CN1675588A - Image forming material having bluish-violet laser-photosensitive resist material layer and resist image forming method therefor - Google Patents

Abstract

An image forming material having a bluish-violet laser-photosensitive resist material layer highly sensitive to a laser beam in a bluish-violet region and free from a decrease in sensitivity even a film thickness is increased. An image forming material comprising a bluish-violet laser-photosensitive resist material layer formed on a substrate to be worked, wherein the photosensitive resist material layer has a bluish-violet laser-photosensitive resist material layer having a film thickness of at least 10 mum and an absorbance at a wavelength of 405 nm of up to 0.3 per film thickness of 1 mum; and a resist image forming method of scanning and exposing the photosensitive resist material layer of the image forming material by a laser beam having a wavelength of 320-450 nm, and then developing the resultant material.

Description

Image forming material and resist imaging method thereof with purple laser-photosensitive anticorrosive additive material layer

Technical field

The present invention relates to a kind of image forming material and resist imaging method thereof with purple laser-photosensitive anticorrosive additive material layer, by with purple laser beam lithography and carry out development treatment, this material layer can form the resist image.Especially, the present invention relates to a kind of image forming material (except the planographic printing plate) and resist imaging method thereof with purple laser-photosensitive anticorrosive additive material layer, by directly writing with purple laser beam method, described image forming material can be used to form the circuit board such as printed circuit board (PCB), plasma scope, the microelectronic circuits such as circuit board, large scale integrated circuit, thin type transistor and semiconductor packages of LCD.

Background technology

In the past, in order to form the circuit board such as printed circuit board (PCB), plasma scope, the microelectronic circuits such as circuit board, large scale integrated circuit, thin type transistor and semiconductor packages of LCD, people have generally adopted for example lithography.This technology adopts a kind of image forming material, and this image forming material has processed substrate and the photonasty anticorrosive additive material layer that is formed on this substrate, also has protective seam in case of necessity on it.The photonasty anticorrosive additive material layer of this image forming material is exposed by the mask irradiation with ultraviolet ray; then mask is peelled off; if matcoveredn then protective seam is peelled off forms pattern by utilizing between exposed portion and the unexposed portion poor solubility in developer solution to develop.Adopt this patterned layer to come the processed substrate of etching, on this processed substrate, to form circuit pattern as mask.

In addition, in recent years, owing to the laser direct-writing method not only can be boosted productivity, and can improve resolution and bearing accuracy etc., so the laser direct-writing method is subject to the people's attention.The laser direct-writing method adopts laser beam not use mask as exposure light source, directly forms image by the numerical information of for example computing machine.Therefore, even in the lithography field, also very active to the research that laser beam is used.

On the other hand, as laser beam, various light sources from the ultraviolet region to the infrared region all are known, as the laser beam that is used for image exposure, consider output, stability, photoperceptivity and cost, those can produce from the visible range to the laser of infrared region light, have very big potentiality such as argon laser, He-Ne Lasers, YAG (yttrium aluminum garnet) laser or semiconductor laser etc.For example, adopting wavelength is that the argon laser of 488nm or the lithography of the FD-YAG laser that wavelength is 532mn have obtained application in practice.

Yet in the imaging method that adopts a kind of like this visible laser bundle, the optical safety under amber light is relatively poor, must be limited in such as the darkroom environment under the red colored lamp illumination to operate.On the other hand, along with the remarkable break-throughs of laser technology in recent years, semiconductor laser is applied, and this semiconductor laser can use this laser to operate in such as the bright room environmental under the amber light illumination in the stable oscillation stationary vibration of purple light district.Yet owing to compare with other visible ranges, the output of semiconductor laser is lower, causes the light sensitivity deficiency of photonasty anticorrosive additive material, and in fact, in laser direct-writing method and lithography, semiconductor laser does not all reach the degree of practical application.

On the other hand, european patent application discloses No. 1148387 and has disclosed a kind of photosensitive lithographic photographic plate that contains the photopolymerizable photosensitive composition floor that forms on carrier, wherein, this photosensitive composition has the peak-peak of spectrum sensitivity in the wavelength coverage of 390nm～430nm, and the minimum exposure amount that is used for imaging under the wavelength of 410nm and 450nm is in particular range.Yet, the thickness of this photosensitive composition layer 2 μ m that only have an appointment.

Yet even with regard to this photosensitive composition, as the photonasty anticorrosive additive material, particularly in the photonasty anticorrosive additive material layer that is formed on processed substrate by the dry film photoresist material, the thickness of this film is at least 10 μ m.In addition, in plating step,,, therefore must improve photonasty in the purple light district so electroplating thickness need be thicker because the live width that connects up in recent years attenuates as for example manufacturing step of printed circuit board (PCB).In addition, in above-mentioned classic method, for the photographic layer that adopts the visible range to infrared region laser, photonasty decline when thickness increases is difficult to find in thickness and photonasty require the photosensitive material that reaches well balanced aspect two.

Summary of the invention

The present invention makes in these cases.The purpose of this invention is to provide image forming material and resist imaging method thereof with purple laser-photosensitive anticorrosive additive material layer, this material layer is extremely sensitive to the laser beam in purple light district, even and when thickness increases its light sensitivity can not descend yet.

The present inventor finds, when using purple laser, particularly when using material during as the anticorrosive additive material layer with specific absorbance, even the thickness of anticorrosive additive material layer increases, photonasty can not descend yet, and therefore can form the image forming material with thick resist material layer, and, this image forming material preferably advantageously obtains by the photosensitive composition that employing contains specific emulsion, thereby realizes the present invention.

Promptly, the invention reside in: a kind of image forming material with purple laser-photosensitive anticorrosive additive material layer, the photonasty anticorrosive additive material layer that this material has processed substrate and forms on this substrate, it is characterized in that, this photonasty anticorrosive additive material layer has the thickness of at least 10 μ m, and has per 1 μ m thickness absorbance of 0.3 at the most at 405nm wavelength place; The dry film photoresist material is characterized in that, forms the photosensitive composition layer on the live load film, and this photosensitive composition constitutes above-mentioned purple laser-photosensitive anticorrosive additive material layer; And the resist imaging method, it is characterized in that, be that the laser beam of 320nm～450nm is carried out scan exposure to the photonasty anticorrosive additive material layer of above-mentioned image forming material with wavelength, carry out development treatment subsequently.

In addition, about the preferred photosensitive composition of the purple laser-photosensitive anticorrosive additive material that constitutes above-mentioned image forming material, it is a kind of novel photosensitive composition that is characterised in that emulsion.Promptly, the present invention also is to contain the photosensitive composition of emulsion and reactive compound, this reactive compound produces free radical or acid by interacting with emulsion through exposure, it is characterized in that, this emulsion is at least 100 and be at most 100 for having at 405nm wavelength place, the following compound of 000 molar absorptivity (ε): general formula hereinafter described (Ia) or the dialkyl amido benzene-like compounds of (Ib) representing, this compounds has alkyl substituent in the 2-position of its tetrahydroquinoline ring; The compound that contains sulfonamido with the representative of hereinafter described general formula (II); 2-naphthyridines ketone compounds or 2-carbostyril compound with the representative of hereinafter described general formula (III); Or with the indoline compounds of hereinafter described general formula (IV) representative.

The present invention also is to be used to make the photosensitive composition of electronic circuit, wherein

(1) maximal value of ratio (D/L) of thickness (D) and minimum feature (L) that contains the photonasty anticorrosive additive material layer of said composition is at least 1.0, this minimum feature (L) is by being that the laser beam of 390nm～430nm is carried out scan exposure to the photonasty anticorrosive additive material layer with above-mentioned thickness (D) with wavelength, carries out development treatment subsequently and obtains; With

(2) at the minimum exposure amount (S that can on this photonasty anticorrosive additive material layer, form image under the wavelength of 410nm ₄₁₀(μ J/cm ²)) be at most 10,000 μ J/cm ²

In addition, the invention reside in the photosensitive composition that is used to make electronic circuit, wherein

(1) maximal value of ratio (D/L) of thickness (D) and minimum feature (L) that contains the photonasty anticorrosive additive material layer of said composition is at least 1.0, this minimum feature (L) is by being that the laser beam of 390nm～430nm is carried out scan exposure to the photonasty anticorrosive additive material layer with above-mentioned thickness (D) with wavelength, carries out development treatment subsequently and obtains; With

(2) obtain above-mentioned D/L and be at most 20mJ/cm than employed exposure ²

In addition, the invention reside in: a kind of image forming material, this material have processed substrate and the photonasty anticorrosive additive material layer that is formed on this processed substrate, contain in this photonasty anticorrosive additive material layer to be useful on the above-mentioned photosensitive composition of making electronic circuit; With the dry film photoresist material, this dry film photoresist material has live load film and the photonasty anticorrosive additive material layer that is formed on this live load film, contains in this photonasty anticorrosive additive material layer to be useful on the above-mentioned photosensitive composition of making electronic circuit.

Embodiment

Image forming material with purple laser-photosensitive anticorrosive additive material layer of the present invention has purple laser-photosensitive anticorrosive additive material layer on processed substrate, this photonasty anticorrosive additive material layer has the peak-peak of spectral response in the wavelength coverage of 320nm～450nm, preferably have the peak-peak of spectral response in the wavelength coverage of 390nm～430nm.If the peak-peak of its spectral response is in being lower than above-mentioned wavelength coverage, then the photonasty of this photonasty anticorrosive additive material layer laser beam that is 320nm～450nm to wavelength is relatively poor, on the other hand, if its peak-peak is in surpassing above-mentioned wavelength coverage, then the optical safety under amber light is relatively poor.

In the present invention, the peak-peak of spectral response is the peak-peak in the spectral response curve that is obtained by following method, this method for example is disclosed in " photopolymer technology " (PhotopolymerTechnology) (inferior husband's work of hillock, clear and 63 years Nikkan Kogyo Shimbuns issue, the 262nd page): use measurement of spectral response instrument, will be from beam split such as light sources such as xenon lamp or tungsten lamps, set exposure wavelength and on X direction, be linear change, and make exposure wavelength on y direction, be the logarithm variation, the photonasty image forming material that contains substrate and the photographic layer that forms on this substrate surface is shone exposure, pass through development treatment subsequently, to obtain image corresponding to the light sensitivity of each exposure wavelength, calculate the exposure energy that can form image by picture altitude, wavelength is plotted on the transverse axis, and the inverse of exposure energy is plotted on the longitudinal axis.

In addition, when on photonasty anticorrosive additive material layer, having protective seam, the minimum exposure amount (S that under the wavelength of 410nm, can form image that the photonasty anticorrosive additive material layer in the image forming material with purple laser-photosensitive anticorrosive additive material layer of the present invention has ₄₁₀) be at most 10,000 μ J/cm ², preferably be at most 200 μ J/cm ², more preferably be at most 100 μ J/cm ², be preferably 50 μ J/cm at the most especially ²Although the time shutter is also depended on the exposure intensity of LASER Light Source, if minimum exposure amount (S ₄₁₀) surpass above-mentioned scope, then can prolonging exposure time, thus reduce its practicality.

In addition, when not having protective seam on photonasty anticorrosive additive material layer, the photonasty anticorrosive additive material layer in the image forming material with purple laser-photosensitive anticorrosive additive material layer of the present invention can form the minimum exposure amount (S of image under the wavelength of 410nm ₄₁₀) be at most 10,000 μ J/cm ², preferably be at most 5,000 μ J/cm ², more preferably be at most 2,000 μ J/cm ²Although the time shutter is also depended on the exposure intensity of LASER Light Source, if minimum exposure amount (S ₄₁₀) surpass above-mentioned scope, the meeting prolonging exposure time, thus reduce its practicality.

Though matcoveredn whether on photonasty anticorrosive additive material layer, minimum exposure amount (S ₄₁₀) lower limit preferably the smaller the better, but be generally at least 1 μ J/cm ², be at least 2.5 μ J/cm in the practice ²

In addition, the photonasty anticorrosive additive material layer in the image forming material with purple laser-photosensitive anticorrosive additive material layer of the present invention has above-mentioned (S ₄₁₀) and minimum exposure amount (S ₄₅₀(μ J/cm ²)) ratio (S of (under the wavelength of 450nm, can form the minimum exposure amount of image) ₄₁₀/ S ₄₅₀) preferably be at most 0.1, more preferably be at most 0.05.If this ratio (S ₄₁₀/ S ₄₅₀) surpass above-mentioned scope, then be difficult to satisfy the photonasty of purple laser and the optical safety under the amber light simultaneously.

In addition, the photonasty anticorrosive additive material layer in the image forming material with purple laser-photosensitive anticorrosive additive material layer of the present invention has at the minimum exposure amount (S that can form image greater than 450nm in the wavelength coverage of 650nm at the most _450～650(μ J/cm ²)) and minimum exposure amount (S ₄₅₀(μ J/cm ²)) ratio (S of (under the wavelength of 450nm, can form the minimum exposure amount of image) _450～650/ S ₄₅₀) be preferably greater than 1.If this ratio (S _450～650/ S ₄₅₀) be lower than above-mentioned scope, then be difficult to satisfy the photonasty of purple laser and the optical safety under the amber light simultaneously.

Under the 410nm wavelength, can form the minimum exposure amount (S of image ₄₁₀), under the 450nm wavelength, can form the minimum exposure amount (S of image ₄₅₀) and greater than 450nm and can form the minimum exposure amount (S of image at the most under the wavelength of 650nm _450～650) calculate and obtain by the picture altitude of said determination method gained, said method utilizes measurement of spectral response instrument that the peak-peak of spectral response is measured.These exposures are meant the minimum exposure amount that can form image under best development conditions, and described best development conditions is decided by the variation such as the development conditions such as type, development temperature and development time of developer.As best development conditions, use following condition usually: is to soak 0.5 minute～3 minutes in 11～14 the alkaline developer at 25 ℃ at pH.

In addition, photonasty anticorrosive additive material layer in the image forming material of the anticorrosive additive material layer with purple laser-photosensitive of the present invention is to have purple laser-photosensitive anticorrosive additive material layer on processed substrate, and the thickness of this photonasty anticorrosive additive material layer preferably is at least 10 μ m, more preferably be at least 15 μ m, and preferably be at most 200 μ m, more preferably be at most 100 μ m.If the thickness of this photonasty anticorrosive additive material layer less than 10 μ m, then can not carry out the plating or the etching of adequate thickness on processed substrate, and if the thickness of this photonasty anticorrosive additive material layer greater than preferable range, then the light sensitivity of resist can reduce.

Past, when adopting when can use the visible range to the photographic layer of infrared region laser, light sensitivity reduces if film is thicker, therefore be difficult to find between a kind of needs that can satisfy thickness and light sensitivity at the same time reach well balanced photosensitive material, and in fact also do not use the anticorrosive additive material layer that thickness is at least 10 μ m.The present inventor finds, when using purple laser, particularly when use has the anticorrosive additive material layer of specific absorbance, even the thickness of this anticorrosive additive material layer increases, its photonasty can not descend yet, so, can form image forming material with thick resist material layer.

That is, this photonasty anticorrosive additive material layer is at most 0.3 in the absorbance of the per 1 μ m thickness in 405nm wavelength place, preferably is at most 0.25, especially preferably is at most 0.1.The lower limit of per 1 μ m thickness absorbance is at least 0.001, preferably is at least 0.005.

Usually, when photonasty anticorrosive additive material layer thickening, the light sensitivity of resist descends, yet, the turnout when considering processed substrate, preferred light sensitivity is less with the intensity of variation of thickness.That is, under the exposure wavelength of anticorrosive additive material layer, if the light sensitivity when thickness is 10 μ m is S1, the light sensitivity when thickness is 20 μ m is S2, and then S2/S1 preferably is at least 1 and be at most 5, more preferably be at most 2, and lower limit preferably is at least 1.When S2/S1 is in this scope,,, also can form preferable image even therefore there is the rank difference different time in processed substrate because the variation meeting of the light sensitivity that the thickness change is caused is very little.In the present invention, the light sensitivity of resist is defined as, and when with purple laser this photographic layer being exposed and developing, makes the film residual rate be at least 90% minimum exposure amount of resist coating thickness.

The photosensitive composition that forms photonasty anticorrosive additive material layer of the present invention is preferably a kind of like this composition: the maximal value of ratio (D/L) of thickness (D) and minimum feature (L) that (1) contains the photonasty anticorrosive additive material layer of said composition is at least 1.0, this minimum feature (L) is by being that the laser beam of 390nm～430nm is carried out scan exposure to the photonasty anticorrosive additive material layer with above-mentioned thickness (D) with wavelength, carries out development treatment subsequently and obtains; (2) at the minimum exposure amount (S that can on this photonasty anticorrosive additive material layer, form image under the wavelength of 410nm ₄₁₀(μ J/cm ²)) be at most 10,000 μ J/cm ²Available live width (L) changes with the thickness of photonasty anticorrosive additive material layer.Therefore, the above-mentioned maximal value meaning is that it is that (L) measures to minimum feature, the maximal value of a plurality of D/L that obtain therefrom when change photonasty anticorrosive additive material tunic is thick.This maximal value preferably is at least 1.3, more preferably is at least 2.0.D/L is preferably high more good more, yet, be at most 10 usually.(S ₄₁₀(μ J/cm ²)) preferable range as mentioned above.

The photosensitive composition that forms photonasty anticorrosive additive material layer of the present invention is preferably a kind of like this composition: the maximal value of ratio (D/L) of thickness (D) and minimum feature (L) that (1) contains the photonasty anticorrosive additive material layer of said composition is at least 1.0, this minimum feature (L) is by being that the laser beam of 390nm～430nm is carried out scan exposure to the photonasty anticorrosive additive material layer with above-mentioned thickness (D) with wavelength, carries out development treatment subsequently and obtains; (2) obtain the employed exposure of above-mentioned D/L and be at most 20mJ/cm ²

The preferable range of D/L as mentioned above.Obtain the employed exposure of above-mentioned D/L and preferably be at most 10mJ/cm ²The lower limit that obtains the employed exposure of above-mentioned D/L is preferably the smaller the better, yet, be at least 1 μ J/cm usually ², be at least 2.5 μ J/cm in the practice ²

The composition that constitutes the photosensitive composition of the photonasty anticorrosive additive material layer in the image forming material with purple laser-photosensitive anticorrosive additive material layer of the present invention is not particularly limited, so long as can satisfy above-mentioned spectral response characteristics and thickness gets final product, and this constituent can be negativity or positivity.Their preferred example is respectively, as the photopolymerizable negative photosensitive composition (N1) and the chemical amplifying type negative photosensitive composition (N2) of negativity, and as the chemically amplified positive photosensitive composition (P1) of positivity.

(N1: photopolymerizable negative photosensitive composition)

As photopolymerizable negative type, preferably contain following ingredients (N1-1), (N1-2) and photopolymerizable photosensitive composition (N1-3):

(N1-1) ethylene linkage unsaturated compound

(N1-2) emulsion

(N1-3) photo-induced polymerization initiator

Ethylene linkage unsaturated compound as the composition (N1-1) that constitutes negative photosensitive composition (N1) photopolymerizable among the present invention is the compound that has the unsaturated ethylene linkage of at least one free redical polymerization in the molecule, when with this photosensitive composition of active light beam irradiates, the effect of the photopolymerization initiator system of the photo-induced polymerization initiator by containing composition as mentioned below (N1-3), make this unsaturated ethylene linkage carry out polyaddition reaction, also carry out crosslinked and curing reaction in some cases.

In the present invention, the ethylene linkage unsaturated compound can be the compound that has a unsaturated ethylene linkage in the molecule, especially, it can be for example unsaturated carboxylic acid or its Arrcostab, (methyl) vinyl cyanide, (methyl) acrylamide or styrene such as (methyl) acrylic acid (in the present invention, the meaning of " (methyl) acrylic acid " is " acrylic acid " and/or " methacrylic acid "), crotonic acid, iso-crotonic acid, maleic acid, itaconic acid or citraconic acid.Yet, consider aggregation property, crosslinked character and in order to increase the dissolubility difference in developer between exposed portion and the non-exposed portion, the compound that preferably in its molecule, has unsaturated ethylene linkage more than 2 or 2, be preferably acrylate compounds especially, its unsaturated link comes from (methyl) acryloyl-oxy group.

As the compound that has unsaturated ethylene linkage more than 2 or 2 in the molecule, typically, can be for example unsaturated carboxylic acid and polyurethane (methyl) acrylate of the ester of polyol, the phosphate that contains methacryloxy, hydroxyl (methyl) acrylate compounds and polyisocyanate compound or epoxy (methyl) acrylate of (methyl) acrylic acid or hydroxyl (methyl) acrylate compounds and polyepoxides.

As ester, especially, can be the reaction product of above-mentioned unsaturated carboxylic acid and following material: such as ethylene glycol, polyglycol (adduct number is 2～14), 1, the 2-propylene glycol, poly-1,2-propylene glycol (adduct number is 2～14), 1, ammediol, 1, the 4-butylene glycol, neopentyl glycol, 1, the 6-hexanediol, 1, the 9-nonanediol, trimethylolethane, tetra methylol ethane, trimethylolpropane, glycerine, pentaerythrite, aliphatic polyhydroxy compound such as dipentaerythritol or D-sorbite, or the addition compound product of the addition compound product of its ethylene oxide or propylene oxide, or diethanolamine or triethanolamine.Specifically, above-mentioned reaction product can be (methyl) acrylic acid ethylene glycol (methyl) acrylate, diethylene glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, TEG two (methyl) acrylate, nine ethylene glycol bisthioglycolates (methyl) acrylate, propylene glycol two (methyl) acrylate, tripropylene glycol two (methyl) acrylate, butylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, hexanediol two (methyl) acrylate, nonanediol two (methyl) acrylate, trimethylolethane trimethacrylate (methyl) acrylate, tetra methylol ethane three (methyl) acrylate, trimethylolpropane two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, trimethylolpropane ethylene oxide addition three (methyl) acrylate, glycerine two (methyl) acrylate, glycerine three (methyl) acrylate, glycerine propylene oxide addition three (methyl) acrylate, pentaerythrite two (methyl) acrylate, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol two (methyl) acrylate, dipentaerythritol three (methyl) acrylate, dipentaerythritol four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate, D-sorbite three (methyl) acrylate, D-sorbite four (methyl) acrylate, D-sorbite five (methyl) acrylate or D-sorbite six (methyl) acrylate, and similar crotonates, the iso-crotonic acid ester, maleate, itaconate and citraconate.

In addition, as ester, can be the reaction product of above-mentioned unsaturated carboxylic acid and following material: such as aromatic polyhydroxy compounds such as p-dihydroxy-benzene, resorcinol, 1,2,3,-thrihydroxy-benzene, Bisphenol F or bisphenol-As, or its ethylene oxide addition compound product or have the addition compound product of the compound of diglycidyl group.Specifically, above-mentioned reaction product can be for example p-dihydroxy-benzene two (methyl) acrylate, resorcinol two (methyl) acrylate, 1,2,3,-thrihydroxy-benzene three (methyl) acrylate, bisphenol-A two (methyl) acrylate, bisphenol-A two [oxygen ethene (methyl) acrylate], bisphenol-A two [three oxygen ethene (methyl) acrylate], bisphenol-A two [five oxygen ethene (methyl) acrylate], bisphenol-A two [hexaoxyethylene (methyl) acrylate] or bisphenol-A two [glycidol ether (methyl) acrylate].In addition, these esters can also be above-mentioned unsaturated carboxylic acids and reaction product such as heterocycle polyols such as three (2-hydroxyethyl) isocyanuric acid esters, and these reaction product are specially two (methyl) acrylate or three (methyl) acrylate of three (2-hydroxyethyl) isocyanuric acid ester; The reaction product of unsaturated carboxylic acid, multi-hydroxy carboxy acid and polyol, these reaction product for example are specifically as follows the condensation product of condensation product, (methyl) acrylic acid, terephthalic acids and pentaerythrite of condensation product, (methyl) acrylic acid, maleic acid and diethylene glycol of (methyl) acrylic acid, phthalic acid and ethylene glycol or the condensation product of (methyl) acrylic acid, hexane diacid, butylene glycol and glycerine.

In addition, as the phosphate that contains (methyl) acryloxy, for example be specifically as follows (methyl) acrylyl oxy-ethyl phosphate, two [(methyl) acrylyl oxy-ethyl] phosphate or (methyl) acryloyl-oxy ethylene glycol phosphate.They can use separately also can mix use.

In addition, as polyurethane (methyl) acrylate, particularly, can be for such as methylol (methyl) acrylate, hydroxyethyl (methyl) acrylate, glycerine two (methyl) acrylate, the reaction product of hydroxyl (methyl) acrylate compounds such as pentaerythrite three (methyl) acrylate or tetra methylol ethane three (methyl) acrylate and following polyisocyanates: for example comprise such as 1, hexamethylene-diisocyanate, 2,4,4-trimethyl-1, hexamethylene-diisocyanate, lysine methyl ester diisocyanate, lysine methyl ester triisocyanate, dimer acid diisocyanate, 1,6,11-11 triisocyanates, 1,3, the own triisocyanate of 6-or 1,8-diisocyanate-aliphatic polyisocyantes such as 4-isocyanates methyloctane; Such as cyclohexane diisocyanate, dimethyl cyclohexane diisocyanate, 4, alicyclic polyisocyanates such as 4-methylene two (cyclohexyl diisocyanate), isophorone diisocyanate or bicycloheptane triisocyanate; Such as to phenylene vulcabond, 2,4-benzal diisocyanate, 2,6-benzal diisocyanate, eylylene diisocyanate, tetramethyl eylylene diisocyanate, 4,4-methyl diphenylene diisocyanate, tolidine diisocyanate, 1, aromatic polyisocyanates such as 5-naphthalene diisocyanate, three (isocyanate benzene methylmethane) or three (isocyanate phenyl) thiophosphate; Or such as heterocycle polyisocyanates such as isocyanuric acid esters.

In addition, as epoxy (methyl) acrylate, particularly, for example can be the reaction product of (methyl) acrylic acid or above-mentioned hydroxyl (methyl) acrylate and following polyepoxides: for example comprise (gathering) ethylene glycol poly epihydric alcohol base ether, (gathering) propylene glycol poly epihydric alcohol base ether, (gathering) butylene glycol poly epihydric alcohol base ether, (gathering) pentanediol poly epihydric alcohol base ether, (gathering) neopentyl glycol poly epihydric alcohol base ether, (gathering) hexanediol poly epihydric alcohol base ether, (gathering) trimethylolpropane poly epihydric alcohol base ether, aliphatic poly epoxy compounds such as (gathering) glycerine poly epihydric alcohol base ether or (gathering) D-sorbite poly epihydric alcohol base ether; Such as phenol novolaks polyepoxides, bromophenol novolaks polyepoxides, (adjacent-,-, to) aromatic series polyepoxidess such as cresols novolaks polyepoxides, polymer with bis phenol A epoxy compound or Bisphenol F polyepoxides; Or such as heterocycle polyepoxidess such as sorbitan poly epihydric alcohol base ether, three-glycidyl based isocyanate or triglycidyl group three (2-hydroxyethyl) isocyanates.

In addition, except above-mentioned substance, as another kind of ethylene linkage unsaturated compound, for example can be for such as (methyl) allylamines such as vinyl two (methyl) allylamines, such as allyl esters such as diallyl phthalates or contain the compound of vinyl such as divinyl phthalic ester etc.Above-mentioned ethylene linkage unsaturated compound can use separately, also can two or more be used in combination.

In above-mentioned ethylene linkage unsaturated compound as composition (N1-1), be preferably ester (methyl) acrylate, the phosphate that contains (methyl) acryloxy or polyurethane (methyl) acrylate in the present invention, be preferably ester (methyl) acrylate especially, and in ester (methyl) acrylate, particularly preferably be, contain for example polyoxyalkylene hydrocarbyl groups such as polyethylene oxide addition compound product of polyglycol, polypropylene glycol or bisphenol-A, and contain ester (methyl) acrylate of at least two (methyl) acryloyl-oxy groups.

Emulsion as the composition (N1-2) that constitutes negative photosensitive composition (N1) photopolymerizable among the present invention is preferably light absorbing dyestuff, this dyestuff effectively absorbing wavelength is the light in the purple light district of 320nm～450nm, and the molar absorptivity (ε) at 405 nm wavelength places is at least 100, preferably be at least 1000, more preferably be at least 10,000, and be at most 100,000, this dyestuff also has photosensitive function simultaneously, this function can be sent to optical excitation the photo-induced polymerization initiator of composition (N1-3) hereinafter described, photo-induced polymerization initiator is decomposed and the generation living radical, this free radical can bring out the polyreaction of the ethylene linkage unsaturated compound of composition (N1-1).

Light absorbing dyestuff as composition of the present invention (N1-2) emulsion, can be the dialkyl amido benzene-like compounds, preferred especially dialkyl amido benzophenone compound or on para-position carbon atom amino on the phenyl ring, have the dialkyl amido benzene-like compounds of heterocyclic substituent.

As this dialkyl amido benzophenone compound, be preferably compound with following general formula (Ia) representative:

(in general formula (Ia), R ¹, R ², R ³And R ⁴Represent alkyl, R each other independently of one another ⁵, R ⁶, R ⁷And R ⁸Represent alkyl or hydrogen atom each other independently of one another, and R ¹With R ², R ³With R ⁴, R ¹With R ⁵, R ²With R ⁶, R ³With R ⁷Or R ⁴With R ⁸Can form nitrogen heterocyclic ring independently.)

In general formula (Ia), alkyl R ¹, R ², R ³And R ⁴Carbon number and work as R ⁵, R ⁶, R ⁷And R ⁸Carbon number during for alkyl is preferably 1～6, when being formed with nitrogen heterocyclic ring, is preferably 5 yuan of rings or 6 yuan of rings, is preferably 6 yuan of rings especially.In the present invention, it is particularly preferred being formed with nitrogenous heterocyclic compound.

In the compound of above-mentioned general formula (Ia) representative, as do not form nitrogenous heterocyclic compound object lesson, can be 4,4-two (dimethylamino) benzophenone and 4,4-two (diethylamino) benzophenone.

In addition, in the compound of above-mentioned general formula (Ia) representative, as being formed with nitrogenous heterocyclic compound, being preferably the compound that is formed with the tetrahydroquinoline ring, more preferably by the compound of following general formula (Ib) representative:

(in general formula (Ib), R ²And R ⁴Representative optionally has substituent alkyl, R independently of one another each other ⁶And R ⁸Represent hydrogen atom each other independently of one another or optionally have substituent alkyl, and R ²With R ⁶Or R ⁴With R ⁸Can form nitrogen heterocyclic ring independently, and these two tetrahydroquinoline rings optionally has another substituting group.)

In general formula (Ib), alkyl R ²And R ⁴Carbon number and work as R ⁶And R ⁸Carbon number during for alkyl is preferably 1～6, works as R ²With R ⁶Or R ⁴With R ⁸When forming nitrogen heterocyclic ring, be preferably 5 yuan of rings or 6 yuan of rings, more preferably 6 yuan of rings, especially preferably R ², R ⁶With the tetrahydroquinoline ring, and R ⁴, R ⁸Form the julolidine ring respectively with the tetrahydroquinoline ring.

In general formula (Ib), alkyl R ², R ⁴, R ⁶And R ⁸In substituting group can be; alkoxy for example; acyl group; acyloxy; alkoxy carbonyl group; aryl; aryloxy group; alkylthio group; arylthio; amino; hydroxyl or halogen atom; substituting group in two tetrahydroquinoline rings separately can for; alkyl for example; alkoxy; acyl group; acyloxy; alkoxy carbonyl group; aryl; aryloxy group; alkylthio group; arylthio; amino; hydroxyl or halogen atom; and in this case; can be by means of alkylidene; imino group; alkyl imino; oxygen atom or sulphur atom make two phenyl ring form ring texture by the ortho position carbon atom bonding with carbonyl.

Object lesson as the compound of above-mentioned general formula (Ib) representative can be the compound of following structure:

In the compound of above-mentioned general formula (Ib) representative, be preferably especially in the 2-position of two tetrahydroquinolines and have alkyl, and the carbon number of this alkyl is preferably 1～10 as substituent compound, be preferably 1～6 especially.Its object lesson as shown in following table 1, below two general formulas all have R as alkyl in the 2-position ⁹And R ¹⁰, these two general formulas are respectively: by following general formula (Ib ₁) shown in the compound of above-mentioned general formula (Ib), wherein phenyl ring forms ring texture by the ortho position carbon atom of carbonyl, has Ra～Rl having on the substituent carbon atom; And by the compound of the above-mentioned general formula (Ib) shown in the following general formula (Ib2), wherein phenyl ring forms ring texture by the ortho position carbon atom of carbonyl, and linking group is Y, and has Ra～Rl having on the substituent carbon atom.

Table 1

	?R 9	?Ra	?Rb	?Rc	?Rd	?Re	?Rf	?R 10	?Rg	?Rh	?Ri	?Rj	Rk	?Rl	Y
																?Ib 1-1	?CH 3	?H	?H	?H	?H	?H	?H	?CH 3	?H	?H	?H	?H	?H	?H	-
?Ib 1-2	?CH 3	?CH 3	?H	?CH 3	?H	?H	?H	?CH 3	?CH 3	?H	?CH 3	?H	?H	?H	-
																?Ib 1-3	?CH 3	?H	?CH 3	?H	?H	?H	?H	?CH 3	?H	?CH 3	?H	?H	?H	?H	-
?Ib 1-4	?CH 3	?H	?H	?CH 3	?H	?H	?H	?CH 3	?H	?H	?CH 3	?H	?H	?H	-
																?Ib 1-5	?CH 3	?H	?H	?H	?OCH 3	?H	?H	?CH 3	?H	?H	?H	?OCH 3	?H	?H	-
?Ib 1-6	?CH 3	?H	?H	?H	?COOCH 3	?H	?H	?CH 3	?H	?H	?H	?COOCH 3	?H	?H	-
																?Ib 1-7	?CH 3	?H	?H	?H	?OH	?H	?H	?CH 3	?H	?H	?H	?OH	?H	?H	-
?Ib 1-8	?CH 3	?H	?H	?H	?Cl	?H	?H	?CH 3	?H	?H	?H	?Cl	?H	?H	-
																?Ib 1-9	?CH 3	?H	?H	?H	?H	?CH 3	?CH 3	?CH 3	?H	?H	?H	?H	?CH 3	?CH 3	-
?Ib 1-10	?C 5H 11	?H	?H	?H	?H	?H	?H	?C 5H 11	?H	?H	?H	?H	?H	?H	-

Table 1 (continuing)

	?R 9	?Ra	?Rb	?Rc	?Rd	?Re	?Rf	?R 10	?Rg	?Rh	?Ri	?Rj	?Rk	?Rl	?Y
																?Ib 2-1	?CH 3	?H	?H	?H	?H	?H	?H	?CH 3	?H	?H	?H	?H	?H	?H	O or S
?Ib 2-2	?CH 3	?H	?H	?CH 3	?H	?H	?H	?CH 3	?H	?H	?CH 3	?H	?H	?H
															?Ib 2-3	?CH 3	?H	?H	?H	?OCH 3	?H	?H	?CH 3	?H	?H	?H	?OCH 3	?H	?H
?Ib 2-4	?CH 3	?H	?H	?H	?COOCH 3	?H	?H	?CH 3	?H	?H	?H	?COOCH 3	?H	?H
															?Ib 2-5	?CH 3	?H	?H	?H	?OH	?H	?H	?CH 3	?H	?H	?H	?OH	?H	?H
?Ib 2-6	?CH 3	?H	?H	?H	?Cl	?H	?H	?CH 3	?H	?H	?H	?Cl	?H	?H
															?Ib 2-7	?CH 3	?H	?H	?H	?H	?CH 3	?CH 3	?CH 3	?H	?H	?H	?H	?CH 3	?CH 3
?Ib 2-8	?C 5H 11	?H	?H	?H	?H	?H	?H	?C 5H 11	?H	?H	?H	?H	?H	?H

In addition, on phenyl ring, have on the carbon atom of amino contraposition in the dialkyl amido benzene-like compounds of heterocyclic substituent, heterocyclic group is preferably 5 yuan of rings or the 6 yuan of rings that contain nitrogen-atoms, oxygen atom or sulphur atom, 5 yuan of rings that especially preferably have fused benzene rings, as this dialkyl amido benzene-like compounds, be preferably compound especially by following general formula (Ic) representative:

(in general formula (Ic), R ¹And R ²Represent alkyl, R each other independently of one another ⁵And R ⁶Represent alkyl or hydrogen atom each other independently of one another, and R ¹With R ², R ¹With R ⁵Or R ²With R ⁶Can form nitrogen heterocyclic ring independently.X represention oxygen atom, sulphur atom, dialkyl group methylene, imino group or alkyl imino, ring A representative optionally has substituent aromatic rings.)

In general formula (Ic), alkyl R ¹And R ²Carbon number and work as R ⁵And R ⁶Carbon number during for alkyl is preferably 1～6, when forming nitrogen heterocyclic ring, is preferably 5 yuan of rings or 6 yuan of rings, is preferably 6 yuan of rings especially.In the present invention, be preferably the nitrogenous heterocyclic compound of formation especially.In addition, when X was the dialkyl group methylene, the carbon number of alkyl was preferably 1～6, and when X was alkyl imino, the carbon number of alkyl was preferably 1～6.Ring A is preferably phenyl ring.

In compound by above-mentioned general formula (Ic) representative, as the object lesson that does not form nitrogenous heterocyclic compound, can be 2-(to dimethylaminophenyl) benzoxazole, 2-is (to diethylamino phenyl) benzoxazole, 2-(to dimethylaminophenyl) benzo [4,5] benzoxazoles, 2-(to dimethylaminophenyl) benzo [6,7] benzoxazoles, 2-(to dimethylaminophenyl) benzothiazole, 2-(to the diethylamino phenyl) benzothiazole, 2-(to dimethylaminophenyl) benzimidazole, 2-(to the diethylamino phenyl) benzimidazole, 2-(to dimethylaminophenyl)-3,3-dimethyl-3H-indoles and 2-(to the diethylamino phenyl)-3,3-dimethyl-3H-indoles.

On phenyl ring, has heterocycle as in the substituent dialkyl amido benzene-like compounds on the para-position carbon atom of amino, except compound by above-mentioned general formula (Ic) representative, do not form nitrogenous heterocyclic compound can for, 2-(to dimethylaminophenyl) pyridine for example, 2-(to the diethylamino phenyl) pyridine, 2-(to dimethylaminophenyl) quinoline, 2-(to the diethylamino phenyl) quinoline, 2-(to dimethylaminophenyl) pyrimidine, 2-(to the diethylamino phenyl) pyrimidine, 2,5-two (to the diethylamino phenyl)-1,3,4-oxadiazole or 2,5-two (to the diethylamino phenyl)-1,3, the 4-thiadiazoles.

In addition, in compound, form nitrogenous heterocyclic compound and be preferably the compound that forms the tetrahydroquinoline ring by above-mentioned general formula (Ic) representative, more preferably by the compound of following general formula (Id) representative:

(in general formula (Id), R ²Representative optionally has substituent alkyl, R ⁶Representative optionally has substituent alkyl or hydrogen atom, R ²With R ⁶Can form nitrogen heterocyclic ring, X represents dialkyl group methylene, imino group or alkyl imino, oxygen atom or sulphur atom, and ring A representative optionally has substituent aromatic rings, and other positions of tetrahydroquinoline ring can have substituting group.)

In general formula (Id), alkyl R ²Carbon number and work as R ⁶Carbon number during for alkyl is preferably 1～6, works as R ²With R ⁶When forming nitrogen heterocyclic ring, be preferably 5 yuan of rings or 6 yuan of rings, more preferably 6 yuan of rings, especially preferably R ²With R ⁶And the tetrahydroquinoline ring forms the julolidine ring.In addition, when X was dialkyl group methylene or dialkyl group imino group, the carbon number of alkyl was preferably 1～6.In addition, ring A is preferably phenyl ring.

Alkyl R in the general formula (Id) ²And R ⁶Substituting group can for; for example alkoxy, acyl group, acyloxy, alkoxy carbonyl group, aryl, aryloxy group, alkylthio group, arylthio, amino, hydroxyl or halogen atom; the substituting group of other positions can be in the tetrahydroquinoline ring, for example alkyl, alkoxy, acyl group, acyloxy, alkoxy carbonyl group, aryl, aryloxy group, alkylthio group, arylthio, amino, hydroxyl or halogen atom.

As object lesson by the compound of above-mentioned general formula (Id) representative, can be for having the compound of following array structure:

In compound by above-mentioned general formula (Id) representative, be preferably especially in the 2-position of tetrahydroquinoline ring and have alkyl, and the carbon number of this alkyl is preferably 1～10 as substituent compound, be preferably 1～6 especially.Its object lesson is as shown in table 2 below, and by following general formula (Id ₁) represent, wherein have R as alkyl in the 2-position ⁹And has Rc～Rf having on the substituent carbon atom.

Table 2

	?R 9	?Rc	?Rd	?Re	?Rf	?X
							?Id 1-1	?CH 3	?H	?H	?H	?H	?C(CH 3) 2, NH, O or S
?Id 1-2	?CH 3	?CH 3	?H	?H	?H
						?Id 1-3	?CH 3	?H	?OCH 3	?H	?H
?Id 1-4	?CH 3	?H	?COOCH 3	?H	?H
						?Id 1-5	?CH 3	?H	?OH	?H	?H
?Id 1-6	?CH 3	?H	?Cl	?H	?H
						?Id 1-7	?CH 3	?H	?H	?CH 3	?CH 3
?Id 1-8	?C 5H 11	?H	?H	?H	?H

In addition, the light absorber as emulsion composition (N1-2) can be the compound with sulphonyl imino group in the present invention, is preferably the compound by following general formula (II) representative especially:

(in general formula (II), R ¹¹And R ¹²Represent hydrogen atom or optional substituting group each other independently of one another, R ¹³The substituting group that representative is optional.)

As R in the general formula (II) ¹¹And R ¹²Preferred group can be for example hydrogen atom; Such as C such as methyl, ethyl, propyl group, isopropyl, normal-butyl, sec-butyl, the tert-butyl group or n-heptyls _1～18The straight or branched alkyl; Such as cyclopropyl, cyclopentyl, cyclohexyl or adamantyl C such as (adamantyl) _3～18Naphthenic base; Such as C such as vinyl, propenyl or hexenyls _2～18The thiazolinyl of straight or branched; Such as C such as cyclopentenyl or cyclohexenyl groups _3～18Cycloalkenyl group; Such as C such as 1-styryl, 2-styryl, 2-cinnamyl group, 1-(Alpha-Naphthyl) vinyl, 2-(Alpha-Naphthyl) vinyl, 1-(betanaphthyl) vinyl or 2-(betanaphthyl) vinyl _8～18Arylalkenyl; Feed saturated or undersaturated heterocyclic radicals such as base, thiazolyl, benzothiazolyl, morpholinyl, pyrrolidinyl or dioxo tetrahydro-thienyl such as 2-thienyl, 2-pyridine radicals, furan; Such as phenyl, tolyl, xylyl or 2,4, C such as 6-trimethylphenyl _6～18Aryl; Such as C such as benzyl or phenethyls _7～20Aralkyl; Such as C such as acetyl group, propiono, positive bytyry, isobutyryl, positive valeryl or isovaleryl _2～18The straight or branched acyl group; Such as C such as methoxyl, ethoxy, positive propoxy, isopropoxy, n-butoxy, sec-butoxy or tert-butoxies _1～18The alkoxy of straight or branched; Such as C such as propenyloxy group, butenyloxy or amylene oxygen bases _3～18The alkenyloxy of straight or branched; Such as C such as methyl mercapto, ethylmercapto group, positive rosickyite base, positive butylthio, secondary butylthio or uncle's butylthios _1～18The alkylthio group of straight or branched; Cyano group; Hydroxyl; Formoxyl; Sulfonic group; Carboxyl; Acyloxy by-OCOR representative; Amino by-NRR representative; Acylamino-by-NHCOR representative; Carbamate groups by-NHCOOR representative; Sulfoamido by-NHSOOR representative; Carboxylic acid ester groups by-COOR representative; Carbamyl by-CONRR representative; Sulfamoyl by-SOONRR representative; Or by-SO ₂The sulfonate group of OR representative.As R ¹³Preferred group except above-mentioned group, can also be for example by the imino group of-N=CRR representative.

As preferred R and R in these groups, for example can be for such as C such as methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, the tert-butyl group or n-heptyls _1～18The straight or branched alkyl; Such as C such as cyclopropyl, cyclopentyl, cyclohexyl or adamantyls _3～18Naphthenic base; Such as C such as vinyl, propenyl or hexenyls _2～18The thiazolinyl of straight or branched; Such as C such as cyclopentenyl or cyclohexenyl groups _3～18Cycloalkenyl group; Such as saturated or undersaturated heterocyclic radicals such as 2-thienyl, 2-pyridine radicals, furyl, thiazolyl, benzothiazolyl, morpholinyl, pyrrolidinyl or dioxo tetrahydro-thienyls; Such as phenyl, tolyl, xylyl or 2,4, C such as 6-trimethylphenyl _6～18Aryl.

As by R ¹¹To R ¹³Groups such as the alkyl of representative, naphthenic base, thiazolinyl, cycloalkenyl group, heterocyclic radical, aryl can further have following substituting group: such as C such as methoxyl, ethoxy and positive propoxy, isopropoxy, n-butoxy, sec-butoxy or tert-butoxies _1～10Alkoxy; Such as C such as methoxy methoxy base, ethoxy methoxyl, the third oxygen methoxyl, ethoxy ethoxy, the third oxygen ethoxy or methoxy butoxy _2～12Alkoxyalkoxy group; Such as C such as methoxy methoxy methoxyl, methoxy methoxy ethoxy, methoxy (ethoxy) methoxyl or ethoxy ethoxy methoxyls _3～15The alcoxyl alkoxyalkoxy group; Allyloxy; Such as phenyl, tolyl or xylyl C such as (these groups can further be substituted base and replace) _6～12Aryl; Such as C such as phenoxy group, toloxyl, xylyloxy or naphthoxys _6～12Aryloxy group; Such as acyl groups such as acetyl group or propionos; Cyano group; Nitro; Hydroxyl; Tetrahydrofuran base; Amino; Such as N, N-dimethylamino or N, C such as N-diethylamino _1～10Alkylamino; Such as C such as sulfonyloxy methyl amino, ethyl sulfonamide base or positive third sulfonamidos _1～6Alkyl sulfonyl amino; Such as halogen atoms such as fluorine atom, chlorine atom or bromine atoms; Such as C such as methoxycarbonyl group, carbethoxyl group or positive butoxy carbonyls _2～7Alkoxy carbonyl group; Such as C such as methyl carbonyl oxygen base, ethyl oxy carbonyl, n-pro-pyl carbonyl oxygen base, isopropyl carbonyl oxygen base or normal-butyl carbonyl oxygen bases _2～7Alkyl carbonyl oxy; Or such as C such as methoxy carbonyl oxygen base, ethoxy carbonyl oxygen base, the positive third oxygen carbonyl oxygen base, the different third oxygen carbonyl oxygen base or positive fourth oxygen carbonyl oxygen bases _2～7Alkyl oxy carbonyl oxygen.

Work as R ¹¹To R ¹³During for alkyl, naphthenic base or cycloalkenyl group, preferred substituted is alkoxy or alkoxyalkoxy group in these substituting groups, and works as R ¹¹To R ¹³During for thiazolinyl, heterocyclic radical or aryl, preferred substituted is alkoxy, alkoxyalkoxy group, aryl, amino, alkylamino, cyano group or hydroxyl.

Compound by above-mentioned general formula (II) representative is preferably R ¹¹, R ¹²And R ¹³In at least one is thiazolinyl, cycloalkenyl group, arylalkenyl, heterocyclic radical, aryl or acylated compound; More preferably following compound, wherein R ¹¹, R ¹²And R ¹³In at least one for optionally having substituent unsaturated heterocycle base, or optionally have substituent aryl; Be preferably following compound especially, wherein R ¹¹Be hydrogen atom, R ¹²And R ¹³Each other independently of one another for optionally having substituent unsaturated heterocycle or optionally having substituent aryl; Especially preferred R ¹²For having amino phenyl, described amino optionally has for example alkyl substituent.

Molecular weight by the compound of above-mentioned general formula (II) representative is generally at least 200, is preferably at the most 2,000, and more preferably at the most 1,000.Object lesson as by the compound of above-mentioned general formula (II) representative can be following compound:

In addition, the light absorbing dyestuff of the emulsion of composition (N1-2) can be 2-naphthyridines ketone (naphthyridone) compounds or 2-carbostyril compound in the present invention, is preferably the compound by following general formula (III) representative especially:

(in general formula (III), Z represents nitrogen-atoms or C-R ²¹, R ¹⁴, R ¹⁵, R ¹⁶, R ¹⁷, R ¹⁸, R ¹⁹, R ²⁰And R ²¹Represent hydrogen atom or optional substituting group each other independently of one another, R ¹⁸With R ¹⁹, R ¹⁹With R ²⁰Or R ²⁰With R ²¹Can form nitrogen heterocyclic ring and R independently ¹⁵To R ¹⁸In can be bonded to ring between adjacent two groups.)

In general formula (III), as R ¹⁴, R ¹⁵, R ¹⁶, R ¹⁷, R ¹⁸, R ¹⁹, R ²⁰And R ²¹Preferably group can be, for example hydrogen atom; Such as C such as methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, the tert-butyl group or n-heptyls _1～18The straight or branched alkyl; Such as C such as cyclopropyl, cyclopentyl, cyclohexyl or adamantyls _3～18Naphthenic base; Such as C such as vinyl, propenyl or hexenyls _2～18The thiazolinyl of straight or branched; Such as C such as cyclopentenyl or cyclohexenyl groups _3～18Cycloalkenyl group; Such as saturated or undersaturated heterocyclic radicals such as 2-thienyl, 2-pyridine radicals, furyl, thiazolyl, benzothiazolyl, morpholinyl, pyrrolidinyl or dioxo tetrahydro-thienyls; Such as phenyl, tolyl, xylyl or 2,4, C such as 6-trimethylphenyl _6～18Aryl; Such as C such as benzyl or phenethyls _7～20Aralkyl; Such as C such as acetyl group, propiono, positive bytyry, isobutyryl, positive valeryl or isovaleryl _2～18The straight or branched acyl group; Such as C such as methoxyl, ethoxy, positive propoxy, isopropoxy, n-butoxy, sec-butoxy or tert-butoxies _1～18The alkoxy of straight or branched; Such as C such as propenyloxy group, butenyloxy or amylene oxygen bases _3～18The alkenyloxy of straight or branched; Such as C such as methyl mercapto, ethylmercapto group, positive rosickyite base, positive butylthio, secondary butylthio or uncle's butylthios _3～18The alkylthio group of straight or branched; Such as halogen atoms such as fluorine atom, chlorine atom or bromine atoms; Nitro; Cyano group; Hydroxyl; Formoxyl; Sulfonic group; Carboxyl; Acyloxy by-OCOR representative; Amino by-NRR representative; Acylamino-by-NHCOR representative; Carbamate groups by-NHCOOR representative; Sulfonamido by-NHSOOR representative; Carboxylic acid ester groups by-COOR representative; Carbamyl by-CONRR representative; Sulfamoyl by-SOONRR representative; Or by-SO ₂The sulfonate group of OR representative.

As preferred R of institute in these groups and R, can be for for example such as C such as methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, the tert-butyl group or n-heptyls _1～18The straight or branched alkyl; Such as C such as cyclopropyl, cyclopentyl, cyclohexyl or adamantyls _3～18Naphthenic base; Such as C such as vinyl, propenyl or hexenyls _2～18The thiazolinyl of straight or branched; Such as C such as cyclopentenyl or cyclohexenyl groups _3～18Cycloalkenyl group; Such as saturated or undersaturated heterocyclic radicals such as 2-thienyl, 2-pyridine radicals, furyl, thiazolyl, benzothiazolyl, morpholinyl, pyrrolidinyl or dioxo tetrahydro-thienyls; Such as phenyl, tolyl, xylyl or 2,4, C such as 6-trimethylphenyl _6～18Aryl.

As by R ¹⁴To R ²¹Groups such as the alkyl of representative, naphthenic base, thiazolinyl, cycloalkenyl group, heterocyclic radical, aryl can further have substituting group, in these substituting groups and the above-mentioned general formula (II) as R ¹¹To R ¹³Group such as alkyl, naphthenic base, thiazolinyl, cycloalkenyl group, heterocyclic radical, aryl substituent similar, they can be C for example _1～10Alkoxy; C _2～12Alkoxyalkoxy group; C _3～15The alcoxyl alkoxyalkoxy group; C _6～12Aryl; C _6～12Aryloxy group; Acyl group; Cyano group; Nitro; Hydroxyl; Tetrahydrofuran base; Amino; C _1～10Alkylamino; C _1～6The alcoxyl sulfonamido; Halogen atom; C _2～7Alkoxy carbonyl group; C _2～7Alkyl carbonyl oxy; Or C _2～7Alkyl oxy carbonyl oxygen.

In above-mentioned general formula (III), R ¹⁴, R ¹⁵, R ¹⁷, R ¹⁸, and R ²¹Can be hydrogen atom each other independently of one another; alkyl; naphthenic base; thiazolinyl; cycloalkenyl group; heterocyclic radical; aryl; aralkyl; acyl group; alkoxy; alkene oxygen base; alkylthio group; halogen atom; nitro; cyano group; hydroxyl; formoxyl; sulfonic group; carboxyl; amino; acylamino-; carbamate groups; sulfoamido; carboxylic acid ester groups; carbamyl; sulfamoyl; sulfonate group etc.; hydrogen atom more preferably; alkyl; thiazolinyl; heterocyclic radical; aryl; aralkyl; acyl group; alkoxy; alkylthio group; halogen atom; nitro; cyano group; hydroxyl; carboxyl; amino; acylamino-; carbamate groups; sulfoamido; carboxylic acid ester groups; carbamyls etc. are preferably hydrogen atom especially; C _1～6Alkyl, C _2～18Thiazolinyl, C _6～18Aryl, C _7～18Aralkyl, C _2～15Acyl group, C _1～6Alkoxy, C _1～6Fluoro-alkyl, C _1～6Fluoroalkyl, C _1～6Fluoroalkane sulfenyl, halogen atom, nitro, cyano group, have substituent amino, carboxylic acid ester groups etc.Two adjacent in them groups can form ring texture by bonding.

For R independent of each other ¹⁴, R ¹⁵, R ¹⁷, R ¹⁸And R ²¹, most preferred being combined as: R ¹⁴Be hydrogen atom, alkyl, naphthenic base, thiazolinyl, cycloalkenyl group, aryl, heterocyclic radical, aralkyl or acyl group, R ¹⁵And R ¹⁸Any group in the above-mentioned group and R respectively do for oneself ¹⁷And R ²¹Be hydrogen atom.

In order to obtain the absorption spectrum to the light sensitization in purple light district, R ¹⁶, R ¹⁹And R ²⁰Be the preferred optional substituting group, R ¹⁶Be preferably alkyl, naphthenic base, thiazolinyl, cycloalkenyl group, heterocyclic radical, aryl, aralkyl, alkoxy, alkene oxygen base, alkylthio group, halogen atom, nitro, cyano group, hydroxyl, formoxyl, sulfonic group, carboxyl, amino, acylamino-, carbamate groups, sulfoamido, carboxylic acid ester groups, carbamyl, sulfamoyl, sulfonate group etc., more preferably alkyl, thiazolinyl, aryl or aralkyl.R ¹⁹And R ²⁰Can be to make amino-NR ¹⁹R ²⁰Be the substituting group of electron donating group, and they are independent separately each other, are preferably alkyl, thiazolinyl, aralkyl or acyl group.Preferred especially R ¹⁶Be C _1～6Alkyl or C _6～18Aryl, and R ¹⁹And R ²⁰Be C each other independently of one another _1～6Alkyl.

In above-mentioned compound, work as R by general formula (III) representative ¹⁸With R ¹⁹, R ¹⁹With R ²⁰, R ²⁰With R ²¹Or R ¹⁵To R ¹⁸In adjacent two group bondings when becoming ring, can be for example following situation: R ¹⁸With R ¹⁹, R ²⁰With R ²¹Or R ¹⁵To R ¹⁸In two adjacent groups form saturated or undersaturated nitrogen heterocyclic ring or hydrocarbon ring, these rings condense the quinoline ring or 1,8 that becomes as basic framework ,-naphthyridines ring; R ¹⁹With R ²⁰Bonding forms such as nitrogen heterocyclic rings such as piperidyl or pyrrolidinyls, or also contains the heterocycle of oxygen atom such as morpholinyl etc.; Or R ¹⁸With R ¹⁹And R ²⁰With R ²¹Bonding forms the julolidine ring.Formed like this ring can further have substituting group.

As the example that forms this ring, can be the compound of following array structure.In following array structure, formed ring structure can have optional substituting group, with above-mentioned general formula (III) in R ¹⁴And R ²¹In the corresponding position, the position of hydrogen atom representative can have optional substituting group.

Molecular weight by the compound of above-mentioned general formula (III) representative is generally at least 200, is preferably at the most 2,000, and more preferably at the most 1,000.Object lesson as by the compound of above-mentioned general formula (III) representative can be following compounds:

In addition, the light absorbing dyestuff of the emulsion of composition (N1-2) can be the dihydroindolines compound in the present invention, and is preferably the compound by following general formula (IV) representative especially:

(in general formula (IV), R ²², R ²³, R ²⁴, R ²⁵, R ²⁶, R ²⁷, R ²⁸, R ²⁹And R ³⁰Represent hydrogen atom or optional substituting group each other independently of one another, R ²²With R ²³Or R ²²With R ³⁰Can form nitrogen heterocyclic ring and R independently ²³To R ³⁰In can be bonded to ring between adjacent two groups.)

As R in the general formula (IV) ²², R ²³, R ²⁴, R ²⁵, R ²⁶, R ²⁷, R ²⁸, R ²⁹And R ³⁰Preferred group can be for example hydrogen atom; Such as C such as methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, the tert-butyl group or n-heptyls _1～18The straight or branched alkyl; Such as C such as cyclopropyl, cyclopentyl, cyclohexyl or adamantyls _3～18Naphthenic base; Such as C such as vinyl, propenyl or hexenyls _2～18The thiazolinyl of straight or branched; Such as C such as cyclopentenyl or cyclohexenyl groups _3～18Cycloalkenyl group; Such as saturated or undersaturated heterocyclic radicals such as 2-thienyl, 2-pyridine radicals, furyl, thiazolyl, benzothiazolyl, morpholinyl, pyrrolidinyl or dioxo tetrahydro-thienyls; Such as phenyl, tolyl, xylyl or 2,4, C such as 6-trimethylphenyl _6～18Aryl; Such as C such as benzyl or phenethyls _7～20Aralkyl; Such as C such as acetyl group, propiono, positive bytyry, isobutyryl, positive valeryl or isovaleryl _2～18The straight or branched acyl group; Such as C such as methoxyl, ethoxy, positive propoxy, isopropoxy, n-butoxy, sec-butoxy or tert-butoxies _1～18The alkoxy of straight or branched; Such as C such as propenyloxy group, butenyloxy or amylene oxygen bases _3～18The alkenyloxy of straight or branched; Such as C such as methyl mercapto, ethylmercapto group, positive rosickyite base, positive butylthio, secondary butylthio or uncle's butylthios _1～18The alkylthio group of straight or branched; Such as halogen atoms such as fluorine atom, chlorine atom or bromine atoms; Nitro; Cyano group; Hydroxyl; Formoxyl; Sulfonic group; Carboxyl; Acyloxy by-OCOR representative; Amino by-NRR representative; Acylamino-by-NHCOR representative; Carbamate groups by-NHCOOR representative; Sulfoamido by-NHSOOR representative; Carboxylic acid ester groups by-COOR representative; Carbamyl by-CONRR representative; Sulfamoyl by-SOONRR representative; By-SO ₂The sulfonate group of OR representative; By-SO ₂The sulfonyl of R representative; Or by following general formula (VI) representative group.

As preferred R and R in these groups; for example can be alkyl similar to the above, naphthenic base, thiazolinyl, cycloalkenyl group, heterocyclic radical, aryl, aralkyl, acyl group, alkoxy, alkene oxygen base, alkylthio group or cyano group; and can also be in addition, such as C such as methoxycarbonyl group, carbethoxyl group, the positive third oxygen carbonyl, tertbutyloxycarbonyl, carbobenzoxy or benzyloxycarbonyl groups _2～18Carboxylic acid ester groups.

In above-mentioned general formula (IV), as the substituent R on the nitrogen-atoms ²²Be preferably hydrogen atom, alkyl, naphthenic base, thiazolinyl, cycloalkenyl group, heterocyclic radical, aryl, aralkyl, acyl group, hydroxyl, sulfonyl etc., more preferably hydrogen atom, alkyl, thiazolinyl, cycloalkenyl group, aryl etc.

In above-mentioned general formula (IV), as the substituent R on nitrogenous 5 yuan of rings ²³, R ²⁴, R ²⁵And R ²⁶, be hydrogen atom, alkyl, naphthenic base, thiazolinyl, cycloalkenyl group etc. independently of one another each other preferably, and in the middle of them, R ²³And/or R ²⁴Alkyl or cycloalkyl more preferably.

In above-mentioned general formula (IV), as the substituent R on the phenyl ring ²⁷And R ³⁰Preferably be hydrogen atom, alkyl, naphthenic base, thiazolinyl, cycloalkenyl group, heterocyclic radical, aryl, aralkyl, acyl group, alkoxy, alkene oxygen base, alkylthio group, halogen atom, nitro, hydroxyl, sulfonic group, carboxyl, amino, acylamino-, carbamate groups, sulfoamido, carboxylic acid ester groups, carbamyl, sulfamoyl, sulfonate group, sulfonyl etc., more preferably hydrogen atom, alkyl, naphthenic base, alkoxy, alkylthio group, nitro, hydroxyl, amino etc. each other independently of one another.

In above-mentioned general formula (IV), as the substituent R on the phenyl ring ²⁸And R ²⁹Preferably be hydrogen atom, alkyl, naphthenic base, thiazolinyl, cycloalkenyl group, heterocyclic radical, aryl, aralkyl, acyl group, alkoxy, alkene oxygen base, alkylthio group, halogen atom, nitro, hydroxyl, amino, acylamino-or each other independently of one another by group of following general formula (IV) representative etc., R ²⁹More preferably hydrogen atom, alkyl, naphthenic base, alkoxy, alkylthio group, amino or acylamino-etc., R ²⁸More preferably by the group of following general formula (IV) representative:

(in general formula (IV), R ³¹Represent hydrogen atom or optional substituting group, bivalent atom or substituting group that W representative is optional, and independent of each other each to radicals R ³¹With R ²⁷Or R ³¹With R ²⁹Bonding is with Cheng Huan mutually.)

At above-mentioned general formula (IV), W is preferably oxygen atom, sulphur atom, replacement or unsubstituted methylene or replacement or unsubstituted imino group etc., W oxygen atom, replacement more preferably or unsubstituted methylene or replacement or unsubstituted imino group etc., as W wherein is methylene oxygen atom, replacement or unsubstituted or compound replacement or unsubstituted imino group, can be for by following general formula (IVa), (IVb), (IVc), (IVd) and (IVe) compound of representative:

(at general formula (IVa), (IVb), (IVc), (IVd) with (IVe), R ²², R ²³, R ²⁴, R ²⁵, R ²⁶, R ²⁷, R ²⁹And R ³⁰Separately such as above-mentioned general formula (IV) qualification, R ³¹, R ³², R ³³, R ³⁴, R ³⁵And R ³⁶Represent hydrogen atom or optional substituting group separately, V represention oxygen atom or N-R ³⁷, R ³⁷Represent hydrogen atom or optional substituting group.)

As above-mentioned general formula (IVa), (IVb), (IVc), (IVd) with the R (IVe) ³¹, R ³², R ³³, R ³⁴, R ³⁵And R ³⁶And the R (IVd) ³⁷, can enumerate with above-mentioned general formula (IV) in R ²², R ²³, R ²⁴, R ²⁵, R ²⁶, R ²⁷, R ²⁸, R ²⁹And R ³⁰The identical group of preferred group.Among them, as R ³¹Preferred group depend on general formula (IVa), (IVb), (IVc), (IVd) and (IVe) change, and they are as shown in following table 3.In following table, zero represents preferred substituted, and ◎ represents particularly preferred substituting group.

Table 3 is (preferably as R ³¹Group)

	????(IVa)	??(IVb)	??(IVc)	??(IVd)	??(IVe)
						Hydrogen atom		??◎	??◎	??◎	??◎
Alkyl	????○	??◎	??◎	??◎	??◎
						Naphthenic base	????○	??◎	??◎	??◎	??◎
Thiazolinyl	????◎	??○	??○	??○	??○
						Cycloalkenyl group	????◎	??○	??○	??○	??○
Heterocyclic radical	????◎	??○	??○	??○	??◎
						Aryl	????◎	??◎	??○	??◎	??◎
Aralkyl
						Acyl group		??○	??○	??◎	??○
Alkoxy	????○	??○	??◎	??◎	??◎
						Alkene oxygen base	????○	??○	??○	??○	??○
Alkylthio group	????○	??○	??◎	??○	??◎
						Halogen atom
Nitro
						Cyano group
Hydroxyl		??○
						Formoxyl
Sulfonic group
						Carboxyl		??○	??○	??○	??○
Acyloxy	????○			??◎	??○
						Amino	????○			??○	??○
Acylamino-
						Carbamate groups
Sulfoamido
						Carboxylic acid ester groups				??○	??○
Carbamyl
						Sulfamoyl
Sulfonate group
						Sulfonyl				??○	??○

In addition, as above-mentioned general formula (IVb), (IVc), (IVd) with the R (IVe) ³², R ³³, R ³⁴, R ³⁵And R ³⁶, can enumerate with above-mentioned general formula (IV) in R ²², R ²³, R ²⁴, R ²⁵, R ²⁶, R ²⁷, R ²⁸, R ²⁹And R ³⁰The identical group of preferred group.Among them, preferred group is respectively as shown in following table 4.In following table, zero represents preferred substituted, and ◎ represents particularly preferred substituting group.

Table 4 is (preferably as R ³²To R ³⁶Group)

	???????????????????(IVb)		???(IVc)	??(IVd)	???(IVe)
							????R 32	????R 33	????R 34	????R 35	????R 36
Hydrogen atom	????◎	????◎	????◎	????◎	????◎
						Alkyl	????◎	????◎	????○	????◎	????◎
Naphthenic base	????◎	????◎	????○	????◎	????◎
						Thiazolinyl	????◎	????◎	????◎	????○	????○
Cycloalkenyl group	????◎	????◎	????◎	????○	????○
						Heterocyclic radical	????○	????○	????○	????◎	????◎
Aryl	????○	????○	????◎	????◎	????◎
						Aralkyl	????○	????○	????○	????○
Acyl group	????◎	????◎	????○	????◎	????○
						Alkoxy	????○	????○	????○	????○	????◎
Alkene oxygen base	????○	????○	????○	????○	????○
						Alkylthio group	????○	????○	????○	????○	????◎
Halogen atom				????○
						Nitro
Cyano group	????◎	????◎		????○
						Hydroxyl			????◎
Formoxyl
						Sulfonic group				????○
Carboxyl	????○			????◎	????○
						Acyloxy	????○	????○			????○
Amino			????○	????○	????○
						Acylamino-			????○	????○
Carbamate groups
						Sulfoamido				????○
Carboxylic acid ester groups	????◎	????◎		????◎	????○
						Carbamyl
Sulfamoyl
						Sulfonate group				????○
Sulfonyl	????○	????○	????◎	????○	????○

In above-mentioned general formula (IVd), when V is N-R ³⁷The time, R ³⁷Preferably can be for example hydrogen atom; C _1～18The straight or branched alkyl; Or C _1～18The straight or branched acyl group; Among them, hydrogen atom or alkyl are particularly preferred.

In addition, in above-mentioned general formula (IV), R ²²With R ²³Or R ²²With R ³⁰Formed nitrogen heterocyclic ring, and R ²²To R ³⁰In the object lesson of adjacent two formed ring texturees of group as follows.

(R ²²With R ³⁰The example of Cheng Huan)

(R ²²With R ²³The example of Cheng Huan)

(R ²⁴With R ²⁵The example of Cheng Huan)

(R ²⁶With R ²⁷The example of Cheng Huan)

(R ²⁷With R ²⁸The example of Cheng Huan)

(R ²⁸With R ²⁹The example of Cheng Huan)

(R ²⁹With R ³⁰The example of Cheng Huan)

Molecular weight by above-mentioned general formula (IV) representative compound is generally at least 200, and is preferably at the most 2,000, and more preferably at the most 1,000.Object lesson as by the compound of above-mentioned general formula (IV) representative can be above-mentioned general formula (IVa), (IVb), (IVc), (IVd) and following compounds (IVe).

Compound by general formula (IVa) representative

Compound by general formula (IVb) representative

Compound by general formula (IVc) representative

Compound by general formula (IVd) representative

Compound by general formula (IVe) representative

In the present invention, when purple laser-photosensitive anticorrosive additive material layer contains photopolymerizable negative photosensitive composition (N1) in the imaging material, if wherein contain the dialkyl amido benzene-like compounds, contain the emulsion that compound, 2-naphthyridines ketone compounds, 2-carbostyril compound or the indoline compounds of sulphonyl imino group come composition (N1-2), light sensitivity can be do not reduced even then film is thicker yet, and the resist image of excellent in resolution can be formed.

The photo-induced polymerization initiator that constitutes the composition (N1-3) of photopolymerizable negative photosensitive composition (N1) of the present invention is a kind of free-radical generating agent as reactive compound, when the emulsion coexistence of this reactive compound and for example composition (N1-2) and when using rayed, the optical excitation that this reactive compound absorbs emulsion can and produce living radical, thereby makes the ethylene linkage unsaturated compound of mentioned component (N1-1) carry out polyreaction.Described photo-induced polymerization initiator can be for example Hexaarylbisimidazolecompounds compounds, two luxuriant titanium compounds, halogenated hydrocarbons derivant, diaryl group iodized salt or organic peroxide.Among them, consider photonasty, to the adhesiveness and the storage stability of substrate as photosensitive composition, be preferably Hexaarylbisimidazolecompounds compounds or two luxuriant titanium compounds, be preferably Hexaarylbisimidazolecompounds compounds especially.

As Hexaarylbisimidazolecompounds compounds, for example be specifically as follows 2,2-two (Chloro-O-Phenyl)-4,4,5,5-tetraphenyl diimidazole, 2,2-two (Chloro-O-Phenyl)-4,4,5,5-four (p-methylphenyl) diimidazole, 2,2-two (Chloro-O-Phenyl)-4,4,5,5-four (p-methoxyphenyl) diimidazole, 2,2-two (Chloro-O-Phenyl)-4,4,5,5-four (to carbethoxy phenyl) diimidazole, 2,2-two (Chloro-O-Phenyl)-4,4,5,5-four (rubigan) diimidazole, 2,2-two (Chloro-O-Phenyl)-4,4,5,5-four (neighbour, right-dichlorophenyl) diimidazole, 2,2-two (neighbour, right-dichlorophenyl)-4,4,5,5-four (neighbour, right-dichlorophenyl) diimidazole, 2,2-two (Chloro-O-Phenyl)-4,4,5,5-four (to fluorophenyl) diimidazole, 2,2-two (Chloro-O-Phenyl)-4,4,5,5-four (neighbour, right-dibromo phenyl) diimidazole, 2,2-two (o-bromophenyl)-4,4,5,5-four (neighbour, right-dichlorophenyl) diimidazole, 2,2-two (o-bromophenyl)-4,4,5,5-four (to iodophenyl) diimidazole, 2,2-two (o-bromophenyl)-4,4,5,5-four (to the methoxyl Chloro-O-Phenyl) diimidazole or 2,2-two (Chloro-O-Phenyl)-4,4,5,5-four (to chloronaphthyl, methylnaphthyl) diimidazole.Among them, be preferably hexaphenyl diimidazole compound, more preferably such diimidazole: this diimidazole has and is bonded to the ortho position by 2 of imidazole ring that halogen atom replaced, phenyl ring on 2, be preferably such diimidazole especially: this diimidazole has and is bonded to 4 on the imidazole ring that is not substituted or is replaced by halogen atom or alkoxy carbonyl group, 4,5,5 phenyl ring.This Hexaarylbisimidazolecompounds compounds preferably uses with the diimidazole compounds, this diimidazole compounds by as Bull.Chem.Soc.Japan for example; 33,565 (1960), J.Org.Chem.; The method preparation that discloses in 36,2262 (1971).

Usually the known Hexaarylbisimidazolecompounds compounds as photo-induced polymerization initiator in photosensitive composition is, its fusing point is at least 190 ℃, for example, from about 196 to about 202 ℃, and at wavelength is in the X-ray diffraction spectrum of 1.54 , has the maximum diffraction peak when being 9.925 ° at Bragg angle (2 θ ± 0.2 °).Consider dissolubility in the coating solvent and the factors such as dispersion stabilization in photosensitive composition, the fusing point of the optimal Hexaarylbisimidazolecompounds compounds of the present invention is at most 180 ℃, particularly mostly be most 175 ℃, and at wavelength is in the X-ray diffraction spectrum of 1.54 , has the maximum diffraction peak when being 21.16 ° at Bragg angle (2 θ ± 0.2 °).As this optimal Hexaarylbisimidazolecompounds compounds, can be for example 2,2-two (Chloro-O-Phenyl)-4,4,5,5-tetraphenyl diimidazole, 2,2-two (neighbours, right-dichlorophenyl)-4,4,5,5-tetraphenyl diimidazole, 2,2-two (o-bromophenyl)-4,4,5,5-tetraphenyl diimidazole, 2,2-two (neighbours, right-dichlorophenyl)-4,4,5,5-four (p-methoxyphenyl) diimidazole among them, is preferably 2 especially, 2-two (Chloro-O-Phenyl)-4,4,5,5-tetraphenyl diimidazole or 2,2-two (neighbour, right-dichlorophenyl)-4,4,5,5-four (p-methoxyphenyl) diimidazole.

In addition, as two luxuriant titanium compounds, particularly, can be for example titanocene dichloride, diphenyl two luxuriant titaniums, two (2, the 4-difluorophenyl), two luxuriant titaniums, (2, the 6-difluorophenyl) two luxuriant titaniums, (2,4, the 6-trifluorophenyl) two luxuriant titaniums, (2,3,5,6-tetrafluoro phenyl) two luxuriant titaniums, (2,3,4,5, the 6-pentafluorophenyl group) two luxuriant titaniums, two (2, the 4-difluorophenyl) two (methyl cyclopentadienyl) titanium, two (2, the 6-difluorophenyl) two (methyl cyclopentadienyl) titanium, two (2,4, the 6-trifluorophenyl) two (methyl cyclopentadienyl) titanium, two (2,3,5,6-tetrafluoro phenyl) two (methyl cyclopentadienyl) titanium, two (2,3,4,5, the 6-pentafluorophenyl group) two (methyl cyclopentadienyl) titaniums or two [2,6-difluoro 3-(1-pyrrole radicals) phenyl], two luxuriant titaniums.Among them, be preferably titanium compound with bicyclopentadiene structure and biphenyl structural, be preferably the cyclohexyl biphenyl that is replaced by halogen atom at the ortho position especially.

In the present invention, the content of forming the photo-induced polymerization initiator of the emulsion of ethylene linkage unsaturated compound, composition (N1-2) of the composition (N1-1) of photopolymerizable negative photosensitive composition (N1) and composition (N1-3) is, ethylene linkage unsaturated compound based on the composition (N1-1) of 100 weight portions, the emulsion of composition (N1-2) is preferably 0.05 weight portion to 20 weight portion, 0.1 weight portion to 10 weight portion more preferably, and the photo-induced polymerization initiator of composition (N1-3) is preferably 1 weight portion to 60 weight portion, more preferably 5 weight portion to 40 weight portions.

For the formation characteristic of improving the photonasty anticorrosive additive material layer on the substrate and developing property etc., except composition (N1-1), (N1-2) with (N1-3), photopolymerizable negative photosensitive composition (N1) of the present invention preferably contains the polymeric binder material of composition (N1-4).Polymeric binder material can be for for example, such as the homopolymer or the multipolymer of (methyl) acrylic acid, (methyl) acrylate, (methyl) vinyl cyanide, (methyl) acrylamide, maleic acid, styrene, vinyl acetate, vinylidene chloride or maleimide; Or polyamide, polyester, polyethers, polyurethane, polyvinyl butyral, polyvinyl alcohol (PVA), polyvinyl pyrrolidone or acetyl group cellulose.Among them, consider alkaline development character, carboxylic vinyl resins is fit to.

As carboxylic vinyl resins, specifically can be the multipolymer of for example following unsaturated carboxylic acid and following vinyl compound.Described unsaturated carboxylic acid for example has (methyl) acrylic acid, crotonic acid, iso-crotonic acid, maleic acid, maleic anhydride, itaconic acid or citraconic acid etc.; Described vinyl compound has styrene; α-Jia Jibenyixi; hydroxy styrenes; (methyl) methyl acrylate; (methyl) ethyl acrylate; (methyl) propyl acrylate; (methyl) butyl acrylate; (methyl) acrylic acid pentyl ester; (methyl) Hexyl 2-propenoate; (methyl) dodecylacrylate; (methyl) 2-ethylhexyl acrylate; (methyl) acrylic acid hydroxyl methyl esters; (methyl) hydroxy-ethyl acrylate; (methyl) glycidyl acrylate; (methyl) benzyl acrylate; (methyl) acrylic acid N; N-dimethyl aminoethyl ester; N-(methyl) acryloyl morpholine; (methyl) vinyl cyanide; (methyl) acrylamide; N-methylol (methyl) acrylamide; N; N-dimethyl (methyl) acrylamide; N, N-dimethylaminoethyl (methyl) acrylamide or vinyl acetate etc.This carboxylic vinyl resins preferably has the acid number of 30 KOH mg/g to 250 KOHmg/g, and when being converted into polystyrene, has 1,000 to 300,000 weight-average molecular weight.

Among them,, be preferably the multipolymer that contains respectively by constitutional repeating units that monomer constituted such as styrene monomer, (methyl) acrylic ester monomer and (methyl) acrylic acid as the polymeric binder material in the negative photosensitive composition (N1).The ratio of monomers such as the styrene monomer of the formation constitutional repeating unit that contains in this multipolymer, (methyl) acrylic ester monomer and (methyl) acrylic acid preferably is respectively 3 moles of %～30 mole %, 10 moles of %～70 mole % and 10 moles of %～60 mole %, especially preferably is respectively 5 moles of %～25 mole %, 20 moles of %～60 mole % and 15 moles of %～55 mole %.

As the styrene monomer in the above-mentioned multipolymer, particularly, can be for example styrene; Ring-alkylated styrenes such as alpha-substituted such as α-Jia Jibenyixi or α-ethyl styrenes; Such as o-methyl styrene, a methyl styrene, p-methylstyrene or 2, nuclear substituted ring-alkylated styrenes such as 5-dimethyl styrene; Such as nuclear substituted hydroxy styrenes such as o-hydroxy ethene, a hydroxy styrenes, para hydroxybenzene ethene or dihydroxy benzenes ethene; Or such as to chlorostyrene, to nuclear substituted halogenated styrenes such as bromstyrol or Dowspray 9s.In addition, as acrylic ester monomer, particularly, can be for example (methyl) acrylic acid Arrcostab, the carbon number of this alkyl is preferably 1～12, more preferably 1～8, it for example is following acrylate: (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) Hexyl 2-propenoate, (methyl) 2-ethylhexyl acrylate or (methyl) 2-ethyl hexyl acrylate, or (methyl) glycidyl acrylate for example, (methyl) benzyl acrylate, (methyl) acrylic-amino ethyl ester or (methyl) acrylic acid N, the Arrcostab that N-dimethyl aminoethyl ester etc. replace.

Except above-mentioned respectively by the constitutional repeating units that monomer constituted such as styrene monomer, (methyl) acrylic ester monomer and (methyl) acrylic acid, but above-mentioned multipolymer can also contain the constitutional repeating unit that monomer constituted by other copolymerization, but the monomer that is somebody's turn to do copolymerization is for for example, such as unsaturated carboxylic acids such as crotonic acid, iso-crotonic acid, maleic acid, maleic anhydride, itaconic acid or citraconic acids; Such as (methyl) vinyl cyanide, (methyl) acrylamide, N-methylol (methyl) acrylamide, N, N-dimethyl (methyl) acrylamide or N, (methyl) acrylic acid derivatives such as N-dimethyl aminoethyl (methyl) allylamine; Or such as vinyl compounds such as vinyl acetate or vinyl chloride.Preferably be at most 10 moles of % of multipolymer total amount by the content of the constitutional repeating unit that above-mentioned other monomers constituted.This multipolymer preferably has the acid number of 30 KOHmg/g to 250 KOH mg/g, and when being converted into polystyrene, has 1,000 to 300,000 weight-average molecular weight.

In addition, as other carboxylic vinyl-based resin, can be on side chain, having the carboxylic vinyl-based resin of unsaturated ethylene linkage.As this carboxylic vinyl-based resin, particularly, can be following material: the unsaturated compound of carboxylic polymkeric substance and fatty family epoxide group or contain the reaction product of the unsaturated compound of alicyclic epoxy group, the carboxyl of 5 moles of %～90 mole % is participated in reaction in this carbonyl bearing polymer, the carboxyl of preferred 30 moles of %～70 mole % is participated in reaction, the unsaturated compound of this fatty family epoxide group is for example allyl glycidyl ether, (methyl) glycidyl acrylate, α-ethyl glycidyl (methyl) acrylate, the crotonic acid ethylene oxidic ester, the iso-crotonic acid ethylene oxidic ester, the crotonyl glycidol ether, monoalkyl list glycidyl itaconate, monoalkyl list glycidyl fumaroyl ester or monoalkyl list glycidyl maleate, this unsaturated compound that contains the alicyclic epoxy group is for example 3,4-epoxycyclohexyl methyl (methyl) acrylate, 2,3-epoxy cyclopentyl-methyl (methyl) acrylate or 7, the 8-epoxy [three the ring [5.2.1.0] last of the ten Heavenly stems-the 2-yl] oxygen methyl (methyl) acrylate; Or below have the compound of at least two types of unsaturated groups with such as unsaturated carboxylic acids such as (methyl) acrylic acid, or further with esters of unsaturated carboxylic acids copolymerization reaction products resulting, the compound that wherein has unsaturated group accounts for 10 moles of %～90 mole % of total amount, be preferably 30 moles of %～80 mole %, described compound with at least two types of unsaturated groups is: such as (methyl) allyl acrylate, 3-allyloxy-2-hydroxypropyl (methyl) acrylate, (methyl) acrylic acid cinnamic ester, (methyl) acrylic acid butene esters, (methyl) acrylic acid methyl allyl ester or N, N-diallyl (methyl) acrylamide etc. has the compound of at least two kinds of unsaturated groups, or such as (methyl) vinyl acrylate, (methyl) acrylic acid 1-vinyl chloride ester, (methyl) acrylic acid 2-phenyl vinyl acetate, (methyl) acrylic acid 1-propylene ester, Vinyl crotonate or vinyl (methyl) acrylamide etc. has the compound of at least two kinds of unsaturated groups.

In addition, as other carboxylic vinyl-based resin, can be the epoxy resin that contains unsaturated group and carboxyl, it is the α at epoxy resin, addition polybasic carboxylic acid or its acid anhydrides obtain on β-unsaturated monocarboxylic addition compound product.

The epoxy resin that contains unsaturated group and carboxyl specifically is, open loop addition α on the epoxide group of epoxy resin, the carboxyl of β-unsaturated monocarboxylic and form ester bond (COO-), introduce unsaturated ethylene linkage by this ester bond, the hydroxyl that generate this moment and the carboxyl reaction of polybasic carboxylic acid or its acid anhydrides form ester bond, introduce carboxyl by this ester bond.

As epoxy resin, be specifically as follows for example bisphenol A epoxide resin, bisphenol F epoxy resin, bisphenol-s epoxy resin, novolac epoxy resin, cresol-novolac epoxy resin or trisphenol epoxy resin, among them, be preferably novolac epoxy resin or cresol-novolac epoxy resin especially.In addition, as α, β-unsaturated monocarboxylic for example is specifically as follows (methyl) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid or citraconic acid.Among them, (methyl) acrylic acid is particularly preferred.In addition, as polybasic carboxylic acid or its acid anhydrides, be specifically as follows for example succinic acid, maleic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, methyltetrahydro phthalic acid, endo-methylene group tetrahydrophthalic acid, methyl endo-methylene group tetrahydrophthalic acid, hexahydro-phthalic acid or methylhexahydrophthalic acid or their acid anhydrides, among them, be preferably maleic anhydride, tetrahydrophthalic anhydride or hexahydro phthalic anhydride, be preferably tetrahydrophthalic anhydride especially.

In the epoxy resin that contains unsaturated group and carboxyl, consider photonasty as photosensitive composition, solubility property and to the adhesiveness of substrate, preferred especially such epoxy resin that contains unsaturated group and carboxyl: wherein epoxy resin is phenol-novolac epoxy resin or cresol-novolac epoxy resin, α, β-unsaturated monocarboxylic is (methyl) acrylic acid, and polybasic carboxylic acid or its acid anhydrides are tetrahydrophthalic anhydride.In addition, preferably this epoxy resin that contains unsaturated group and carboxyl has the acid number of 20 KOH mg/g to 200 KOH mg/g and 2,000 to 200,000 weight-average molecular weight.

In the present invention, in photopolymerizable negative photosensitive composition (N1), ethylene linkage unsaturated compound based on the composition (N1-1) of 100 weight portions, the content of the polymeric binder material of composition (N1-4) is preferably 50 weight portions～500 weight portions, more preferably 70 weight portions～200 weight portions.

In addition, in order to improve for example photopolymerization initiating power, preferred photopolymerizable negative photosensitive composition (N1) of the present invention also contains the hydrogen supply compound of composition (N1-5).The hydrogen supply compound for example can be, such as 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 3-sulfydryl-1,2,4-triazole, 2-sulfydryl-4 (3H)-quinazoline, β-mercaptonaphthalene, two propane thioic acid glycol esters, trimethylolpropane tris thiopropionate or pentaerythrite tetrathio propionic ester etc. contain the compound of sulfydryl; Such as multi-functional group thiol's compounds such as ethanthiol, trimethylolpropane tris sulfo-gluconate or pentaerythrite tetrathio propionic esters; N, N-dialkyl amido benzoic ether; Or such as N-phenylglycine or derivatives thereof (the amino acid or derivatives thereof that has aromatic ring such as its ester, its salt such as its ammonium salt or sodium salt or its dipole ion compound etc.; Or phenylalanine or such as derivants such as its ester, its salt such as its ammonium salt or sodium salt or its dipole ion compounds.In the present invention, wherein be preferably compounds containing thiol groups or amino acid or amino acid whose derivant.

In the present invention, in photopolymerizable negative photosensitive composition (N1), based on the ethylene linkage unsaturated compound of the composition (N1-1) of 100 weight portions, the content of the hydrogen supply compound of composition (N1-5) is preferably 1 weight portion～50 weight portions, more preferably 10 weight portions～40 weight portions.

In addition, in order to improve for example storage stability of photosensitive composition, photopolymerizable negative photosensitive composition (N1) of the present invention also preferably contains the amines of composition (N1-6).Amines for example can be, any fatty amine, cycloaliphatic amines or aromatic amine, and amines is not limited to monoamine, can be such as polyamines such as diamines or triamines, and can be any primary amine, secondary amine and tertiary amine.Yet, be preferably pKb and be at most 7 amine.As amines, for example be specifically as follows, can be such as butylamine, dibutylamine, tri-n-butylamine, amylamine, diamylamine, triamylamine, hexylamine, dihexylamine, trihexylamine, allylamine, diallylamine, triallylamine, triethanolamine, benzylamine, dibenzylamine or tribenzylamine etc. by the fatty amine of hydroxyl or phenyl replacement.In the present invention, wherein be preferably tribenzylamine.

In the present invention, in photopolymerizable negative photosensitive composition (N1), based on the ethylene linkage unsaturated compound of the composition (N1-1) of 100 weight portions, the content of the amines of composition (N1-6) is preferably 1 weight portion～20 weight portions, more preferably 5 weight portions～10 weight portions.

In addition, in order to improve for example paintability on substrate and the developing performance of anticorrosive additive material layer when forming photonasty anticorrosive additive material layer, preferred photopolymerizable negative photosensitive composition (N1) of the present invention also contains nonionic, negative ion, kation, both sexes, fluorine class or other surfactants of composition (N1-7).As non-ionic surfactant, for example specifically can be, polyethylene oxide alkyl ethers, polyoxyethylene PPOX alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene Arrcostab, polyoxyethylene fatty acid esters, glycerine fatty acid ester, polyoxyethylene glycerine fatty acid ester, pentaerythritol fatty ester, polyoxyethylene pentaerythritol fatty ester, D-sorbite fatty acid ester, polyoxyethylene D-sorbite fatty acid ester, D-sorbite fatty acid ester or polyoxyethylene D-sorbite fatty acid ester; As anionic surfactant, for example can be, alkyl sulfonate, alkyl benzene sulfonate, alkylnaphthalene sulfonate, polyethylene oxide alkyl ethers sulfonate, alkyl sulfate, alkyl sulfate, higher alcohol sulfate, aliphatic alcohol sulfate, polyethylene oxide alkyl ethers sulfate, polyoxyethylene alkyl phenyl ether sulfate, alkylphosphonic, polyethylene oxide alkyl ethers phosphate or polyoxyethylene alkyl phenyl ether phosphate; As cationic surfactant, for example can be, quaternary ammonium salt, imidazolidine derivatives or amine salt; As amphoteric surfactant, for example can be, betaines compound, imidazoline salt, imidazoline or amino acid.

In the present invention, in photopolymerizable negative photosensitive composition (N1), based on the ethylene linkage unsaturated compound of the composition (N1-1) of 100 weight portions, the content of the surfactant of composition (N1-7) is preferably 0.1 weight portion～10 weight portions, more preferably 1 weight portion～5 weight portions.

In addition, in order for example to improve the adhesion property of substrate, photopolymerizable negative photosensitive composition (N1) of the present invention can also contain the silane compound of composition (N1-8), the known silane coupling agent that is called as of this silane compound.As silane compound, for example specifically can be, vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three (2-methoxy ethoxy) silane, vinyl trichlorosilane, the 3-methyl allyl acyloxypropyl trimethoxysilane, 3-methacryloxypropyl triethoxysilane, 3-glycidyl oxygen propyl trimethoxy silicane, 3-glycidyl oxygen propyl-triethoxysilicane, 3-glycidyl oxygen propyl group methyl dimethoxysilane, 3-glycidyl oxygen propyl group methyldiethoxysilane, 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, 2-(3, the 4-epoxycyclohexyl) ethyl triethoxysilane, the 3-TSL 8330, the 3-aminopropyltriethoxywerene werene, 3-[N-(2-amino-ethyl) amino] propyl trimethoxy silicane, 3-[N-(2-amino-ethyl) amino] propyl-triethoxysilicane, 3-[N-(2-amino-ethyl) amino] the propyl group methyl dimethoxysilane, 3-[N-(2-amino-ethyl) amino] the propyl group methyldiethoxysilane, 3-(N-allyl-N-glycidyl-amino) propyl trimethoxy silicane, 3-(N-allyl-N-glycidyl-amino) propyl-triethoxysilicane, 3-(N, N-diglycidyl amino) propyl trimethoxy silicane, 3-(N, N-diglycidyl amino) propyl-triethoxysilicane, 3-(N-phenyl amino) propyl trimethoxy silicane, 3-(N-phenyl amino) propyl-triethoxysilicane, 3-sulfydryl propyl trimethoxy silicane, 3-sulfydryl propyl-triethoxysilicane, the 3-chloropropyltrimethoxy silane, the 3-chloropropyltriethoxandlane, or N-glycidyl-N, N-two [3-(trimethoxysilyl) propyl group] amine, N-glycidyl-N, N-two [3-(triethoxysilyl) propyl group] amine, N-glycidyl-N, N-two [3-(methyl dimethoxy oxygen base silicyl) propyl group] amine or N-glycidyl-N, N-two [3-(methyl diethoxy silicyl) propyl group] amine.

In the present invention, in photopolymerizable negative photosensitive composition (N1), based on the ethylene linkage unsaturated compound of the composition (N1-1) of 100 weight portions, the content of the silane compound of composition (N1-8) preferably is at most 10 weight portions, more preferably is at most 5 weight portions.

In addition, photopolymerizable negative photosensitive composition (N1) of the present invention can also contain various adjuvants, for example, content be at most 2 weight portions such as thermal polymerizations such as p-dihydroxy-benzene, p methoxy phenol or 2,6 ditertiary butyl p cresol; Content is at most comprising of 20 weight portions of organic or colorants such as inorganic dyestuff or pigment; Content be at most 40 weight portions such as plastifier such as dioctyl phthalate, phthalic acid dodecane ester or tricresyl phosphates; Content be at most 10 weight portions such as sensitometric characteristic improvers such as tertiary amine or mercaptan; Or content is at most the dyestuff former of 30 weight portions, and above-mentioned each content is all based on the ethylene linkage unsaturated compound of the composition (N1-1) of 100 weight portions.

(N2: chemical amplifying type negative photosensitive composition)

In addition, the photosensitive composition that constitutes photonasty anticorrosive additive material layer of the present invention is preferably and contains following ingredients (N2-1), (N2-2) and chemical amplifying type negative photosensitive composition (N2) (N2-3).

(N2-1) alkali soluble resins

(N2-2) crosslinking chemical of under acid condition, having an effect with alkali soluble resins

(N2-3) light acid propellant

Be not particularly limited for the alkali soluble resins that constitutes the composition (N2-1) of chemical amplifying type negative photosensitive composition (N2) among the present invention, as long as non-exposed portion is alkali-soluble when developing, and can be dissolved in the alkaline developer and get final product, usually for example can use, such as phenol resin such as novolac resin or resol, polyvinylphenol resin, polyacrylic acid, polyvinyl alcohol (PVA), phenylethylene/maleic anhydride resin or contain acrylic acid, vinyl alcohol or vinylphenol as polymer of monomers, or derivatives thereof.Among them, be preferably the resin that contains band phenolic hydroxyl group polymerized unit especially, and novolac resin or polyvinylphenol resin are preferred.

As novolac resin, can be for example in the presence of acid catalyst, by making at least a phenol and at least a aldehydes or ketones carry out the novolac resin that polycondensation obtains, described phenol is such as phenol, orthoresol, metacresol, paracresol, 2, the 5-xylenols, 3, the 5-xylenols, o-ethyl phenol, m-ethylphenol, paraethyl phenol, propylphenol, normal-butyl phenol, tert-butyl phenol, the 1-naphthols, beta naphthal, 4,4-biphenyl glycol, bisphenol-A, catechol, resorcinol, p-dihydroxy-benzene, pyrogallol, 1,2,4-benzenetriol or phloroglucin; Described aldehyde is such as formaldehyde, paraformaldehyde, acetaldehyde, paraldehyde, propionic aldehyde, benzaldehyde or furfural; Described ketone is such as acetone, methyl ethyl ketone or methyl isobutyl ketone.As resol,, can obtain by the polycondensation process identical with above-mentioned novolac resin except with base catalyst rather than with the acid catalyst.

Novolac resin is preferably by at least a orthoresol, metacresol, the paracresol, 2 of being selected from, 5-xylenols, 3, the phenol of 5-xylenols and resorcinol and at least a resin that is selected from the aldehyde polycondensation of formaldehyde, acetaldehyde and propionic aldehyde and obtains, preferred especially novolac resin is that mol ratio is 70 to 100/0 to 30/0 to 20/0 to 20/0 to 20 metacresol/paracresol/2,5-xylenols/3, the phenol mixture of 5-xylenols/resorcinol and polycondensation product as the formaldehyde of aldehyde.In addition, be preferably 1,000 to 15,000, be preferably 1,500 to 10,000 especially by the weight-average molecular weight (Mw) of gel permeation chromatography when being converted into polystyrene.

The polyvinylphenol resin can be obtained by following method: in the presence of radical polymerization initiator or cationic polymerization initiators; by for example following one or more hydroxy styrenes polymerizations or further with another kind of vinylic chemical compound copolymerization; described hydroxy styrenes is for example o-hydroxy ethene; between hydroxy styrenes; para hydroxybenzene ethene; dihydroxy benzenes ethene; trihydroxy benzene ethene; tetrahydroxy benzene ethene; penta hydroxy group styrene; 2-(o-hydroxy-phenyl) propylene; 2-(hydroxy phenyl) propylene and 2-(p-hydroxybenzene) propylene etc.; described another kind of vinylic chemical compound has for example styrene; have such as alkyl; alkoxy; acyl group; acyloxy; allyloxy; the styrene of aryloxy group or halogen atom etc. has the substituent styrene beyond the hydroxyl-removal; (methyl) acrylic acid; (methyl) acrylate; maleic acid or maleimide etc.; perhaps the hydroxyl of hydroxy styrenes is used such as tertbutyloxycarbonyl; blocking group such as pyranose or furyl protects; make this styrene derivative carry out similar polymerization or copolymerization with blocking group; subsequently blocking group is dissociated, thereby obtain above-mentioned polyvinylphenol resin.

The polyvinylphenol resin is preferably especially and contains the resin that hydroxyl-removal does not have other substituent hydroxy styrenes in addition, and pass through gel permeation chromatography measurement, when being converted into polystyrene, this resin preferably has 1,000 to 100,000 weight-average molecular weight is preferably 1 especially, 500 to 50,000.

About constituting the crosslinking chemical of under acid condition, having an effect of the composition (N2-2) of chemical amplifying type negative photosensitive composition (N2) among the present invention with alkali soluble resins, when with active light beam irradiates photosensitive composition, this crosslinking chemical can be gone up at alkali soluble resins (N2-1) and form cross-linked structure.This crosslinking chemical is not particularly limited, so long as can get final product with the compound of used alkali soluble resins generation cross-linking reaction.Typically, this crosslinking chemical can be for example amino-compound, and this amino-compound has the alkoxyl-methyl that obtains as two or more methylols of functional group or the pure condensation and modification by this methylol or acetoxy-methyl etc.This crosslinking chemical can be for example by melamine and the resulting melamine formaldehyde resin of formaldehyde condensation polymer; By benzoguanamine and the resulting benzoguanamine resin of formaldehyde condensation polymer; By glycoluril and the resulting glycoluril resin of formaldehyde condensation polymer; By urea and the resulting Lauxite of formaldehyde condensation polymer; By two or more for example melamine, benzoguanamine, glycoluril and urea and the resulting resin of formaldehyde condensation copolymerization; Or the resulting modified resin of pure condensation and modification of the methylol by this resin.

Particularly, melamine resin and modified resin thereof can be " CYMEL " (trade marks) 300 of for example being made by Mitsui Cytec Ltd., 301,303,350,736,738,370,771,325,327,703,701,266,267,285,232,235,238,1141,272,254,202,1156 and 1158, and " NIKALAC " (trade mark) E-2151 that makes by Sanwa Chemical Co., MW-100LM and MX-750LM, benzoguanamine resin and modified resin thereof can be " CYMEL " (trade marks) 1123 for example, 1125 and 1128, glycoluril resin and modified resin thereof can be " CYMEL " (trade marks) 1170 for example, 1171,1174 and 1172 and " NIKALAC " (trade mark) MX-270, Lauxite and modified resin thereof can be " UFR " (trade mark) 65 of for example being made by Mitsui Cytec Ltd. and 300 and " NIKALAC " (trade mark) MX-290.

In addition, as crosslinking chemical, it can also be the compound that contains epoxide group, as the compound that contains epoxide group, can be the compound from the low-molecular-weight to the high molecular that constitutes the repetitive of so-called epoxy resin, react resulting poly epihydric alcohol base ether compound, polybasic carboxylic acid compound and epichlorohydrine such as polyol and epichlorohydrine and react resulting poly epihydric alcohol base ester compounds and many ammoniates and epichlorohydrine and react resulting poly epihydric alcohol ylamine compounds.

As this poly epihydric alcohol base ether compound, be specifically as follows for example diglycidyl ether class epoxide of polyglycol, the diglycidyl ether class epoxide of two (4-hydroxy phenyls), the diglycidyl ether class epoxide of two (3,5-dimethyl-4-hydroxy phenyl), the diglycidyl ether based epoxy resin of Bisphenol F, the diglycidyl ether class epoxide of bisphenol-A, the diglycidyl ether class epoxide of the diglycidyl ether class epoxide of tetramethyl bisphenol-A or the bisphenol-A of oxirane addition, phenol novolaks epoxide or cresols novolaks epoxide.For this glycidyl ether compound, can be with acid anhydrides or divalent acid compound and residual hydroxyl reaction to introduce carboxyl.In addition, as poly epihydric alcohol base ester compounds, for example be specifically as follows the diglycidyl ether class epoxide of hexahydro-phthalic acid or the diglycidyl ether class epoxide of phthalic acid; As the poly epihydric alcohol ylamine compounds, for example be specifically as follows the diglycidyl amine epoxy thing of two (4-aminophenyl) methane or the triglycidyl group amine epoxy thing of isocyanuric acid.

As the compound that contains epoxide group, be specifically as follows for example by Tohto Kasei Co., Ltd. " YDP N-638,701,702,703 and 704 " and " YH-434 " of Zhi Zaoing, by Japan EpoxyResins Co., " Epikote 825,826,827,828,1001,1002,1003,1055,1004,1007,1009 and 1010 " that Ltd. makes.

In the present invention, in this crosslinking chemical, melamine resin or Lauxite are preferred.

In addition, about constituting the light acid propellant of the composition (N2-3) of chemical amplifying type negative photosensitive composition (N2) among the present invention, when with active light beam irradiates photosensitive composition, it is can acidic reactive compound.Light acid propellant for example can be, such as halide-containing, salt or the sulphones such as 1,3,5-triazines derivant of halogen alkane substitute or halomethylation, and in the present invention, is preferably the 1,3,5-triazines derivant or the sulphones of halomethylation especially.

Halogen alkane substitute as in the halide-containing for example is specifically as follows, methylene chloride, methenyl choloride, 1,2-ethylene dichloride or 1,2-ethylene dibromide.

In addition, 1,3 of the halomethylation in the halide-containing, the 5-pyrrolotriazine derivatives for example is specifically as follows, and 2,4,6-three (chloromethyl)-1,3,5-triazines, 2,4,6-three (dichloromethyl)-1,3,5-triazines, 2,4,6-three (trichloromethyl)-1,3,5-triazines, 2-methyl-4,6-two (trichloromethyl)-1,3, the 5-triazine, 2-n-pro-pyl-4,6-two (trichloromethyl)-1,3, the 5-triazine, 2-(α, α, β-three chloroethyl)-4,6-two (trichloromethyl)-1,3, the 5-triazine, 2-phenyl-4,6-two (trichloromethyl)-1,3, the 5-triazine, 2-(p-methoxyphenyl)-4,6-two (trichloromethyl)-1,3, the 5-triazine, 2-(3, the 4-ethoxyl phenenyl)-4,6-two (trichloromethyl)-1,3, the 5-triazine, 2-(rubigan)-4,6-two (trichloromethyl)-1,3,5-triazines, 2-[1-(p-methoxyphenyl)-2, the 4-butadienyl]-4,6-two (trichloromethyl)-1,3,5-triazines, 2-styryl-4,6-two (trichloromethyl)-1,3, the 5-triazine, 2-(to methoxyl-styrene)-4,6-two (trichloromethyl)-1,3, the 5-triazine, 2-(to hydroxystyrene based between methoxyl)-4,6-two (trichloromethyl)-1,3, the 5-triazine, 2-(to the isopropoxystyrene base)-4,6-two (trichloromethyl)-1,3,5-triazines, 2-(p-methylphenyl)-4,6-two (trichloromethyl)-1,3, the 5-triazine, 2-(to the methoxyl naphthyl)-4,6-two (trichloromethyl)-1,3, the 5-triazine, 2-(to the ethoxy naphthyl)-4,6-two (trichloromethyl)-1,3, the 5-triazine, 2-(to the ethoxy carbonyl naphthyl)-4,6-two (trichloromethyl)-1,3,5-triazines, 2-thiophenyl-4,6-two (trichloromethyl)-1,3, the 5-triazine, 2-benzyl sulfenyl-4,6-two (trichloromethyl)-1,3, the 5-triazine, 2,4,6-three (two bromomethyls)-1,3, the 5-triazine, 2,4,6-three (trisbromomethyl)-1,3, the 5-triazine, 2-methyl-4,6-two (trisbromomethyl)-1,3,5-triazine or 2-methoxyl-4,6-two (trisbromomethyl)-1,3,5-triazines.Among them, be preferably two (trihalomethyl group)-1,3, the 5-triazine is preferably for example 2-methyl-4 especially, 6-two (trichloromethyl)-1,3, the 5-triazine, 2-phenyl-4,6-two (trichloromethyl)-1,3, the 5-triazine, 2-(p-methoxyphenyl)-4,6-two (trichloromethyl)-1,3, the 5-triazine, 2-(3, the 4-epoxy and phenyl)-4,6-two (trichloromethyl)-1,3,5-triazines, 2-[1-(p-methoxyphenyl)-2, the 4-butadienyl]-4,6-two (trichloromethyl)-1,3, the 5-triazine, 2-(to methoxyl-styrene)-4,6-two (trichloromethyl)-1,3,5-triazines, 2-(to hydroxystyrene based between methoxyl)-4,6-two (trichloromethyl)-1,3,5-triazine or 2-(to the isopropoxystyrene base)-4,6-two (trichloromethyl)-1,3, the 5-triazine.

In addition, as salt, for example can be, such as ammonium salts such as tetramethylammonium bromide or tetraethylammonium bromides; Such as salt compounded of iodine such as hexafluoroarsenate diphenyl iodine, tetrafluoro boric acid diphenyl iodine, p-toluenesulfonic acid diphenyl iodine, camphorsulfonic acid diphenyl iodine, hexafluoroarsenate dicyclohexyl iodine, tetrafluoro boric acid dicyclohexyl iodine, p-toluenesulfonic acid dicyclohexyl iodine or camphorsulfonic acid dicyclohexyl iodine; Or such as sulfonium salts such as hexafluoroarsenate triphenylsulfonium, tetrafluoro boric acid triphenylsulfonium, p-toluenesulfonic acid triphenylsulfonium, camphorsulfonic acid triphenylsulfonium, hexafluoroarsenate thricyclohexyl sulfonium, tetrafluoro boric acid thricyclohexyl sulfonium, p-toluenesulfonic acid thricyclohexyl sulfonium or camphorsulfonic acid thricyclohexyl sulfoniums.

As sulphones, for example specifically can be, such as two (sulfonyl) methane compounds such as two (phenyl sulfonyl) methane, two (p-hydroxybenzene sulfonyl) methane, two (p-methoxyphenyl sulfonyl) methane, two (Alpha-Naphthyl sulfonyl) methane, two (betanaphthyl sulfonyl) methane, two (cyclohexyl sulfonyl) methane, two (tert-butyl group sulfonyl) methane or phenyl sulfonyl (cyclohexyl sulfonyl) methane; Such as carbonyl (sulfonyl) methane compounds such as phenylcarbonyl group (phenyl sulfonyl) methane, naphthyl carbonyl (phenyl sulfonyl) methane, phenylcarbonyl group (naphthyl sulfonyl) methane, cyclohexyl-carbonyl (phenyl sulfonyl) methane, tert-butyl group carbonyl (phenyl sulfonyl) methane, phenylcarbonyl group (cyclohexyl sulfonyl) methane or phenylcarbonyl group (tert-butyl group sulfonyl) methane; Such as two (sulfonyl) diazomethane compounds such as two (phenyl sulfonyl) diazomethane, two (p-hydroxybenzene sulfonyl) diazomethane, two (p-methoxyphenyl sulfonyl) diazomethane, two (Alpha-Naphthyl sulfonyl) diazomethane, two (betanaphthyl sulfonyl) diazomethane, two (cyclohexyl sulfonyl) diazomethane, two (tert-butyl group sulfonyl) diazomethane or phenyl sulfonyl (cyclohexyl sulfonyl) diazomethanes; Such as carbonyl (sulfonyl) diazomethane compounds such as phenylcarbonyl group (phenyl sulfonyl) diazomethane, naphthyl carbonyl (phenyl sulfonyl) diazomethane, phenylcarbonyl group (naphthyl sulfonyl) diazomethane, cyclohexyl-carbonyl (phenyl sulfonyl) diazomethane, tert-butyl group carbonyl (phenyl sulfonyl) diazomethane, phenylcarbonyl group (cyclohexyl sulfonyl) diazomethane or phenylcarbonyl group (tert-butyl group sulfonyl) diazomethanes; Or by the following general formula (Va) and (Vb) compound of representative:

(at general formula (Va) with (Vb), R ³⁸, R ³⁹, R ⁴¹And R ⁴²Represent hydrogen atom or optional substituting group each other independently of one another, R ⁴⁰And R ⁴³Represent optional substituting group each other independently of one another, and the R in the general formula (Vb) ⁴¹With R ⁴²Can form nitrogen heterocyclic ring.)

As R ³⁸, R ⁴¹And R ⁴²Group preferably can be for example hydrogen atom; Such as C such as methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, the tert-butyl group or n-heptyls _1～18The straight or branched alkyl; Such as C such as cyclopropyl, cyclopentyl, cyclohexyl or adamantyls _3～18Naphthenic base; Such as C such as vinyl, propenyl or hexenyls _2～18The thiazolinyl of straight or branched; Such as C such as cyclopentenyl or cyclohexenyl groups _3～18Cycloalkenyl group; Such as saturated or undersaturated heterocycles such as 2-thienyl, 2-pyridine radicals, furyl, thiazolyl, benzothiazolyl, morpholinyl, pyrrolidinyl or dioxo tetrahydro-thienyls; Such as phenyl, tolyl, xylyl or 2,4, C such as 6-trimethylphenyl _6～18Aryl; Such as C such as benzyl or phenethyls _7～20Aralkyl; Such as C such as acetyl group, propiono, positive bytyry, isobutyryl, positive valeryl or isovaleryl _2～18The straight or branched acyl group; Such as C such as methoxyl, ethoxy, positive propoxy, isopropoxy, n-butoxy, sec-butoxy or tert-butoxies _1～18The alkoxy of straight or branched; Such as C such as propenyloxy group, butenyloxy or amylene oxygen bases _3～18The alkenyloxy of straight or branched; Such as C such as methyl mercapto, ethylmercapto group, positive rosickyite base, positive butylthio, secondary butylthio or uncle's butylthios _1～18The alkylthio group of straight or branched; Such as halogen atoms such as fluorine atom, chlorine atom or bromine atoms; Nitro; Cyano group; Hydroxyl; Formoxyl; Sulfonic group; Carboxyl; Acyloxy by-OCOR representative; Amino by-NRR representative; Acylamino-by-NHCOR representative; Carbamate groups by-NHCOOR representative; Sulfoamido by-NHSOOR representative; Carboxylic acid ester groups by-COOR representative; Carbamyl by-CONRR representative; Sulfamoyl by-SOONRR representative; Or by-SO ₂The sulfonate group (R herein and R are alkyl) of OR representative.

In addition, R ⁴¹With R ⁴²Can form nitrogen heterocyclic ring, and nitrogen heterocyclic ring further condensation be saturated or undersaturated hydrocarbon ring or heterocycle.

As R ³⁹Group preferably can be thiazolinyl, cycloalkenyl group, aryl, aralkyl, acyl group, acyloxy, alkoxy carbonyl group, aryloxy carbonyl, nitro, cyano group or the carboxyl of the alkyl of for example hydrogen atom, straight or branched, naphthenic base, straight or branched, and they can further contain substituting group.Among them, more preferably acyl group, alkoxy carbonyl group, nitro or cyano group are preferably alkoxy carbonyl group or cyano group especially.

In addition, as R ⁴⁰With R ⁴³Group preferably can be thiazolinyl, cycloalkenyl group, heterocyclic radical, aryl, aralkyl or the camphoryl of the alkyl of for example straight or branched, naphthenic base, straight or branched.Hydrogen atom in this group can be replaced by fluorine atom, and this group can also have other substituting groups.

In the above-mentioned group as R ³⁸To R ⁴³Substituting group and by R ⁴¹With R ⁴²Substituting group in the nitrogen heterocyclic ring that forms can be for example such as C such as methoxyl, ethoxy and positive propoxy, isopropoxy, n-butoxy, sec-butoxy or tert-butoxies _1～10Alkoxy; Such as C such as methoxy methoxy base, ethoxy methoxyl, the third oxygen methoxyl, ethoxy ethoxy, the third oxygen ethoxy or methoxy butoxy _2～12Alkoxyalkoxy group; Such as C such as methoxy methoxy methoxyl, methoxy methoxy ethoxy, methoxy (ethoxy) methoxyl or ethoxy ethoxy methoxyls _3～15The alcoxyl alkoxyalkoxy group; Allyloxy; Such as phenyl, tolyl or xylyl C such as (this group can further have substituting group) _6～12Aryl; Such as C such as phenoxy group, toloxyl, xylyloxy or naphthoxys _6～12Aryloxy group; Such as acyl groups such as acetyl group or propionos; Cyano group; Nitro; Hydroxyl; Tetrahydrofuran base; Amino; Such as N, N-dimethylamino or N, C such as N-diethylamino _1～10Alkylamino; Such as C such as sulfonyloxy methyl amido, ethyl sulfonamide base or n-pro-pyl sulfoamidos _1～6Alkyl sulfonyl amino; Such as halogen atoms such as fluorine atom, chlorine atom or bromine atoms; Such as C such as methoxycarbonyl group, carbethoxyl group or positive butoxy carbonyls _2～7Alkoxy carbonyl group; Such as C such as methyl carbonyl oxygen base, ethyl oxy carbonyl, n-pro-pyl carbonyl oxygen base, isopropyl carbonyl oxygen base or normal-butyl carbonyl oxygen bases _2～7Alkyl carbonyl oxy; Or such as C such as methoxy carbonyl oxygen base, ethoxy carbonyl oxygen base, the positive third oxygen carbonyl oxygen base, the different third oxygen carbonyl oxygen base or positive fourth oxygen carbonyl oxygen bases _2～7Alkyl oxy carbonyl oxygen, and the hydrogen atom in these substituting groups can be substituted by fluorine atom.

By above-mentioned general formula (Va) with (Vb) in the sulphones of representative, R wherein ⁴¹With R ⁴²The object lesson that forms nitrogenous heterocyclic compound is as follows.

In the present invention, content about the light acid propellant of the crosslinking chemical of the alkali soluble resins of the composition (N2-1) in chemical amplifying type negative photosensitive composition (N2), composition (N2-2) and composition (N2-3), the crosslinking chemical of composition (N2-2) is preferably 1 weight portion to 80 weight portion, 5 weight portion to 60 weight portions more preferably, the light acid propellant of composition (N2-3) is preferably 0.001 weight portion to 30 weight portion, 0.005 weight portion to 10 weight portion more preferably, each content are all based on the alkali soluble resins of the composition (N2-1) of 100 weight portions.

In order to improve for example photonasty of photonasty anticorrosive additive material layer, except mentioned component (N2-1), (N2-2) with (N2-3), the chemical amplifying type negative photosensitive composition (N2) among the present invention preferably contains the emulsion of composition (N2-4).The emulsion of composition (N2-4) is preferably the light absorbing dyestuff of light that effective absorbing wavelength is the purple light district of 320nm～450nm, this dyestuff has photosensitive function simultaneously, optical excitation can be able to be sent to the light acid propellant of composition (N2-3), this light acid propellant decomposes generation acid, and the alkali soluble resins generation cross-linking reaction of composition (N2-1) is lured in this acid into by the crosslinking chemical of composition (N2-2).As light absorbing dyestuff, can be the identical light absorbing dyestuff of emulsion with photopolymerizable negative photosensitive composition (among the N1) composition (N1-2).Utilize this light absorbing dyestuff,, also can suppress sensitivity decrease, and can form the resist image of excellent in resolution even the photonasty anticorrosive additive material layer that is made of chemical amplifying type negative photosensitive composition (N2) is thicker.

In the present invention, the content of the emulsion of composition (N2-4) in chemical amplifying type negative photosensitive composition (N2), alkali soluble resins based on the composition (N2-1) of 100 weight portions is preferably 0.1 weight portion to 30 weight portion, is preferably 0.5 weight portion to 20 weight portion especially.

Chemical amplifying type negative photosensitive composition of the present invention (N2) can also contain the various adjuvants that are generally used for photosensitive composition when needed, such as coating performance improver, adhesion property improver, photonasty improver, lipid emulsion, colorant and developing performance improver.

(P1: the chemically amplified positive photosensitive composition)

In addition, the photosensitive composition that constitutes photonasty anticorrosive additive material layer of the present invention is preferably and contains following ingredients (P1-1) and chemically amplified positive photosensitive composition (P1) (P1-2).

(P1-1) contain the resin of sour decomposability group

(P1-2) light acid propellant

The resin that contains sour decomposability group that constitutes the composition (P1-1) of chemically amplified positive photosensitive composition of the present invention (P1) is the resin that contains following sour decomposability group: when with active light beam irradiates photosensitive composition, the acid that this acid decomposability group can be produced by hereinafter described composition (P1-2) light acid propellant is decomposed, thereby gives alkali solubility for resin itself.As sour decomposability group, for example be specifically as follows: ethers, for example, such as C such as methoxyl, ethoxy, isopropoxy or tert-butoxies _1～15Alkoxy grp, or such as C such as methoxy methoxy base, dimethoxy methoxyl, ethoxy methoxyl, 1-methoxyethoxy, 1-ethoxy ethoxy, the 1-third oxygen ethoxy, uncle's 1-fourth oxygen ethoxy, 1-cyclohexyloxy ethoxy or 1-ethoxy propoxyl group _2～15Alkoxyalkoxy group group; Carbonates, for example, such as C such as methoxycarbonyl group oxygen base, ethoxycarbonyl-oxygen base, the positive third oxygen ketonic oxygen base, the different third oxygen ketonic oxygen base, positive butoxy carbonyl oxygen groups or tertbutyloxycarbonyl oxygen bases _2～15Alkoxycarbonyloxy, or such as C such as carbethoxyl group Oxymethoxy, the positive third oxygen ketonic oxygen ylmethoxy, the different third oxygen ketonic oxygen ylmethoxy, positive butoxy carbonyl Oxymethoxy or tertbutyloxycarbonyl Oxymethoxies _2～15The alkoxycarbonyloxy alkoxy grp; Or the silicyl ethers, such as siloxies such as trimethylsiloxy or trimethoxy siloxies; Or have the group of alkoxy for example or siloxy at least at its end, and among them, ethers is preferred.

In addition, as the resin that contains this acid decomposability group, particularly, preferred example can be a kind of like this resin: in resin such as phenolic hydroxy groups such as phenols resins, to the small part phenolic hydroxyl group by etherificate or esterification, to introduce above-mentioned sour decomposability group; Described phenolic resin resin be such as with above-mentioned in chemical amplifying type negative photosensitive composition (N2) as the identical novolac resin of the alkali soluble resins of composition (N2-1), resol or polyvinylphenol resin.In the present invention, more preferably in novolac resin or polyvinylphenol resin, introduce the resin of above-mentioned sour decomposability group, particularly preferably in the resin of introducing above-mentioned sour decomposability group in the polyvinylphenol resin.The resin that contains sour decomposability group comprises the resin of introducing sour decomposability group and the potpourri of not introducing the resin of sour decomposability group.

In addition, as the resin that contains this acid decomposability group, preferred example can for carboxylic vinyl resins to the esterified resin of introducing above-mentioned sour decomposability group of small part carboxyl.Carboxylic vinyl resins can be identical with the carboxylic vinyl resins of the polymeric binder material of composition (N1-4) in the aforementioned photopolymerizable negative photosensitive composition (N1).

In addition, the light acid propellant that constitutes the composition (P1-2) of chemically amplified positive photosensitive composition of the present invention (P1) is, can acidic compound when with active light beam irradiates photosensitive composition, and this light acid propellant can be identical with the light acid propellant of composition (N2-3) in the aforementioned chemical amplifying type negative photosensitive composition (N2).In the present invention, wherein the 1,3,5-triazines derivant of halomethylation or sulphones are particularly preferred.

In the present invention, content about the light acid propellant of the resin that contains sour decomposability group of composition (P1-1) in chemically amplified positive photosensitive composition (P1) and composition (P1-2), the sour decomposability group resin that contains based on the composition (P1-1) of 100 weight portions, the light acid propellant of composition (P1-2) is preferably 0.1 weight portion to 50 weight portion, more preferably 0.5 weight portion to 20 weight portion.

In addition, in order to improve for example photonasty of photonasty anticorrosive additive material layer, except mentioned component (P1-1) with (P1-2), the chemically amplified positive photosensitive composition (P1) among the present invention preferably contains the emulsion of composition (P1-3).Be preferably the light absorbing dyestuff of light that effective absorbing wavelength is the purple light district of 320nm～450nm as the emulsion of composition (P1-3), this dyestuff has sensitization function simultaneously, optical excitation can be able to be sent to the light acid propellant of composition (P1-2), this light acid propellant is decomposed and generation acid, this acid lures that the resin that contains sour decomposability group of composition (P1-1) decomposes into.This light absorbing dyestuff can be identical with the light absorbing dyestuff of the emulsion of composition (N1-2) in the above-mentioned photopolymerizable negative photosensitive composition (N1).Utilize this light absorbing dyestuff,, also can suppress sensitivity decrease, and can form the resist image of excellent in resolution even the photonasty anticorrosive additive material layer that is made of chemically amplified positive photosensitive composition (P1) is thicker.

In the present invention, content about the emulsion of composition (P1-3) in chemically amplified positive photosensitive composition (P1), the resin that contains sour decomposability group based on 100 weight portions as composition (P1-1), this content is preferably 1 weight portion to 30 weight portion, is preferably 5 weight portion to 20 weight portions especially.

In addition, cover the developing performance of performance and photonasty anticorrosive additive material layer in order for example to improve when the forming photonasty anticorrosive additive material layer coating on substrate, preferred chemically amplified positive photosensitive composition of the present invention (P1) also contains nonionic, negative ion, kation, both sexes, fluorine class or other surfactants of composition (P1-4).Described surfactant can be identical with surfactant as composition (N1-7) in the aforementioned photopolymerizable negative photosensitive composition (N1), and the resin that contains sour decomposability group as composition (P1-1) based on 100 weight portions, the content of this surfactant is preferably 0.1 weight portion～10 weight portions, more preferably 1 weight portion～5 weight portions.

As required, chemically amplified positive photosensitive composition of the present invention (P1) can also contain the various adjuvants that are generally used for photosensitive composition, such as paintability improver, adhesion property improver, photonasty improver, lipid emulsion, colorant and developing performance improver.

The photosensitive composition of the anticorrosive additive material layer that constitutes image forming material of the present invention is illustrated above.Particularly, when use be selected from by above-mentioned general formula (Ib) or (Id) representative and have the compound of alkyl substituent 2 of tetrahydroquinoline ring, by the compound of above-mentioned general formula (II) representative, by the compound of above-mentioned general formula (III) representative with by the compound of above-mentioned general formula (IV) representative during as emulsion, even when the anticorrosive additive material layer is thick at least when reaching 10 μ m, can obtain having the image forming material of anticorrosive additive material layer, the light sensitivity of described anticorrosive additive material layer can not descend and have good resolution character and picture shape yet.

In the present invention, the sexy light composition of above-mentioned negative or positive is formed into the picture material in order to method down usually: above-mentioned each composition is dissolved in appropriate solvent or disperse with the preparation coating fluid, be coated on the provisional carrier film this liquid and drying, surface with formed photosensitive composition layer covers with overlay film when needed, to obtain so-called dry film photoresist material.The photosensitive composition layer by the situation that overlay film covered under, after coverlay peelled off, with the photosensitive composition layer one side lamination of dry film photoresist material on processed substrate; Or above-mentioned each composition dissolved in appropriate solvent or disperse and with the preparation coating fluid this liquid directly is coated on the provisional carrier film, carry out drying subsequently, to obtain having the image forming material of the photonasty anticorrosive additive material layer that is formed on the processed substrate.Preferred formation method is, is that the purple laser of 320nm～450nm carries out scan exposure to the photonasty anticorrosive additive material layer of image forming material with wavelength, makes image developing by development treatment subsequently.

Under the situation that adopts the dry film photoresist material, as provisional carrier film, can adopt conventionally known film, such as polyethylene terephthalate film, polyimide film, polyamidoimide film, polypropylene screen or polystyrene film.In the case, when this film has solvent resistance and thermotolerance etc., the photosensitive composition coating fluid directly can be coated on this provisional carrier film, subsequently by dry with preparation dry film photoresist material.In addition, if the solvent resistance of this film and thermotolerance etc. are lower, then at first the photosensitive composition layer is formed on such as teflon or stripping film etc. and has on the film of stripping ability, then lower provisional carrier film such as solvent resistance and thermotolerance are laminated on the above-mentioned layer, the film that will have stripping ability is peelled off then, prepares the dry film photoresist material thus.As overlayer, can use such as conventionally known films such as polyethylene film, polypropylene screen or poly tetrafluoroethylenes.

The employed solvent of coating fluid is not particularly limited,, and can provides good film character to get final product as long as it can be for employed composition provides suitable solubleness.For example, can be: such as cellosolve kind solvents such as methyl cellosolve, ethyl cellosolve, methylcellosolve acetate or ethyl cellosolve acetates; Such as propandiols solvents such as propylene glycol monomethyl ether, propylene glycol list ethylether, propylene glycol single-butyl ether, propylene glycol monomethyl ether, propylene glycol list ethylether acetic acid esters, propylene glycol single-butyl ether acetic acid esters or dipropylene glycol dimethyl ethers; Such as esters solvents such as butyl acetate, pentyl acetate, ethyl butyrate, butyl butyrate, diethy-aceto oxalate, ethyl pyruvate, 2-3-hydroxyethyl butyrate, ethyl acetoacetate, methyl lactate, ethyl lactate or 3-methoxypropionic acid methyl esters; Such as alcohols solvents such as enanthol, hexanol, diacetone alcohol or furancarbinols; Such as ketones solvents such as cyclohexanone or methyl amyl ketones; Such as intensive polar solvents such as dimethyl formamide, dimethyl acetamide, N-Methyl pyrrolidone; Or their mixed solvent; Or in these solvents, add the solvent of aromatic hydrocarbon.The weight ratio of solvent part is generally about 1 times to about 20 times of photosensitive composition gross weight.

In addition, as painting method, can adopt such as spin coating, the excellent coating that winds the line, spraying, dip-coating, air knife blade coating, roller coat, scraper plate coating, sieve and be coated with conventionally known methods such as (screen coating) or curtain coating.As coated weight, build is at least 10 μ m, more preferably is at least 15 μ m, is preferably 200 μ m at the most, more preferably is at most 100 μ m.Baking temperature is for example about 30 ℃～about 150 ℃, is preferably about 40 ℃～about 110 ℃, and be for example about 5 seconds～about 60 minutes drying time, is preferably about 10 seconds～about 30 minutes.

Above-mentioned dry film photoresist material layer at photosensitive composite layer one side (when being coated with overlay film, this overlay film being peelled off) and substrate lamination, is then heated, operation such as pressurization; Or the coating fluid of above-mentioned photosensitive composition directly is coated on the substrate, carry out drying subsequently, thereby make image forming material.The substrate that uses in the described image forming material of preparation is, with purple laser formed photonasty anticorrosive additive material layer on the substrate is carried out scan exposure, carry out development treatment subsequently, thereby obtain image as resist, by described image is carried out for example etching or plating, thereby form the substrate of circuit or electrode pattern thereon.Though this substrate itself can be sheet metals such as copper, aluminium, gold, silver, chromium, zinc, tin, lead or nickel for example, but usually preferably adopt a kind of metal level compressing tablet, it is the conductive layer on this carrier surface of being formed at of about 1 μ m～about 100 μ m for the insulating carrier of about 0.02mm～about 10mm and thickness that this metal level compressing tablet has thickness.Described insulating carrier is formed from a resin, for example, and such as thermoset resins such as epoxy resin, polyimide resin, bimaleimide resin, unsaturated polyester resin, phenol resin or melamine resins; Such as saturated polyester resin, polycarbonate resin, polysulfone resin, acrylic resin, polyamide, polystyrene resin, Corvic, polyolefin resin or fluororesin or etc. thermoplastic resin; Paper; Glass; Such as inorganic material such as aluminium oxide, silica, barium sulphate or lime carbonate; Or such as the epoxy resin of glass cloth base material, the epoxy resin of glass non-woven fabrics base material, the epoxy resin of paper base material or the compound substances such as phenol resin of paper base material.Can perhaps with metal sputtering, vapour deposition or plating, thereby described conductive layer be formed on the described carrier surface by with above-mentioned metal or such as the metal forming heated lamination of the metal oxides such as tin oxide of indium oxide, tin oxide, doped indium oxide.

In the present invention, image forming material has the photonasty anticorrosive additive material layer that contains photopolymerizable negative photosensitive composition formed thereon.Can on the photosensitive resist agent material layer that is formed on the substrate, form protective seam or transmittance regulating course etc.; described protective seam is for example oxygen barrier layer; described oxygen barrier layer is used for preventing the inhibition of the oxygen in the photopolymerizable composition, and described transmittance regulating course is used for regulating the wavelength coverage of the maximum peak of above-mentioned spectral response.

The material that constitutes oxygen barrier layer can be a water-soluble polymers or such as non-soluble polymers such as polyethylene terephthalates, described water-soluble polymers can be water-soluble or water and such as the mixed solvent of water miscibility organic solvents such as alcohol or tetrahydrofuran, particularly, this class material for example can be: polyvinyl alcohol (PVA) or derivant, described derivant is such as its part acetalation product, or its quaternary ammonium salt cationic modified product for example, or its anion-modified product of sodium sulfonate for example; Polyvinylpyrrolidone, polyoxyethylene, methylcellulose, carboxymethyl cellulose, hydroxyethyl cellulose or hydroxypropyl cellulose etc.

Among them, consider for example oxygen barrier performance, the polyvinyl alcohol (PVA) or derivatives thereof is preferred, for example considers that to the bond properties of photonasty anticorrosive additive material layer, vinylpyrrolidone base polymer for example multipolymer such as polyvinylpyrrolidone or vinylpyrrolidone/vinyl acetate is preferred.As oxygen barrier layer of the present invention, preferably use the potpourri of polyvinylpyrrolidone--type polymer and 100 weight account polyethylenes alcohol or derivatives thereof, the consumption of polyvinylpyrrolidone is preferably 1 weight portion～20 weight portions, more preferably 3 weight portions～15 weight portions.

For giving its storage stability, oxygen barrier layer preferably contains such as organic acids such as succinic acid or such as organic acid salt such as ethylenediamine tetraacetic acids, and it can contain such as non-ionic surfactants such as polyoxyethylene alkyl phenyl ethers, such as anionic surfactants such as neopelexes, such as cationic surfactants such as alkyl trimethylammonium chloride, defoamer, dyestuff, plastifier, pH regulator agent etc.Their total content preferably is at most 10 weight %, more preferably is at most 5 weight %.

By using and the identical painting method of above-mentioned photonasty anticorrosive additive material layer, adopt the mixed solvent of aqueous solution or water and water-miscible organic solvent to form oxygen barrier layer, to press build and calculate, its coated weight is preferably 1g/m ²～10g/m ², 1.5g/m more preferably ²～7g/m ²

In addition, as the material that constitutes the transmittance regulating course, can be by adding resulting material in the polymeric binder material such as the light absorbing dyestuff of visible ranges such as Coumarins dyestuff.By adopting above-mentioned polyvinyl alcohol (PVA) or derivatives thereof that is used for oxygen barrier layer or polyvinylpyrrolidone--type polymer, can obtain having the protective seam of oxygen barrier performance and transmittance adjusting function as polymeric binder material.

On the image forming material with purple laser-photosensitive material layer of the present invention,, form the resist image by development treatment subsequently by photonasty anticorrosive additive material layer is carried out scan exposure with laser beam.

As the laser explosure light source, can be for example HeNe laser, argon laser, YAG laser, HeCd laser, semiconductor laser or ruby laser, being preferably especially to be the light source of the purple light district generation laser beam of 320nm～450nm at wavelength.Although be not particularly limited, particularly, can use the InGaN semiconductor laser of the 410nm laser beam of for example can vibrating.

In addition, the scan exposure method not being particularly limited, can be for example flat scanning exposure method, external drum scan exposure method or interior bulging scan exposure method.The laser output light intensity of scan exposure is preferably 100nW～100mW on galley, 1 μ W～70mW more preferably, its oscillation wavelength is preferably 320nm～450nm, 390nm～430nm more preferably, be preferably 400nm～420nm especially, and used beam spot diameter, is preferably 0.5 μ m～30 μ m, 1 μ m～20 μ m more preferably, sweep velocity is preferably 50 meter per seconds～500 meter per seconds, 100 meter per seconds～400 meter per seconds more preferably, scanning density preferably is at least 2,000dpi (dpi (dots per inch)), more preferably be at least 4,000dpi.

Development treatment behind the laser scanning exposure is preferably undertaken by the water developer that use contains alkaline components and surfactant.Alkaline components for example can be, such as inorganic alkaline metal salt such as sodium silicate, potassium silicate, lithium metasilicate, ammonium silicate, sodium metasilicate, potassium metasilicate, NaOH, potassium hydroxide, lithium hydroxide, sodium carbonate, sodium bicarbonate, sal tartari, sodium hydrogen phosphate, tertiary sodium phosphate, diammonium hydrogen phosphate, triammonium phosphate, sodium borate, potassium borate or ammonium borates; Or such as organic amine compounds such as monomethyl amine, dimethyl amine, Trimethylamine, an ethylamine, diethylamide, triethylamine, an isopropylamine, diisopropylamine, monobutyl amine, monoethanolamine, diethanolamine, triethanolamine, an isopropanolamine or diisopropanolamines, and its employed concentration is about 0.1 weight %～about 5 weight %.

In addition, as surfactant, can be identical with the above-mentioned photopolymerizable employed surfactant of negative photosensitive composition, among them, be preferably nonionic, negative ion or amphoteric surfactant, be preferably amphoteric surfactant especially, especially preferred betaines compound.The working concentration of surfactant is preferably 0.0001 weight %～20 weight %, and more preferably 0.0005 weight %～10 weight % are preferably 0.001 weight %～5 weight % especially.

In addition, can in developer, add when needed such as organic solvents such as isopropyl alcohol, phenmethylol, ethyl cellosolve, butyl cellosolve, ethylene glycol monophenyl ether, propylene glycol or diacetone alcohols.In addition, the pH value of developer is preferably 9～14, and more preferably 11～14.

Development can be carried out with common known developing method, for example after exposure, image forming material is immersed in the above-mentioned developer, or after exposure, spray above-mentioned developer to image forming material, development temperature is preferably about 10 ℃～about 50 ℃, more preferably about 15 ℃～about 45 ℃, development time is about 5 seconds～about 10 minutes.Protective seam can be removed with for example water in advance, also can remove when developing.

Embodiment

The present invention will be described in more detail below with reference to embodiment.Yet in the scope that does not exceed purport of the present invention, the present invention is not limited to the following example.Image forming material evaluation method in the following example and the comparative example is as follows.

{ absorbance }

For the build that forms on glass substrate is the photonasty anticorrosive additive material layer of 10 μ m, utilize spectrophotometer (" UV-3100PC ", make by company of Shimadzu Seisakusho Ltd.) measure absorbance at the 405nm wavelength, and calculate per 1 micron absorbance divided by thickness with measured value.

{ peak-peak of spectral response }

The size that image forming material is cut into 50mm * 60mm is to obtain sample, adopt xenon lamp (" UI-501C ", make by USHIO INC.) as light source, utilize diffraction spectrum irradiation devices (" RM-23 ", make by Narumi K.K.) this sample is exposed, its method is: use the interior photoirradiation after beam split of 320nm～650nm wavelength coverage 10 seconds, make exposure wavelength be linear change in X direction, and exposure intensity is the logarithm variation at y direction.Then, under the development conditions disclosed in each embodiment, sample is carried out development treatment, thereby obtain and the corresponding image of the light sensitivity of each exposure wavelength.The exposure energy that can form image is calculated by picture altitude, is plotted in respectively on the transverse axis and the longitudinal axis with wavelength with at the inverse of the exposure energy under this wavelength, to obtain spectral response curve, can read peak-peak from this curve.

{(S ₄₁₀/S ₄₅₀)，(S _450～650/S ₄₅₀)}

When use with above-mentioned { peak-peak of spectral response } in employed identical method, expose by in 320nm～650nm wavelength coverage, changing wavelength, when carrying out exposure-processed subsequently, can obtain under the wavelength of 410nm, can forming the minimum exposure amount (S of image ₄₁₀(mJ/cm ²)) and under the wavelength of 450nm, can form the minimum exposure amount (S of image ₄₅₀(mJ/cm ²)), and greater than 450nm and can form the minimum exposure amount (S of image at the most under the wavelength of 650nm _450～650(mJ/cm ²)), calculate their ratio (S ₄₁₀/ S ₄₅₀) and (S _450～650/ S ₄₅₀), estimate by following standard.

{ S ₄₁₀/ S ₄₅₀Evaluation criterion

A:S ₄₁₀/ S ₄₅₀Be at most 0.03.

B:S ₄₁₀/ S ₄₅₀Greater than 0.03 and be at most 0.05.

C:S ₄₁₀/ S ₄₅₀Greater than 0.05 and be at most 0.1.

D:S ₄₁₀/ S ₄₅₀Greater than 0.1.

{ S _450～650/ S ₄₅₀Evaluation criterion

A:S _450～650/ S ₄₅₀Greater than 10.

B:S _450～650/ S ₄₅₀Greater than 5 and be at most 10.

C:S _450～650/ S ₄₅₀Greater than 1 and be at most 5.

D:S _450～650/ S ₄₅₀Be at most 1.

{D/L}

By changing resist thickness (D), use with the employed identical method of above-mentioned measurement { spectral response } and carry out laser scanning exposure, image is developed, obtain in following the minimum feature that can access of each resist thickness (D) (L), calculate the D/L ratio.In addition, the light sensitivity when obtaining D/L than maximal value is as S3.

{ exposure light sensitivity }

The photonasty anticorrosive additive material layer of image forming material is carried out scan exposure, used LASER Light Source (" NLHV 500C ", make by Nichia Chemical Industries, Ltd) centre wavelength be 405nm, laser is output as 5mW, under the beam spot diameter, of the image briliancy of 2 μ W and 2.5 μ m, when changing beam flying spacing and sweep velocity, carry out scan exposure.Then, under the development conditions disclosed in each embodiment, develop, thereby image manifested,, obtain and be the needed minimum exposure amount of the live width of reproducing 10 μ m for resulting image, with this as described light sensitivity.

In addition, measure above-mentioned light sensitivity S1 and the above-mentioned light sensitivity S2 when thickness is 20 μ m when thickness is 10 μ m, to calculate its ratio (S2/S1).

{ optical safety under the amber light }

With image forming material in amber light illumination (with wavelength smaller or equal to the excluded condition of the light of about 470nm) placement 1 minute, 2 minutes, 5 minutes, 10 minutes, 20 minutes or 30 minutes down, carry out scan exposure and development treatment with method same as described above then, to obtain comparing the standing time when image changes, estimate based on following standard with above-mentioned image:

A: at least 20 minutes.

B: at least 10 minutes and less than 20 minutes.

C: at least 1 minute and less than 10 minutes.

D: less than 1 minute.

{ resist image }

For resulting resist image, reproducibility live width and pattern form under each thickness disclosed in the his-and-hers watches are observed, and calculate the value of " thickness (μ m)/reproducible live width (μ m) ", with this measuring as resolution.

{ storage stability of photosensitive composition coating fluid }

At 25 ℃ the photosensitive composition coating fluid was kept in Dark Place 7 days, forms the resist image then, with on the scanning electron microscope observation resist image whether crystal deposition being arranged, and estimate based on following standard:

A: there is not deposition fully, and before storage and storage back light sensitivity and the equal no change of image.

B: do not find deposition, but light sensitivity descends slightly after storage.

C: a small amount of deposition is arranged, and light sensitivity descends after storage.

Embodiment 1-1

As photopolymerizable negative photosensitive composition (N1), build is that the consumption of 10 μ m or 20 μ m is coated on coating fluid on the glass substrate to make to utilize the excellent spreader of coiling, subsequently 170 ℃ of dryings 2 minutes to form photonasty anticorrosive additive material layer.The preparation method of described coating fluid is, following ingredients is added in the mixed solvent of methyl cellosolve of the methyl ethyl ketone of 740 weight portions and 400 weight portions, at room temperature stirs subsequently.And then; build is the mixed aqueous solution (polyvinyl alcohol (PVA): polyvinylpyrrolidone=95 weight %s: 5 weight %s) be coated on above-mentioned photonasty anticorrosive additive material layer on of the consumption of 3 μ m with polyvinyl alcohol (PVA) and polyvinylpyrrolidone to make to utilize the excellent spreader of coiling; subsequently 50 ℃ of dryings 3 minutes forming protective seam (oxygen barrier layer), thereby preparation photonasty image forming material.

{ (N1-1) ethylene linkage unsaturated compound }

(N1-1a) following compounds, 10 weight portions

(N1-1b) following compounds, 5 weight portions

(N1-1c) following compounds, 8 weight portions

(N1-1d) six acrylic acid dipentaerythritol ester, 22 weight portions

(N1-1a)

(N1-1b)

With

1: 1 potpourri

(N1-1c)

(N1-2) emulsion

(N1-2a) 4,4-two (diethylamino) benzophenone is (at the molar absorptivity of 404nm wavelength: 14,540): 9 weight portions

(N1-3) photo-induced polymerization initiator

(N1-3a) 2,2-two (Chloro-O-Phenyl)-4,4,5,5-tetraphenyl diimidazole (fusing point: 196 ℃ is in the X-ray diffraction spectrum of 1.54 at wavelength, has the maximum diffraction peak when being 9.925 ° at Bragg angle (2 θ ± 0.2 °)): 15 weight portions

(N1-4) polymeric binder material

(N1-4a) styrene/α-Jia Jibenyixi/acrylic copolymer (mol ratio: 55/15/30) with 3, the reaction product of 4-epoxycyclohexyl methacrylate (acrylic component of 50 moles of % reacts with epoxide group): 45 weight portions

{ (N1-5) hydrogen supply compound }

(N1-5a) 2-mercaptobenzothiazole: 5 weight portions

(N1-5b) N-phenylglycine benzyl ester: 10 weight portions

(N1-6) amines

(N1-6a) tribenzyl amine: 10 weight portions

(N1-7) surfactant

(N1-7a) non-ionic surfactant (" EMULGEN 104P " made by Hua Wangshe): 2 weight portions

(N1-7b) fluorine class surfactant (" S-381 " made by Asahi Glass society): 0.3 weight portion

{ other }

Copper phthalocyanine (visual reagent): 4 weight portions

Spreading agent (" Disperbyk 161 " are made by BYK Chemie): 2 weight portions

Under the condition of above-mentioned exposure light sensitivity evaluation method, photonasty anticorrosive additive material layer to resulting photonasty image forming material carries out scan exposure, wash oxygen barrier layer with water and it is peeled off, 26 ℃ with the photonasty image forming material at sodium carbonate that contains 0.1 weight % and 0.1 weight % anionic surfactant (" PELEX NBL ", make by Hua Wangshe) aqueous solution in soaked 60 seconds, subsequently with sponge wiping 5 times to carry out development treatment, to obtain being formed with on the surface the processed substrate of resist image.According to absorbance, the peak-peak of spectral response, exposure the light sensitivity, (S of said method to the photonasty anticorrosive additive material layer of this moment ₄₁₀/ S ₄₅₀) and (S _450～650/ S ₄₅₀) and amber light under optical safety and resulting resist image estimate, the result is as shown in table 5.S ₄₁₀Be 0.1mJ/cm ²

Embodiment 1-2

As chemical amplifying type negative photosensitive composition, build is that the consumption of 10 μ m or 20 μ m is coated on coating fluid on the glass substrate to make to utilize spin coating, subsequently 90 ℃ of dryings 10 minutes to form photonasty anticorrosive additive material layer, with preparation photonasty image forming material.Described coating fluid is by being added to following ingredients in the propylene glycol monomethyl ether of 300 weight portions, and at room temperature stirring prepares subsequently.

(N2-1) alkali soluble resins

(N2-1a) poly-(para hydroxybenzene ethene) (weight-average molecular weight is 5,000): 100 weight portions

(N2-2) crosslinking chemical

(N2-2a) methoxy melamine (" NIKALAC E-2151 ", by SanwaChemical Co., Ltd. makes): 50 weight portions

(N2-3) light acid propellant

(N2-3a) 2-(to carboxyl acetoxyethoxy styryl)-4,6-two (trichloromethyl)-1,3,5-triazines: 1 weight portion

Under the condition of above-mentioned exposure light sensitivity evaluation method, photonasty anticorrosive additive material layer to resulting photonasty image forming material carries out scan exposure, in 100 ℃ baking oven, carry out 10 minutes back heat treated subsequently, in the aqueous solution of 20 ℃ of potassium hydroxide that the photonasty image forming material contained 1 weight %, soak 90 seconds then to carry out development treatment, to obtain being formed with on the surface the processed substrate of resist image.Then, use the same method and estimate.S ₄₁₀Be 4mJ/cm ²In addition, when resist thickness (D) was 20 μ m, available minimum feature (L) was 10 μ m, and the maximal value of D/L is 2.0.In addition, light sensitivity S3 is 7mJ/cm at this moment ²

Embodiment 1-3

Except light acid propellant (N2-3) being become following material, carry out identical operations with embodiment 1-2, with preparation photonasty image forming material, thereby obtain being formed with on the surface the processed substrate of resist image.Estimate with identical method.S ₄₁₀Be 4mJ/cm ²In addition, when resist thickness (D) was 20 μ m, available minimum feature (L) was 10 μ m, and the maximal value of D/L is 2.0.In addition, light sensitivity S3 is 11mJ/cm at this moment ²

(N2-3b) 2-(to methoxyl-styrene)-4,6-two (trichloromethyl)-1,3,5-triazines

Embodiment 1-4

Except being that the processed substrate of the copper coating of 1 μ m replaces the glass substrate with having the thickness that is applied on the silicone substrate, carry out identical operations with embodiment 1-2, with preparation photonasty image forming material, thereby obtain being formed with on the surface the processed substrate of resist image.Estimate with identical method.

Embodiment 1-5

Except being that the processed substrate of the copper coating of 1 μ m replaces the glass substrate with having the thickness that is applied on the silicone substrate, carry out identical operations with embodiment 1-3, with preparation photonasty image forming material, thereby obtain being formed with on the surface the processed substrate of resist image.Estimate with identical method.

Embodiment 1-6

As chemically amplified positive photosensitive composition (P), build is that the consumption of 10 μ m or 20 μ m is coated on coating fluid on the glass substrate by spin coating to make, subsequently 90 ℃ of dryings 10 minutes to form photonasty anticorrosive additive material layer, with preparation photonasty image forming material.The preparation method of described coating fluid is, following ingredients is added in the mixed solvent of methyl cellosolve of the propylene glycol list ethylether acetic acid esters of 640 weight portions and 240 weight portions, at room temperature stirs subsequently.

The resin of sour decomposability group { (P1-1) contain }

(P1-1a): in poly-(para hydroxybenzene ethene) hydroxyl of about 45mol% by etherificate with the resin of introducing 1-ethoxy ethoxy as containing of sour decomposability group of sour decomposability group: 100 weight portions

(P1-2) light acid propellant

(P1-2a) 2-(to hydroxystyrene based between methoxyl)-4,6-two (trichloromethyl)-1,3,5-triazines: 2 weight portions

Under the condition of above-mentioned exposure light sensitivity evaluation method, photonasty anticorrosive additive material layer to resulting photonasty image forming material carries out scan exposure, in 90 ℃ baking oven, carry out 2 minutes back heat treated subsequently, in the aqueous solution of 20 ℃ of potassium hydroxide that the photonasty image forming material contained 2 weight %, soak 90 seconds then to carry out development treatment, to obtain being formed with on the surface the processed substrate of resist image.Use the same method and estimate.S ₄₁₀Be 15mJ/cm ²In addition, when resist thickness (D) was 20 μ m, available minimum feature (L) was 10 μ m, and the maximal value of D/L is 2.0.In addition, light sensitivity S3 is 20mJ/cm at this moment ²

Embodiment 1-7

Except being that the processed substrate of the copper coating of 1 μ m replaces the glass substrate with having the thickness that is applied on the silicone substrate, carry out identical operations with embodiment 1-6, with preparation photonasty image forming material, thereby obtain being formed with on the surface the processed substrate of resist image.Estimate with identical method.

Embodiment 2-1

As photopolymerizable negative photosensitive composition (N1), build is that the consumption of 10 μ m or 20 μ m is coated on coating fluid on the polyethylene terephthalate film (thickness is 19 μ m) as provisional carrier film to make to utilize spreader, subsequently in 90 ℃ baking oven dry 5 minutes to form the photosensitive composition layer, lamination is as the polyethylene film (thickness is 25 μ m) of coverlay on the said composition layer, and places one day with preparation dry film photoresist material.Described coating fluid is by in methyl ethyl ketone/isopropyl alcohol (weight ratio the is 8/2) mixed solvent that following ingredients is added to 100 weight portions, and at room temperature stirring prepares subsequently.

{ (N1-1) ethylene linkage unsaturated compound }

(N1-1e) following compounds, 15 weight portions

(N1-1f) following compounds, 30 weight portions

(N1-1e)

(N1-1f)

(N1-2) emulsion

(N1-2b) following compounds is (at the molar absorptivity of 405nm wavelength: 1,200): 0.2 weight portion

(N1-2b)

(N1-3) photo-induced polymerization initiator

(N1-3a) 2,2-two (Chloro-O-Phenyl)-4,4,5,5-tetraphenyl diimidazole (fusing point: 196 ℃ is in the X-ray diffraction spectrum of 1.54 at wavelength, has the maximum diffraction peak when being 9.925 ° at Bragg angle (2 θ ± 0.2 °)): 15 weight portions

(N1-4) polymeric binder material

(N1-4b) methyl methacrylate/n-butyl acrylate/methacrylic acid copolymer (mol ratio: 45/15/40, weight-average molecular weight is 70,000) with 3, the reaction product of 4-epoxycyclohexyl methacrylate (carboxyl of the methacrylic acid composition of 37.5 moles of % and epoxide group reaction): 48 weight portions

{ (N1-5) hydrogen supply compound }

(N1-5b) N-phenylglycine benzyl ester: 3 weight portions

(N1-5c): the dipole ion compound of N-phenylglycine: 2 weight portions

In addition, for flat surface, (thickness is 1.5mm, and the copper foil surface that is of a size of 250mm * 200mm) polishes, and washes and use the airflow drying with water to copper-clad laminated base plate with polishing roll to utilize " the Scotch-Brite SF " that produced by Sumitomo 3M society.Described coating foil laminated base plate has the Copper Foil on this resin of being bonded in that polyimide resin and thickness are 35 μ m.Then, substrate is preheated in baking oven to 60 ℃, then on the Copper Foil of copper-clad laminated plate, when peelling off polyethylene film, utilize type hand roll-type laminating machine that the above-mentioned dry film photoresist material that obtains is carried out lamination with preparation photonasty image forming material peeling off side, roll temperature during lamination is 100 ℃, and roll-in is 0.3MPa, and lamination speed is 1.5m/min (meter/minute).The photonasty anticorrosive additive material layer that resulting photonasty image forming material has copper-clad laminated base plate and forms on this substrate.

Under the condition of above-mentioned exposure light sensitivity evaluation method, photonasty anticorrosive additive material layer to resulting photonasty image forming material carries out scan exposure, peel off the polyethylene terephthalate film then, to under the pressure of 0.15MPa, spray as the aqueous solution of the sodium carbonate of 32 ℃ 1 weight % of developer, handle to carry out spray developing, thereby obtain being formed with on the surface the processed substrate of resist image.According to absorbance, the peak-peak of spectral response, exposure the light sensitivity, (S of said method to the photonasty anticorrosive additive material layer of this moment ₄₁₀/ S ₄₅₀) and (S _450～650/ S ₄₅₀) and amber light under optical safety and resulting resist image estimate, the result is as shown in table 5.S ₄₁₀Be 1.1mJ/cm ²In addition, when resist thickness (D) was 25 μ m, available minimum feature (L) was 10 μ m, and the maximal value of D/L is 2.5.In addition, light sensitivity S3 is 0.9mJ/cm at this moment ²

Embodiment 2-2

Except polymeric binder material (N1-4) being changed into following material, carry out identical operations with embodiment 2-1, with preparation photonasty image forming material, thereby obtain being formed with on the surface the processed substrate of resist image.Estimate with identical method.S ₄₁₀Be 1.0mJ/cm ²In addition, when resist thickness (D) was 25 μ m, available minimum feature (L) was 10 μ m, and the maximal value of D/L is 2.5.In addition, light sensitivity S3 is 0.7mJ/cm at this moment ²

(N1-4c) styrene/methacrylic acid methyl esters/n-butyl acrylate/methacrylic acid copolymer (mol ratio is 15/45/15/25, and weight-average molecular weight is 70,000, and acid number is 140 KOH mg/g)

Embodiment 2-3

Except emulsion (N1-2) being changed into following material, carry out identical operations with embodiment 2-1, with preparation photonasty image forming material, thereby obtain being formed with on the surface the processed substrate of resist image.Estimate with identical method.S ₄₁₀Be 1.6mJ/cm ²In addition, when resist thickness (D) was 25 μ m, available minimum feature (L) was 10 μ m, and the maximal value of D/L is 2.5.In addition, light sensitivity S3 is 1.0mJ/cm at this moment ²

(N1-2c) the following compound (molar absorptivity under the 405nm wavelength: 100)

(N1-2c)

Embodiment 2-4

Except not using dipole ion compound as the N-phenylglycine benzyl ester of hydrogen supply compound (N1-5) and N-phenylglycine, carry out identical operations with embodiment 2-2, with preparation photonasty image forming material, thereby obtain being formed with on the surface the processed substrate of resist image.Estimate with identical method.S ₄₁₀Be 1.5mJ/cm ²In addition, when resist thickness (D) was 25 μ m, available minimum feature (L) was 10 μ m, and the maximal value of D/L is 2.5.In addition, light sensitivity S3 is 1.0mJ/cm at this moment ²

Embodiment 2-5

Except Photoepolymerizationinitiater initiater (N1-3) is changed into the following material matter, carry out identical operations with embodiment 2-2, with preparation photonasty image forming material, thereby obtain being formed with on the surface the processed substrate of resist image.Estimate with identical method.S ₄₁₀Be 0.6mJ/cm ²In addition, when resist thickness (D) was 25 μ m, available minimum feature (L) was 10 μ m, and the maximal value of D/L is 2.5.In addition, light sensitivity S3 is 0.5mJ/cm at this moment ²

(N1-3b) 2,2-two (Chloro-O-Phenyl)-4,4,5,5-tetraphenyl diimidazole (fusing point: 172 ℃ is in the X-ray diffraction spectrum of 1.54 at wavelength, has the maximum diffraction peak when being 21.16 ° at Bragg angle (2 θ ± 0.2 °))

Embodiment 2-6

Except emulsion (N1-2) being changed into following material, carry out identical operations with embodiment 2-1, with preparation photonasty image forming material, thereby obtain being formed with on the surface the processed substrate of resist image.Estimate with identical method.S ₄₁₀Be 1.8mJ/cm ²In addition, when resist thickness (D) was 25 μ m, available minimum feature (L) was 10 μ m, and the maximal value of D/L is 2.5.In addition, light sensitivity S3 is 1.3mJ/cm at this moment ²

(N1-2d) the following compound (molar absorptivity under the 405nm wavelength (ε): 1,300)

(N1-2d)

Embodiment 2-7

Except emulsion (N1-2) being changed into following material, carry out identical operations with embodiment 2-1, with preparation photonasty image forming material, thereby obtain being formed with on the surface the processed substrate of resist image.Estimate with identical method.S ₄₁₀Be 2.4mJ/cm ²In addition, when resist thickness (D) was 25 μ m, available minimum feature (L) was 10 μ m, and the maximal value of D/L is 2.5.In addition, light sensitivity S3 is 1.6mJ/cm at this moment ²

(N1-2e) the following compound (molar absorptivity under the 405nm wavelength (ε): 1,300)

(N1-2e)

Embodiment 2-8

Except emulsion (N1-2) being changed into following material, carry out identical operations with embodiment 2-1, with preparation photonasty image forming material, thereby obtain being formed with on the surface the processed substrate of resist image.Estimate with identical method.S ₄₁₀Be 2.0mJ/cm ²In addition, when resist thickness (D) was 25 μ m, available minimum feature (L) was 10 μ m, and the maximal value of D/L is 2.5.In addition, light sensitivity S3 is 1.4mJ/cm at this moment ²

(N1-2f) the following compound (molar absorptivity under the 405nm wavelength (ε): 100)

(N1-2f)

Embodiment 3-1

As chemical amplifying type negative photosensitive composition (N2), build is that the consumption of 10 μ m or 20 μ m is coated on coating fluid on the glass substrate to make to utilize spin coating, subsequently 90 ℃ of dryings 10 minutes to form photonasty anticorrosive additive material layer, with preparation photonasty image forming material.Described coating fluid is by being added to following ingredients in the propylene glycol monomethyl ether of 290 weight portions, and at room temperature stirring prepares subsequently.

(N2-1) alkali soluble resins

(N2-1a) poly-(para hydroxybenzene ethene) (weight-average molecular weight is 5,000): 100 weight portions

(N2-2) crosslinking chemical

(N2-2a) methoxy melamine (" NIKALAC E-2151 ", by SanwaChemical Co., Ltd. makes): 50 weight portions

(N2-3) light acid propellant

(N2-3c) following compound: 5 weight portions

(N2-3c)

(N2-4) emulsion

(N2-4a) following compound is (at the molar absorptivity of 405nm wavelength: 32,500): 1 weight portion

(N2-4a)

Under the condition of above-mentioned exposure light sensitivity evaluation method, photonasty anticorrosive additive material layer to resulting photonasty image forming material carries out scan exposure, in 100 ℃ baking oven, carry out 10 minutes back heat treated subsequently, in the aqueous solution of 20 ℃ of potassium hydroxide that the photonasty image forming material contained 0.5 weight %, soak 60 seconds then to carry out development treatment, to obtain being formed with on the surface the processed substrate of resist image.According to absorbance, the peak-peak of spectral response, exposure the light sensitivity, (S of said method to the photonasty anticorrosive additive material layer of this moment ₄₁₀/ S ₄₅₀) and (S _450～650/ S ₄₅₀) and amber light under optical safety and resulting resist image estimate, the result is as shown in table 5.

Embodiment 3-2

Except light acid propellant (N2-3) being changed into following material, carry out identical operations with embodiment 3-1, with preparation photonasty image forming material, thereby obtain being formed with on the surface the processed substrate of resist image.Estimate with identical method.

(N2-3d) following compound

(N2-3d)

Embodiment 3-3

Except emulsion (N2-4) being changed into following material, carry out identical operations with embodiment 3-2, with preparation photonasty image forming material, thereby obtain being formed with on the surface the processed substrate of resist image.Estimate with identical method.

(N2-4b) following compound is (at the molar absorptivity of 405nm wavelength: 51,600)

(N2-4b)

Embodiment 3-4

As photopolymerizable negative photosensitive composition (N1), build is that the consumption of 10 μ m or 20 μ m is coated on coating fluid on the polyethylene terephthalate film (thickness is 19 μ m) as provisional carrier film to make to utilize applicator, subsequently in 90 ℃ baking oven dry 5 minutes to form the photosensitive composition layer, lamination is as the polyethylene film (thickness is 25 μ m) of coverlay on the said composition layer, and places one day with preparation dry film photoresist material.Described coating fluid is by in methyl ethyl ketone/isopropyl alcohol (weight ratio the is 8/2) mixed solvent that following ingredients is added to 100 weight portions, and at room temperature stirring prepares subsequently.

{ (N1-1) ethylene linkage unsaturated compound }

(N1-1e) above-claimed cpd, 11.5 weight portions

(N1-1g) following compounds, 10 weight portions

(N1-1h) following compounds, 23.5 weight portions

(N1-1g)

(N1-1h)

(N1-2) emulsion

(N1-2g) following compounds is (at the molar absorptivity of 405nm wavelength: 7,320): 0.6 weight portion

(N1-2g)

(N1-3) photo-induced polymerization initiator

(N1-3a) 2,2-two (Chloro-O-Phenyl)-4,4,5,5-tetraphenyl diimidazole (fusing point: 196 ℃ is in the X-ray diffraction spectrum of 1.54 at wavelength, has the maximum diffraction peak when being 9.925 ° at Bragg angle (2 θ ± 0.2 °)): 12 weight portions

(N1-4) polymeric binder material

(N1-4c) styrene/methacrylic acid methyl esters/methacrylic acid 2-hydroxyethyl ester/methacrylic acid copolymer (mol ratio is 10/50/20/20, and weight-average molecular weight is 68,000, and acid number is 129KOHmg/g): 55 weight portions

{ (N1-5) hydrogen supply compound }

(N1-5c): the dipole ion compound of N-phenylglycine: 0.2 weight portion

{ other }

Leuco crystal violet: 0.4 weight portion

9-phenylacridine: 0.2 weight portion

In addition, for flat surface, (thickness is 1.5mm, and the copper foil surface that is of a size of 250mm * 200mm) polishes, and washes and use the airflow drying with water to copper-clad laminated base plate with polishing roll to utilize " the Scotch-Brite SF " that produced by Sumitomo 3M society.Described coating foil laminated base plate has the Copper Foil on this resin of being bonded in that polyimide resin and thickness are 35 μ m.Then, substrate is preheated in baking oven to 60 ℃, then on the Copper Foil of copper-clad laminated plate, when peelling off polyethylene film, utilize type hand roll-type laminating machine that the above-mentioned dry film photoresist material that obtains is carried out lamination with preparation photonasty image forming material peeling off side, roll temperature during lamination is 100 ℃, and roll-in is 0.3MPa, and lamination speed is 1.5m/min (meter/minute).The photonasty anticorrosive additive material layer that resulting photonasty image forming material has copper-clad laminated base plate and forms on this substrate.

Under the condition disclosed in the above-mentioned exposure light sensitivity evaluation method, photonasty anticorrosive additive material layer to resulting photonasty image forming material carries out scan exposure, peel off the polyethylene terephthalate film then, to under the pressure of 0.15MPa, spray as the aqueous sodium carbonate of 30 ℃ 0.7 weight % of developer, handle to carry out spray developing, obtain being formed with on the surface the processed substrate of resist image.Estimate with identical method.

Embodiment 4-1

As chemical amplifying type negative photosensitive composition (N2), build is that the consumption of 10 μ m or 20 μ m is coated on coating fluid on the glass substrate to make to utilize spin coating, subsequently 90 ℃ of dryings 10 minutes forming photonasty anticorrosive additive material layer, thereby preparation photonasty image forming material.Described coating fluid is by being added to following ingredients in the propylene glycol monomethyl ether of 290 weight portions, and at room temperature stirring prepares subsequently.

(N2-1) alkali soluble resins

(N2-1a) poly-(para hydroxybenzene ethene) (weight-average molecular weight is 5,000): 100 weight portions are crosslinking chemical (N2-2)

(N2-2a) methoxy melamine (" NIKALAC E-2151 ", by SanwaChemical Co., Ltd. makes): 50 weight portions

(N2-3) light acid propellant

(N2-3c) above-claimed cpd: 5 weight portions

(N2-4) emulsion

(N2-4c) following compound is (at the molar absorptivity of 405nm wavelength: 14,200): 1 weight portion

(N2-4c)

Under the condition of above-mentioned exposure light sensitivity evaluation method, photonasty anticorrosive additive material layer to resulting photonasty image forming material carries out scan exposure, in 100 ℃ baking oven, carry out 10 minutes back heat treated subsequently, in the aqueous solution of 20 ℃ of potassium hydroxide that the photonasty image forming material contained 0.5 weight %, soak 60 seconds then to carry out development treatment, to obtain being formed with on the surface the processed substrate of resist image.According to absorbance, the peak-peak of spectral response, exposure the light sensitivity, (S of said method to the photonasty anticorrosive additive material layer of this moment ₄₁₀/ S ₄₅₀) and (S _450～650/ S ₄₅₀) and amber light under optical safety and resulting resist image estimate, the result is as shown in table 5.

Embodiment 4-2

Except light acid propellant (N2-3) being changed into following material, carry out identical operations with embodiment 4-1, with preparation photonasty image forming material, thereby obtain being formed with on the surface the pending substrate of resist image.Estimate with identical method.

(N2-3d) above-claimed cpd

Embodiment 4-3

Except emulsion (N2-4) being changed into following material, carry out identical operations with embodiment 4-1, with preparation photonasty image forming material, thereby obtain being formed with on the surface the pending substrate of resist image.Estimate with identical method.

(N2-4d) following compound is (at the molar absorptivity of 405nm wavelength: 4,300)

(N2-4d)

Embodiment 4-4

Except light acid propellant (N2-3) being changed into following material, carry out identical operations with embodiment 4-3, with preparation photonasty image forming material, thereby obtain being formed with on the surface the processed substrate of resist image.Estimate with identical method.

(N2-3d) above-claimed cpd

Embodiment 4-5

Except emulsion (N2-4) being changed into following material, carry out identical operations with embodiment 4-1, with preparation photonasty image forming material, thereby obtain being formed with on the surface the processed substrate of resist image.Estimate with identical method.

(N2-4e) following compound is (at the molar absorptivity of 405nm wavelength: 11,200): 1 weight portion

(N2-4e)

Embodiment 4-6

Except light acid propellant (N2-3) being changed into following material, carry out identical operations with embodiment 4-5, with preparation photonasty image forming material, thereby obtain being formed with on the surface the processed substrate of resist image.Estimate with identical method.

(N2-3d) above-claimed cpd

Embodiment 4-7

Except emulsion (N2-4) being changed into following material, carry out identical operations with embodiment 4-1, with preparation photonasty image forming material, thereby obtain being formed with on the surface the processed substrate of resist image.Estimate with identical method.

(N2-4f) following compound is (at the molar absorptivity of 405nm wavelength: 5,300)

(N2-4f)

Embodiment 4-8

Except having of usefulness is applied to thickness on the silicone substrate is that the processed substrate of the copper coating of 1 μ m replaces the glass substrate, carry out identical operations with embodiment 4-5, with preparation photonasty image forming material, thereby obtain being formed with on the surface the processed substrate of resist image.Estimate with identical method.

Embodiment 4-9

As photopolymerizable negative photosensitive composition (N1), build is that the consumption of 10 μ m or 20 μ m is coated on coating fluid on the polyethylene terephthalate film (thickness is 19 μ m) as provisional carrier film to make to utilize applicator, subsequently in 90 ℃ baking oven dry 5 minutes to form the photosensitive composite layer, lamination is as the polyethylene film (thickness is 25 μ m) of coverlay on the said composition layer, and places one day with preparation dry film photoresist material.Described coating fluid is by in methyl ethyl ketone/isopropyl alcohol (weight ratio the is 8/2) mixed solvent that following ingredients is added to 100 weight portions, and at room temperature stirring prepares subsequently.

{ (N1-1) ethylene linkage unsaturated compound }

(N1-1e) above-claimed cpd, 11.5 weight portions

(N1-1g) above-claimed cpd, 10 weight portions

(N1-1h) above-claimed cpd, 23.5 weight portions

(N1-2) emulsion

(N1-2h) compound identical with above-mentioned (N2-4e) is (at the molar absorptivity of 405 nm wavelength: 11,200): 0.6 weight portion

(N1-3) photo-induced polymerization initiator

(N1-3a) 2,2-two (Chloro-O-Phenyl)-4,4,5,5-tetraphenyl diimidazole (fusing point: 196 ℃ is in the X-ray diffraction spectrum of 1.54 at wavelength, has the maximum diffraction peak when being 9.925 ° at Bragg angle (2 θ ± 0.2 °)): 12 weight portions

(N1-4) polymeric binder material

(N1-4c) styrene/methacrylic acid methyl esters/methacrylic acid 2-hydroxyethyl ester/methacrylic acid copolymer (mol ratio is 10/50/20/20, and weight-average molecular weight is 68,000, and acid number is 129KOHmg/g): 55 weight portions

{ (N1-5) hydrogen supply compound }

(N1-5c): the dipole ion compound of N-phenylglycine: 0.2 weight portion

{ other }

Leuco crystal violet (Leuco Crystal Violet): 0.4 weight portion

9-phenylacridine: 0.2 weight portion

In addition, for flat surface, (thickness is 1.5mm to " the Scotch-Brite SF " that utilization is produced by Sumitomo 3M society to copper-clad laminated base plate with polishing roll, the copper foil surface that is of a size of 250mm * 200mm) polishes, wash and use the airflow drying with water, described copper-clad laminated base plate has polyimide resin and thickness is that 35 μ m are bonded in the Copper Foil on this resin.Then, substrate is preheated in baking oven to 60 ℃, then on the Copper Foil of copper-clad laminated plate, when peelling off polyethylene film, utilize type hand roll-type laminating machine that the above-mentioned dry film photoresist material that obtains is carried out lamination with preparation photonasty image forming material peeling off side, roll temperature during lamination is 100 ℃, and roll-in is 0.3MPa, and lamination speed is 1.5m/min (meter/minute).The photonasty anticorrosive additive material layer that resulting photonasty image forming material has copper-clad laminated base plate and forms on this substrate.

Under the condition of above-mentioned exposure light sensitivity evaluation method, photonasty anticorrosive additive material layer to resulting photonasty image forming material carries out scan exposure, peel off the polyethylene terephthalate film then, to under the pressure of 0.15MPa, spray as the aqueous solution of the sodium carbonate of 30 ℃ 0.7 weight % of developer, handle to carry out spray developing, thereby obtain being formed with on the surface the processed substrate of resist image.Estimate with identical method.

Embodiment 5-1

As chemical amplifying type negative photosensitive composition (N2), build is that the consumption of 10 μ m or 20 μ m is coated on coating fluid on the glass substrate to make to utilize spin coating, subsequently 90 ℃ of dryings 10 minutes forming photonasty anticorrosive additive material layer, thereby preparation photonasty image forming material.Described coating fluid is by being added to following ingredients in the propylene glycol monomethyl ether of 290 weight portions, and at room temperature stirring prepares subsequently.

(N2-1) alkali soluble resins

(N2-1a) poly-(para hydroxybenzene ethene) (weight-average molecular weight is 5,000): 100 weight portions are crosslinking chemical (N2-2)

(N2-2a) methoxy melamine (" NIKALAC E-2151 ", by SanwaChemical Co., Ltd. makes): 50 weight portions

(N2-3) light acid propellant

(N2-3d) above-claimed cpd: 6 weight portions

(N2-4) emulsion

(N2-4g) following compound is (at the molar absorptivity of 405 nm wavelength: 4,300): 1 weight portion

(N2-4g)

Under the condition of above-mentioned exposure light sensitivity evaluation method, photonasty anticorrosive additive material layer to resulting photonasty image forming material carries out scan exposure, in 100 ℃ baking oven, carry out 10 minutes back heat treated subsequently, in 20 ℃ of potassium hydroxide aqueous solutions that the photonasty image forming material contained 0.5 weight %, soak 60 seconds then carrying out development treatment, thereby obtain being formed with on the surface the processed substrate of resist image.According to absorbance, the peak-peak of spectral response, exposure the light sensitivity, (S of said method to the photonasty anticorrosive additive material layer of this moment ₄₁₀/ S ₄₅₀) and (S _450～650/ S ₄₅₀) and amber light under optical safety and resulting resist image estimate, the result is as shown in table 5.

Embodiment 5-2

Except emulsion (N2-4) being changed into following material, carry out identical operations with embodiment 5-1, with preparation photonasty image forming material, thereby obtain being formed with on the surface the processed substrate of resist image.Estimate with identical method.

(N2-4h) following compound is (at the molar absorptivity of 405nm wavelength: 300)

(N2-4h)

Embodiment 5-3

Except emulsion (N2-4) being changed into following material, carry out identical operations with embodiment 5-1, obtain being formed with on the surface the processed substrate of resist image with preparation photonasty image forming material.Estimate with identical method.

(N2-4i) following compound is (at the molar absorptivity of 405nm wavelength: 120)

(N2-4i)

Embodiment 5-4

As photopolymerizable negative photosensitive composition (N1), build is that the consumption of 10 μ m or 20 μ m is coated on coating fluid on the polyethylene terephthalate film (thickness is 19 μ m) as provisional carrier film to make to utilize applicator, subsequently in 90 ℃ baking oven dry 5 minutes to form the photosensitive composition layer, lamination is as the polyethylene film (thickness is 25 μ m) of coverlay on the said composition layer, and places one day with preparation dry film photoresist material.Described coating fluid is by in methyl ethyl ketone/isopropyl alcohol (weight ratio the is 8/2) mixed solvent that following ingredients is added to 100 weight portions, and at room temperature stirring prepares subsequently.

{ (N1-1) ethylene linkage unsaturated compound }

(N1-1e) above-claimed cpd, 15 weight portions

(N1-1f) above-claimed cpd, 30 weight portions

(N1-2) emulsion

(N1-2i) compound identical with above-mentioned (N2-4g) is (at the molar absorptivity of 405 nm wavelength: 4,300): 0.3 weight portion

(N1-3) photo-induced polymerization initiator

(N1-3b) 2,2-two (Chloro-O-Phenyl)-4,4,5,5-tetraphenyl diimidazole (fusing point: 172 ℃ is in the X-ray diffraction spectrum of 1.54 at wavelength, has the maximum diffraction peak when being 21.16 ° at Bragg angle (2 θ ± 0.2 °)): 12 weight portions

(N1-4) polymeric binder material

(N1-4c) styrene/methacrylic acid methyl esters/methacrylic acid 2-hydroxyethyl ester/methacrylic acid copolymer (mol ratio is 10/50/20/20, and weight-average molecular weight is 68,000, and acid number is 129KOHmg/g): 55 weight portions

{ (N1-5) hydrogen supply compound }

(N1-5c): the dipole ion compound of N-phenylglycine: 0.2 weight portion

{ other }

Leuco crystal violet: 0.4 weight portion

9-phenylacridine: 0.2 weight portion

In addition, for flat surface, (thickness is 1.5mm, and the copper foil surface that is of a size of 250mm * 200mm) polishes, and washes and use the airflow drying with water to copper-clad laminated base plate with polishing roll to utilize " the Scotch-Brite SF " that produced by Sumitomo 3M society.Described copper-clad laminated base plate has polyimide resin and thickness is that 35 μ m are bonded in the Copper Foil on this resin.Then, substrate is preheated in baking oven to 60 ℃, then on the Copper Foil of copper-clad laminated plate, when peelling off polyethylene film, utilize type hand roll-type laminating machine that the above-mentioned dry film photoresist material that obtains is carried out lamination with preparation photonasty image forming material peeling off side, roll temperature during lamination is 100 ℃, and roll-in is 0.3MPa, and lamination speed is 1.5m/min (meter/minute).The photonasty anticorrosive additive material layer that resulting photonasty image forming material has copper-clad laminated base plate and forms on this substrate.

Under the condition of above-mentioned exposure light sensitivity evaluation method, photonasty anticorrosive additive material layer to resulting photonasty image forming material carries out scan exposure, peel off the polyethylene terephthalate film then, to under the pressure of 0.15MPa, spray as the aqueous sodium carbonate of 30 ℃ 1 weight % of developer, handle to carry out spray developing, thereby obtain being formed with on the surface the processed substrate of resist image.According to absorbance, the peak-peak of spectral response, exposure the light sensitivity, (S of said method to the photonasty anticorrosive additive material layer of this moment ₄₁₀/ S ₄₅₀) and (S _450～650/ S ₄₅₀) and amber light under optical safety and resulting resist image estimate, the result is as shown in table 5.

Comparative example 1

Except in the photopolymerizable negative photosensitive composition (N1) of embodiment 5-4 not the usability photo etching (N1-2), carry out identical operations with embodiment 5-4, has the image forming material that thickness is the photonasty anticorrosive additive material layer of 10 μ m with preparation, carry out scan exposure and development treatment, make exposed portion dissolving fully in developer thus, and do not form image.

Comparative example 2

Except changing the emulsion (N1-2) in the photopolymerizable negative photosensitive composition (N1) of embodiment 5-4 into following material, and its consumption changed into beyond 1 weight portion, carry out with embodiment 5-4 identical operations with preparation photonasty image forming material, thereby obtain being formed with on the surface the processed substrate of resist image.Estimate with identical method.To having thickness is that the image forming material of the photonasty anticorrosive additive material layer of 20 μ m carries out scan exposure and development treatment, makes exposed portion dissolving fully in developer thus, and does not form image.

(N1-2j) the following compound (molar absorptivity under the 405nm wavelength: 82,700)

(N1-2j)

Comparative example 3

Except in the chemical amplifying type negative photosensitive composition (N2) of embodiment 3-2 not the usability photo etching (N2-4), carry out identical operations with embodiment 3-2, has the image forming material that thickness is the photonasty anticorrosive additive material layer of 10 μ m with preparation, carry out scan exposure and development treatment, make exposed portion dissolving fully in developer thus, and do not form image.

Comparative example 4

Except the emulsion (N2-4) in the chemical amplifying type negative photosensitive composition (N2) of embodiment 3-2 being become following material, carry out with embodiment 3-2 identical operations with preparation photonasty image forming material, thereby obtain being formed with on the surface the processed substrate of resist image.Estimate with identical method.To having thickness is that the image forming material of the photonasty anticorrosive additive material layer of 20 μ m carries out scan exposure and development treatment, makes exposed portion dissolving fully in developer thus, and does not form image.

(N2-4j) compound (the molar absorptivity under 405nm wavelength: 82,700) identical with above-mentioned (N1-2j)

Table 5

	Photonasty anticorrosive additive material layer										The resist image		Coating fluid
															Types of compositions	Emulsion type (general formula)	Absorbance (/ thickness μ m)	The peak-peak of spectral response (nm)	Light sensitivity (S1) (mJ/cm 2)	Light sensitivity (S2) (mJ/cm 2)	? ??S2/S1	??(S 410/ ??S 450	??(S 450～650??/S 450)	Optical safety	Thickness (μ m)/live width (μ m)	Pattern form	Storage stability
Embodiment 1-1 embodiment 1-2 embodiment 1-3 embodiment 1-4 embodiment 1-5 embodiment 1-6 embodiment 1-7	?N1 ?N2 ?N2 ?N2 ?N2 ?P1 ?P1	(Ia) do not have	?0.218 ?0.036 ?0.051 ?0.036 ?0.051 ?0.086 ?0.086	?410 ?410 ?410 ?410 ?410 ?410 ?410	??1 ??4 ??4 ??4 ??4 ??15 ??15	?5 ?7 ?11 ?7 ?11 ?20 ?20	??5.0 ??1.75 ??2.75 ??1.75 ??2.75 ??1.3 ??1.3	??A ??A ??A ??A ??A ??A ??A	??A ??A ??A ??A ??A ??A ??A	?A ?A ?A ?A ?A ?A ?A	?10/10＝1.0 ?10/7＝1.4 ?10/7＝1.4 ?10/10＝1.0 ?10/10＝1.0 ?10/7＝1.4 ?10/10＝1.0	Rectangle rectangle rectangle rectangle rectangle rectangle rectangle	??A ??B ??B ??B ??B ??B ??B
														Embodiment 2-1 embodiment 2-2 embodiment 2-3 embodiment 2-4 embodiment 2-5 embodiment 2-6 embodiment 2-7 embodiment 2-8	?N1 ?N1 ?N1 ?N1 ?N1 ?N1 ?N1 ?N1	?(Ib) ?(Ib) ?(Id) ?(Ib) ?(Ib) ?(Ib) ?(Ib) ?(Id)	?0.001 ?0.001 ?0.0001 ?0.0004 ?0.001 ?0.001 ?0.001 ?0.0001	?410 ?410 ?410 ?410 ?410 ?410 ?410 ?410	??0.5 ??0.3 ??0.3 ??0.4 ??0.2 ??0.5 ??0.5 ??0.4	?0.8 ?0.7 ?0.9 ?0.9 ?0.5 ?1.1 ?1.4 ?1.2	??1.6 ??2.3 ??3.0 ??2.3 ??2.5 ??2.2 ??2.8 ??3.0	??A ??A ??A ??A ??A ??A ??A ??A	??A ??A ??A ??A ??A ??A ??A ??A	?A ?A ?A ?A ?A ?A ?A ?A?	?25/10＝2.5 ?25/10＝2.5 ?25/10＝2.5 ?25/10＝2.5 ?25/10＝2.5 ?25/10＝2.5 ?25/10＝2.5 ?25/10＝2.5	Rectangle rectangle rectangle rectangle rectangle rectangle rectangle rectangle	??A ??A ??A ??A ??A ??C ??C ??C
Embodiment 3-1 embodiment 3-2 embodiment 3-3 embodiment 3-4	?N2 ?N2 ?N2 ?N1	?(II) ?(II) ?(II) ?(II)	?0.132 ?0.132 ?0.218 ?0.084	?410 ?410 ?410 ?410	??8 ??10 ??8 ??3	?14 ?16 ?30 ?8	??1.8 ??1.6 ??3.8 ??2.7	??A ??A ??A ??A	??A ??A ??A ??A	?A ?A ?A ?A	?10/5＝2.0 ?10/7＝1.4 ?10/5＝2.0 ?20/10＝2.0	Rectangle rectangle rectangle rectangle	??A ??A ??A ??A

Table 5 (continuing)

	Photonasty anticorrosive additive material layer										The resist image		Coating fluid
															Types of compositions	Emulsion type (general formula)	Absorbance (/ thickness μ m)	The peak-peak of spectral response (nm)	Light sensitivity (S1) (mJ/cm 2)	Light sensitivity (S2) (mJ/cm 2)	? ??S2/S1	????(S 410/ ?????S 450	??(S 450～650???/S 450)	Optical safety	Thickness (μ m)/live width (μ m)	Pattern form	Storage stability
Embodiment 4-1 embodiment 4-2 embodiment 4-3 embodiment 4-4 embodiment 4-5 embodiment 4-6 embodiment 4-7 embodiment 4-8 embodiment 4-9	??N2 ??N2 ??N2 ??N2 ??N2 ??N2 ??N2 ??N2 ??N1	??(III) ??(III) ??(III) ??(III) ??(III) ??(III) ??(III) ??(III) ??(III)	??0.058 ??0.058 ??0.017 ??0.017 ??0.048 ??0.048 ??0.019 ??0.048 ??0.008	??410 ??410 ??410 ??410 ??410 ??410 ??410 ??410 ??410	??5 ??10 ??4 ??3 ??10 ??8 ??10 ??8 ??6	????8 ????14 ????5 ????4 ????14 ????12 ????15 ????12 ????16	??1.6 ??1.4 ??1.3 ??1.3 ??1.4 ??1.5 ??1.5 ??1.5 ??2.7	????A ????A ????A ????A ????A ????A ????A ????A ????A	??A ??A ??A ??A ??A ??A ??A ??A ??A	??A ??A ??A ??A ??A ??A ??A ??A ??A	??10/7＝1.4 ??10/10＝1.0 ??10/10＝1.0 ??10/7＝1.4 ??10/5＝2.0 ??10/5＝2.0 ??10/5＝2.0 ??10/5＝2.0 ??20/15＝1.3	Rectangle rectangle rectangle rectangle rectangle rectangle rectangle rectangle rectangle	????A ????A ????A ????A ????A ????A ????A ????A ????A
														Embodiment 5-1 embodiment 5-2 embodiment 5-3 embodiment 5-4	??N2 ??N2 ??N2 ??N1	??(IV) ??(IV) ??(IV) ??(IV)	??0.017 ??0.001 ??0.001 ??0.003	??410 ??410 ??410 ??410	??8 ??10 ??10 ??4	????10 ????12 ????12 ????8	??1.3 ??1.2 ??1.2 ??2.0	????A ????A ????A ????A	??A ??A ??A ??A	??A ??A ??A ??A	??10/5＝2.0 ??10/7＝1.4 ??10/7＝1.4 ??25/6＝1.7	Rectangle rectangle rectangle rectangle	????A ????A ????A ????A
Comparative example 1 comparative example 2 comparative examples 3 comparative examples 4	??N1 ??N1 ??N2 ??N2	No ketocoumaran does not have ketocoumaran	??0 ??0.383 ??0 ??0.383	??＜320 ??450 ??＜320 ??450	??- ??2 ??- ??12	????- ????- ????- ????-	??- ??∞ ???- ??∞	????- ????D ????- ????D	??- ??D ??- ??D	??- ??D ??- ??D	??- ??10/20＝0.5 ??- ??10/7＝1.4	-trapezoidal-trapezoidal	????- ????A ????- ????A

"-" therefore estimates owing to do not form image

Industrial applicibility

The invention provides a kind of image forming material and resist imaging method thereof with purple laser-photosensitive anticorrosive additive material layer, described image forming material is extremely sensitive to the laser beam in purple light district, even while its light sensitivity when film is thicker can not reduce yet.

Claims (46)

1. the image forming material that has purple laser-photosensitive anticorrosive additive material layer, the photonasty anticorrosive additive material layer that this image forming material has processed substrate and forms on described substrate, it is characterized in that, the thickness of described photonasty anticorrosive additive material layer is at least 10 μ m, and has per 1 μ m thickness at 405nm wavelength place and be at most 0.3 absorbance.

2. the image forming material with purple laser-photosensitive anticorrosive additive material layer as claimed in claim 1, the S2/S1 of wherein said photonasty anticorrosive additive material layer is at most 5, described S1 represents the light sensitivity under exposure wavelength when thickness is 10 μ m, and described S2 represents the light sensitivity when thickness is 20 μ m.

3. the image forming material with purple laser-photosensitive anticorrosive additive material layer as claimed in claim 1 or 2, the thickness of wherein said photonasty anticorrosive additive material layer is at most 200 μ m.

4. as each described image forming material with purple laser-photosensitive anticorrosive additive material layer in the claim 1～3, wherein said photonasty anticorrosive additive material layer has the maximum absorption peak of spectral response in the wavelength coverage of 320nm～450nm.

5. as each described image forming material with purple laser-photosensitive anticorrosive additive material layer in the claim 1～4, wherein said photonasty anticorrosive additive material layer has and is at most 0.1 S ₄₁₀/ S ₄₅₀Ratio, described S ₄₁₀For under the wavelength of 410nm, forming the minimum exposure amount of image, described S ₄₅₀For under the wavelength of 450nm, forming the minimum exposure amount of image, S ₄₁₀And S ₄₅₀Unit be μ J/cm ²

6. as each described image forming material with purple laser-photosensitive anticorrosive additive material layer in the claim 1～5, wherein said photonasty anticorrosive additive material layer has the S greater than 1 _450～650/ S ₄₅₀Ratio, described S _450～650For greater than 450nm and be at most the minimum exposure amount that can form image in the wavelength coverage of 650nm, described S ₄₅₀For under the wavelength of 450nm, forming the minimum exposure amount of image, S _450～650And S ₄₅₀Unit be μ J/cm ²

7. as each described image forming material with purple laser-photosensitive anticorrosive additive material layer in the claim 1～6, wherein said photonasty anticorrosive additive material layer comprises have following ingredients (N1-1), (N1-2) and photopolymerizable negative photosensitive composition (N1) (N1-3):

(N1-1) ethylene linkage unsaturated compound,

(N1-2) emulsion,

(N1-3) photo-induced polymerization initiator.

8. the image forming material with purple laser-photosensitive anticorrosive additive material layer as claimed in claim 7, wherein said photonasty anticorrosive additive material layer contains (methyl) esters of acrylic acid material, it is as the ethylene linkage unsaturated compound of composition (N1-1) in the photopolymerizable negative photosensitive composition (N1), should have polyalkylene oxide groups by (methyl) esters of acrylic acid material, and have at least two (methyl) acryloyl-oxy groups.

9. as claim 7 or 8 described image forming materials with purple laser-photosensitive anticorrosive additive material layer, wherein said photonasty anticorrosive additive material layer contains at least a compound that is selected from the group of being made up of the following material emulsion as composition (N1-2) in the photopolymerizable negative photosensitive composition (N1): the dialkyl amido benzene-like compounds; The compound that contains the sulphonyl imino group; 2-naphthyridines ketone compounds or 2-carbostyril compound; With the indoline compounds.

10. as each described image forming material in the claim 7～9 with purple laser-photosensitive anticorrosive additive material layer, wherein said photonasty anticorrosive additive material layer contains Hexaarylbisimidazolecompounds compounds, and it is as the photo-induced polymerization initiator of composition (N1-3) in the photopolymerizable negative photosensitive composition (N1).

11. as each described image forming material with purple laser-photosensitive anticorrosive additive material layer in the claim 1～6, wherein said photonasty anticorrosive additive material layer comprises have following ingredients (N2-1), (N2-2) and chemical amplifying type negative photosensitive composition (N2) (N2-3):

(N2-1) alkali soluble resins,

(N2-2) crosslinking chemical of under acid condition, having an effect with alkali soluble resins,

(N2-3) light acid propellant.

12. the image forming material with purple laser-photosensitive anticorrosive additive material layer as claimed in claim 11, wherein said photonasty anticorrosive additive material layer contains the resin of phenolic hydroxy group, and it is as the alkali soluble resins of composition (N2-1) in the chemical amplifying type negative photosensitive composition (N2).

13. as claim 11 or 12 described image forming materials with purple laser-photosensitive anticorrosive additive material layer, wherein said photonasty anticorrosive additive material layer contains melamine resin or Lauxite, and it is as the crosslinking chemical of composition (N2-2) in the chemical amplifying type negative photosensitive composition (N2).

14. as each described image forming material in the claim 11～13 with purple laser-photosensitive anticorrosive additive material layer, wherein said photonasty anticorrosive additive material layer contains 1 of halomethylation, 3, the 5-pyrrolotriazine derivatives, it is as the light acid propellant of composition (N2-3) in the chemical amplifying type negative photosensitive composition (N2).

15. as each described image forming material with purple laser-photosensitive anticorrosive additive material layer in the claim 11～14, the chemical amplifying type negative photosensitive composition (N2) that wherein constitutes described photonasty anticorrosive additive material layer also contains at least a emulsion composition (N2-4) that is selected from the group of being made up of following material: dialkyl amido benzene-like compounds, the compound that contains the sulphonyl imino group, 2-naphthyridines ketone compounds or 2-carbostyril compound and indoline compounds.

16. as each described image forming material with purple laser-photosensitive anticorrosive additive material layer in the claim 1～6, wherein said photonasty anticorrosive additive material layer comprises have following ingredients (P1-1) and chemically amplified positive photosensitive composition (P1) (P1-2):

(P1-1) contain the resin of sour decomposability group,

(P1-2) light acid propellant.

17. the image forming material with purple laser-photosensitive anticorrosive additive material layer as claimed in claim 16, wherein said photonasty anticorrosive additive material layer contains the polyvinylphenol resin, it is as the resin that contains sour decomposability group of composition (P1-1) in the chemically amplified positive photosensitive composition (P1), and described polyvinylphenol resin is at least at its terminal sour decomposability group with alkoxy of introducing.

18. as claim 16 or 17 described image forming materials with purple laser-photosensitive anticorrosive additive material layer, wherein said photonasty anticorrosive additive material layer contains 1 of halomethylation, 3, the 5-pyrrolotriazine derivatives, it is as the light acid propellant of composition (P1-2) in the chemically amplified positive photosensitive composition (P1).

19. as each described image forming material with purple laser-photosensitive anticorrosive additive material layer in the claim 16～18, the chemically amplified positive photosensitive composition (P1) that wherein constitutes described photonasty anticorrosive additive material layer also contains at least a emulsion composition (P1-3) that is selected from the group of being made up of following material: the dialkyl amido benzene-like compounds; The compound that contains the sulphonyl imino group; 2-naphthyridines ketone compounds or 2-carbostyril compound; With the indoline compounds.

20. as each described image forming material in the claim 9,15 and 19 with purple laser-photosensitive anticorrosive additive material layer, be that described emulsion is used as composition (N1-2), the composition (N2-4) in the chemical amplifying type negative photosensitive composition (N2) or the composition (P1-3) in chemically amplified positive photosensitive composition (P1) in the photopolymerizable negative photosensitive composition (N1) that constitutes photonasty anticorrosive additive material layer by the following general formula (Ib) or (Id) compound of representative wherein as the dialkyl amido benzene-like compounds of emulsion:

In general formula (Ib), R ²And R ⁴Representative independently of one another optionally has substituent alkyl, R ⁶And R ⁸Represent hydrogen atom independently of one another or optionally have substituent alkyl, and R ²With R ⁶Or R ⁴With R ⁸Optionally independent formation nitrogen heterocyclic ring, and these two tetrahydroquinoline rings optionally have other substituting groups;

In general formula (Id), R ²Representative optionally has substituent alkyl, R ⁶Represent hydrogen atom or optionally have substituent alkyl, R ²With R ⁶Optionally form nitrogen heterocyclic ring, X represents dialkyl group methylene, imino group or alkyl imino, oxygen atom or sulphur atom, and ring A representative optionally has substituent aromatic rings, and the tetrahydroquinoline ring optionally has other substituting groups.

21. as each described image forming material in the claim 9,15 and 19 with purple laser-photosensitive anticorrosive additive material layer, be compound by following general formula (II) representative as the compound that contains the sulphonyl imino group of emulsion wherein, described emulsion is used as composition (N1-2), the composition (N2-4) in the chemical amplifying type negative photosensitive composition (N2) or the composition (P1-3) in the chemically amplified positive photosensitive composition (P1) in the photopolymerizable negative photosensitive composition (N1) that constitutes photonasty anticorrosive additive material layer:

In general formula (II), R ¹¹And R ¹²Represent hydrogen atom or optional substituting group independently of one another, R ¹³The substituting group that representative is optional.

22. as each described image forming material in the claim 9,15 and 19 with purple laser-photosensitive anticorrosive additive material layer, be compound by following general formula (III) representative as the 2-naphthyridines ketone compounds of emulsion or 2-carbostyril compound wherein, described emulsion is used as composition (N1-2), the composition (N2-4) in the chemical amplifying type negative photosensitive composition (N2) or the composition (P1-3) in the chemically amplified positive photosensitive composition (P1) in the photopolymerizable negative photosensitive composition (N1) that constitutes photonasty anticorrosive additive material layer:

In general formula (III), Z represents nitrogen-atoms or C-R ²¹, R ¹⁴, R ¹⁵, R ¹⁶, R ¹⁷, R ¹⁸, R ¹⁹, R ²⁰And R ²¹Represent hydrogen atom or optional substituting group independently of one another, R ¹⁸With R ¹⁹, R ¹⁹With R ²⁰Or R ²⁰With R ²¹Optionally independent formation nitrogen heterocyclic ring, and R ¹⁵To R ¹⁸In optionally be bonded to ring between adjacent two groups.

23. as each described image forming material in the claim 9,15 or 19 with purple laser-photosensitive anticorrosive additive material layer, be compound by following general formula (IV) representative as the indoline compounds of emulsion wherein, described emulsion is used as composition (N1-2), the composition (N2-4) in the chemical amplifying type negative photosensitive composition (N2) or the composition (P1-3) in chemically amplified positive photosensitive composition (P1) in the photopolymerizable negative photosensitive composition (N1) that constitutes photonasty anticorrosive additive material layer:

In general formula (IV), R ²², R ²³, R ²⁴, R ²⁵, R ²⁶, R ²⁷, R ²⁸, R ²⁹And R ³⁰Represent hydrogen atom or optional substituting group independently of one another, R ²²With R ²³Or R ²²With R ³⁰Optionally form nitrogen heterocyclic ring independently, and R ²³To R ³⁰In optionally be bonded to ring between adjacent two groups.

24. a dry film photoresist material, this material comprise provisional carrier film and on described provisional carrier film, form as each described photosensitive composition layer in the claim 7～23.

25. as each described image forming material in the claim 1～6 with purple laser-photosensitive anticorrosive additive material layer, wherein with the described dry film photoresist material of claim 24 at photosensitive composition layer one side and processed substrate lamination, to form photonasty anticorrosive additive material layer.

26. resist imaging method, it is characterized in that, the laser beam that with wavelength is 320nm to 450nm is carried out development treatment subsequently to carrying out scan exposure as each described photonasty anticorrosive additive material layer with image forming material of purple laser-photosensitive anticorrosive additive material layer in claim 1～23 and 25.

27. contain the photosensitive composition of emulsion and reactive compound, described reactive compound produces free radical or acid by interacting with emulsion through exposure, it is characterized in that, described emulsion is by the general formula (Ib) or (Id) the dialkyl amido benzene-like compounds of representative, described dialkyl amido benzene-like compounds has under the 405nm wavelength and is at least 100 and be at most 100,000 molar absorptivity ε, and have alkyl substituent in the 2-position of its tetrahydroquinoline ring.

28. contain the photosensitive composition of emulsion and reactive compound, described reactive compound produces free radical or acid by reacting with the emulsion through exposing, it is characterized in that, described emulsion is the compound that contains the sulphonyl imino group by general formula (II) representative, the described compound that contains the sulphonyl imino group has at 405nm wavelength place and is at least 100 and be at most 100,000 molar absorptivity ε.

29. photosensitive composition as claimed in claim 28, the wherein said compound that contains the sulphonyl imino group is the compound by general formula (II) representative, wherein R ¹¹Be hydrogen atom, R ¹²And R ¹³Independently of one another for optionally having substituent heterocyclic group or optionally having substituent aryl.

30. contain the photosensitive composition of emulsion and reactive compound, described reactive compound produces free radical or acid by reacting with the emulsion through exposing, it is characterized in that, described emulsion is 2-naphthyridines ketone compounds or the 2-carbostyril compound by general formula (III) representative, described 2-naphthyridines ketone compounds or 2-carbostyril compound have at 405nm wavelength place and are at least 100 and be at most 100,000 molar absorptivity ε.

31. photosensitive composition as claimed in claim 30, wherein said 2-naphthyridines ketone compounds or 2-carbostyril compound are C-R for Z in general formula (III) ²¹The 2-carbostyril compound.

32. contain the photosensitive composition of emulsion and reactive compound, described reactive compound produces free radical or acid by reacting with the emulsion through exposing, it is characterized in that, described emulsion is the indoline compounds by general formula (IV) representative, described indoline compounds has under the 405nm wavelength and is at least 100 and be at most 100,000 molar absorptivity ε.

33. photosensitive composition as claimed in claim 32, wherein said indoline compounds are R in general formula (IV) ²⁸Compound for the group of following general formula (IV) representative:

In general formula (IV), R ³¹Represent hydrogen atom or optional substituting group, optional bivalent atom or the substituting group of W representative, and R ³¹With R ²⁷Or R ³¹With R ²⁹Optionally independent keys is synthetic encircles.

34. R in the photosensitive composition as claimed in claim 33, its formula of (IV) ²⁸For the compound of the group of general formula (IV) representative is by following general formula (IVa), (IVb), (IVc), (IVd) and (IVe) any in the compound of representative:

At general formula (IVa), (IVb), (IVc), (IVd) with (IVe), R ²², R ²³, R ²⁴, R ²⁵, R ²⁶, R ²⁷, R ²⁹And R ³⁰Identical with the group defined in the above-mentioned general formula (IV), R ³¹, R ³², R ³³, R ³⁴, R ³⁵And R ³⁶Represent hydrogen atom or optional substituting group separately, V represention oxygen atom or N-R ³⁷, and R ³⁷Represent hydrogen atom or optional substituting group.

35. dry film photoresist material, this material comprises provisional carrier and the purple laser-photosensitive anticorrosive additive material layer that forms on described provisional carrier, it is characterized in that, the thickness of described photonasty anticorrosive additive material layer is at least 10 μ m, and has per 1 μ m thickness be at most 0.3 absorbance under the wavelength of 405nm.

36. be used to prepare the photosensitive composition of electronic circuit, wherein

(1) maximal value of thickness D and the ratio D/L of minimum feature L that contains the photonasty anticorrosive additive material layer of described composition is at least 1.0, described minimum feature L is by being that the laser beam of 390nm～430nm is carried out scan exposure to the photonasty anticorrosive additive material layer with above-mentioned thickness D with wavelength, carries out development treatment subsequently and obtains; With

(2) at the minimum exposure amount S that can on this photonasty anticorrosive additive material layer, form image under the wavelength of 410nm ₄₁₀Be at most 10,000 μ J/cm ²

37. the photosensitive composition that is used to prepare electronic circuit as claimed in claim 36, wherein D/L is at least 1.3.

38. the photosensitive composition that is used to prepare electronic circuit as claimed in claim 37, wherein D/L is at least 2.0.

39. be used to prepare the photosensitive composition of electronic circuit, wherein

(1) maximal value of thickness D and the ratio D/L of minimum feature L that contains the photonasty anticorrosive additive material layer of described composition is at least 1.0, described minimum feature L is by being that the laser beam of 390nm～430nm is carried out scan exposure to the photonasty anticorrosive additive material layer with above-mentioned thickness D with wavelength, carries out development treatment subsequently and obtains; With

(2) obtain above-mentioned D/L and be at most 20mJ/cm than employed exposure ²

40. the photosensitive composition that is used to prepare electronic circuit as claimed in claim 39, the maximal value of wherein said D/L is at least 1.3.

41. the photosensitive composition that is used to prepare electronic circuit as claimed in claim 40, the maximal value of wherein said D/L is at least 2.0.

42. the photosensitive composition that is used to prepare electronic circuit as claimed in claim 39 wherein obtains described D/L and is at most 10mJ/cm than employed exposure ²

43. the photosensitive composition that is used to prepare electronic circuit as claimed in claim 42, the maximal value of wherein said D/L is at least 1.3.

44. the photosensitive composition that is used to prepare electronic circuit as claimed in claim 43, the maximal value of wherein said D/L is at least 2.0.

45. have the image forming material of processed substrate and photonasty anticorrosive additive material layer, wherein said photonasty anticorrosive additive material layer contain on described processed substrate, form as each described photosensitive composition that is used to prepare electronic circuit in the claim 36～44.

46. have the dry film photoresist material of provisional carrier and photonasty anticorrosive additive material layer, wherein said photonasty anticorrosive additive material layer contain on described provisional carrier, form as each described photosensitive composition that is used to prepare electronic circuit in the claim 36～44.