer dispersants. The photo solder resist ink of the present invention is prepared by a known kneading method using a three-hole nozzle, a ball mill, a sand mill and the like. In the photo solder resist ink of the present invention, the components need not be completely and uniformly mixed in advance. For example, for example, a liquid mixture 1 composed of the components (E) and (D) and a liquid 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 form a photo solder resist on the portion. The ink is cured. Thereafter, the photo-solder-resist ink which is developed by removing the non-exposed portion in a dilute alkaline solution and not removed by the post-baking process becomes a permanent protective film. The dilute solution used as a developer is preferably an aqueous solution, For example, it may be an aqueous solution containing a hydrophilic organic solvent such as 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 (practically Is between 0.1 and 300 ppm), optimally below 150 ppm (actually between 0.1 and 150 ppm). This significantly reduces the generation of toxic halogen gas during combustion. Further, according to the present invention, there are provided “a polymer having an epoxy group in a side chain” in the component (A-1), an ethylenically unsaturated monomer having an epoxy group used in the production thereof, and (E) a polyfunctional compound. The epoxy compound and the ethylenically unsaturated monomer having an epoxy group used in the production thereof are not particularly limited, and the halogen content in the cured film can be reduced by using an industrially available monomer. As described above, the concentration can be reduced to 500 ppm or less (actually, 0.1 to 500 ppm). Conventionally, as an epoxy resin conjugate for preparing a photo solder resist ink, an epoxy resin derived from a polycyclic phenol resin compound, an ethylene resin having a darisidyl group such as glycidyl methacrylate, etc. These compounds have been widely used for unsaturated monomers, but these are industrially labeled with epichlorohydrin! It was produced by mouth and desorption of HC1, and the product contained high concentrations of halogen as reaction by-products and impurities. For this reason, it is difficult to reduce the halogen content in the cured film formed on the substrate to 150 ppm or less in the photo solder-resist ink prepared using the epoxy compound thus produced. It was. According to the present invention, on the other hand, 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 50 ppm or less. It is preferred to use like this

When the component (A-1) and / or the component (E) are used, the halogen content in the permanent protective film formed from the photoresist-resist ink of the present invention is significantly reduced as compared with the related art. Therefore, it can be reduced to 150 ppm or less. 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 peracids (for example, formic acid, peracetic acid, perbenzoic acid, etc.). And an ethylenically unsaturated monomer containing an epoxy group. They are halogen-free because they do not use epichlorohydrin in the manufacturing process. An example of such an epoxy resin S is, for example, 力 Ε Η Ρ Ε—3150 ”(manufactured by Daicel Chemical Industries, Ltd., alicyclic epoxy resin). Examples of the saturated monomer include Cycloma A-200 (manufactured by Daicel Chemical Industries, Ltd., an ethylenically unsaturated monomer containing an alicyclic epoxy group), Cycloma M-100, M -101 (a product of Daicel Chemical Industries, Ltd., an ethylenically unsaturated monomer containing an alicyclic epoxy group). Although it was not synthesized by an epoxidation reaction with a peracid, for example, chlorine-reduced epoxy group-containing ethylenically unsaturated monomers such as Bremma-GS (manufactured by NOF CORPORATION, chlorine free (Glycidyl methacrylate) is also preferably used because the halogen concentration is 10 ppm or less.

(II) UV-curable solder resist ink On the other hand, when the solder resist ink of the present invention is used as an ultraviolet-ray or line-curable solder resist ink, the ultraviolet-curable component as the component (A) is not particularly limited. 3) An esterified compound of epoxy (meth) acrylate and polyether of Z or polyhydric phenol with (meth) acrylic acid, and (A-4) ethylenically unsaturated compound other than A-3 component Power favorable

That is, this ultraviolet-curable solder resist ink is obtained by mixing (A-3) an epoxy (meth) acrylate and / or a polyether of polyhydric phenol with an ester of (meth) acrylic acid, and other than the component (A-3). (A-4) an ethylenically unsaturated compound, (B) a photopolymerization initiator and (C) at least one halogen atom in the structural formula, and a halogen content in the molecular weight. Consists of less than 25% copper phthalocyanine pigment. In the present invention, the term “ultraviolet-curable solder resist ink” refers to an ink capable of forming a permanent protective film by forming a desired pattern by a printing method, for example, such as screen printing on a substrate. The solder resist ink printed using a conventionally well-known printing method is entirely exposed to ultraviolet light, and the solder resist ink at the exposed portion is hardened. A type of solder-resist ink that provides a permanent protective film for a turn.

(A-3) Epoxy (meth) acrylates and esterified products of polyethers of Z or polyhydric phenols with (meth) acrylic acid

The epoxy (meth) acrylate of the component (A-3) used in the ultraviolet hardening type solder resist ink of the present invention is an epoxy which can be produced by an esterification reaction between an epoxy compound and (meth) acrylic acid. Total esterification or partial As the epoxy (meth) acrylate, which is a stelate, any of the conventionally known epoxy (meth) acrylates can be used alone or in appropriate combination.

The epoxy compounds that form the epoxy (meth) acrylate are, for example, bisphenol A, bisphenol F, bisphenol A resin, bisphenol F resin, cresol nopolak resin, and phenol novolo. Resins obtained by reacting polyhydric phenols such as rack resins with epichlorohydrin, and alicyclic epoxy resins (for example, a peracetic acid epoxy resin substantially free of halogen, manufactured by Daicel Chemical Industries, Ltd.) Resin Γ Ε Η Ρ Ε—3 150 ”)). On the other hand, as the (A-3) component, the polyether compound of polyhydric phenol and the esterified product of (meth) acrylic acid are the polyether compound of polyhydric phenol and (meth)

) All or partially esterified compounds which can be produced by an Esterich reaction with acrylic acid.

The polyether of the above polyhydric phenol can be obtained, for example, by adding ethylene oxide, propylene oxide, petylene oxide, or hydraprolactone to polyhydric phenol. can get. The amount of the component (A-3) in the ultraviolet curing type solder-resist ink of the present invention is not particularly limited, but preferably, the component (A-3) is the ultraviolet curing type solder of the present invention. One resist ink contains 10 to 70% by weight, more preferably 15 to 65% by weight, and most preferably 15 to 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. (A-4) Ethylene unsaturated compound other than A-3 component

The ultraviolet hardening type solder resist ink of the present invention contains, in addition to the component (A-3), an ethylenically unsaturated compound other than the component (A_3) as the component (A-4). The component (A-4) that exerts a high force is as exemplified 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 10 to 7%. 0% by weight, more preferably 15 to 65% by weight, and most preferably 20 to 60% by weight. The ultraviolet hardened solder resist ink of the present invention containing the component (A-4) in the above range can be cured by irradiation with ultraviolet rays to obtain a cured 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, but the total of the component (A-3) and the component (A-4) is 10%. The amount of the component (A-3) in 0 parts by weight is preferably about 10 to 70 parts by weight, more preferably 10 to 60 parts by weight, and particularly preferably 15 to 50 parts by weight. preferable. (A-3) component and (A-4) component; ^ UV curable type that forms a permanent protective film with excellent printability and curability and heat resistance when compounded in the above range. Can be prepared.

When the component (A-3) and the component (A-4) are used in combination, the types and mixing ratios of the component (B) and the color pigment (C) used are as described above. ) As described above, the second pigment may be used in combination with the component. The ultraviolet-curable solder resist ink of the present invention has printability, heat resistance, and the like. Other components may be contained as long as they do not adversely affect properties such as insulation and insulating properties. Examples of such components include extender pigments such as talc, silica, barium sulfate, alumina, calcium carbonate, and my power. , Inorganic pigments, adhesion improvers, reppelling agents, thixotropic agents, defoamers, polymerization inhibitors and the like. The ultraviolet-curable 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 hardening type solder resist ink of the present invention can significantly reduce the halogen content in the ultraviolet hardening type solder resist ink by using the above pigment. it can. Specifically, the ultraviolet curable solder resist ink of the present invention has a halogen content of 500 ppm or less (actually, 0.1 to 500 ppm), preferably 400 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 ray hardening type solder resist ink of the present invention, the amount of halogen gas generated during combustion is significantly reduced, while the epoxy compound is used for the production of the component (A-3). When used, a compound having a halogen content of 50 ppm or less can be selected as the epoxy compound. This makes it possible to significantly reduce the halogen content in the permanent protective film formed from the ultraviolet hardening type solder-resist ink of the present invention, as compared with the conventional case, and set it to 150 ppm or less. This is the same as in the case of the photo solder resist ink described earlier. BEST MODE FOR CARRYING OUT THE INVENTION Next, the present invention will be described in more detail based on examples, but the present invention is not limited to the following examples.

The “parts” and “%” shown below are all based on weight. Example 1

(I) Photo solder resist ink

Samples I-1 to I-11 according to the present invention and samples I112 to I-14 of comparative examples were prepared with the composition shown in Table 1.

The UV-curable resins (A-1-1), (A-l-2), (A-1-3) and (A-1-4) described in Table 1 were prepared as follows. Things.

(Synthesis of A-1-1)

70 parts of Bremma-GS (manufactured by Nippon Oil & Fats, chlorinated glycidyl methacrylate, halogen content of 1 ppm or less) in a four flask equipped with a reflux condenser, thermometer, glass tube for nitrogen replacement and a stirrer Then, 30 parts of methyl methacrylate, 100 parts of carbitol acetate and 3 parts of azobisisobutyronitrile are added, and the mixture is polymerized by heating at 80 ° C. for 5 hours under a nitrogen stream with stirring to 50%. A copolymer solution was obtained. To the obtained 50% copolymer solution was added 0.05 part of hydroquinone, 37 parts of acrylic acid and 0.2 part of dimethylbenzylamine, and the mixture was added to 100 parts. An addition reaction was performed at C for 24 hours. Subsequently, 45 parts of tetrahydrophthalic anhydride and 79 parts of carboxylate were added and reacted at 100 ° C for 3 hours to obtain a 50% solution (A-1-1) of an ultraviolet curable resin. .

Synthesis of CA-1-2)

EHPE 3150 (Saikan Epoxy resin, Daisenore Chemical Industry Co., Ltd., Epoki 1 equivalent of 1-9, no halogen (halogen was not detected) 1) 79 parts were dissolved in 60 parts of carbitol acetate, and with stirring, 74 parts of atalinoleic acid, 0.1 part of hydroquinone and dimethyl 0.7 parts of benzylamine was added, and the mixture was reacted at 90 to 100 ° C. for 24 hours by a conventional method. 95 parts of carbitol acetate was added to the reaction solution, and the mixture was stirred to obtain an epoxy acrylate solution. Subsequently, 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-1-2). Was obtained.

[Synthesis of A-1-3]

In place of the GS used in the synthesis of (A-1-1) above, acrylic ester G (manufactured by Yoryo Rayon Co., Ltd., containing halogen as an impurity obtained using epichlorohydrin) Except that 70 parts of glycidyl methacrylate and a halogen content of 1600 ppm were used, a 50% solution of an ultraviolet-curable resin was prepared in the same manner as in the synthesis of (A-11). A-1-3) was obtained.

[Synthesis of A—1_4]

In place of EHPE 315 used in the synthesis of (A-1-2), Epiclone N-680 (Cresol novolak type epoxy resin manufactured by Dainippon Ink & Chemicals, Inc., epoxy equivalent 2 14 and halogen content of 1 050 parts per million), and the amount of carbitol acetate mixed with the addition of acid anhydride was changed to 78 parts. Except for the above, a 60% solution (A-1-4) of an ultraviolet curable resin was obtained in the same manner as in the synthesis of (A-1-2). Further, EHPE 315 shown in Table 1 is an epoxy resin manufactured by Daiceli Dagaku Kogyo Co., Ltd., and Epiclone N-680 is Crezo manufactured by Dainippon Ink and Chemicals, Inc. It is a lunovolak type epoxy resin. TEP IC-S is a triglycidyl isocyanurate (having a halogen content of 800 ppm) manufactured by Nissan Chemical Industries, Ltd., and both are polyfunctional epoxy compounds. The polyfunctional epoxy compound solution (E-1) was prepared as follows.

[Synthesis of E-1]

Four Rofrasco equipped with a reflux condenser, thermometer, glass tube for purging nitrogen and a stirrer, 80 parts of Bremma GS (manufactured by NOF CORPORATION, glycidyl methacrylate with reduced chlorine), butyl acrylate 20 Parts, 67 parts of carbitol acetate and 3 parts of azobisisobutyronitrile were added and polymerized at 85 ° C for 5 hours under a nitrogen stream with stirring to obtain a 60% solution of the polyfunctional epoxy compound. Was. Next, as a component (C) of the present invention, as a copper phthalocyanine pigment having at least one halogen atom in the structural formula and having a halogen content of 25% or less in the molecular weight, Used was Cyanine Blue 5025 (a copper phthalocyanine pigment CI 15: 1 having only one chlorine as a halogen in the chemical structural formula manufactured by Dainichi Seika Kogyo Co., Ltd.). As the L and yellow pigment containing no halogen in the chemical structural formula, Chromophtaleilro-1 RF (I. Pigment Yellow 139 manufactured by Ciba Specialty Chemicals Co., Ltd.) was used. A yellow pigment having at least one halogen atom in the chemical structural formula and having a halogen content of 25% or less in the molecular weight includes Seika Firth Toyero-1 10GH (Dainichi Seika Kogyo Co., Ltd. Pigment Toy Company Erotic 1) was used. As the L and orange pigment containing no halogen in the chemical structural formula, Seika First Orange 3064 (CI Pigment Orange 5 manufactured by Dainichi Seika Kogyo Co., Ltd.) was used. Orange pigments having at least one halogen atom in the structural formula and having a halogen content of 25% or less in the molecular weight include Seika First Orange 900 (Dainichi Seika Kogyo Co., Ltd.) I. Pigment Range 13) manufactured by Co., Ltd. was used. As the blue pigment containing no halogen in the chemical structural formula in the present invention, Chromo Fineble I 5008 (CI Pigment Blue 15: (Phthalocyanine blue manufactured by Dainichi Seika Kogyo Co., Ltd.)) was used. As the green pigment contained, 2GN (CI Pigment Green 7: Phthalocyanine Green manufactured by Dainichi Seika Kogyo Co., Ltd.) was used as a photopolymerization initiator, Irgacure-1907 (Ciba-Geigy-1) and Kacura DETX-S (manufactured by Nippon Kayaku Co., Ltd.) was used, and Modaf Kuchiichi (manufactured by Monsanto) was used as a leveling agent, and silica with an average particle size of 1 / m was used. The components thus prepared were uniformly mixed at the mixing ratios shown in Table 1 and thoroughly mixed with a three-roll roll manufactured by Inoue Manufacturing Co., Ltd. Solder - resist ink I-. 1 to I one 11 and Comparative Examples photo solder one resist ink Samples 12 to 14 were prepared. The photo solder resist ink I-11-1-1-1 and I1-12-1-11 obtained as described above were coated with a copper-clad layer composed of a glass epoxy base material having a copper foil of 35 m. It is applied by screen printing to the entire surface of the printed wiring board on which a pattern has been formed by etching the board in advance, and pre-dried at 80 ° C for 20 minutes to evaporate the solvent and evaporate the solvent. An im dried coating film was obtained. Then, There are directly applied to the coating surface a mask the patterned, 1 5 O mJ / cm ² of ultraviolet rays were irradiated, then 1% carbonate sodium © anhydrous solution to form a pattern by developing as a developer Then, heat hardening was performed at 150 at 60 minutes to prepare test pieces I-1 to I-11 according to the present invention and test pieces I112 to I-14 that are out of the scope of the present invention. Example 2

(II) Ultraviolet hard solder type solder resist ink

In order to prepare an ultraviolet-curable solder resist ink as an example, first, the following epoxy acrylates (A-3-1) to (A-3-6) were prepared. Epoxy acrylate (A-3-1)

This was prepared by an esterification reaction between Epikote 154 (phenol novolac type epoxy resin manufactured by Yuka Shell Epoxy Co., Ltd.) and acrylic acid. This is a total esterification of epoxy groups. Epoxy acrylate (A-3-2)

This was prepared by an esterification reaction between Epicort 8288 (bisphenol A type epoxy resin manufactured by Yuka Shell Epoxy Co., Ltd.) and acrylic acid. This is the total esterification of the epoxy group. Epoxy acrylate (A-3-3)

This was prepared by an esterification reaction of EPP N-201 (a phenol novolak type epoxy resin manufactured by Nippon Kayaku Co., Ltd.) with acrylic acid. This is the all esterified epoxy group. Epoxy acrylate (A-3-4)

This was prepared by an esterification reaction between Epiclone N-695 (cresol novolak type epoxy resin manufactured by Dainippon Ink and Chemicals, Inc.) and acrylic acid. This is an all-esterified product of an epoxy group. Epoxy acrylate (A-3-5)

This was prepared by an esterification reaction between Epicort 152 (a phenolic novolak type epoxy resin manufactured by Yuka Shell Epoxy Co., Ltd.) and acrylic acid. This is a total esterification of epoxy groups. Epoxy acrylate (A-3-6)

This was prepared by an esterification reaction of Epiclone N-680 (Taresol novolak type epoxy resin manufactured by Dainippon Ink and Chemicals, Inc.) with acrylic acid. This is an all-esterol of the epoxy group. .

Light ester PA manufactured by Kyoeisha Chemical Co., Ltd. was used for 2-acryloyloxetyl acid phosphate. Light ester PM manufactured by Kyoeisha Chemical Co., Ltd. was used as 2-methacryloyloxyshethyl acid phosphate. In addition, orange pigments and blue pigments that do not contain a halogen in the chemical structural formula are described in Examples. The same pigment as 1 was used. In addition, the same green pigment as that used in Example 1 was used as a conventional green organic coloring pigment used as a comparative example. The components thus prepared were uniformly mixed at the compounding ratios shown in Table 2 and thoroughly kneaded with a three-roll roll manufactured by Inoue Seisakusho Co., Ltd. to cure the ultraviolet-curable solder resist according to the present invention. Ink II—1 to: [I-11 and UV-curable solder resist inks of Comparative Examples II—12 to: CI—14 were prepared. Next, the ultraviolet-curable solder resist ink thus obtained was printed and applied on a printed wiring board having a pattern formed by a screen printing method using a 225 mesh stirrer, respectively. After that, a metal halide lamp (or high-pressure mercury lamp) of 12 OW / cm (or 80 W / cm) is used to irradiate the light by irradiating the light with a light intensity of 100 mJ / cm ^2. According to the present invention, test pieces II-1 to Π-7 and test pieces out of the scope of the present invention II-11 to: [I-12] were obtained. For the test pieces prepared from (I) photo solder resist ink and (II) UV-curable solder resist ink obtained in each of the examples and comparative examples, a lead brush hardness test, a grid adhesion test, a solder A heat resistance test, a solvent resistance test, a chemical resistance test, an insulation resistance test, and a property evaluation test regarding halogen content were performed. The results obtained are shown in Tables 1 and 2.

In addition, the method of these characteristic evaluation tests is as follows. Pencil hardness test: Conducted according to JISK-540, 8.4. Using a pencil (Mitsubishi Uji), the highest hardness without scratching was measured. Cross-cut adhesion test: Performed according to JISK-5400, 8.5. The cured films were cut vertically and horizontally one by one using an Ericssen cross-cut tester, and a cellophane-peeling test was performed. The remaining number in the 100 grid was counted. Solder heat resistance test: Performed according to JISC-6468, 5.5. Using LONCO CF-350 (water-soluble flux from London Chemical) as a flux, first apply a flux to the test piece, and then immerse it in a molten solder bath at 260 ° C for 10 seconds. Then, immediately thereafter, it was poured into cooling water. By observing the substrate surface immediately after this test, the presence or absence of blisters or peeling was confirmed. Solvent resistance test: Immerse in 2-propanol and 1,1,1-trichloroethane for 1 hour at room temperature, observe the substrate surface and check for blisters or peeling.

¾, then. Chemical resistance test: After immersing the substrate in 10 wt% hydrochloric acid and 10 wt% sodium hydroxide aqueous solution at room temperature for 1 hour, observe the substrate surface to check for blisters or peeling did. Insulation resistance test: The resistance between the opposing electrodes of the IPC-B-25 comb pattern having the cured coating film of the present invention was measured. For the halogen content, in the case of the photo solder resist ink of Example 1, 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. The content of chlorine, bromine and fluorine in the absorbing solution which absorbed the gas generated by burning in the flask was quantified by ion chromatography analysis. On the other hand, in the case of the UV-hardened solder resist ink of Example 2, the ink before curing and the cured coating film were weighed as samples, and the halogen content was measured in the same manner as in Example 1 above. Was quantified.

Ratio ¾Example Sample 畨 Ag 1-4

UV curable resin solution -υ 50

UV curable resin solution

Polyfunctional epoxy compound solution (e-epiclone

Sian Nimble

Chromophthaleuello

Seika First Yellow

Seika First Orange

Chromo Fine Bull I

(Phthalocyanine "lean"

Irgacure 1F 4

Kyakuya I

Carbitol acetate

Modaf Mouth One (Levelinge agent)

Silica

Barium sulfate

Melamine

Diventa erythritol hexaacrylate

Color 靑 Blue 綠綠綠綠綠綠靑 Pencil hardness

Crosscut adhesion test (pcs)

Resistance to soldering blisters or peeling No No 轭 No No No No No No No No No No No No No (Yes / No)

Degree of discoloration of cured film 〇〇〇 0 〇〇 0 0 〇〇 0 Solvent resistance (Yes / No) No No No No No No No No No No No No No No No Chemical resistance (Yes No) No No No No No No No No No No No No No No No

/, Ink ingredients excluding organic solvents including logene

Medium 90

Yes

Cured coating

According to the results shown in Table 1, the coating formed from the photo solder resist ink and the ultraviolet-curable solder resist of the present invention shows that the conventional photo solder resist ink and the ultraviolet-curable solder resist that 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.

Further, the coating film formed from the photo-photoresist ink and the UV-hardened solder resist according to the present invention has an extremely lower halogen content than the film formed from the conventional ink. . Therefore, the amount of halogen gas generated during the burning of this coating film is considered to be significantly lower than before. Further, the coloring pigment used in the present invention had good dispersibility, so that it could be easily prepared by mixing and mixing the respective components. In particular, in Tables 1 and 2, in Examples I-2, 1-3. II-2 and II-13, and Comparative Examples 1-12 and II-11, the permanent coating was colored blue. Only blue pigments are used as color pigments.

However, in Examples I-12, I-13, II-2 and II-3, the coloring pigment used (C) (a copper phthalocyanine cyanine pigment having at least one halogen atom in the chemical structural formula) Comparative Examples in which 1.2 parts of a blue coloring pigment having no halogen atom in the chemical structural formula was blended despite the low content of 0.8 part and 0.6 part — It had a blue color as good as the case of 12. Also, in the case of giving a green color by combining color pigments, in Examples I-14-1-1-1 and II-14-II-11 of the present application, the total amount of the color pigments was 0.8 parts. Despite the small amount, Comparative Example I, which used only 1.0 part of a combination of no-no-colorogen coloring pigment, exhibited a green color equivalent to that of I-13 and II-13.

Claims

Scope of word blue

1. (A) UV curable component,

(B) a photopolymerization initiator, and

(C) A solder resist ink comprising a copper phthalocyanine pigment having at least one halogen atom in the chemical structural formula and having a halogen content of 25% or less in the molecular weight.

2. The component (A) according to claim 1, wherein the component (A-1) comprises an ultraviolet-curable resin having an ethylenically unsaturated group and a carboxyl group in a side chain. Solder resist ink.

3. The solder resist ink according to claim 2, wherein the component (A) further contains (A-4) an ethylenically unsaturated monomer.

4. The solder resist ink according to claim 2, comprising (D) an organic solvent.

5. The solder resist ink according to any one of claims 2 to 4, wherein the solder resist ink contains (E) a polyfunctional epoxy compound.

6. The solder resist ink according to any one of claims 2 to 5, wherein a halogen content in a cured product of the solder resist ink is 500 ppm or less. .

7. The (A-1) ultraviolet ray dangling property measurement and the (E) polyfunctional epoxy compound It is prepared from a halogen-free epoxy compound synthesized by a peracid method, or an epoxy compound subjected to a treatment for reducing halogen, and the halogen content in the cured product of the solder resist ink is reduced. The solder resist ink according to any one of claims 2 to 6, wherein the content of the solder resist is 150 ppm or less. The solder resist ink according to any one of claims 1 to 7, further comprising a second coloring pigment having a halogen content of 25% or less in the molecular weight. The component (A) is (A-3) an epoxy (meth) acrylate and / or a polyether of polyhydric phenol and an esterified product of (meth) acrylic acid, and a component other than the component (A-3). (A-4) The solder resist ink according to claim 1, wherein the solder resist ink comprises an ethylenically unsaturated compound. 10. The solder resist ink according to claim 9, wherein the content of hagage in the cured product of the solder resist ink is 500 ppm or less. 1. The above (A-3) is prepared from a halogen-free epoxy compound synthesized by a peracid method, or a epoxy compound that has been subjected to a treatment for reducing rhogens, The solder resist ink according to claim 9 or 10, wherein the content of hagage in the cured product of the solder resist ink is 150 ppm or less. 2. The solder resist ink according to claim 9, which comprises a second coloring pigment having a halogen content of 25% or less in the molecular weight.

13. A printed wiring board comprising the solder-resist ink hardened product according to any one of claims 1 to 12.