CN101403856B - Composition, dry film, curing article and printed circuit board - Google Patents

Abstract

The invention provides a composition, dry film, condensate and printed circuit board. The present invention provides a composition, specifically to a resist composition, which can realize compromise of both surface solidifying performance and solidifying depth. The composition is characterized in that when the dry coated film has a thickness of 25 [mu]m before exposure, the absorbency L400 of a 400nm laser wavelength is 0.5-1.2, the absorbency L400 of a 410nm laser wavelength is 0.01-0.5, and L400> L410.

Description

Composition, dry film, solidfied material and printed-wiring board (PWB)

Technical field

The dry film, solidfied material and the printed-wiring board (PWB) that the present invention relates to be suitable for the composition of resist and be suitable for said composition, wherein, this resist be used for by laser oscillation wavelength be the laser generation light source of 400～410nm carry out direct pattern plotter, by the diluted alkaline aqueous solution develop, with the operation of formed pattern photocuring and heat curing.

Background technology

In recent years, as resource-saving or economize the photolithography of the such consideration environment of energy, directly the describe mode (laser direct imaging) of laser as light source is practical.The speciality of this method is essential mask pattern, can shorten manufacturing process and significantly reduces cost, and is suitable for multi-varieties and small-batch, lacks delivery period.

Directly drawing apparatus is because whole exposure simultaneously of exposure portion that can't existing mask pattern exposure is such, thereby in order to obtain being necessary to select with equal time shutter of existing mask pattern exposure the resist and the high-power light source of ISO.And then, the existing mask pattern employed light source that exposes is the wide light source to 300～500nm of metal halide lamp equiwavelength, with respect to this, the light source of direct drawing apparatus and the most using gases laser of wavelength, laser diode, Solid State Laser etc., wavelength is 355nm, 405nm, 488nm.

Wherein, recently, use the direct drawing apparatus of the 405nm of laser diode to be attracted attention, as the laser generation light source of this oscillation wavelength, well-known bluish-violet laser diode.But bluish-violet laser diode does not then have sufficient power as the exposure light source that is used for direct pattern plotter separately.For this reason, Shi Ji laser direct imaging apparatus bundlees several laser diodes of dozens of to hundred and makes light source.The light of each laser diode vibration single wavelength, but this wavelength is had nothing in common with each other from 400nm to 410nm.Therefore, the laser that sends from the direct drawing apparatus that uses bluish-violet laser diode has distribution in the scope of 400nm～410nm.

Therefore, for example, even if regulate the resist composition absorbance so that its be suitable for centre wavelength, be 405nm, also can't take into account the surface cure and the curing depth of expectation, must more exposure in order to take into account.Even if this adjusts too according to the mode that is suitable for 400nm, 410nm.

On the other hand, the resist as corresponding to the laser direct imaging apparatus of 400nm～410nm has patent documentation 1: TOHKEMY 2007-78893 communique.The technical scheme of putting down in writing in this communique is for having proposed a kind of photosensitive composite, it is characterized in that, smaller to form stable epithelium for the light sensitivity difference that makes each wavelength in the scope of 400～410nm, containing more than 2 kinds greatly, absorbing wavelength is the sensitizer of 340～500nm.Show in this invention: have the maximum value of beam split light sensitivity in the wavelength region may of 380～420nm, and the minimum exposure amount S of the formed pattern in the zone of 400～410nm is 210mJ/cm ²Below, and the maximal value Smax of the minimum exposure amount in should the zone and the minimum value Smin of minimum exposure amount satisfy following formula: Smax/Smin≤1.2 can make light sensitivity adapt by this method.

But, the resolution of resist (pattern form of resist), particularly as the such Film Thickness Ratio of solder resist thicker in the situation of colour system resist, owing to also exist the absorption region of toner, thereby the shape that Different Light may not be certain the line of each wavelength because light sensitivity is identical is certain, not talkative being resolved on the problem of resolution.

In addition, patent documentation 2: TOHKEMY 2007-102184 communique discloses a kind of photosensitive polymer combination, it is characterized in that, the absorbance of the light of 365nm and 405nm is respectively more than 0.1 in the scope below 0.9.In the technical scheme of putting down in writing in this communique, obtained the resolution preferable image when using the light source of 365nm and 405nm respectively, the light source that the present invention becomes problem has the situation of distribution from 400nm to 410nm, if do not apply many exposures then can not get clean and tidy shape.And then as solder resist such Film Thickness Ratio thicker in the situation of colour system resist, also must consider for the painted and uptake stable on heating colorant that uses.That is, colorant has scope of the present invention, is the absorption spectrum that can not ignore among the 400-410nm that it finds expression in absorbance.At this moment, even if absorbance also nearly all is colored the absorption of agent in the scope of regulation, can not get also variation of light sensitivity, resolution this moment.

So discoveries such as the inventor according to the distribution of the scope of the 400nm～410nm of laser, by adjusting the absorbance of composition, can take into account desired surface cure and curing depth and need not more exposure, and finish the present invention.

Patent documentation 1: TOHKEMY 2007-78893 communique (claims etc.)

Patent documentation 2: TOHKEMY 2007-102184 communique (claims etc.)

Summary of the invention

The problem that invention will solve

The invention provides a kind of composition, resist composition particularly, wherein, said composition is to the laser of distribution with 400nm～410nm, design absorbance, design absorbance at long wavelength side than the lowland than the highland at short wavelength side, thereby can take into account surface cure and curing depth.

And then the objective of the invention is to, a kind of composition, particularly printed-wiring board (PWB) solder resist composition is provided, wherein, even if said composition also can make resolution good by selecting colorant to make to be the colour system resist effectively.

And then the objective of the invention is to, obtain being suitable for dry film, solidfied material and the printed-wiring board (PWB) of said composition.

The method of dealing with problems

(1) a kind of composition, it is characterized in that, it forms the back by the composition of laser explosure for dry coating, wherein, with the absorbance of wavelength 400nm be made as L400, when the absorbance of wavelength 410nm is made as L410, during the thick 25 μ m of dry coating, absorbance L400 is that 0.5-1.2, absorbance L410 are 0.01-0.5 before the exposure, and, absorbance L400〉and absorbance L410.

(2) as (1) described composition, it is the resist composition.

As (1) or (2) described composition, it is characterized in that (3) when the absorbance of wavelength 405nm was made as L405, during the thick 25 μ m of dry coating, absorbance L405 was 0.3-0.9, and absorbance L400 before the exposure〉absorbance L405〉absorbance L410.

As each described composition of (1)～(3), it is characterized in that (4) before the exposure during the thick 25 μ m of dry coating, poor (L400-L410) of absorbance L400 and absorbance L400 is in 0.1～0.5 the scope.

(5) as each described composition of (1)～(4), it contains (A) and contains carboxylic acid resin, (B) Photoepolymerizationinitiater initiater and (C) colorant.

(6) as each described composition of (1)～(5), it is characterized in that (B) Photoepolymerizationinitiater initiater is for being selected from:

Oxime ester shown in the following general formula (I) be Photoepolymerizationinitiater initiater,

Aminoacetophenone shown in the following general formula (II) be Photoepolymerizationinitiater initiater,

Acylphosphine oxide shown in the following general formula (III) be Photoepolymerizationinitiater initiater and

Luxuriant titanium shown in the following general formula (IV) is a Photoepolymerizationinitiater initiater

Photoepolymerizationinitiater initiater more than a kind in the group of being formed.

[Chemical formula 1]

(in the formula, R ¹The alkyl or phenyl of expression hydrogen atom, carbon number 1～7, R ²The alkyl or phenyl of expression carbon number 1～7.R ³, R ⁴The alkyl or aryl alkyl of expression carbon number 1～12, R ⁵, R ⁶Expression hydrogen atom, the alkyl of carbon number 1～6 or the cyclic alkyl of both be combined intos.R ⁷, R ⁸The straight chain shape of expression carbon number 1～6 or the alkyl of chain, alkoxy, cyclohexyl, cyclopentyl, aryl or the aryl that is replaced by halogen atom, alkyl or alkoxy or any are the carbonyl of carbon number 1～20.R ⁹, R ¹⁰Expression halogen atom, aryl, halogenated aryl, contain the halogenated aryl of heterocycle.)

As each described composition of (1)～(6), it is characterized in that (7) the oxime ester shown in the aforementioned formula (I) is that Photoepolymerizationinitiater initiater (B1) is a Photoepolymerizationinitiater initiater for the oxime ester shown in the following formula (V).

Chemical formula 2

As each described composition of (1)～(7), it is characterized in that (8) colorant (C) is a phthalocyanine blue.

(9) as each described composition of (1)～(8), also contain (D) sensitizer.

As (9) described composition, it is characterized in that (10) (D) sensitizer is the compound that thioxanthones is and/or has dialkyl amido benzene structure.

As (10) described composition, it is characterized in that (11) aforementioned compound with dialkyl amido benzene structure is dialkyl amido benzophenone or coumarin compound.

(12) a kind of dry film of Photosetting and thermosetting, it is applied to carrier film and dry and obtain with each described composition of (1)～(11).

(13) a kind of solidfied material, it is with each described light solidifying/heat solidifying resin composition of (1)～(11) or the described dry film of aforementioned claim 12 photocuring and obtaining on copper.

(14) a kind of solidfied material, it is that the laser photocuring of 400～410nm obtains with each described light solidifying/heat solidifying resin composition of (1)～(11) or the described dry film of aforementioned claim 12 by wavelength.

(15) a kind of printed-wiring board (PWB), it with each described light solidifying/heat solidifying resin composition of (1)～(11) or the described dry film of aforementioned claim 12 at thickness from 10 μ m to the scope that is 100 μ m to the maximum by wavelength is behind the laser photocuring of 400～410nm, heat curing obtains.

The invention effect

Composition of the present invention has a plurality of laser diodes to make the laser of the distribution with 400～410nm of exposure light source, design absorbance, design absorbance at long wavelength side than the lowland than the highland at its short wavelength side to binding, thereby can realize taking into account surface cure and curing depth.

Description of drawings

Fig. 1 represents the synoptic diagram of cross sectional shape of the resin combination of the embodiment that obtains by exposure imaging and comparative example, and A～E represents the shape of different separately evaluations (index of curing depth characteristic).

The explanation of symbol

The design load of 1a live width

Resin combination behind the 1b exposure imaging

The 1c substrate

Embodiment

At first, each composition that constitutes composition of the present invention is described.

(A) contain the carboxylic acid resin

As composition of the present invention contained contain carboxylic acid resin (A), list following cited resin.

(1) make the reaction of multi-functional epoxy compound and unsaturated monocarboxylic, the hydroxyl that generated and saturated or unsaturated multi-anhydride reacted and obtain contain the carboxylic acid resin,

(2) make hydroxyl that the reaction of hydroxyl polymer-containing such as polyol derivative and saturated or unsaturated multi-anhydride obtains and carboxylic acid resin,

(3) at least 1 alcohol hydroxyl group in multi-functional epoxy compound, unsaturated monocarboxylic, a part, with the reaction product that has with the compound reaction of 1 beyond the alcohol hydroxyl group of epoxy reaction reactive base, with saturated or unsaturated multi-anhydride reaction obtain contain the carboxylic acid resin,

(4) primary hydroxyl that has in a part in the modification oxetane resin of the reaction of the multifunctional oxetane compound of at least 2 oxetanes rings and unsaturated monocarboxylic, gained reacts the carboxylic acid resin that contains who obtains with saturated or unsaturated multi-anhydride.

But be not limited to the carboxylic acid resin that contains that these enumerate, can have polyester construction, polyether structure, polycarbonate structure, polyurethane structural.

In the middle of these, (1), (3) and (4) have had unsaturated double-bond, from the photonasty aspect and preferred.

In addition, in this instructions, so-called (methyl) acrylate is meant the term of general name acrylate, methacrylate and their potpourri, also is the same meaning about other similar terms.

Above-mentioned such carboxylic acid resin (A) that contains owing to have more free carboxyl on the side chain of main chain (backbone) polymkeric substance, therefore can develop by the diluted alkaline aqueous solution.

In addition, the above-mentioned carboxylic acid resin's of containing (A) acid number is the scope of 40～200mgKOH/g, more preferably the scope of 45～120mgKOH/g.If when containing carboxylic acid resin's acid number deficiency 40mgKOH/g, alkali develops and becomes difficult, on the other hand, if it surpasses 200mgKOH/g, then for the dissolving of the exposed portion that carries out being produced by developer solution, line is thinner than needed, and according to circumstances, exposed portion and unexposed portion indistinguishably are developed the liquid dissolving and peel off, and are difficult to describe normal corrosion-resisting pattern, and be therefore not preferred.

In addition, the above-mentioned weight-average molecular weight that contains carboxylic acid resin (A) is different because of resin matrix, and it is generally 2000～150000 scope, and 5000～100000 scope more preferably.If weight-average molecular weight less than 2000, then tack-free degradation, the moisture-proof of filming after the exposure is poor, produce film and reduce when developing, and resolution deteriorates significantly.On the other hand, if weight-average molecular weight surpasses 150000, the remarkable variation of development property then, storage-stable is poor.

This carboxylic acid resin's of containing (A) use level is preferably 20～60 quality % in all compositions, more preferably 30～50 quality %.When being less than above-mentioned scope, coating strength reduces, and is therefore not preferred.On the other hand, during more than above-mentioned scope, viscosity uprises, and reductions such as coating are therefore not preferred.

(B) Photoepolymerizationinitiater initiater

As Photoepolymerizationinitiater initiater (B), the acylphosphine oxide that the alpha-aminoacetophenone that preferred use that to be selected from the oxime ester with the group shown in the above-mentioned general formula (I) is Photoepolymerizationinitiater initiater (B1), has a group shown in the above-mentioned general formula (II) is Photoepolymerizationinitiater initiater (B2), have a group shown in the above-mentioned formula (III) is that the luxuriant titanium shown in Photoepolymerizationinitiater initiater (B3) and the above-mentioned formula (IV) is the Photoepolymerizationinitiater initiater more than a kind in the group formed of Photoepolymerizationinitiater initiater.

(B1) the oxime ester is a Photoepolymerizationinitiater initiater

As the oxime ester with the group shown in the above-mentioned general formula (I) is Photoepolymerizationinitiater initiater, except 2-(acetoxyl group iminomethyl) thioxanthene-9-one shown in the above-mentioned general formula (V), also can enumerate the compound shown in the following general formula (VI)

[chemical formula 3]

(in the formula, R ⁹The alkanoyl of the alkyl of expression hydrogen atom, halogen atom, carbon number 1～12, cyclopentyl, cyclohexyl, phenyl, benzyl, benzoyl, carbon number 2～12, the alkoxy carbonyl of carbon number 2～12 (carbon number that constitutes the alkyl of alkoxy is 2 when above, alkyl optional by the hydroxyl more than 1 replace, the alkyl middle-of-chain chooses the oxygen atom that has more than 1 wantonly) or phenyloxycarbonyl,

R ¹⁰, R ¹²The alkyl of independent separately expression phenyl (optional replaced), carbon number 1～20 by the alkyl of carbon number 1～6, phenyl or halogen atom (optional by the hydroxyl more than 1 replace, the optional oxygen atom that has more than 1 of alkyl middle-of-chain), the alkanoyl of the naphthenic base of carbon number 5～8, carbon number 2～20 or benzoyl (optional is that 1～6 alkyl or phenyl replaces by carbon number),

R ¹¹The alkyl of expression hydrogen atom, phenyl (optional replaced), carbon number 1～20 by the alkyl of carbon number 1～6, phenyl or halogen atom (optional by the hydroxyl more than 1 replace, the optional oxygen atom that has more than 1 of alkyl middle-of-chain), the alkanoyl of the naphthenic base of carbon number 5～8, carbon number 2～20 or benzoyl (optional is that 1～6 alkyl or phenyl replaces by carbon number)), the compound shown in the following general formula (VII)

Chemical formula 4

(in the formula, R ¹³And R ¹⁴The alkyl of independent separately expression carbon number 1～12, R ¹⁵, R ¹⁶, R ¹⁷, R ¹⁸And R ¹⁹The alkyl of independent separately expression hydrogen atom or carbon number 1～6, M represent S, O ,-NH, and n and m represent 0～5 integer).

2-shown in the preferred especially above-mentioned general formula (V) (acetoxyl group iminomethyl) thioxanthene-9-one and the more preferably compound shown in the formula (VI) in the middle of these compounds.As commercially available product, can enumerate CGI-325, Irgacure OXE01 that Xiba Special Chemical Product Co.,Ltd makes, Irgacure OXE02 etc.These oxime esters are that Photoepolymerizationinitiater initiater can use more than 2 kinds alone or in combination.

(B2) aminoacetophenone is a Photoepolymerizationinitiater initiater

As alpha-aminoacetophenone is Photoepolymerizationinitiater initiater, 2-methyl isophthalic acid-[4-(methyl sulphur) phenyl]-2-morpholino acetone-1,2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butane-1-ketone, 2-(dimethylamino)-2-[(4-aminomethyl phenyl) methyl]-1-[4-(4-morpholinyl) phenyl]-1-butanone, N, N-dimethylamino benzoylformaldoxime etc.As commercially available product, Irgacure907, the Irgacure369 that Xiba Special Chemical Product Co.,Ltd makes, Irgacure379 etc.

(B3) acylphosphine oxide is a Photoepolymerizationinitiater initiater

As acylphosphine oxide is Photoepolymerizationinitiater initiater, can enumerate 2,4; 6-trimethylbenzoyl diphenyl phosphine oxide, two (2,4, the 6-trimethylbenzoyl)-phenyl phosphine oxide, two (2; 6-dimethoxy benzoyl)-2,4,4-trimethyl-amyl group phosphine oxide etc.As commercially available product, can enumerate LUCIRIN TPO, the LUCIRIN TPO-L of BASF AG's manufacturing, the Irgacure819 that Xiba Special Chemical Product Co.,Ltd makes etc.

(B4) luxuriant titanium is a Photoepolymerizationinitiater initiater

As the luxuriant titanium shown in the aforementioned formula (VI) is Photoepolymerizationinitiater initiater, can enumerate two (η 5-cyclopentadiene)-two (2,6-two fluoro-3-(1H-pyrroles-1-yl) phenyl) titanium.As commercially available product, can enumerate the Irgacure784 of Xiba Special Chemical Product Co.,Ltd's manufacturing etc.

(cooperation of Photoepolymerizationinitiater initiater)

The use level of such Photoepolymerizationinitiater initiater (B) is the scope that can be selected from 0.01～30 mass parts, be preferably 0.5～15 mass parts with respect to the aforementioned carboxylic acid resin of containing (A) 100 mass parts.During less than 0.01 mass parts, the photo-curable deficiency on the copper is filmed and is peeled off, or coating characteristic such as chemical proofing reduces, so not preferred.On the other hand, when surpassing 30 mass parts, it is fierce that the light absorption of the solder resist film coated surface of Photoepolymerizationinitiater initiater (B) becomes, and so the tendency that has the deep curable to reduce is not preferred.

In addition, at the oxime ester with the group shown in the aforementioned formula (I) is in the situation of Photoepolymerizationinitiater initiater, and its use level is preferably 0.01～20 mass parts, the scope of 0.01～5 mass parts more preferably of being selected from respect to the aforementioned carboxylic acid resin of containing (A) 100 mass parts expectations.

(C) colorant

(kind of colorant)

The colorant of one of feature of the present invention (C) is the colorant that uses as painted purpose usually, when finding to use the laser of 400～410nm of the present invention, the colorant that adds blue pigment (for example, phthalocyanine blue) can obtain reflecting feel luminosity with lower exposure.

This blue pigment (for example, indeterminate on the reason of the sensitization effect phthalocyanine blue series pigments), but as can be known for example in scope of the present invention, promptly be that to add phthalocyanine blue and make absorbance in the resin combination below 0.5 be can hang down exposure more than 0.5 to obtain sufficient surface cure during the absorbance of 25 μ m.In addition, this sensitization effect has effect on the reactivity (improving gloss) on surface, and curing depth is variation on the contrary.That is, play the such effect of reflector laser.This effect also stabilization to the shape of resist is effective.

For example, when observing the cross sectional shape of resist, do not contain phthalocyanine blue, absorbance is lower than at 0.5 o'clock, the cross sectional shape of resist is that the bottom is big, the shape of broad, in addition, the also lusterless situation of film coated surface portion is arranged.In addition, do not containing phthalocyanine blue, absorbance, the situation that has the big broad of skin section, bottom to attenuate greater than 0.5 o'clock.But, when discovery contains blue pigment (C ') at the proper range of absorbance of the present invention, the resist thickness is in the scope of 10～100 μ m, obtained having size and LASER Light Source irradiation size bottom much at one the resist shape and obtained surface gloss.

The suitable addition of such colorant (C) then can add arbitrarily as long as the absorbance of the wavelength of the 400nm of dry coating is 0.5～1.2 scope when being 25 μ m.

As such blue pigment (C '), can enumerate phthalocyanine blue series pigments such as α type copper phthalocyanine indigo plant, α type monochloro copper phthalocyanine blue, beta-type copper phthalocyanine indigo plant, ε type copper phthalocyanine indigo plant, cobalt phthalocyanine blue, metal-free phthalocyanine blue, inorganic pigment such as dark blue, preferred especially phthalocyanine blue series pigments.

In addition, can be as follows with the colorant that does not exceed scope interpolation of the present invention.

Blue colorant

Blue colorant is except above-mentioned phthalocyanine is, can enumerate anthraquinone system, the compound that is categorized as pigment (Pigment) can be enumerated by pigment system, the material that the concrete color index (distribution of C.I.:TheSociety of Dyers and Colourists company) for having as following is numbered.

Pigment blue 15, pigment blue 15: 1, pigment blue 15: 2, pigment blue 15: 3, pigment blue 15: 4, pigment blue 15: 6, pigment blue 16, pigment blue 60,

As dyestuff system, can use

Solvent blue 35, solvent blue 63, solvent blue 68, solvent blue 70, solvent blue 83, solvent blue 87, solvent blue 94, solvent blue 97, solvent blue 19 22, solvent blue 19 36, solvent blue 67, solvent blue 70 etc.

Except above-mentioned, also can use metal to replace or do not have the phthalocyanine compound of metal replacement.

Green colourant

As green colourant phthalocyanine system, anthraquinone system are arranged equally, can use specifically that pigment Green 7, pigment green 36, solvent green 3, solvent are green 5, solvent is green 20, solvent green 28 etc.

Except that above-mentioned, can use metal to replace or do not have the phthalocyanine compound of metal replacement.

Yellow colorants

As yellow colorants, monoazo system, bisdiazo system, condensation azo system, benzimidazolone system, isoindolinone system, anthraquinone system etc. are arranged, specifically can enumerate following material.

(anthraquinone system)

Solvent yellow 16 3, pigment yellow 24, pigment yellow 108, pigment yellow 193, pigment yellow 147, pigment yellow 199, pigment yellow 202

(isoindolinone system)

Pigment yellow 110, pigment yellow 109, pigment yellow 13 9, pigment yellow 17 9, pigment yellow 185

(condensation azo system)

Pigment yellow 93, pigment yellow 94, pigment yellow 95, pigment Yellow 12 8, pigment yellow 155, pigment yellow 166, pigment yellow 180

(benzimidazolone)

Pigment Yellow 12 0, pigment yellow 151, pigment yellow 154, pigment yellow 156, pigment yellow 17 5, pigment yellow 181

(monoazo)

Pigment yellow 1,2,3,4,5,6,9,10,12,61,62,62:1,65,73,74,75,97,100,104,105,111,116,167,168,169,182,183,

(bisdiazo)

Pigment Yellow 12,13,14,16,17,55,63,81,83,87,126,127,152,170,172,174,176,188,198

Red stain

As red stain, monoazo system, bisdiazo system, azo lake system, benzimidazolone Xi, perylene system, pyrrolopyrrole diketone system, condensation azo system, anthraquinone system, quinacridone etc. are arranged, specifically can enumerate following material.

(monoazo system)

Paratonere 1,2,3,4,5,6,8,9,12,14,15,16,17,21,22,23,31,32,112,114,146,147,151,170,184,187,188,193,210,245,253,258,266,267,268,269,

(bisdiazo system)

Pigment red 37,38,41

(monoazo color lake)

Pigment red 4 8:1,48:2,48:3,48:4,49:1,49:2,50:1,52:1,52:2,53:1,53:2,57:1,58:4,63:1,63:2,64:1,68

(benzimidazolone)

Paratonere 171, paratonere 175, paratonere 176, paratonere 185, paratonere 208

The (perylene)

Solvent of red 135, solvent red 179, pigment red 123, pigment red 149, paratonere 166, paratonere 178, paratonere 179, paratonere 190, paratonere 194, paratonere 224

(pyrrolopyrrole diketone system)

Paratonere 254, paratonere 255, paratonere 264, paratonere 270, paratonere 272

(condensation azo)

Paratonere 220, paratonere 144, paratonere 166, pigment red 21 4, paratonere 220, paratonere 221, paratonere 242

(anthraquinone system)

Paratonere 168, paratonere 177, pigment red 21 6, solvent red 149, solvent red 150, solvent red 52, solvent red 207

(quinacridone)

Pigment red 122, paratonere 202, paratonere 206, Pigment Red 207, paratonere 209

In order to adjust other tones, can add purple, orange, colorant such as dark brown, black.

Concrete example is shown with pigment violet 19,23,29,32,36,38,42, solvent violet 13,36

C.I. pigment orange 1, C.I. pigment orange 5, C.I. pigment orange 13, C.I. pigment orange 14, C.I. pigment orange 16, C.I. pigment orange 17, C.I. pigment orange 24, C.I. pigment orange 34, C.I. pigment orange 36, C.I. pigment orange 38, C.I. pigment orange 40, C.I. pigment orange 43, C.I. pigment orange 46, C.I. pigment orange 49, C.I. pigment orange 51, C.I. pigment orange 61, C.I. pigment orange 63, C.I. pigment orange 64, C.I. pigment orange 71, C.I. pigment orange 73, C.I. bistre 23, C.I. bistre 25; C.I. pigment black 1, C.I. pigment black 7 etc.

(cooperation of colorant)

The cooperation ratio of colorant is 0.010～5 mass parts with respect to containing carboxylic acid resin (A) 100 mass parts, be preferably 0.1～3 mass parts, be preferably 0.5～2 mass parts especially.

(D) sensitizer

As the sensitizer that uses among the present invention, be preferably thioxanthones compound and tertiary amine compound.The object lesson of enumerating (D1) thioxanthones and be the thioxanthones compound is for example: 2, and 4-dimethyl thioxanthones, 2,4-diethyl thioxanthone, 2-clopenthixal ketone, 2,4-diisopropyl thioxanthones.

(D2) has the compound of dialkyl amido benzene structure

(dialkyl amido benzo phenol/coumarin compound etc.)

As compound with dialkyl amido benzene structure, for example, 4,4 '-dimethylamino benzophenone (the NISSO CURE MABP that Japanese Cao Da company makes), 4,4 '-diethylamino benzophenone dialkyl amido benzophenone such as (EAB that hodogaya chemical company makes), 7-(diethylamino)-4-methyl-2H-1-chromen-2-one (7-(diethylamino)-4-methylcoumarin) etc. contains the coumarin compound of dialkyl amido, 4-dimethylamino ethyl benzoate (the KAYACURE EPA that Japanese chemical drug corporate system is made), 2-dimethylamino ethyl benzoate (the Quantacure DMB that InternationalBiosynthetic Inc. makes), 4-dimethylamino benzoic acid (n-butoxy) ethyl ester (the Quantacure BEA that International Biosynthetic Inc. makes), to dimethylamino benzoic acid isopentyl ethyl ester (the KAYACURE DMBI that Japanese chemical drug corporate system is made), 4-dimethylamino benzoic acid 2-Octyl Nitrite (Esolol507 that VanDyk company makes), 4,4 '-diethylamino benzophenone (EAB that hodogaya chemical company makes).

In the middle of above-mentioned,, preferably in composition of the present invention, contain the thioxanthones compound from curable aspect, deep, wherein, preferred 2,4-dimethyl thioxanthones, 2,4-diethyl thioxanthone, 2-clopenthixal ketone, 2, thioxanthones compounds such as 4-diisopropyl thioxanthones.

As the use level of such thioxanthones compound,, be preferably following, the following ratio of 10 mass parts more preferably of 20 mass parts with respect to above-mentioned carboxylic acid resin (A) 100 mass parts that contain.When the use level of thioxanthones compound was too much, the thick film curable reduced, and the cost of product rises thereupon, so not preferred.

As tertiary amine compound, preferably have the compound of dialkyl amido benzene structure, wherein, preferred especially dialkyl amido benzophenone cpd, maximum absorption wavelength are at the coumarin compound that contains dialkyl amido of 350～410nm.As the dialkyl amido benzophenone cpd, 4,4 '-diethylamino benzophenone is low preferred because of toxicity.Maximum absorption wavelength at the coumarin compound that contains dialkyl amido of 350～410nm since maximum absorption wavelength in the ultraviolet range, thereby can provide painted less, water white photosensitive composite, this is certain, and uses coloring pigment that the painted solder resist film of reflection coloring pigment self color can be provided.Particularly because 7-(diethylamino)-4-methyl-2H-1-chromen-2-one because to the sensitization effect of the laser display excellence of wavelength 400～410nm and preferred.

As the use level of such tertiary amine compound,, be preferably 0.1～20 mass parts, the ratio of 0.1～10 mass parts more preferably with respect to above-mentioned carboxylic acid resin (A) 100 mass parts that contain.The use level of tertiary amine compound is 0.1 mass parts when following, and the tendency that can't obtain sufficient sensitization effect is arranged.When surpassing 20 mass parts, tertiary amine compound makes the light absorption on the surface that dry solder resist is filmed become fierce, the tendency that has the deep curable to reduce.

These Photoepolymerizationinitiater initiaters, light-initiated auxiliary agent and sensitizer can use separately or as the potpourri more than 2 kinds.

(E) other Photoepolymerizationinitiater initiater, light-initiated auxiliary agent, sensitizer

As removing this can be fit to use in composition of the present invention Photoepolymerizationinitiater initiater, light-initiated auxiliary agent and sensitizer, can enumerate benzoin compound, acetophenone compound, anthraquinone compounds, ketal compound, benzophenone cpd, xanthone compound and tertiary amine compound etc.

Enumerating the object lesson of benzoin compound, for example is benzoin, benzoin methyl ether, benzoin ethylether, benzoin isopropyl ether.

Enumerating the object lesson of acetophenone compound, for example is acetophenone, 2,2-dimethoxy-2-phenyl acetophenone, 2,2-diethoxy-2-phenyl acetophenone, 1,1-dichloroacetophenone.

Enumerating the object lesson of anthraquinone compounds, for example is 2-methylanthraquinone, 2-EAQ, 2-tert-butyl group anthraquinone, 1-chloroanthraquinone.

Enumerating the object lesson of ketal compound, for example is acetophenone dimethyl ketal, benzil dimethyl ketal.

Enumerating the object lesson of benzophenone cpd, for example is benzophenone, 4-benzoyl diphenylsulfide, 4-benzoyl-4 '-dimethyl diphenyl sulfide, 4-benzoyl-4 '-ethyl diphenylsulfide, 4-benzoyl-4 '-propyl group diphenylsulfide.

These Photoepolymerizationinitiater initiaters, light-initiated auxiliary agent and sensitizer can use separately or as the potpourri more than 2 kinds.

The total amount of such Photoepolymerizationinitiater initiater, light-initiated auxiliary agent and sensitizer contains resin (A) 100 mass parts with respect to aforementioned carboxylic acid and is preferably the following scope of 35 mass parts.When surpassing 35 mass parts, the tendency because of these light absorption deep curable reduction is arranged.

(compound that has the olefinic unsaturated group more than 2 in the molecule)

Composition of the present invention can comprise the compound of the olefinic unsaturated group that has in the molecule more than 2.Photocuring makes the aforementioned carboxylic acid resin (A) that contains who contains the olefinic unsaturated group be insoluble to alkaline aqueous solution or help to make it to be insoluble to alkaline aqueous solution to this compound by the active energy beam irradiation.As this compound, can enumerate the diacrylate class of glycol such as ethylene glycol, methoxyl TEG, polyglycol, propylene glycol; The multicomponent methacrylate class of polyvalent alcohols such as hexanediol, trimethylolpropane, pentaerythrite, dipentaerythritol, tris(2-hydroxy ethyl)isocyanurate or their ethylene oxide adduct or propylene oxide adduct etc.; The multicomponent methacrylate class of the ethylene oxide adduct of acrylic acid benzene oxygen ester, bisphenol a diacrylate and these phenol or propylene oxide adduct etc.; The multicomponent methacrylate class of glycidol ethers such as glycerine diglycidyl ether, glycerine triglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, triglycidyl group isocyanuric acid ester; And melamine acrylate and/or corresponding to each methyl acrylic ester of aforesaid propylene acid esters etc.

Further, can enumerate polyfunctional epoxy resins such as making acrylic acid and cresols phenolic resin varnish type epoxy resin reaction and Epocryl or half urethanes that further makes diisocyanate such as hydroxy acrylate such as pentaerythritol triacrylate and isophorone diisocyanate with the hydroxyl reaction of this epoxy acrylate resin must epoxy radicals urethane acrylate compound etc.This epoxy acrylate is that resin can not make the dry to touch reduction, can improve photo-curable.

The use level that has the compound of the olefinic unsaturated group more than 2 in this molecule, with respect to aforementioned contain the olefinic unsaturated group contain carboxylic acid resin (A) 100 mass parts, be 5～100 mass parts, the ratio of 1～70 mass parts more preferably.During aforementioned use level less than 5 mass parts, photo-curable reduces, and is difficult to develop by the postradiation alkali of active energy beam and forms pattern, and is therefore not preferred.On the other hand, when it surpasses 100 mass parts, the dissolubility of alkaline aqueous solution is reduced, and film and become fragile, therefore not preferred.

(hot curing resin composition)

In order to give thermotolerance, can in composition of the present invention, add heat-curing resin.Particularly preferably be the ring-type ether that has in the molecule more than 2 and/or the Thermocurable composition of cyclic thioether base (following province is ring-type (sulphur) ether slightly).

The Thermocurable composition that has ring-type (sulphur) ether more than 2 in this molecule, compound for the group of the ring-type ether that has 3,4 or 5 yuan of rings more than 2 in the molecule or cyclic thioether base any one or 2 kinds, for example can enumerate, the compound that has the epoxy radicals more than at least 2 in the molecule is that the compound that has the oxetanyl more than at least 2 in multi-functional epoxy compound, the molecule is that the compound that has the thioether group more than 2 in multifunctional oxetane compound, the molecule is an episulfide resin etc.

As aforementioned multi-functional epoxy compound, for example can enumerate the EPICOAT 828 that japan epoxy resin company makes, EPICOAT 834, EPICOAT 1001, EPICOAT 1004, the EPICLON840 that big Japanese ink chemical industrial company makes, EPICLON 850, EPICLON 1050, EPICLON 2055, Dongdu changes into the EPOTOHTO YD-011 that company makes, YD-013, YD-127, YD-128, the D.E.R.317 that Dow Chemical makes, D.E.R.331, D.E.R.661, D.E.R.664, the ARALDITE 6071 of Xiba Special Chemical Product Co.,Ltd, ARALDITE 6084, ARALDITE GY250, ARALDITE GY260, the SUMI-EPOXY ESA-011 that Sumitomo Chemical Co. Ltd. makes, E SA-014, ELA-115, ELA-128, the A.E.R.330 that industrial group of Asahi Chemical Industry makes, A.E.R.331, A.E.R.661, A.E.R.664 etc. (being trade name) bisphenol A type epoxy resin; The EPICOATYL903 that japan epoxy resin company makes, the EPICLON152 that big Japanese ink chemical industrial company makes, EPICLON165, Dongdu changes into the EPOTOHTOYDB-400 that company makes, YDB-500, the D.E.R.542 that Dow Chemical makes, the ARALDITE8011 that Xiba Special Chemical Product Co.,Ltd makes, the SUMI-EPOXY ESB-400 that Sumitomo Chemical Co. Ltd. makes, E SB-700, the A.E.R.711 that industrial group of Asahi Chemical Industry makes, A.E.R.714 etc. (being trade name) brominated epoxy resin; The EPICOAT152 that japan epoxy resin company makes, EPICOAT154, the D.E.N.431 that Dow Chemical makes, D.E.N.438, the EPICLON N-730 that big Japanese ink chemical industrial company makes, EPICLONN-770, EPICLONN-865, Dongdu changes into the EPOTOHTOYDCN-701 that company makes, YDCN-704, the ARALDITE ECN1235 that Xiba Special Chemical Product Co.,Ltd makes, ARALDITE ECN1273, ARALDITEECN1299, ARALDITE XPY307, the EPPN-201 that Japan's chemical drug corporate system is made, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, the SUMI-EPOXYES CN-195X that Sumitomo Chemical Co. Ltd. makes, ESCN-220, the A.E.R.ECN-235 that industrial group of Asahi Chemical Industry makes, ECN-299 etc. (being trade name) phenolic resin varnish type epoxy resin; (being trade name) bisphenol f type epoxy resins such as ARALDITE XPY306 that EPOTOHTO YDF-170, YDF-175, YDF-2004, the Xiba Special Chemical Product Co.,Ltd that EPICOAT807, Dongdu that the EPICLON830 that big Japanese ink chemical industrial company makes, japan epoxy resin company make company that changes into makes makes; Dongdu changes into EPOTOHTO ST-2004, ST-2007, the ST-3000 hydrogenation bisphenol A type epoxy resins such as (trade names) that company makes; The EPOTOHTO YH-434 that EPICOAT604, Dongdu that japan epoxy resin company makes company that changes into makes, the ARALDITEMY720 that Xiba Special Chemical Product Co.,Ltd makes, (being trade name) glycidyl amine type epoxy resins such as SUMI-EPOXY ELM-120 that Sumitomo Chemical Co. Ltd. makes; The ARALDITE CY-350 hydantoins type epoxy resin such as (trade names) that Xiba Special Chemical Product Co.,Ltd makes; (being trade name) alicyclic epoxy resins such as ARALDITECY175, CY179 that the CELLOXIDE2021 that Daicel chemical industrial company makes, Xiba Special Chemical Product Co.,Ltd make; (being trade name) trihydroxy benzene methylmethane type epoxy resin such as T.E.N., the EPPN-501 that the YL-933 that japan epoxy resin company makes, Dow Chemical make, EPPN-502; YL-6056, YX-4000, YL-6121 di-cresols type or biphenyl type epoxy resin or their potpourris such as (being trade name) that japan epoxy resin company makes; The EXA-1514 bisphenol-s epoxy resins such as (trade names) that the EPX-30 that the EBPS-200 that Japan's chemical drug corporate system is made, Asahi Electro-Chemical Co. Ltd make, big Japanese ink chemical industrial company make; The bisphenol-A phenolic varnish epoxy resin of the EPICOAT157S (trade name) that japan epoxy resin company makes etc.; Four phenol ethane type epoxy resin such as ARALDITE163 (being trade name) that the EPICOATYL-931 that japan epoxy resin company makes, Xiba Special Chemical Product Co.,Ltd make; (being trade name) hetero ring type epoxy resin such as TEPIC that the ARALDITEPT810 that Xiba Special Chemical Product Co.,Ltd makes, daily output chemical industrial company make; The o-phthalic acid diglycidyl ester resins such as BLEMMER DGT that Nof Corp. makes; Dongdu changes into the four glycidyl group dimethylbenzene phenolic group ethane resin such as ZX-1063 that company makes; HP-4032, the EXA-4750 that ESN-190, the ESN-360 that iron chemical company made in new day, big Japanese ink chemical industrial company make, EXA-4700 etc. contain the epoxy resin of naphthyl; HP-7200, the HP-7200H etc. that big Japanese ink chemical industrial company makes have the epoxy resin of bicyclopentadiene skeleton; The glycidyl methacrylate copolymerization such as CP-50S, CP-50M that Nof Corp. makes are epoxy resin; And, the copolymerization epoxy resin of cyclohexyl maleimide and glycidyl methacrylate; Epoxide modified polybutadiene rubber derivant (for example the PB-3600 that makes of Daicel chemical industry etc.), CTBN modified epoxy (for example Dongdu changes into YR-102, the YR-450 etc. that company makes) etc., but be not limited to these.These epoxy resin can use separately or be used in combination more than 2 kinds.Wherein, preferred especially phenolic resin varnish type epoxy resin, hetero ring type epoxy resin, bisphenol A type epoxy resin or their potpourri.

As aforementioned multifunctional oxetane compound, can enumerate two [(3-methyl-3-oxetanes ylmethoxy) methyl] ethers, two [(3-ethyl-3-oxetanes ylmethoxy) methyl] ether, 1, two [(3-methyl-3-oxetanes ylmethoxy) methyl] benzene of 4-, 1, two [(3-ethyl-3-oxetanes ylmethoxy) methyl] benzene of 4-, methacrylic acid (3-methyl-3-oxetanyl) ester, methacrylic acid (3-ethyl-3-oxetanyl) ester, methacrylic acid (3-methyl-3-oxetanyl) methyl esters, the polyfunctional group oxetanes class of methacrylic acid (3-ethyl-3-oxetanyl) methyl esters or their oligomer or multipolymer etc., in addition, can also enumerate oxa-cyclobutanol and novolac resin, poly-(para hydroxybenzene ethene), cardo type bisphenols, calixarene kind, the resorcinol calixarene kind, or silsesquioxane etc. has the etherate etc. of the resin of hydroxyl.Remove this multipolymer that can also enumerate unsaturated monomer with oxetanes ring and (methyl) alkyl acrylate etc.

As the compound that has 2 above cyclic thioether bases in the aforementioned molecule, for example, can enumerate the bisphenol A-type episulfide resin YL7000 of japan epoxy resin company manufacturing etc.In addition, also can use with same synthetic method and the oxygen atom of the epoxy radicals in the phenolic resin varnish type epoxy resin is replaced to sulphur atom and episulfide resin of obtaining etc.

The use level that has the Thermocurable composition of ring-type (sulphur) ether more than 2 in the aforementioned molecule with respect to aforementioned carboxyl 1 equivalent that contains the carboxylic acid resin, is preferably 0.6～2.5 equivalent, the scope of 0.8～2.0 equivalent more preferably.When having the use level less than 0.6 of Thermocurable composition of ring-type (sulphur) ether more than 2 in the molecule, the residual carboxyl of solder resist film, so reductions such as thermotolerance, alkali resistance, electrical insulating property are not preferred.On the other hand, when surpassing 2.5 equivalents, because low-molecular-weight ring-type (sulphur) ether residues in dry coating, so the reductions such as intensity of filming are therefore not preferred.

(Thermocurable catalyzer)

When using the Thermocurable composition of ring-type (sulphur) ether that has in the above-mentioned molecule more than 2, preferably contain thermal curing catalyst.As this thermal curing catalyst, imidazoles, glyoxal ethyline, 2-ethyl imidazol(e), 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-imdazole derivatives such as 2-ethyl-4-methylimidazole are for example arranged; Dicyandiamide, benzyl dimethylamine, 4-(dimethylamino)-N, N-dimethyl benzyl amine, 4-methoxyl-N, N-dimethyl benzyl amine, 4-methyl-N, amines such as N-dimethyl benzyl amine; Hydrazine compound such as adipic dihydrazide, sebacic dihydrazide; Phosphorus compounds such as triphenyl phasphine etc.; In addition as commercially available product, for example there are four countries to change into 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (being the trade name of imidazole compound all) that industrial group makes, U-CAT3503N, U-CAT3502T (being the trade name of the block isocyanate compound of dimethyl amine all), DBU, DBN, U-CATSA102, U-CAT5002 (being two ring type amidine compound and salt thereof all) etc. that SAN-APRO company makes.Particularly, it is not limited to these compounds, so long as the thermal curing catalyst of epoxy resin or oxetane compound, maybe can promote that the material of epoxy radicals and/or oxetanyl and carboxyl reaction is just passable, it can use separately or mix more than 2 kinds and use.In addition, also can use guanamines, acetylguanamine, benzoguanamine, melamine, 2,4-diamido-6-methacryloxyethyl-s-triazine, 2-vinyl-2,4-diamido-s-triazine, 2-vinyl-4,6-diamido-s-triazine isocyanuric acid addition product, 2, the Striazine derivative of 4-diamido-6-methacryloxyethyl-s-triazine isocyanuric acid addition product etc., and preferably these compound and aforementioned hot curing catalysts that also play the effect of adaptation imparting agent are used in combination.

The use level of these thermal curing catalysts is that the ratio of common amount is just passable, for example with respect to Thermocurable composition 100 mass parts that contain ring-type (sulphur) ether that has in carboxylic acid resin (A) or the molecule more than 2, be preferably 0.1～20 mass parts, 0.5～15.0 mass parts more preferably.

(cooperation of filler)

Composition of the present invention is in order to improve this physical strength of filming etc. and can cooperate filler as required.As such filler, can use known habitual inorganic or organic filler, particularly preferably use barium sulphate, spherical silicon dioxide and talcum.Further also can use NANOCRYL (trade name) XP0396 of the Hanse-Chemie company manufacturing that in compound with the olefinic unsaturated group more than 1 or aforementioned polyfunctional epoxy resin (D-1), is dispersed with nano silicon, XP0596, XP0733, XP0746, XP0765, XP0768, XP0953, XP0954, XP1045 (being the product hierarchy title), NANOPOX (trade name) XP0516 that Hanse-Chemie company makes, XP0525, XP0314 (being the product hierarchy title).They can separately or cooperate more than 2 kinds.

The use level of these fillers, with respect to above-mentioned carboxylic acid resin (A) 100 mass parts that contain, be preferably 300 mass parts following, more preferably 0.1～300 mass parts, be preferably 0.1～150 mass parts especially.When the use level of filler surpassed 300 mass parts, the viscosity of composition uprised, printing reduces.Solidfied material becomes fragile, so not preferred.

(cooperation of organic solvent)

Further, for the synthetic above-mentioned carboxylic acid resin of containing (A), to regulate composition or in order being used for its viscosity that is applied on substrate or the carrier film to be regulated, composition of the present invention can be with an organic solvent.

As this organic solvent, can enumerate ketone, aromatic hydrocarbon based, glycol ethers, glycol ethers acetate esters, ester class, alcohols, aliphatic hydrocarbon, oil series solvent etc.More particularly, be ketones such as MEK, cyclohexanone; Toluene, dimethylbenzene, durene etc. are aromatic hydrocarbon based; Glycol ethers such as cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, Triethylene glycol ethyl ether; Ester classes such as ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetic acid esters, propylene glycol methyl ether acetate, propylene-glycol ethyl ether acetic acid esters, propylene glycol butyl ether acetic acid esters; Alcohols such as ethanol, propyl alcohol, ethylene glycol, propylene glycol; Aliphatic hydrocarbon such as octane, decane; Oil series solvents such as sherwood oil, naphtha, hydrogenated naphtha, solvent naphtha etc.This organic solvent can use separately or as the potpourri more than 2 kinds.

(cooperation of other composition)

Composition of the present invention can further cooperate as required known habitual tackifier such as known habitual hot polymerization inhibitor such as quinhydrones, Hydroquinone monomethylether, tert-butyl catechol, 1,2,3,-thrihydroxy-benzene, phenothiazine, fine particle silica, organobentonite, polynite, silicon-type, fluorine system, macromolecular etc. so known habitual additive kinds such as silane coupling agent, antioxidant, rust preventive such as defoamer and/or levelling agent, imidazoles, thiazoles, triazole type.

(the absorbance distribution character of composition)

Composition of the present invention designs absorbance, designs absorbance at long wavelength side than the lowland than the highland at short wavelength side in the scope of wavelength 400～410nm.Oscillation wavelength before the composition exposure during the thick 25 μ m of dry coating is a absorbance that absorbance that the absorbance of 400nm is made as L400, same 405nm is made as L405,410nm when being made as L410, L400〉L405〉L410.Surface cure reduction during the absorbance step-down is difficult to obtain curing depth when absorbance uprises, thereby the absorbance L400 of oscillation wavelength 400nm is preferably 0.5～1.2.The absorbance L405 of oscillation wavelength 405nm is preferably 0.3～0.9.Oscillation wavelength is that the absorbance L410 of 410nm is preferably 0.01～0.5, is preferably 0.3～0.9 especially.

The difference L400-L410 of absorbance L400 and absorbance L410 is preferably 0.1～0.5.When difference is too small, must more exposure in order to take into account surface cure and curing depth.When difference is excessive, can not get surface cure and curing depth.

(dry film)

Composition of the present invention also can be made into the form of dry film that possesses carrier film and be formed at the layer of above-mentioned composition on this carrier film.

During dry film, can photosensitive polymer combination dilution of the present invention be suitable viscosity with aforementioned organic solvent, with comma coating machine, knife type coater, lip formula coating machine (lip coater), rod be coated with machine, extrusion coater (squeeze coater), oppositely coating machine (reverse coater), transfer printing roll coater, intaglio plate coating machine (gravurecoater), flush coater etc. are coated with into homogeneous thickness on supporter, obtain film being generally under 50～130 ℃ the temperature dry 1～30 minute.Coating film thickness is not particularly limited, general dried thickness at 10～100 μ m, be preferably in the scope of 15～40 μ m and suitably select.

Use plastic sheeting as carrier film, preferably use plastic sheetings such as mylar, Kapton, polyamidoimide film, polypropylene film, plasticon such as polyethylene terephthalate.The thickness of carrier film is not particularly limited, general suitably selection in the scope of 10～150 μ m.

After film forming on the carrier film, and then in order to prevent that dust attached to the surface of film etc., is desirably in the stacked strippable cover film in film surface.

As strippable cover film, can use for example polyethylene film, polytetrafluoroethylene film, polypropylene film, surface treated paper etc., when peeling off cover film, the bounding force of film and cover film gets final product less than the bounding force of film and supporter.

(one of composition makes use-case)

Composition of the present invention, for example adjust to the viscosity that is suitable for coating process with aforementioned organic solvent, the methods such as method, silk screen print method, curtain Tu Fa that are coated with by dip coating, flow coat method, rolling method, rod are applied on the substrate, and under about 60～100 ℃ temperature, make organic solvent volatile dry contained in the composition (temporary transient dry), can form tack-free filming thus.In addition, be applied to above-mentioned composition on the carrier film and make it dry and make film and reel, then the gained material is fitted on the substrate, can form resin insulating barrier thus.By the direct pattern exposure of the direct exposure machine of royal purple laser, and use diluted alkaline aqueous solution (for example 0.3～3% aqueous sodium carbonate) that unexposed portion is developed, form corrosion-resisting pattern thus.Further, for example make its heat curing under about 140～180 ℃ temperature by being heated to, make the ring-type ether that has in the aforementioned carboxylic acid resin's of containing (A) carboxyl and the molecule more than 2 and/or the Thermocurable composition reaction of cyclic thioether base, thereby can form the cured coating film of each excellent such as thermotolerance, chemical proofing, anti-hydroscopicity, adaptation, electrical characteristics.

As the aforesaid substrate base material, can enumerate the HF link of using paper phenolics, paper epoxy resin, glass cloth epoxy resin, glass polyimide, glass cloth/nonwoven fabrics epoxy resin, glass cloth/paper epoxy resin, synthon epoxy resin, fluorine tygon PPO cyanate etc. copper clad laminate with all models (FR-4 etc.) of materials such as copper clad laminate, and polyimide film, PET film, glass substrate, ceramic substrate, wafer board etc.

Be coated with the volatile dry that carries out after the composition of the present invention, can use heated air circulation type drying oven, IR stove, heating plate, convection furnace etc. (have the device that carries out the thermal source of air heat mode with steam, make hot blast in the dryer carry out the method for counter current contacting and blow to mode on the supporter) to carry out by nozzle by use.

As described below, be coated with Photocurable resin composition of the present invention and volatile dry after, expose (irradiation of active energy beam) that gained is filmed.The exposed portion of filming (by the part of active energy beam irradiation) solidifies.

As the exposure machine that is used for above-mentioned active energy beam irradiation, can use direct drawing apparatus (by directly shine the direct imaging device of rendering image from the cad data of computer) with direct active energy beam.As active energy beam, can use the direct drawing apparatus of bluish-violet laser diode as light source.In addition, this exposure is according to thickness etc. and different, but can be 5～200mJ/cm usually ², be preferably 5～100mJ/cm ², 5～50mJ/cm more preferably ²Scope in.As above-mentioned direct drawing apparatus, can use for example Hitachi Via Mechanics, Ltd., device, ORC that the device of making, Fuji film company make make one mounting arrangement between mounting etc., be not only bluish-violet laser diode, when being used in combination the different light source of wavelength so long as use the device of laser diode then can use arbitrary device.

As aforementioned developing method, can utilize infusion process, spray process, spray-on process, brushing method etc., as developer solution, can use alkaline aqueous solutions such as potassium hydroxide, NaOH, sodium carbonate, sal tartari, sodium phosphate, sodium silicate, ammonia, amine.

Embodiment

Below, embodiment is shown and comparative example is specifically described the present invention, but the present invention is not limited to following embodiment certainly.In addition, use level is all represented mass parts.

Resin synthesis example 1

In having 2 liters removable flask of stirrer, thermometer, reflux condensing tube, tap funnel and nitrogen ingress pipe, (Japanese chemical drug (strain) is made to import 660g cresols phenolic resin varnish type epoxy resin, EOCN-104S, softening point is 92 ℃, epoxide equivalent is 220), 421.3g carbitol acetic acid esters and 180.6g solvent naphtha, be heated to 90 ℃ and stirring, make its dissolving.Then, temporarily be cooled to 60 ℃, add 216g acrylic acid, 4.0g triphenylphosphine, 1.3g methylnaphthohydroquinone, under 100 ℃, make its reaction 12 hours, obtain the reaction product that acid number is 0.2mgKOH/g.Add the 241.7g tetrabydrophthalic anhydride therein, be heated to 90 ℃ and make its reaction 6 hours.Obtain acid number thus and be 50mgKOH/g, two key equivalent (the g weight of the resin of per 1 mole of unsaturated group) and be 400, weight-average molecular weight is 7000 the solution that contains carboxylic acid resin (A).Below, this solution that contains the carboxylic acid resin is called A-1 varnish.

Cooperate example

Various compositions shown in embodiment and the comparative example are cooperated with the ratio (mass parts) that cooperates example, and by after the stirring machine premixed, mixing in 3 roller roller mills, preparation solder resist photosensitive polymer combination.Here, the particle size analyzer made from ERICHSEN Gmbh company is measured granularity and is estimated the dispersion degree of gained photosensitive polymer combination, and the result is below the 15 μ m.

Embodiment, comparative example are shown in table 1.

Table 1-1

Table 1-2

Remarks

*1:2-(acetoxyl group iminomethyl) thioxanthene-9-one *2:1,2-octadione-1-[4-(thiophenyl)-2-(O-benzoyl oximes)] *3:1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl]-1-(O-acetyl oxime) ethyl ketone *4:2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholino propane-1-ketone *5:2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide *6: two (η 5-2,4-cyclopentadiene-1-yl)-two (2,6-two fluoro-3-(1H-pyrroles-1-yl) phenyl) titanium *7:2, the 4-diethyl thioxanthone *8:4,4 '-two diethylamino benzophenone *9: anthraquinone is a yellow uitramarine *10: six acrylic acid dipentaerythritol acid esters *11: the trimethylolpropane tris propionic ester *12: barium sulphate (Sakai chemical industrial company makes B-30) *13: phenolic resin varnish type epoxy resin (EPPN-201 that Japanese chemical drug corporate system is made) *14: di-toluene phenol-type epoxy resin (YX-4000 that japan epoxy resin company makes) *15: the dipropylene glycol methyl ether acetic acid esters *16: the fragrant family organic solvent that bright dipping petrochemistry company makes

Table 2

Resist performance evaluation:

＜absorbance 〉

In the mensuration of absorbance, use ultraviolet-visible pectrophotometer (Japanese beam split Co., Ltd. makes, Ubest-V-570DS) and integrating sphere device (manufacturing of Japanese beam split Co., Ltd., ISN-470).Use applicator will cooperate after the resin combination of the Photosetting and thermosetting of example 1～10 is coated on the glass plate, use the heated air circulation type drying oven, drying is 30 minutes under 80 ℃, makes the dry coating of light solidifying/heat solidifying resin composition on glass plate.Use ultraviolet-visible pectrophotometer and integrating sphere device, on the glass plate identical, measure the absorbance baseline under 500～300nm with the glass plate that has been coated with light solidifying/heat solidifying resin composition.Measure the absorbance of the glass plate that has dry coating of made, can calculate the absorbance of dry coating, obtain the absorbance under the light wavelength 405nm of target by baseline.In order to prevent departing from of absorbance that departing from of coating film thickness causes, to carry out this operation with coating thickness 4 stages of change that applicator forms, make the curve of the absorbance under coating thickness and the 405nm, calculate the absorbance that thickness is the dry coating of 25 μ m from this approximate expression, as absorbance separately.

The evaluation result of its absorbance is shown in table 2.

＜correct exposure amount 〉

Thick to copper is after the line pattern substrate of 70 μ m polishes grinding, washing, drying then by the light solidifying/heat solidifying resin composition of silk screen print method whole coating previous embodiment and comparative example, makes its dry 60 minutes in 80 ℃ heated air circulation type drying oven.After the drying, the direct drawing apparatus (PENTAX company make DI-μ) that use is equipped with bluish-violet laser diode (KodakNo2) expose by stage metraster (step tablet), when the pattern of residual stage metraster is 6 sections when carrying out development in 60 seconds (30 ℃, 0.2MPa, 1 quality % aqueous sodium carbonate) as the correct exposure amount.

＜surface cure 〉

Thick to copper is after the line pattern substrate of 35 μ m polishes grinding, washing, drying then by the light solidifying/heat solidifying resin composition of silk screen print method whole coating previous embodiment and comparative example, makes its dry 60 minutes in 80 ℃ heated air circulation type drying oven.After the drying, use direct drawing apparatus (the DI-μ that PENTAX company makes) that bluish-violet laser diode is installed by with each correct exposure amount exposure, (30 ℃, 0.2MPa, 1 quality % aqueous sodium carbonate) carry out developing for 60 seconds.Thereafter, 150 ℃ were heated 60 minutes down in circulating hot-air drying stove, formed solder mask layer.At this moment, the gloss intensity on Visual Confirmation surface.Evaluation result is as follows.

Zero: there is uniform gloss on the surface.

*: there are lacklustre part in surface portion or whole.

＜cross sectional shape 〉

Thick to line/be spaced apart 300/300, copper is after the line pattern substrate of 50 μ m polishes grinding, washing, drying, and use the silk screen print method coating to cooperate the light solidifying/heat solidifying resin composition of example 1～10, in 80 ℃ heated air circulation type drying oven, make its dry 30 minutes.After the drying, use the exposure device that is equipped with high-pressure sodium lamp to expose.Exposing patterns uses spacer portion to describe the pattern of the line of 100 μ m.Exposure is as the exposure that obtains by the evaluation of following correct exposure amount.After the exposure, develop to form pattern, under high-pressure sodium lamp, carry out 1000mJ/cm by aqueous sodium carbonate ²Ultraviolet ray irradiation after, carry out 150 ℃, 60 minutes heat curing, thereby obtain cured coating film.Observe the sectional view of the design load 100 μ m lines part of cured coating film this moment.

As the synoptic diagram of Fig. 1 record this cross sectional shape being divided into A～E5 rank estimates.Among Fig. 1, the synoptic diagram when estimating A～E and representing to take place as following development.Particularly, when A estimates, from departing from of design load from line top to the bottom all be in the 5 μ m.This results are shown in table 2.The wherein the poorest E that is evaluated as.

A estimates: the perfect condition as the design width

B estimates: the corrosion of the superficial layer that causes because of anti-development deficiency etc. takes place

C estimates: the undercutting state

D estimates: broadening of the line that causes because of halation etc. taken place

E estimates: the line that superficial layer takes place broadens and undercutting

Here, the A evaluation is a good horizontal as solder resist.With respect to this, though D estimates and can be used as solder resist and use, not preferred from the viewpoint of the repeatability of size, it is big that the degree that its size can't be ignored according to thickness (thin situation) becomes.In addition, E is evaluated as the level that line, undercut portions are peeled off easily, can not be used as solder resist.

Can confirm from table 1,2, the composition of the absorbency characteristics of the scope of wavelength 400～410 embodiment 1-6 within the scope of the invention, its surface cure and cross sectional shape (index of curing depth) are all good.Relative therewith, absorbency characteristics departs from the middle of the comparative example of scope of the present invention, the little and comparative example 1 that do not have blue colorant of L400, though its cross sectional shape is better, surface cure is poor.Though the surface cure of comparative example 2 is excellent, cross sectional shape (curing depth) is poor.

Claims (15)

1. composition; it is characterized in that; it carries out laser explosure for dry coating forms the back by a plurality of laser diodes being bundled laser generation light source that the laser oscillation wavelength of making exposure light source has the distribution of 400～410nm; contain (A) and contain the carboxylic acid resin; (B) Photoepolymerizationinitiater initiater and (C) composition of colorant; wherein; the absorbance of wavelength 400nm is made as L400; when the absorbance of wavelength 410nm is made as L410; before the exposure during the thick 25 μ m of dry coating; absorbance L400 is 0.5-1.2; absorbance L410 is 0.01-0.5; and; absorbance L400＞absorbance L410; aforementioned (B) Photoepolymerizationinitiater initiater is a Photoepolymerizationinitiater initiater for being selected from the oxime ester shown in the following general formula (I); aminoacetophenone shown in the following general formula (II) is a Photoepolymerizationinitiater initiater; acylphosphine oxide shown in the following general formula (III) is that the luxuriant titanium shown in Photoepolymerizationinitiater initiater and the following general formula (IV) is the Photoepolymerizationinitiater initiater more than a kind in the group formed of Photoepolymerizationinitiater initiater; and it is 0.01～30 mass parts that the use level of aforementioned (B) Photoepolymerizationinitiater initiater contains the carboxylic acid resin with respect to 100 mass parts aforementioned (A); the use level of aforementioned (C) colorant is 0.01～5 mass parts with respect to the aforementioned carboxylic acid resin of containing of 100 mass parts

[Chemical formula 1]

In the formula, R ¹The alkyl or phenyl of expression hydrogen atom, carbon number 1～7, R ²The alkyl or phenyl of expression carbon number 1～7; R ³, R ⁴The alkyl or aryl alkyl of expression carbon number 1～12, R ⁵, R ⁶Expression hydrogen atom, the alkyl of carbon number 1～6 or the cyclic alkyl of both be combined intos; R ⁷, R ⁸The straight chain shape of expression carbon number 1～6 or the alkyl of chain, alkoxy, cyclohexyl, cyclopentyl, aryl or the aryl that is replaced by halogen atom, alkyl or alkoxy or any are the carbonyl of carbon number 1～20; R ⁹, R ¹⁰Expression halogen atom, aryl, halogenated aryl, contain the halogenated aryl of heterocycle.

2. composition according to claim 1, it is the resist composition.

3. composition according to claim 1 is characterized in that, when the absorbance of wavelength 405nm was made as L405, during the thick 25 μ m of dry coating, absorbance L405 was 0.3-0.9, and absorbance L400＞absorbance L405＞absorbance L410 before the exposure.

4. composition according to claim 1 is characterized in that, before the exposure during the thick 25 μ m of dry coating, poor (L400-L410) of absorbance L400 and absorbance L410 is in 0.1～0.5 the scope.

5. the acid number that composition according to claim 1, aforementioned (A) contain the carboxylic acid resin is that scope, the weight-average molecular weight of 40～200mgKOH/g is 2000～150000.

6. composition according to claim 1 is characterized in that, the oxime ester shown in the aforementioned formula (I) is that Photoepolymerizationinitiater initiater (B1) is a Photoepolymerizationinitiater initiater for the oxime ester shown in the following formula (V).

[Chemical formula 2]

7. composition according to claim 1 is characterized in that, colorant (C) is a phthalocyanine blue.

8. composition according to claim 1 also contains (D) sensitizer.

9. composition according to claim 8 is characterized in that, (D) sensitizer is the compound that thioxanthones is and/or has dialkyl amido benzene structure.

10. composition according to claim 9 is characterized in that, aforementioned compound with dialkyl amido benzene structure is dialkyl amido benzophenone or coumarin compound.

11. the dry film of a Photosetting and thermosetting, it is applied to carrier film and dry and obtain with each described composition of claim 1～10.

12. a solidfied material, it is with each described light solidifying/heat solidifying resin composition of aforementioned claim 1～10 or at coating said composition on the carrier film and the dry film that makes its dry and Photosetting and thermosetting of obtaining photocuring and obtaining on copper.

13. solidfied material, it is the laser of 400～410nm by wavelength, with each described light solidifying/heat solidifying resin composition of aforementioned claim 1～10 or on carrier film coating said composition and make the dry film photocuring of its dry and Photosetting and thermosetting of obtaining and obtain.

14. printed-wiring board (PWB), it is the laser of 400～410nm by wavelength, with each described light solidifying/heat solidifying resin composition of aforementioned claim 1～10 or coating said composition on the carrier film and the dry film that makes its dry and Photosetting and thermosetting of obtaining thickness from 15 μ m to the scope photocuring that is 100 μ m to the maximum, heat curing and obtaining.

15. the manufacture method of a composition; it carries out laser explosure for dry coating forms the back by a plurality of laser diodes being bundled laser generation light source that the laser oscillation wavelength of making exposure light source has the distribution of 400～410nm; contain (A) and contain the carboxylic acid resin; (B) Photoepolymerizationinitiater initiater and (C) manufacture method of the composition of colorant; aforementioned (B) Photoepolymerizationinitiater initiater is a Photoepolymerizationinitiater initiater for being selected from the oxime ester shown in the following general formula (I); aminoacetophenone shown in the following general formula (II) is a Photoepolymerizationinitiater initiater; acylphosphine oxide shown in the following general formula (III) is that the luxuriant titanium shown in Photoepolymerizationinitiater initiater and the following general formula (IV) is the Photoepolymerizationinitiater initiater more than a kind in the group formed of Photoepolymerizationinitiater initiater; and it is 0.01～30 mass parts that the use level of aforementioned (B) Photoepolymerizationinitiater initiater contains the carboxylic acid resin with respect to 100 mass parts aforementioned (A); the use level of aforementioned (C) colorant is 0.01～5 mass parts with respect to the aforementioned carboxylic acid resin of containing of 100 mass parts; in described each scope, adjust the content of aforementioned (B) Photoepolymerizationinitiater initiater and aforementioned (C) colorant; the absorbance of wavelength 400nm is made as L400; when the absorbance of wavelength 410nm is made as L410; before the exposure during the thick 25 μ m of dry coating; absorbance L400 is 0.5-1.2; absorbance L410 is 0.01-0.5; and; absorbance L400＞absorbance L410

[Chemical formula 1]

In the formula, R ¹The alkyl or phenyl of expression hydrogen atom, carbon number 1～7, R ²The alkyl or phenyl of expression carbon number 1～7; R ³, R ⁴The alkyl or aryl alkyl of expression carbon number 1～12, R ⁵, R ⁶Expression hydrogen atom, the alkyl of carbon number 1～6 or the cyclic alkyl of both be combined intos; R ⁷, R ⁸The straight chain shape of expression carbon number 1～6 or the alkyl of chain, alkoxy, cyclohexyl, cyclopentyl, aryl or the aryl that is replaced by halogen atom, alkyl or alkoxy or any are the carbonyl of carbon number 1～20; R ⁹, R ¹⁰Expression halogen atom, aryl, halogenated aryl, contain the halogenated aryl of heterocycle.