CN1705913B

CN1705913B - Negative blue-violet laser photosensitive composition, image forming material, image former and method of image formation

Info

Publication number: CN1705913B
Application number: CN200480001373.5A
Authority: CN
Inventors: 水上润二; 龟山泰弘; 利光惠理子; 瑞穗右二
Original assignee: Nippon Synthetic Chemical Industry Co Ltd
Current assignee: Changxing Materials Industry Co ltd; Nippon Mining Holdings Inc
Priority date: 2003-09-25
Filing date: 2004-09-22
Publication date: 2011-11-30
Anticipated expiration: 2024-09-22
Also published as: CN101165593A; CN1705913A

Abstract

A negative blue-violet laser photosensitive composition that is highly sensitive to laser beams of blue-violet region, excelling in not only safe light properties under a yellow light but also the resolution and rectangularity of obtained image, which negative blue-violet laser photosensitive composition especially can appropriately be used as a dry film resist material and used in direct lithography by blue-violet laser beams. There are further provided, using the negative blue-violet laser photosensitive composition, an image forming material, image former and method of image formation. In particular, there is provided a negative blue-violet laser photosensitive composition wherein the minimum exposure intensity at which the exposure by blue-violet laser beams causes the residual film ratio to be 90% or higher is 40 mJ/cm<2> or less and wherein with respect to a residual film ratio - exposure intensity curve obtained by plotting the residual film ratio at exposed part [t(%)] against the logarithm of exposure intensity by blue-violet laser beams [logE(mJ/cm<2>)], the gamma value of straight line binding point at a residual film ratio of 15% with point at a residual film ratio of 80%, t = gammalogE + delta, is 4.0*10<2> or more. There are further provided, using the negative blue-violet laser photosensitive composition, an image forming material, image former and method of image formation.

Description

Negative blue-violet laser photosensitive composition, Image forming material, image formation component and image forming method

Technical field

The present invention relates to a kind of negative blue-violet laser photosensitive composition, said composition is used for as resist or electroplates protective agent, described resist or electroplate protective agent and be used for as printed-wiring board (PWB), liquid crystal display cells, Plasma Display, large scale integrated circuit, thin type transistor, semiconductor packages, form in color filter or the organic electroluminescent body as conductor circuit or electrode substrate processing, specifically, the present invention relates to be applicable to the direct-recording negative blue-violet laser photosensitive composition of blue-violet laser bundle with wavelength coverage 390 to 430nm, adopt the Image forming material of said composition, image formation component and image forming method.

Background technology

Up to now, in for example printed circuit board (PCB), liquid crystal display cells, Plasma Display, large scale integrated circuit, thin type transistor, semiconductor packages, color filter or organic electroluminescent body, the photosensitive composite that is used to form conductor circuit for example or electrode substrate processing can be following two types.Promptly, known two class photosensitive composites: negative photosensitive composition and positive light sensitivity composition, as negative photosensitive composition, usually have following two kinds: one of composition comprises alefinically unsaturated compounds, Photoepolymerizationinitiater initiater and alkali soluble resins (for example carboxylic resin), make described alefinically unsaturated compounds polymerization and curing by rayed, thereby make said composition in alkaline developer, become insoluble; Or composition two, said composition comprises the resin (for example polyvinylphenol resin) of phenolic hydroxy group, the crosslinking chemical that is used for described resin, the resin (resol that for example contains epoxy radicals) that contains acid crosslinkable groups and light acid producing agent (for example halomethylation Striazine derivative), described smooth acid producing agent produces acid under rayed, be insoluble to alkaline developer thereby described acid makes said composition that crosslinked becoming be taken place.In addition, as positive light sensitivity composition, usually have and comprise the resin (the polyvinylphenol resin that for example comprises sour decomposability group such as alkoxy) that contains sour decomposability group and composition of light acid producing agent (for example halomethylation Striazine derivative) etc., described smooth acid producing agent produces acid under rayed, described acid makes said composition decompose and become and dissolve in alkaline developer.

In addition, in order to form for example conductor circuit or electrode substrate processing, be extensive use of lithography, it comprises the following steps: that (1) forms this photosensitive composite layer on interim supporting film, with the surface that covered this photosensitive composite layer by overlay film to obtain the dry film erosion resistant, peeling off this is laminated on the processed substrate described dry film erosion resistant with the preparation image formation component after by overlay film, or directly on processed substrate, form the photosensitive composite layer and according to circumstances need to form protective seam thereon, with the preparation image formation component, the photosensitive composite layer of this image formation component carries out image exposure by the mask that is decorated with circuit or electrode pattern; (2) lift-off mask then; (3) in addition, if form interim supporting film or protective seam etc., then it is peeled off; (4) with alkaline developer dissolving and remove as the unexposed portion of no image section (under the minus situation) or with the alkaline developer dissolving and remove exposed portion, with the formation resist image corresponding with circuit pattern as no image section (under the eurymeric situation); (5) to being that the processed substrate of resist carries out for example etching or plating with the resist image, remove the resist image then, thereby forming circuit pattern or the electrode pattern of being described on the mask on the described processed substrate.

In addition, in recent years, the direct recording method of laser has received concern, this method is according to for example numerical information of computing machine, adopt laser beam as exposure light source, do not use mask directly to form image, because so not only can improve production performance but also can improve resolution performance, bearing accuracy etc.Therefore, people are also studying the application of laser beam in lithography energetically.As laser beam, known have various from the ultraviolet region light source to infrared region, but as the laser beam that is used for image exposure, consider output power, stability, exposure performance, cost etc., at present main employing can produce from the visible region to light such as infrared region as Argon ion laser, helium-neon laser, yttrium aluminum garnet (YAG) laser instrument or semiconductor laser.For example, used the lithography of FD-YAG (frequency multiplication YAG) laser instrument of the Argon ion laser that adopts wavelength 488nm or wavelength 532nm in the practice, and corresponding to the material that the is used for printed-wiring board (PWB) commercialization of 365nm ultraviolet laser.

Yet, the tradition photosensitive composite not necessarily has appropriate sensitivity in the direct recording method that utilizes laser beam, and when adopting visible laser beam, this photosensitive composite lacks the safety light performance under amber light, and exist need be in the environment of darkroom for example with the restriction of operation in the environment of red light illumination.On the other hand, along with the marked improvement of laser technology in recent years, the semiconductor laser that can stably vibrate in livid purple look zone has become useful, and this laser instrument can operation in the environment that bright light environments is for example thrown light on amber light.Yet, since with other laser beam for example the laser beam of visible region compare, the output power of this laser instrument is lower, therefore not only must improve the sensitivity of this photosensitive composite, and, particularly for the erosion resistant that under the thicker state of photosensitive composite layer, uses, the high resolving power performance of said composition and the image that will obtain, rectangle performance etc. are not corresponding, and in fact this photosensitive composite in direct recording method and all do not reach realistic scale in the lithography.

On the other hand, as photosensitive composite, in order to improve the sensitivity in the livid purple look zone, a kind of optical polymerism composition that is used for lithography has been proposed, said composition comprises compound that at least one position of having at least one vinyl and ortho position and contraposition in the aromatic rings replaces by sulphur atom as sensitizer, and is used in combination two luxuriant titanium type compounds as polymerization initiator (JP-A-2002-169282).Yet, for photosensitive composite as erosion resistant, the photosensitive composite that on the substrate of need processing, forms via the dry film erosion resistant particularly, its thickness is bigger, is at least 10 microns.In addition, in as the plating step of producing the step in the printed-wiring board (PWB) for example,, require electroplating thickness thicker, therefore still need to improve the sensitivity in the livid purple look zone because the live width of circuit attenuates in recent years.On the other hand, when having high sensitivity, composition exists in the problem that the safety light performance is easy to reduce under the amber light.

In addition, attempted the above-mentioned material corresponding with Ultra-Violet Laser is applied to the blue-violet laser bundle, yet for the high sensitivity type, the image that obtains is relatively poor in resolution performance and rectangle aspect of performance, and the high resolving power type is relatively poor aspect sensitivity.

Summary of the invention

Obtained the present invention under these conditions, the purpose of this invention is to provide negative blue-violet laser photosensitive composition, said composition has high sensitivity to the laser beam in the livid purple look zone and have excellent safety light performance under amber light, in addition, said composition will make resulting image have excellent resolution performance and rectangle performance, especially, said composition can be used as the photographic layer of dry film erosion resistant, and it is applicable to the direct record that utilizes the blue-violet laser bundle.In addition, the present invention also aims to provide a kind of Image forming material, image formation component and image forming method that adopts said composition.

For overcoming the problems referred to above, the inventor has made broad research, found that between exposure by making blue-violet laser bundle in this photosensitive composite and the film residual rate or have particular kind of relationship between developing powder and the exposure, can reach above-mentioned purpose, therefore finished the present invention.

That is, of the present inventionly will be intended to a kind of negative blue-violet laser photosensitive composition, it is characterized in that, said composition makes the film residual rate reach at least 90% minimum exposure amount and is at most 40mJ/cm when being exposed to the blue-violet laser bundle ², and, with the logH (logE (mJ/cm of the film residual rate on the exposed portion (t (%)) to the blue-violet laser bundle ²)) mapping, in the film residual rate/exposure curve that obtains, the γ value of straight line that connects 15% of described film residual rate and following formula (1) at 80% is at least 4.0 * 10 ²:

t＝γlogE+δ(1)

In addition, of the present inventionly will be intended to a kind of negative blue-violet laser bundle photosensitive composite, it is characterized in that, said composition makes the film residual rate reach at least 90% minimum exposure amount and is at most 40mJ/cm when being exposed to the blue-violet laser bundle ²And, after calculating dissolving films rate (100-t (%)) by the film residual rate (t (%)) at exposed portion place, at the logH (logE (mJ/cm of the developing powder that obtains divided by development time (T (second)) with this dissolving films rate (100-t (%)) (s={100-t}/T (%/second)) to the blue-violet laser bundle ²)) mapping and in developing powder/exposure curve of obtaining, the α value of straight line that connects 80% of maximum developing powder and following formula (2) at 20% is at least 12:

s＝-αlogE+β(2)

Find in addition, when described photosensitive composite is when comprising alefinically unsaturated compounds and Photoepolymerizationinitiater initiater as the negative photosensitive composition (being sometimes referred to as optical polymerism composition hereinafter) of basic composition, can realize above-mentioned purpose, the amount of the polymerization inhibitor in the wherein said composition is specific more a small amount of, and the compound that more preferably will have absorption maximum in particular range of wavelengths is as sensitizer.Promptly, as the preferred embodiment of the invention, above-mentioned photosensitive composite is a negative photosensitive composition, and said composition comprises alefinically unsaturated compounds and Photoepolymerizationinitiater initiater as basic composition, wherein, the content of polymerization inhibitor is 5 to 60ppm in the described photosensitive composite.In addition, as another preferred embodiment, above-mentioned photosensitive composite is included in 330 to 450nm the wavelength coverage has the compound of absorption maximum as sensitizer.

Here, for optical polymerism composition, to add polymerization inhibitor in the alefinically unsaturated compounds of the necessary component in being considered to optical polymerism composition and be and polymerization to take place in order preventing to produce or in order to give product with storage stability.In addition, in order to give optical polymerism composition, can according to circumstances need during production polymerization inhibitor is added the polymeric binder material that will use with layering.And, except polymerization inhibitor being added alefinically unsaturated compounds and polymeric binder material to prevent for example optical polymerism composition thermal polymerization or the polymerization in time, also when the preparation composition, add polymerization inhibitor to guarantee the stability of optical polymerism composition, in conjunction with the amount of all the other photopolymerization inhibitors, the polymerization inhibitor total amount is at least 100ppm usually.Therefore, the content of polymerization inhibitor is relatively small amount and those skilled in the art's general knowledge contradiction in the control optical polymerism composition.

In addition, of the present inventionly to be intended to: a kind of negative blue-violet laser photosensitive Image forming material, it is characterized in that, on interim supporting film, form the layer of above-mentioned negative blue-violet laser photosensitive composition; A kind of negative blue-violet laser photosensitive image formation component is characterized in that, on the substrate of need processing, at the above-mentioned negative blue-violet laser photosensitive Image forming material of described negative blue-violet laser photosensitive composition layer one side lamination; And a kind of image forming method, it is characterized in that, with the laser beam of wavelength 390 to 430nm the negative blue-violet laser photosensitive composition layer of above-mentioned negative blue-violet laser photosensitive image formation component is carried out scan exposure, subsequently it is carried out development treatment with developed image.

The invention effect

The present composition has high sensitivity to the laser beam in livid purple look zone, has excellent safety light performance under amber light, and makes resulting image have excellent resolution performance and rectangle performance.Especially, the invention provides and a kind ofly can be used as dry film erosion resistant photographic layer and be applicable to the direct-recording negative blue-violet laser photosensitive composition that utilizes the blue-violet laser bundle and adopt Image forming material, image formation component and the image forming method of said composition.

Description of drawings

Fig. 1 is the embodiment of the

invention

1 and 2 and the film residual rate/exposure curve of the blue-violet laser photosensitive composition of Comparative Examples 1 to 3.

Fig. 2 is the embodiment of the

invention

1 and 2 and developing powder/exposure the curve of the blue-violet laser photosensitive composition of Comparative Examples 1 to 3.

Embodiment

{ minimum exposure amount }

Negative blue-violet laser photosensitive composition of the present invention (negative blue-violet laser photosensitive composition of the present invention hereinafter can abbreviate blue-violet laser photosensitive composition as sometimes) makes the film residual rate reach at least 90% minimum exposure amount and is 40mJ/cm at the most when being exposed to the blue-violet laser bundle ², be preferably 20mJ/cm at the most ², especially preferred 10mJ/cm at the most ²Make the film residual rate reach at least 90% minimum exposure amount and be meant that the film residual rate that makes that obtains under the following conditions reaches at least 90% minimum exposure amount: by changing exposure, to be of a size of 0.5cm * 0.5cm and thickness be the blanket exposure that 5 to 100 microns photosensitive composite layer applies the blue-violet laser bundle of wavelength coverage 400 to 410nm to forming on holder, then at 25 ℃, 0.15MPa on the said composition layer, spray aqueous sodium carbonate down as 0.7 weight % of developer, and develop, the time of described development is for making unexposed photosensitive composite layer dissolve 1.5 times of required time (breakpoint) fully by development under the same conditions.The lower limit of minimum exposure amount is not particularly limited, be preferably as far as possible little, but be generally 1mJ/cm at least ²

{ film residual rate/exposure curve and γ value }

Say that further requisite for blue-violet laser photosensitive composition of the present invention is that minimum exposure amount when making the film residual rate reach at least 90% is at most 40mJ/cm ², in addition, with the logarithm (logE (mJ/cm of the film residual rate on the exposed portion (t (%)) to blue-violet laser bundle exposure ²)) mapping and in film residual rate/exposure curve of obtaining, the γ value of straight line that connects 15% of the film residual rate and following formula (1) at 80% is at least 4.0 * 10 ²The γ value is preferably at least 4.5 * 10 ², be preferably at least 5.0 * 10 especially ², most preferably be at least 5.5 * 10 ²In the straight line of following formula (1), the value δ that equals t when logE=0 is not the value that Special Significance is arranged among the present invention:

t＝γlogE+δ (1)

If the γ value is less than above-mentioned scope, the image that obtains will lack resolution performance and rectangle performance.In addition, the γ value is high more, and visual resolution performance that obtains and rectangle performance are excellent more, but the upper limit is generally about 1.0 * 10 ⁴With the logarithm (logE (mJ/cm of the film residual rate on the exposed portion (t (%)) to blue-violet laser bundle exposure ²)) mapping and in film residual rate/exposure curve of obtaining, it is desirable to, what the film residual rate showed in the zone of exposure deficiency is to be similar to 0% constant value, be at least in exposure and make the film residual rate reach the zone of at least 90% minimum exposure amount, the film residual rate shows is at least 90% constant value, intermediate exposures amount zone is the zone that exposure is at least critical exposure, exposure in this zone is not enough to form the image with at least 90% film residual rate but can obtains to a certain degree film residual rate, and in this intermediate exposures amount zone, curve from left to right is linearity and is inclined upwardly.Among the present invention, the linear gradient in the intermediate exposures amount zone in film residual rate/exposure curve is considered as connecting the slope γ of straight line of 15% of film residual rate and above-mentioned formula (1) at 80%, and is defined as and is at least a particular value.That is, shone by many leak light with the part that exposed portion is contiguous, certainly, the amount of described leak light mostly is the minimum exposure amount most and is at least critical exposure, therefore forms film on the part that should not be exposed, thereby causes the rectangle mis-behave.Therefore, limit slope γ and be at least a particular value, reducing intermediate exposures amount zone (part that the amount of being exposed is light-struck for the leakage of critical at least exposure, contiguous with exposed portion), thereby suppress the film forming that causes by the leak light that is radiated at the contiguous part of exposed portion.

{ developing powder/exposure curve and α value }

Say that further requisite for blue-violet laser photosensitive composition of the present invention is to make the film residual rate reach at least 90% minimum exposure amount to be at most 40mJ/cm ²In addition, after calculating dissolving films rate (100-t (%)) by the film residual rate (t (%)) at exposed portion place, at the logarithm (logE (mJ/cm of the developing powder that obtains divided by development time (T (second)) with this dissolving films rate (100-t (%)) (s={100-t}/T (%/second)) to blue-violet laser bundle exposure ²)) mapping and in development time/exposure curve of obtaining, the α value of straight line that connects 80% of maximum developing powder and following formula (2) at 20% is at least 12.The α value is preferably at least 13, and more preferably at least 14.The value β that equals s in the straight line of following formula (2) when logE=0 is not the value that acquires a special sense among the present invention:

s＝-αlogE+β (2)

If the α value is less than above-mentioned scope, the image that obtains will lack resolution performance and rectangle performance.In addition, the α value is high more, and visual resolution performance that obtains and rectangle performance are excellent more, but the upper limit is generally about 100.In addition, obtain the logarithm (logE (mJ/cm of developing powder (s={100-t}/T (%/second)) back by dissolving films rate (100-t (%)) (the film residual rate (t (%)) by the exposed portion place calculates) divided by development time (T (second)) to blue-violet laser bundle exposure ²)) mapping and in developing powder/exposure curve of obtaining, it is desirable to, in the zone of exposure deficiency, the dissolving films rate is near 100%, and developing powder is high-caliber constant value, be at least in exposure the dissolving films rate is reached in the zone of maximum 10% minimum exposure, developing powder is low-level constant value, intermediate exposures amount zone is that wherein exposure is at least the zone of critical exposure, exposure in this zone is not enough to obtain maximum 10% dissolving films rate but can obtains to a certain degree dissolving films rate, in this intermediate exposures amount zone, it is linear downward-sloping that curve is from left to right.Among the present invention, linear gradient in the intermediate exposures amount zone in developing powder/exposure curve is considered as connecting the slope α of straight line of 80% of maximum developing powder (this developing powder dissolving films rate (100-t (%)) when carrying out following the development equals 0 o'clock developing powder) and above-mentioned formula (2) at 20%, and limits it and be at least a particular value.Here, as maximum developing powder, employing be the developing powder when dissolving films rate (100-t (%))=100% when under following condition, developing.

Make above-mentioned film residual rate/exposure curve and above-mentioned developing powder/exposure curve as follows.(1), the photosensitive composite layer of 5 to 100 microns of size 0.5cm * 0.5cm, thickness is carried out blanket exposure with the blue-violet laser bundle of 400 to 410nm wavelength coverages by changing exposure; (2) then, under 25 ℃, 0.15MPa, on this photosensitive composite layer, spray 0.7 weight % aqueous sodium carbonate as developer, to develop, the time of described development is for making unexposed photosensitive composite layer dissolve 1.5 times of required time (breakpoint), MEASUREMENTS OF THIN residual rate thus fully by development under the same conditions; (3-1) for film residual rate/exposure curve, with the film residual rate (t (%)) of exposed portion logarithm (logE (mJ/cm to described exposure ²)) mapping; Or (3-2) for developing powder/exposure curve, film residual rate (100-t (%)) by exposed portion calculates dissolving films rate (100-t (%)), after obtaining developing powder (s={100-t}/T (%/second)) by this dissolving films rate (100-t (%)) divided by development time (T (second)), with the logarithm (logE (mJ/cm of this developing powder (s={100-t}/T (%/second)) to described exposure ²)) mapping.

{ sensitizer }

For the effect of bringing into play above-mentioned film residual rate/exposure characteristic or above-mentioned developing powder/exposure characteristic effectively and reaching above-mentioned minimum exposure amount, blue-violet laser photosensitive composition of the present invention preferably be contained in have absorption maximum in 330 to 450nm the wavelength coverage compound as sensitizer with sensitizing function, when with this photosensitive composite of active light beam irradiates, described sensitizing function is decomposed described active substance and is produced for example free radical or sour isoreactivity kind for the optical excitation energy is transferred to active substance for example Photoepolymerizationinitiater initiater or hereinafter described smooth acid producing agent.

As described sensitizer, for example, can be (i) be disclosed in JP-A-2000-10277 for example or Japanese patent application No. 2002-362326 have the diaminobenzophenone type compound of following structural as basic framework, what (ii) be disclosed in JP-A-2004-198446 for example has the aminophenyl benzimidazole/benzoxazole/benzothiazole type compound of following structural as basic framework, what (iii) be disclosed in Japanese patent application No. 2004-424180 for example has the sulphonyl imido fundamental mode compound of following structural as basic framework, what (iv) be disclosed in Japanese patent application No. 2003-392404 for example has the aminoquinolone type compound of following structural as basic framework, (v) be disclosed in for example JP-A-2002-169282, JP-A-2004-191938 has the merocyanine-type compounds of following structural as basic framework, (what vi) be disclosed in JP-A-2002-268239 for example has the thiazolidone type compound of following structural as basic framework, (what vii) be disclosed in Japanese patent application No. 2003-291606 for example has the imide-type compound of following structural as basic framework, (viii) have the benzimidazole/benzoxazole/benzothiazole type compound of following structural as basic framework, (ix) have the triazole-type compound of following structural as basic framework, (x) have the cyano styrene fundamental mode compound of following structural as basic framework, (xi) have the Stilbene type compound of following structural as basic framework, (xii) has following structural as basic framework De oxadiazole/thiadiazoles type compound, (xiii) have the pyrazoline type compound of following structural as basic framework, (xiv) have the coumarin type compound of following structural as basic framework, (xv) following structural that has that is disclosed in Japanese patent application No. 2004-218915 for example as the triphenylamine type compound of basic framework and (xvi) has the acridone type compound of following structural as basic framework.

In the following structural, each X and Z represent nitrogen-atoms, oxygen atom, sulphur atom or C-R independently of one another, and Y represents optionally linking group, and n is 0 or greater than 0 integer.In addition; each compound of the structural formula of following representative basic framework can have following substituting group: for example alkyl, naphthenic base, alkenyl, cycloalkenyl group, alkoxy, alkylthio group, aryl, aryloxy group, aralkyl, alkene oxygen base, alkenylthio group, acyl group, acyloxy, amino, acylamino-, carboxyl, carboxylic acid ester groups, carbamate groups, carbamyl, sulfamoyl, sulfonate group, saturated or undersaturated heterocyclic radical; and this substituting group can further have substituting group, and a plurality of substituting group mutually bond connected form ring texture:

As the sensitizer in the photosensitive composite of the present invention, wherein preferred sensitizer is to have the triphenylamine type compound that has the triphenyl structure in the dialkyl amido benzoid compound of dialkyl amido benzene structure and the structure in the structure.Especially, as the former, preferably dialkyl amido diphenyl ketone type compound, have heterocyclic radical has the substituent dialkyl amido benzoid compound that comprises the sulfimide base and forms the quinolone skeleton as substituent dialkyl amido benzoid compound, on the para-position carbon atom with respect to amino on the phenyl ring dialkyl amido benzoid compound on the para-position carbon atom with respect to amino on the phenyl ring.

As dialkyl amido diphenyl ketone type compound, the compound of being represented by following general formula (I) is preferred:

(in the general formula (I), R ¹, R ², R ⁵And R ⁶Representative optionally has substituent alkyl, R independently of one another separately ³, R ⁴, R ⁷And R ⁸Representative optionally has substituent alkyl or hydrogen atom, R independently of one another separately ¹And R ², R ⁵And R ⁶, R ¹And R ³, R ²And R ⁴, R ⁵And R ⁷Perhaps R ⁶And R ⁸Can form nitrogen heterocyclic ring independently.)

In the general formula (I), alkyl R ¹, R ², R ⁵And R ⁶Carbon number, and R ³, R ⁴, R ⁷And R ⁸Carbon number when being alkyl preferably 1 to 6.In addition, when forming nitrogen heterocyclic ring, preferably 5 yuan are encircled or 6 yuan of rings, and preferred R ¹And R ³, R ²And R ⁴, R ⁵And R ⁷Perhaps R ⁶And R ⁸Form 6 yuan of tetrahydroquinoline rings, preferred especially R ¹, R ², R ³And R ⁴And/or R ⁵, R ⁶, R ⁷And R ⁸Form the julolidine ring.In addition, be more preferably at 2 and have alkyl, or comprise the julolidine ring of described tetrahydroquinoline ring as substituent tetrahydroquinoline ring.

As the compound instantiation of above-mentioned general formula (I) representative, can be for example 4,4 '-compound shown in two (dimethylamino) benzophenone, 4,4 '-two (diethylamino) benzophenone and the following array structure.

In addition, has heterocyclic radical on the para-position carbon atom with respect to amino on its phenyl ring as in the substituent dialkyl amido benzoid compound, preferred heterocyclic radical is 5 yuan of rings or 6 yuan of rings of nitrogen atom, oxygen atom or sulphur atom, special 5 yuan of rings that preferably have fused benzene rings, preferred compound are the compounds of following general formula (II) representative:

(in the general formula (II), R ¹And R ²Represent selectivity to have substituent alkyl, R separately independently of one another ³And R ⁴Represent selectivity to have substituent alkyl or hydrogen atom, R separately independently of one another ¹And R ², R ¹And R ³, or R ²And R ⁴Can form nitrogen heterocyclic ring independently, X represention oxygen atom, sulphur atom, dialkyl group methylene, imino group or alkyl imino have substituting group with heterocyclic fused phenyl ring selectivity.)

In the general formula (II), alkyl R ¹And R ²Carbon number, and R ³And R ⁴Carbon number when being alkyl preferably 1 to 6.In addition, when forming nitrogen heterocyclic ring, preferably 5 yuan are encircled or 6 yuan of rings, and preferred R ¹And R ³, R ²And R ⁴, R ⁵And R ⁷Perhaps R ⁶And R ⁸Form 6 yuan of tetrahydroquinoline rings, preferred especially R ¹, R ², R ³And R ⁴And/or R ⁵, R ⁶, R ⁷And R ⁸Form the julolidine ring.In addition, be more preferably at 2 and have alkyl, or comprise the julolidine ring of described tetrahydroquinoline ring as substituent tetrahydroquinoline ring.In addition, when X is the dialkyl group methylene, the carbon number of alkyl preferably 1 to 6, when it is alkyl imino, the carbon number of alkyl preferably 1 to 6.

As the compound instantiation of above-mentioned general formula (II) representative can be for example 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, 2-(to the diethylamino phenyl)-3, the compound of 3-dimethyl-3H-indoles and following array structure.

In addition, as having heterocycle as substituent dialkyl amido benzoid compound on the carbon atom with respect to the contraposition of amino on the phenyl ring, except the compound of above-mentioned general formula (II) representative, it can also be 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, two (to the diethylamino phenyl)-1 of 5-, 3,4-oxadiazole or 2, two (to the diethylamino phenyl)-1 of 5-, 3, the 4-thiadiazoles.

In addition, as on the para-position carbon atom with respect to amino on the phenyl ring, having the substituent dialkyl amido benzoid compound that contains the sulphonyl imino group, the compound of preferably following general formula (III) representative:

(in the general formula (III), R ¹And R ²Represent selectivity to have substituent alkyl, R separately independently of one another ³And R ⁴Represent selectivity to have substituent alkyl or hydrogen atom, R separately independently of one another ¹And R ², R ¹And R ³Perhaps R ²And R ⁴Can form nitrogen heterocyclic ring, R independently ⁹Represent monoradical or hydrogen atom, R ¹⁰Represent monoradical.)

In the general formula (III), alkyl R ¹And R ²Carbon number, and R ³And R ⁴Carbon number when being alkyl all preferably 1 to 6.In addition, when forming nitrogen heterocyclic ring, preferably 5 yuan are encircled or 6 yuan of rings, yet, R ³And R ⁴Hydrogen atom preferably.In addition, as monoradical R ⁹And R ¹⁰, can be for example alkyl, naphthenic base, alkenyl, cycloalkenyl group, alkoxy, alkenyloxy, acyl group, acyloxy, aryl, aryloxy group, aralkyl, arylalkenyl, hydroxyl, aldehyde radical, carboxyl, carboxylic acid ester groups, carbamyl, amino, acylamino-, carbamate groups, sulfoamido, sulfonic group, sulfonate group, sulfamoyl, alkylthio group, imino group, cyano group or heterocyclic radical.Wherein, preferred R ⁹Be hydrogen atom, R ¹⁰It is aryl.

In addition, as the dialkyl amido benzoid compound that forms the quinolone skeleton, the compound of preferably following general formula (IV) representative:

(in the general formula (IV), R ¹, R ²And R ¹¹Represent selectivity to have substituent alkyl, R separately independently of one another ³And R ⁴Represent selectivity to have substituent alkyl or hydrogen atom, R separately independently of one another ¹And R ², R ¹And R ³Perhaps R ²And R ⁴Can form nitrogen heterocyclic ring, R independently ¹²Represent selectivity to have substituent alkyl, selectivity has substituent aryl or hydrogen atom.)

In the general formula (IV), alkyl R ¹, R ²And R ¹¹Carbon number, and R ³, R ⁴And R ¹²Carbon number when being alkyl all preferably 1 to 6.In addition, when forming nitrogen heterocyclic ring, preferably 5 yuan are encircled or 6 yuan of rings, yet, R ³And R ⁴Hydrogen atom preferably.In addition, R ¹²Phenyl preferably.

Among the present invention, in the sensitizer of above-mentioned dialkyl amido benzoid compound, the dialkyl amido diphenyl ketone type compound of especially preferably above-mentioned general formula (I) representative, the substituent dialkyl amido benzoid compound that comprises the sulphonyl imino group by on the carbon atom with respect to the contraposition of amino on the phenyl ring, having of above-mentioned general formula (III) representative or the dialkyl amido benzoid compound that forms the quinolone skeleton of above-mentioned general formula (IV) representative.

In addition, as the preferred sensitizer of the present invention, can be to have the compound (following general formula (XI) comprises above-mentioned triphenylamine type compound) that key is connected at least two aromatic rings of nitrogen-atoms in its structure of following general formula (XI) to (XIII) representative.

(in the above-mentioned general formula (XI)～(XIII), ring A～G has aromatic hydrocarbon ring or the aromatic heterocycle as basic framework separately independently of one another, and ring A and B, ring D and E or ring F and G bond connected mutually form the bonding ring that comprises N; In the above-mentioned general formula (XII), linking group L representative comprises the linking group of aromatic hydrocarbon ring and/or aromatic heterocycle, and linking group L and N connect by described aromatic hydrocarbon ring or aromatic heterocycle key, and the n representative is at least 2 integer; In the general formula (XIII), on behalf of selectivity, R have substituent alkyl; Ring A～G and linking group L selectivity have substituting group, and the optionally mutual key of this substituting group is linked to be ring.)

In the above-mentioned general formula (XI)～(XIII),, can be for example phenyl ring, naphthalene nucleus, anthracene nucleus, phenanthrene ring, azulenes, fluorenes ring, acenaphthylene ring or indenes ring as aromatic hydrocarbon ring by ring A～G representative.In addition, as the aromatic heterocycle of ring A～G representative, can be for example furan nucleus, thiphene ring, pyrrole ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, imidazole ring, pyrazoles ring, furazan ring, triazole ring, pyranoid ring, thiadiazoles Huan, oxadiazole ring, pyridine ring, pyridazine ring, pyrimidine ring or pyrazine ring.Preferably as aromatic hydrocarbon ring A～G be phenyl ring, naphthalene nucleus or anthracene nucleus, be more preferably phenyl ring.In addition, preferably as aromatic heterocycle A～G be furan nucleus, thiphene ring, pyrrole ring, pyridine ring, oxazole ring or thiazole ring, be more preferably furan nucleus, thiphene ring or pyrrole ring.

In addition, the ring that comprises among ring A, B, D, E, F and G and linking group L bond connected mutually forms the condensed ring that contains N, as the example of this situation, can be to form the carbazole ring that comprises N atom (each ring key is connected on this N atom).Form therein in the situation of carbazole ring, any ring among ring A～G can not have ring texture without any exception and can be the substituting group of choosing wantonly, in this case, preferably optionally has substituent alkyl.

Ring A～G can have optional substituting group separately at an arbitrary position, and this substituting group mutually bond connected form to encircle.

In the above-mentioned general formula (XII), linking group L is the linking group that comprises one or more aromatic hydrocarbon ring and/or aromatic heterocycle, N directly with described linking group L in aromatic hydrocarbon ring or aromatic heterocycle bonding.

As aromatic hydrocarbon ring that comprises among the linking group L and aromatic heterocycle, can be and the aromatic hydrocarbon ring ring of enumerating as the example of ring A～G identical with aromatic heterocycle.The aromatic hydrocarbon ring that comprises among the preferred linking group L is phenyl ring, naphthalene nucleus or anthracene nucleus, is more preferably phenyl ring.In addition, the aromatic heterocycle that comprises among the preferred linking group L is furan nucleus, thiphene ring, pyrrole ring, pyridine ring, oxazole ring, thiazole ring, thiadiazoles Huan Huo oxadiazole ring, is more preferably furan nucleus, thiphene ring or pyrrole ring.

When linking group L comprises two or more aromatic hydrocarbon ring and/or aromatic heterocycle, this ring can directly connect or via divalence or be higher than divalent linking group (and, this linking group is not limited to divalence or is higher than the group of divalence, but comprises divalence or be higher than the atom of divalence) connect.In this case, as divalence or be higher than divalent linking group, can be the alkylene shown in the known for example following general formula:

(m is not less than 1 integer)

Amido, O atom, S atom, ketone group, thioketones base ,-C (=O) O-, acylamino-, metallic atom (for example Se, Te, P, As, Sb, Bi, Si or B), aromatic hydrocarbons cyclic group, fragrant heterocyclic radical (unsaturated heterocycle base), nonaromatic heterocycles base (saturated heterocyclyl) or its combination in any.

May reside in the aromatic hydrocarbon ring that comprises among the linking group L and/or the alkylene shown in the preferably following general formula of the linking group between the aromatic heterocycle:

(m is not less than 1 integer)

Amido, O atom, S atom, ketone group ,-C (=O) O-, acylamino-, aromatic hydrocarbons cyclic group, fragrant heterocyclic radical ,-C=N-,-C=N-N=, saturated or undersaturated heterocyclic radical, be more preferably C _1-3Alkylene ,-OCH ₂O-,-OCH ₂CH ₂O-,-O-, ketone group, phenyl ring base, furans cyclic group, thiophene cyclic group or pyrroles's cyclic group.In addition, in the above-mentioned general formula (XII), n preferably 2 to 5.

For described linking group L, preferably regulate the combination of described aromatic hydrocarbon ring or aromatic heterocycle and unsaturated linking group, make absorption maximum and suitable the absorption be in 350 to 430nm.

The ring that comprises among the linking group L and the linking group of abutment ring can have optional substituting group at an arbitrary position, and described substituting group mutually bond connected form ring.

As the optional substituting group that ring A～G and linking group L optionally have, can be halogen atom for example, as fluorine atom, chlorine atom, bromine atoms or iodine atom; Hydroxyl; Nitro; Cyano group; Or the unit price organic group, and as this unit price organic group, can be following groups:

C _1-18Linearity or branched-alkyl, for example methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl, the tert-butyl group, amyl group, tertiary pentyl, n-hexyl, n-heptyl, n-octyl or uncle's octyl group; C _3-18Naphthenic base, for example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or adamantyl; C _2-18Linearity or branching thiazolinyl, for example vinyl, propenyl or hexenyl; C _3-18Cycloalkenyl group, for example cyclopentenyl or cyclohexenyl group; C _1-18Linearity or branched alkoxy, for example methoxyl, ethoxy, positive propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, amoxy, uncle's amoxy, just own oxygen base, positive heptan oxygen base, n-octyloxy or uncle's octyloxy; C _1-18Linearity or branching alkylthio group, for example methyl mercapto, ethylmercapto group, positive rosickyite base, different rosickyite base, positive butylthio, secondary butylthio, uncle's butylthio, penta sulfenyl, uncle's penta sulfenyl, just own sulfenyl, positive heptan sulfenyl, positive hot sulfenyl or the hot sulfenyl of uncle; C _6-18Aryl, for example phenyl, tolyl, xylyl or 2,4,6-trimethylphenyl; C _7-18Aralkyl, for example benzyl or phenethyl; C _2-18Linearity or branching alkenyloxy, for example ethyleneoxy, propenyloxy group or hexene oxygen base; C _2-18Linearity or branching alkenylthio group, for example ethene sulfenyl, propylene sulfenyl or hexene sulfenyl; By-COR ²¹The acyl group of representative; Carboxyl; By-OCOR ²²The acyloxy of representative; By-NR ²³R ²⁴The amino of representative; By-NHCOR ²⁵The acylamino-of representative; By-NHCOOR ²⁶The carbamate groups of representative; By-CONR ²⁷R ²⁸The carbamyl of representative; By-COOR ²⁹The carboxylic acid ester groups of representative; By-SO ₃NR ³⁰R ³¹The sulfamoyl of representative; By-SO ₃R ³²The sulfonate group of representative; By-C=NR ³³The group of representative; By C=N-NR ³⁴R ³⁵The group of representative; Perhaps saturated or undersaturated heterocyclic radical, for example 2-Sai Evil base, 2-pyridine radicals, furyl, oxazolyl, benzoxazolyl, thiazolyl, benzothiazolyl, morpholino base, pyrrolidinyl or titanium dioxide tetrahydro-thienyl.

R ²¹To R ³⁵Represent independently of one another separately hydrogen atom, optionally have substituent alkyl, optionally have substituent thiazolinyl, optionally have a substituent aryl or optionally have substituent aralkyl.In the above-mentioned substituting group, alkyl, naphthenic base, alkenyl, cycloalkenyl group, alkoxy, alkylthio group, aryl, aralkyl, alkenyloxy and alkenylthio group can further have substituting group.

The ring A～G last with linking group L on this substituent the position of substitution be not particularly limited, when having a plurality of substituting group, they can be identical or different.

Ring A～G and linking group L is preferably unsubstituted or have a following substituting group: halogen atom; cyano group; optionally has substituent alkyl; optionally has substituent naphthenic base; optionally has substituent thiazolinyl; optionally has substituent alkoxy; optionally has substituent aryl; optionally has substituent aralkyl; optionally has substituent alkene oxygen base; optionally has substituent alkenylthio group; optionally has substituent amino; optionally has substituent acyl group; carboxyl; by-C=NR ³³The group of representative, by-C=N-NR ³⁴R ³⁵Group, the saturated or undersaturated heterocyclic radical of representative, and when they have substituting group, more preferably substituting group be halogen atom, cyano group, optionally have substituent alkyl, optionally have substituent naphthenic base, optionally have substituent thiazolinyl, optionally have substituent alkoxy, optionally have substituent aryl, optionally have substituent aralkyl, optionally have substituent amino, by-C=NR ³³The group of representative, by-C=N-NR ³⁴R ³⁵The group or the saturated or undersaturated heterocyclic radical of representative.

When the above-mentioned optional substituting group that may have as ring A～G and linking group L further had optional substituting group, this substituent preferred embodiment can be: C for example _1-10Alkoxy is as methoxyl, ethoxy, positive propoxy, isopropoxy, n-butoxy, sec-butoxy or tert-butoxy; C _2-12Alkoxyalkoxy group, for example methoxy methoxy base, ethoxy methoxyl, the third oxygen methoxyl, ethoxy ethoxy, the third oxygen ethoxy or methoxy butoxy; C _3-15Alkoxyalkoxy group alkoxy, for example methoxy methoxy ylmethoxy, methoxy methoxy base oxethyl, methoxy (ethoxy) ylmethoxy, methylamino ethoxy Oxymethoxy or ethoxy ethoxy methoxy base; C _6-12Aryl, for example phenyl, tolyl or xylyl (they can further have substituting group); C _6-12Aryloxy group, for example phenoxy group, toloxyl, xylyloxy or naphthoxy; C _2-12Alkene oxygen base, for example ethyleneoxy or allyloxy; Acyl group, for example acetyl group or propiono; Cyano group; Nitro; Hydroxyl; Tetrahydrofuran; Amino; C _1-10Alkyl amino, N for example, N-dimethylamino or N, N-diethylamino; C _1-6Alkyl sulfonyl amino, for example sulfonyloxy methyl amino, ethyl sulfonamido or n-pro-pyl sulfonamido; Halogen atom, for example fluorine atom, chlorine atom or bromine atoms; C _2-7Alkoxy carbonyl group, for example methoxycarbonyl group, carbethoxyl group, the positive third oxygen carbonyl, the different third oxygen carbonyl or positive butoxy carbonyl; C _2-7Alkyl carbonyl oxy, for example methyl carbonyl oxygen base, ethyl oxy carbonyl, n-pro-pyl carbonyl oxygen base, isopropyl carbonyl oxygen base or normal-butyl carbonyl oxygen base; C _2-7Alkoxy carbonyl oxygen base, for example methoxyl carbonyl oxygen base, ethoxy carbonyl oxygen base, positive propoxy carbonyl oxygen base, isopropoxy carbonyl oxy, n-butoxy carbonyl oxygen base or tert-butoxy carbonyl oxygen base; C _2-18Linearity or branching thiazolinyl, for example vinyl, propenyl or hexenyl.

Be used for the sensitizer of representing separately by above-mentioned general formula (XI) to (XIII) of the present invention and have suitable absorption in 390 to 430nm wavelength coverage, therefore, it preferably has absorption maximum in 330 to 450nm wavelength coverage, preferably its absorption maximum 350 to 430nm.For this reason, preferably have four or in its per molecule, more preferably have five or more than five aromatic hydrocarbon ring and/or aromatic heterocycle more than four aromatic hydrocarbon ring and/or aromatic heterocycle.

The instantiation of the sensitizer of above-mentioned general formula (XI) to (XIII) representative is as follows, yet described sensitizer is not limited thereto:

The sensitizer example of above-mentioned general formula (XI):

The example of the sensitizer of above-mentioned general formula (XII):

(in above-mentioned (XII-g), it is any two phenyl ring in terminal two phenyl and terminal two tolyls that the key vicinal is put.)

The sensitizer example of above-mentioned general formula (XIII):

Described sensitizer can use separately maybe can be used in combination two or more.

{ polymerization inhibitor }

To describe the composition of blue-violet laser photosensitive composition of the present invention hereinafter in detail, preferably comprise alefinically unsaturated compounds and Photoepolymerizationinitiater initiater negative photosensitive composition N as basic composition ₁Particularly in order effectively to bring into play above-mentioned film residual rate/exposure characteristic or above-mentioned developing powder/exposure characteristic and the effect that reaches above-mentioned minimum exposure amount, preferably the above-mentioned compound that has absorption maximum in particular range of wavelengths is used as sensitizer, in addition, the content of polymerization inhibitor is 5 to 60ppm in this photosensitive composite.The upper limit of level of inhibitor is 50ppm especially preferably, and lower limit is 10ppm especially preferably.

That is, as mentioned above, polymerization inhibitor is added the alefinically unsaturated compounds be considered to the necessary component in the optical polymerism composition, to prevent when producing polymerization or to be used to give product with storage stability.In addition, according to circumstances require in its production, polymerization inhibitor to be added used polymeric binder material, form performance to give the optical polymerism layer.In addition, except polymerization inhibitor being added alefinically unsaturated compounds and polymeric binder material to prevent for example optical polymerism composition thermal polymerization or the polymerization in time, also in the preparation composition, add polymerization inhibitor to guarantee the stability of optical polymerism composition, in conjunction with other photopolymerization inhibitor, the total amount of polymerization inhibitor is generally 100ppm at least.In contrast, in the preferred embodiments of the invention, reduced the content of polymerization inhibitor.

If negative photosensitive composition N ₁The content of middle polymerization inhibitor is too low, the storage stability of photosensitive composite coating fluid may be relatively poor when producing hereinafter described image formation component against corrosion, therefore cause gelation, or often be difficult to prevent generation thermal polymerization of negative photosensitive composition layer or polymerization in time.On the other hand, if the too high levels of polymerization inhibitor, the pattern of resulting resist pattern picture can have circle or the bottom can not fully be cut, thereby the phenomenon of ruffle (footing) may occur being called as, and resolution performance variation often.

In the present invention, for the content of controlling polymerization inhibitor in the photosensitive composite in above-mentioned scope, can adopt: for example, (i) for the content that is included in the polymerization inhibitor in the alefinically unsaturated compounds, the addition of restriction polymerization inhibitor or the alefinically unsaturated compounds that employing has the low content polymerization inhibitor, (ii) for the content that is included in the polymerization inhibitor in the polymeric binder material, the addition or the employing of restriction polymerization inhibitor have the polymeric binder material of low content polymerization inhibitor, (iii) when producing image formation component against corrosion, come dry described photosensitive composite coating fluid by for example adopting high temperature and condition such as long-time, with the consumption polymerization inhibitor, or the step that for example consumes polymerization inhibitor by heating is set when producing image formation component against corrosion (iv).Wherein, consider deterioration and the productivity for example avoided as optical polymerism composition, preferably said method (i) or (ii).

In addition, in the present invention, polymerization inhibitor is not particularly limited, as long as it is the compound that is used for this type of optical polymerism composition usually with the polymerization inhibitor name, specifically, described polymerization inhibitor can be: for example, have the hydroquinone derivative of p-dihydroxy-benzene structure in its structure, as p-dihydroxy-benzene, methyl hydroquinone, TBHQ, 2,5 di tert butyl hydroquinone or p methoxy phenol; Or the 1,4-benzoquinone derivant that has the 1,4-benzoquinone structure in its structure, for example 1,4-benzoquinone, methyl-1,4-benzoquinone, tert-butyl group 1,4-benzoquinone or 2,5-diphenyl 1,4-benzoquinone.Wherein, the hydroquinone derivative is preferred, and p methoxy phenol is particularly preferred.

In the present invention, be coated with interim support with the photosensitive composite coating fluid, obtain image formation component against corrosion by drying subsequently, based on the analytic curve that makes with the acetone standard solution with vapor-phase chromatography, for 10 weight % solution of the photosensitive composite layer of this image formation component against corrosion, determine the content of polymerization inhibitor in the described photosensitive composite according to the measured value of vapor-phase chromatography.

Blue-violet laser photosensitive composition of the present invention preferably comprises the negative photosensitive composition of above-claimed cpd as sensitizer.As negative photosensitive composition, can be following N ₁～N ₃, N preferably wherein ₁

{ negative photosensitive composition N ₁}

In the blue-violet laser photosensitive composition of the present invention, as negative photosensitive composition, can be for example with above-claimed cpd as sensitizer and comprise alefinically unsaturated compounds and Photoepolymerizationinitiater initiater as the negative photosensitive composition N of basic composition ₁

In the present invention, constitute negative photosensitive composition N ₁Alefinically unsaturated compounds be the compound that has the ethylenic unsaturated bond of at least one free redical polymerization in the per molecule, with active light beam irradiates photosensitive composite the time, under the effect of the photopolymerization initiator system of the Photoepolymerizationinitiater initiater that comprises the following stated, addition polymerization can take place in described compound, and sometimes can take place crosslinked and curing.

In the present invention, described alefinically unsaturated compounds can be the compound that has an ethylenic unsaturated bond in the molecule, specifically, it for example can be: unsaturated carboxylic acid, as (methyl) acrylic acid (in the present invention, " (methyl) acrylic acid " is meant " acrylic acid " and/or " methacrylic acid "), crotonic acid, iso-crotonic acid, maleic acid, itaconic acid or citraconic acid, or its Arrcostab; (methyl) vinyl cyanide, (methyl) acrylamide or styrene.Especially, consider polymerization, cross-linking properties and thus due to exposed portion and the difference between the solubility of unexposed portion in developer increase, preferably have two or more than the compound of two ethylenic unsaturated bond, especially preferably its unsaturated link is derived from the acrylate compounds of (methyl) acryloxy in the per molecule.

As having two or in the per molecule, can be epoxy radicals (methyl) acrylate of for example (methyl) propenoic methyl carbamate, (methyl) acrylic acid or hydroxyl (methyl) acrylate compounds that form of the ester, the phosphate that contains (methyl) acryloxy, hydroxyl (methyl) acrylate compounds and the polyisocyanate compound that form of unsaturated carboxylic acid and polyol and polyepoxy compound formation usually more than the compound of two ethylenic unsaturated bond.

As described ester, specifically, it can be the reaction product of for example above-mentioned unsaturated carboxylic acid and aliphatic polyhydroxy compound, described aliphatic polyhydroxy compound is for example ethylene glycol, polyglycol (adduct number is 2 to 14), 1, the 2-propylene glycol, poly-1,2-propylene glycol (adduct number is 2 to 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, bipentaerythrite or sorbierite, or their ethylene oxide adduct or propylene oxide adduct; Or diethanolamine or triethanolamine; Specifically, can be two (methyl) acrylic acid second diester, 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 oxirane addition three (methyl) acrylate, glycerine two (methyl) acrylate, glycerine three (methyl) acrylate, glycerine epoxypropane addition three (methyl) acrylate, pentaerythrite two (methyl) acrylate, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, bipentaerythrite two (methyl) acrylate, bipentaerythrite three (methyl) acrylate, bipentaerythrite four (methyl) acrylate, bipentaerythrite five (methyl) acrylate, bipentaerythrite six (methyl) acrylate, sorbierite three (methyl) acrylate, sorbierite four (methyl) acrylate, sorbierite five (methyl) acrylate or sorbierite six (methyl) acrylate and similar crotonates, the iso-crotonic acid ester, maleate, itaconate and citraconate.

In addition, as described ester, it can be for example above-mentioned unsaturated carboxylic acid and fragrant polyol (p-dihydroxy-benzene for example, resorcinol, 1,2,3,-thrihydroxy-benzene, Bisphenol F or bisphenol-A) or their ethylene oxide adduct or the reaction product of the addition product of glycidyl compound, specifically, can be 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 ethylidene (methyl) acrylate], bisphenol-A two [three oxygen ethylidene (methyl) acrylate], bisphenol-A two [five oxygen ethylidene (methyl) acrylate], bisphenol-A two [six oxygen ethylidene (methyl) acrylate] or bisphenol-A two [glycidol ether (methyl) acrylate].In addition, it can be the reaction product of for example above-mentioned unsaturated carboxylic acid and heterocycle polyol (for example three (2-hydroxyethyl) isocyanuric acid ester), specifically, can be 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 specifically, can be the condensation product of (methyl) acrylic acid, phthalic acid and ethylene glycol; The condensation product of (methyl) acrylic acid, maleic acid and diethylene glycol; The condensation product of (methyl) acrylic acid, terephthalic acid (TPA) and pentaerythrite; The condensation product of (methyl) acrylic acid, hexane diacid, butylene glycol and glycerine.

In addition, described containing, the phosphate of (methyl) acryloxy was not particularly limited, as long as it is the phosphate compound that comprises (methyl) acryloxy, and especially preferably following general formula (Va) or the compound of (Vb) representing:

(general formula (Va) and (Vb) in, R ¹³Represent hydrogen atom or methyl, n is 1 to 25 integer, and m is 1,2 or 3.)

N preferably 1 to 10, preferred especially 1 to 4.As instantiation, can be for example (methyl) acryloxy ethyl phosphonic acid ester, two [(methyl) acryloxy ethyl] phosphate and (methyl) acryloyl-oxy ethyl glycol phosphate.They can use separately or use with potpourri.

In addition, as described (methyl) propenoic methyl carbamate, specifically, can be the reaction product of for example following hydroxyl (methyl) acrylate compounds and following polyisocyanate compound, described hydroxyl (methyl) acrylate compounds be for example methylol (methyl) acrylate, hydroxyethyl (methyl) acrylate, glycerine two (methyl) acrylate, pentaerythrite three (methyl) acrylate or tetra methylol ethane three (methyl) acrylate; Described polyisocyanate compound is an aliphatic polyisocyante for example, as hexamethylene diisocyanate, 2,4,4-trimethyl hexamethylene diisocyanate, lysine methyl ester diisocyanate, lysine methyl ester triisocyanate, dimer acid diisocyanate, 1,6,11-undecane triisocyanate, 1,3,6-hexa-methylene triisocyanate or 1,8-diisocyanate-4-isocyanates methyloctane; Alicyclic polyisocyanates, for example cyclohexane diisocyanate, dimethyl cyclohexane diisocyanate, 4,4 '-di-2-ethylhexylphosphine oxide (cyclohexyl isocyanate), isophorone diisocyanate or norbornane triisocyanate; Aromatic polyisocyanate, for example to phenylene vulcabond, 2,4-toluenediisocyanate, 2,6-toluenediisocyanate, eylylene diisocyanate, tetramethyl eylylene diisocyanate, 4,4 '-'-diphenylmethane diisocyanate, tolidine diisocyanate, 1,5-naphthalene diisocyanate, three (isocyanates phenylmethane) or three (isocyanate phenyl) thiophosphate; Or heterocycle polyisocyanates, for example isocyanuric acid ester.

Wherein, preferred (methyl) propenoic methyl carbamate is to have at least four amino-formate bonds in the per molecule (NH-CO-O-) and the compound of at least four (methyl) acryloxies.This compound can have at least four by for example making (i) per molecule, the compound of preferred at least six isocyanate group and (ii) per molecule have at least one hydroxyl and at least two, the compound reaction of preferably at least three (methyl) acryloxies obtains, described compound (i) has: compound (i-1) for example, this compound are by making the compound (for example pentaerythrite or polyglycerol) that has at least four hydroxyls in the per molecule and diisocyanate cpd (hexamethylene diisocyanate for example, trimethyl hexamethylene diisocyanate, isophorone diisocyanate or toluenediisocyanate) reaction obtains; Compound (i-2), this compound is by the compound that has at least three isocyanate group at least in the compound (for example ethylene glycol) that has two hydroxyls in the per molecule and the per molecule (for example the biuret type is as " Duranate 24A-100 ", " Duranate 22A-75PX ", " Duranate 21S-75E " or " Duranate 18H-70B ", or addition product type for example " Duranate P-301-75E ", " DuranateE-402-90T " or " Duranate E-405-80T " (producing by industry society of Asahi Chemical Industry)) reaction is obtained; Or compound (i-3), this compound by polymerization or copolymerization for example (methyl) acrylic acid isocyanates ethyl ester obtain, specifically, " DuranateME20-100 " that produces by industry society of Asahi Chemical Industry for example; Compound (ii) has for example pentaerythrite two (methyl) acrylate, pentaerythrite three (methyl) acrylate, bipentaerythrite two (methyl) acrylate, bipentaerythrite three (methyl) acrylate, bipentaerythrite four (methyl) acrylate or bipentaerythrite five (methyl) acrylate.

Above-claimed cpd (i) has preferred 500 to 200000 weight-average molecular weight, and preferred especially 1000 to 150000.In addition, above-mentioned (methyl) propenoic methyl carbamate has preferred 600 to 150000 weight-average molecular weight.In addition, it preferably has at least six, especially preferred at least eight amino-formate bonds, and it preferably has at least six, preferred especially eight (methyl) acryloxies.

Can produce this (methyl) propenoic methyl carbamate by the following method: for example, at organic solvent for example in toluene or the ethyl acetate, the molar ratio of the isocyanate group of above compound (i) and above compound hydroxyl (ii) is 1/10 to 10/1, and the catalyzer of requirement use according to circumstances for example normal-butyl tin dilaurate (ii) reacted compound (i) and compound 5 minutes to 3 hours at 10～150 ℃.

In the present invention, in above-mentioned (methyl) propenoic methyl carbamate, particularly preferably be compound by following general formula (VI) representative:

(in the general formula (VI), the group of Ra representative has alkylidene oxygen base or arlydene oxygen basic weight complex structure and has 4 to 20 oxygen bases that can key be connected to Rb, and Rb and Rc represent C separately independently of one another _1-10Alkylidene, the Rd representative has organic residue of 1 to 10 (methyl) acryloxy, and Ra, Rb, Rc and Rd optionally have substituting group, and x is 4 to 20 integer, and y is 0 to 15 integer, z is 1 to 15 integer.)

In the general formula (VI),, can be the repetitive structure of derived from propylene triol, glycerine or pentaerythrite for example as the repetitive structure of Ra alkylidene oxygen base, repetitive structure as arlydene oxygen base, can be for example derived from 1,2,3,-thrihydroxy-benzene or 1,3, the repetitive structure of 5-benzene triol.In addition, the carbon number of Rb independent of each other and Rc alkylidene preferably 1 to 5, the quantity of (methyl) acryloxy preferably 1 to 7 among the Rd.In addition, preferred x is 4 to 15, and y is 1 to 10, and z is 1 to 10.

In addition, one of especially preferably following general formula of Ra (in the general formula, k is 2 to 10 integer), Rb independent of each other and Rc be dimethylene, monomethyl dimethylene or trimethylene especially preferably, and Rd is one of following general formula especially preferably:

In addition, as epoxy (methyl) acrylate, specifically, it can be the reaction product of (methyl) acrylic acid or above-mentioned hydroxyl (methyl) acrylate compounds and polyepoxide for example, described polyepoxide is: for example, the aliphatic poly epoxy compound is as (gathering) ethylene glycol polyglycidyl ether, (gathering) propylene glycol polyglycidyl ether, (gathering) butylene glycol polyglycidyl ether, (gathering) pentanediol polyglycidyl ether, (gathering) neopentyl glycol polyglycidyl ether, (gathering) hexanediol polyglycidyl ether, (gathering) trimethylolpropane polyglycidyl ether, (gathering) glycerine polyglycidyl ether or (gathering) D-sorbite polyglycidyl ether; Aromatic series polyepoxide, for example phenolic aldehyde polyepoxide, bromination line style phenolic aldehyde polyepoxide, (adjacent,, to) cresols-line style phenolic aldehyde polyepoxide, polymer with bis phenol A epoxide or Bisphenol F polyepoxide; Or heterocycle polyepoxide, for example sorbitan polyglycidyl ether, triglycidyl group isocyanuric acid ester or triglycidyl group three (2-hydroxyethyl) isocyanuric acid ester.

In addition, as another kind of alefinically unsaturated compounds, except above-mentioned, can be (methyl) acrylamide for example, as ethylenebis (methyl) acrylamide; Allyl ester, for example diallyl phthalate; Or contain the compound of vinyl, for example phthalic acid divinyl ester.Above-mentioned alefinically unsaturated compounds may be used alone or two or more kinds used in combination.

In the above-mentioned alefinically unsaturated compounds, preferably ester (methyl) acrylate, the phosphate that contains (methyl) acryloxy or (methyl) propenoic methyl carbamate among the present invention, particularly preferably be ester (methyl) acrylate, in ester (methyl) acrylate, particularly preferably be following ester (methyl) acrylate, this ester (methyl) acrylate comprises polyoxy alkylidene (for example polyoxy alkylidene of the polyoxyethylene addition product of polyglycol, polypropylene glycol or bisphenol-A), and comprises at least two (methyl) acryloxies.

In addition, among the present invention, negative photosensitive composition N ₁In Photoepolymerizationinitiater initiater be a kind of like this reactive compound: when with the coexistence of described sensitizer and by rayed, this compound is accepted the optical excitation energy of sensitizer and is produced free radical as spike, thereby makes above-mentioned alefinically unsaturated compounds generation polymerization.Described Photoepolymerizationinitiater initiater can be for example Hexaarylbiimidazole type compound, two luxuriant titanium type compounds, halogenated hydrocarbons derivant, salt compounded of iodine or organic borate.Wherein, consider sensitivity as photosensitive composite, with the adhesion property and the storage stability of substrate, preferably Hexaarylbiimidazole type compound, two luxuriant titanium type compound or organic borates.Consider the safety light performance under amber light, especially preferably Hexaarylbiimidazole type compound.

As Hexaarylbiimidazole type compound, specifically, can be for example 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 (neighbours, right-dichlorophenyl)-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 (neighbours, 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 (neighbours, right-dibromo phenyl) diimidazole, 2,2 '-two (o-bromophenyl)-4,4 ', 5,5 '-four (neighbours, 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 (adjacent chlorine p-methoxyphenyl) diimidazole or 2,2 '-two (Chloro-O-Phenyl)-4,4 ', 5,5 '-four (to chloronaphthyl, methylnaphthyl) diimidazole.Wherein, hexaphenyl diimidazole compound preferably is more preferably and has the diimidazole that key is connected to the phenyl ring of 2,2 '-position on the imidazole ring, and this imidazole ring is replaced at the ortho position by halogen atom; Especially preferably have key and be connected on the imidazole ring diimidazole of the phenyl ring of 4,4 ', 5,5 '-position, this imidazole ring is unsubstituted or is replaced by halogen atom or alkoxy carbonyl group.

The Hexaarylbiimidazole type compound that in the past was known as the Photoepolymerizationinitiater initiater in the photosensitive composite is the Hexaarylbiimidazole type compound of the following stated: the fusing point with at least 190 ℃, for example about 196 ℃ to about 202 ℃ fusing point, and wavelength is in the X-ray diffraction spectrum of 1.54 dusts, and it locates to have the maximum diffraction peak for 9.925 ° at Bragg angle (2 θ+0.2 °).Consider the dissolubility in coating solvent, the dispersion stabilization in photosensitive composite etc., Hexaarylbiimidazole compound of the present invention is optimum to have maximum 180 ℃ fusing points, particularly maximum 175 ℃, and wavelength is in the X-ray diffraction spectrum of 1.54 dusts, and it locates to have the maximum diffraction peak for 21.16 ° at Bragg angle (2 θ+0.2 °).As this only Hexaarylbiimidazole type compound, can be 2,2 '-two (Chloro-O-Phenyl)-4 for example, 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, wherein, preferred especially 2,2 '-two (Chloro-O-Phenyl)-4,4 ', 5,5 '-tetraphenyl diimidazole or 2,2 '-two (neighbours, right-dichlorophenyl)-4,4 ', 5,5 '-four (p-methoxyphenyl) diimidazole.

In addition, as two luxuriant titanium type compounds, specifically, for example can be, titanocene dichloride, diphenyl two luxuriant titaniums, two (2, the 4-difluorophenyl) two luxuriant titaniums, two (2, the 6-difluorophenyl) two luxuriant titaniums, two (2,4, the 6-trifluorophenyl) two luxuriant titaniums, two (2,3,5,6-tetrafluoro phenyl) two luxuriant titaniums, two (2,3,4,5, the 6-pentafluorophenyl group) two luxuriant titaniums, two (2, the 6-difluorophenyl) two (methyl cyclopentadienyl) titanium, two (2,3,4,5, the 6-pentafluorophenyl group) two (methyl cyclopentadiene) titaniums or two [2,6-two fluoro-3-(1-pyrrole radicals) phenyl] two luxuriant titaniums.The titanium compound that wherein preferably has dicyclopentadiene structure and diphenyl structure especially preferably has the hexichol basic ring that is replaced at the ortho position by halogen atom.

In addition, as the halogenated hydrocarbons derivant, can be for example halogenated paraffin, halomethylation Striazine derivative or halomethylation 1,3,4-oxadiazole derivant is as halogenated paraffin, specifically, can be for example methylene chloride, methenyl choloride, 1,2-ethylene dichloride or 1,2-ethylene dibromide.

In addition, as the halomethylation Striazine derivative, specifically, can be for example 2,4,6-three (monochloro methyl)-s-triazine, 2,4,6-three (dichloromethyl)-s-triazine, 2,4,6-three (trichloromethyl)-s-triazine, 2-methyl-4, two (the trichloromethyl)-s-triazine of 6-, 2-n-pro-pyl-4, two (the trichloromethyl)-s-triazine of 6-, 2-(α, α, β-three chloroethyl)-4, two (the trichloromethyl)-s-triazine of 6-, 2-phenyl-4, two (the trichloromethyl)-s-triazine of 6-, 2-(p-methoxyphenyl)-4, two (the trichloromethyl)-s-triazine of 6-, 2-(3, the 4-epoxy-phenyl)-4, two (the trichloromethyl)-s-triazine of 6-, 2-(rubigan)-4, two (the trichloromethyl)-s-triazine of 6-, 2-[1-(p-methoxyphenyl)-2, the 4-butadienyl]-4, two (the trichloromethyl)-s-triazine of 6-, 2-styryl-4, two (the trichloromethyl)-s-triazine of 6-, 2-(to the methoxy styryl)-4, two (the trichloromethyl)-s-triazine of 6-, 2-(to hydroxystyrene based between methoxyl)-4, two (the trichloromethyl)-s-triazine of 6-, 2-(to the isopropoxystyrene base)-4, two (the trichloromethyl)-s-triazine of 6-, 2-(p-methylphenyl)-4, two (the trichloromethyl)-s-triazine of 6-, 2-(to methoxy-naphthyl)-4, two (the trichloromethyl)-s-triazine of 6-, 2-(to the ethoxy naphthyl)-4, two (the trichloromethyl)-s-triazine of 6-, 2-(to the carbethoxyl group naphthyl)-4, two (the trichloromethyl)-s-triazine of 6-, 2-thiophenyl-4, two (the trichloromethyl)-s-triazine of 6-, 2-benzylthio-4, two (the trichloromethyl)-s-triazine of 6-, 2,4,6-three (two bromomethyls)-s-triazine, 2,4,6-three (trisbromomethyl)-s-triazine, 2-methyl-4, two (trisbromomethyl)-s-triazine of 6-or 2-methoxyl-4, two (the trisbromomethyl)-s-triazine of 6-.Wherein, preferably two (trihalomethyl group)-s-triazine, 2-methyl-4 for example especially preferably, two (the trichloromethyl)-s-triazine of 6-, 2-phenyl-4, two (the trichloromethyl)-s-triazine of 6-, 2-(p-methoxyphenyl)-4, two (the trichloromethyl)-s-triazine of 6-, 2-(3, the 4-epoxy-phenyl)-4, two (the trichloromethyl)-s-triazine of 6-, 2-[1-(p-methoxyphenyl)-2, the 4-butadienyl]-4, two (the trichloromethyl)-s-triazine of 6-, 2-(to the methoxy styryl)-4, two (the trichloromethyl)-s-triazine of 6-, 2-(to hydroxystyrene based between methoxyl)-4, two (trichloromethyl)-s-triazine of 6-or 2-(to the isopropoxystyrene base)-4, two (the trichloromethyl)-s-triazine of 6-.

As halogen Jia Jiization oxadiazole derivant, specifically, can be 2-(p-methoxyphenyl)-5-trichloromethyl-1,3 for example, 4-oxadiazole, 2-(to the methoxy styryl)-5-trichloromethyl-1,3,4-oxadiazole, 2-(adjacent benzofuranyl)-5-trichloromethyl-1,3,4-oxadiazole or 2-[β-(adjacent benzofuranyl) vinyl]-5-trichloromethyl-1,3, the 4-oxadiazole.

In addition,, specifically, can be as salt compounded of iodine: diaryl group iodized salt for example, as hexafluoroarsenate diphenyl iodine, tetrafluoro boric acid diphenyl iodine, p-toluenesulfonic acid diphenyl iodine or camphorsulfonic acid diphenyl iodine; Or the bicyclic alkyl salt compounded of iodine, for example hexafluoroarsenate dicyclohexyl iodine, tetrafluoro boric acid dicyclohexyl iodine, p-toluenesulfonic acid dicyclohexyl iodine or camphorsulfonic acid dicyclohexyl iodine, wherein preferred diaryl group iodized salt.

In addition, as organic borate, can be for example organic boronic ammonium complex compound, You machine Peng Suan Phosphonium complex compound, organic boronic sulfonium complex compound, organic boronic oxo sulfonium complex compound, organic boronic iodo-complexes or organic boronic transition metal coordination complexes.As organic boronic root negative ion, alkyl-triphenyl borine acid radical anion preferably, normal-butyl-triphenyl borine acid radical anion for example, normal-butyl-three (2,4, the 6-trimethylphenyl) borate anion, normal-butyl-three (p-methoxyphenyl) borate anion, normal-butyl-three (to fluorophenyl) borate anion, normal-butyl-three (fluorophenyl) borate anion, normal-butyl-three (3-fluoro-4-aminomethyl phenyl) borate anion, normal-butyl-three (2, the 6-difluorophenyl) borate anion, normal-butyl-three (2,4, the 6-trifluorophenyl) borate anion, normal-butyl-three (2,3,4,5, the 6-pentafluorophenyl group) borate anion, normal-butyl-three (rubigan) borate anion, normal-butyl-three (2,6-two fluoro-3-pyrrole radicals phenyl) borate anion, as anti-lotus kation, compound ammonium cation for example preferably; phosphonium cation, sulfonium cation or iodine kation, especially preferably organic ammonium kation, for example tetra-allkylammonium.

In the blue-violet laser photosensitive composition of the present invention, as negative photosensitive composition N ₁In the content of sensitizer, alefinically unsaturated compounds and Photoepolymerizationinitiater initiater, based on negative photosensitive composition N ₁Total amount, preferred described sensitizer is 0.05～20 weight %, alefinically unsaturated compounds is 10～90 weight %, Photoepolymerizationinitiater initiater is 0.5～50 weight %, preferred especially sensitizer is 0.1～10 weight %, alefinically unsaturated compounds is 20～70 weight %, and Photoepolymerizationinitiater initiater is 1～30 weight %.

Except sensitizer, alefinically unsaturated compounds and Photoepolymerizationinitiater initiater, negative photosensitive composition N of the present invention ₁Preferably also comprise alkali soluble resins, to improve the formation performance of photosensitive composite layer on substrate, developing performance etc.As alkali soluble resins, can be the resin or the carboxylic vinyl-type resin of for example phenolic hydroxy group, for negative photosensitive composition N ₁, preferably carboxylic vinyl-type resin.

As carboxylic vinyl-type resin; specifically; it can be the multipolymer of unsaturated carboxylic acid and another kind of vinyl compound for example; described unsaturated carboxylic acid for example has (methyl) acrylic acid; crotonic acid; iso-crotonic acid; maleic acid; maleic anhydride; itaconic acid or citraconic acid; described another kind of vinyl compound has for example 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 methylol ester; (methyl) hydroxyethyl acrylate; (methyl) acrylic acid glycidyl esters; (methyl) benzyl acrylate ester; (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-dimethyl aminoethyl (methyl) acrylamide or vinyl acetate.This carboxylic vinyl-type resin has the acid number of preferred 50～300KOHmg/g, preferred especially 100～250KOHmg/g.In addition, its weight-average molecular weight is calculated with polystyrene and is preferably 10000～200000, preferred especially 20000～100000.

Wherein, preferred negative photosensitive composition N of the present invention ₁The alkali soluble resins that is comprised is the multipolymer that comprises derived from the constitutive character repetitive of styrene type monomer, (methyl) acrylic ester type monomer and the various monomers of (methyl) acrylic acid.The preferred proportion derived from the constitutive character repetitive of styrene type monomer, (methyl) acrylic ester type monomer and each monomer of (methyl) acrylic acid that this multipolymer comprises is respectively 3～30mol% (mole %), 10～80mol% and 10～60mol%, and preferred especially each ratio is respectively 5～25mol%, 20～80mol% and 15～55mol%.

As the styrene type monomer in the above-mentioned multipolymer, specifically, can be styrene for example; The alpha-substituted ring-alkylated styrenes is as α-Jia Jibenyixi or α-ethyl styrene; Nuclear substituted alkyl styrene, for example o-methyl styrene, a methyl styrene, p-methylstyrene or 2,5-dimethyl styrene; Nuclear substituted hydroxy styrene, for example o-hydroxy ethene, a hydroxy styrenes, para hydroxybenzene ethene or dihydroxy benzenes ethene; Or nuclear replaces halogenated styrenes, for example to chlorostyrene, to bromstyrol or Dowspray 9.In addition, as the acrylic ester type monomer, specifically, can be that for example (methyl) acrylic acid alkyl carbon number is preferred 1～12, more preferably 1 to 8 Arrcostab, for example (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) acrylic acid substituted alkyl ester, as (methyl) acrylic acid methylol ester, (methyl) hydroxyethyl acrylate, (methyl) acrylic acid glycidyl esters, (methyl) benzyl acrylate ester, (methyl) acrylic-amino ethyl ester or (methyl) acrylic acid-N, N-dimethyl aminoethyl ester.

Except above-mentioned constitutive character repetitive derived from styrene type monomer, (methyl) acrylic ester type monomer and each monomer of (methyl) acrylic acid, above-mentioned multipolymer can also further comprise the constitutive character repetitive derived from another copolymerisable monomer, described another copolymerisable monomer is a unsaturated carboxylic acid for example, as crotonic acid, iso-crotonic acid, maleic acid, maleic anhydride, itaconic acid or citraconic acid; (methyl) acrylic acid derivative, for example (methyl) vinyl cyanide, (methyl) acrylamide, N-methylol (methyl) acrylamide, N, N-dimethyl (methyl) acrylamide or N, N-dimethyl aminoethyl (methyl) acrylamide; Or vinyl compound, for example vinyl acetate or vinyl chloride.Derived from the content of the constitutive character repetitive of described another monomer preferably based on maximum 10mol% of whole multipolymer.

In addition, as other carboxylic vinyl-type resins, can be the carboxylic vinyl-type resin that has ethylenic unsaturated bond at side chain.As this carboxylic vinyl-type resin, specifically, can be following reaction product: for example, the reaction product that unsaturated compound by making carboxylic polymkeric substance and fatty family epoxy radicals or the unsaturated compound that contains alicyclic epoxy base reaction obtain, the unsaturated compound of described fatty family epoxy radicals are allyl glycidyl ethers for example, (methyl) acrylic acid glycidyl esters, (methyl) acrylic acid α-ethyl glycidyl esters, the crotonic acid glycidyl esters, the iso-crotonic acid glycidyl esters, the crotonyl glycidol ether, itaconic acid mono alkyl ester list glycidyl esters, fumaric acid mono alkyl ester list glycidyl esters or maleic acid mono alkyl ester list glycidyl esters; The described unsaturated compound that contains the alicyclic epoxy base is (methyl) acrylic acid 3 for example, 4-epoxycyclohexyl methyl ester, (methyl) acrylic acid 2,3-epoxide ring amyl group methyl ester or (methyl) acrylic acid 7,8-epoxy radicals [three rings [5.2.1.0] last of the ten Heavenly stems-2-yl] oxygen methyl ester, the reacting dose of the carboxyl of described carboxylic polymkeric substance is 5～90mol%, preferred about 30mol%～about 70mol%; Perhaps, by the reaction product that compound copolymerization with at least two class unsaturated groups is obtained, described compound with at least two class unsaturated groups is for example (methyl) acrylic acid allyl ester, (methyl) acrylic acid 3-allyloxy-2-hydroxypropyl ester, (methyl) acrylic acid cinnamic ester, (methyl) acrylic acid crotonyl ester, (methyl) acrylic acid methacrylic ester or N, N-diallyl (methyl) acrylamide; Or by making for example (methyl) acrylic acid copolymer of compound with at least two class unsaturated groups and unsaturated carboxylic acid, or the reaction product that further obtains with the esters of unsaturated carboxylic acids copolymerization, described compound with unsaturated group is 10～90mol% with respect to the ratio of total amount, preferred about 30mol% is to about 80mol%, described compound with at least two class unsaturated groups is (methyl) acrylic acid allyl ester for example, (methyl) acrylic acid 3-allyloxy-2-hydroxypropyl ester, (methyl) acrylic acid cinnamic ester, (methyl) acrylic acid crotons ester, (methyl) acrylic acid methacrylic ester or N, N-diallyl (methyl) acrylic acid amides; Or (methyl) acrylic acid vinyl esters, (methyl) acrylic acid 1-chlorovinyl ester, (methyl) acrylic acid 2-phenyl vinyl ester, (methyl) acrylic acid 1-propenyl ester, crotonic acid vinyl esters or vinyl (methyl) acrylamide.

In addition, as other carboxylic vinyl-type resins, can be the epoxy resin that comprises unsaturated group and carboxyl, it comprises the α of epoxy resin, β-unsaturated monocarboxylic addition product and add to multi-hydroxy carboxy acid or its acid anhydrides in this addition product.Specifically, this epoxy resin that comprises unsaturated group and carboxyl is a kind of like this material: it has following ethylenic unsaturated bond, described ethylenic unsaturated bond is to pass through α, the carboxyl of β-unsaturated monocarboxylic (COO-) adds the formed ester bond of open loop addition of the epoxy radicals of epoxy resin, in addition, the epoxy resin that comprises unsaturated group and carboxyl also has the residual carboxyl of the following stated, and this residual carboxyl is that the carboxyl by multi-hydroxy carboxy acid or its acid anhydrides adds with the formed ester bond of hydroxyl reaction that is formed by above-mentioned reaction.

As epoxy resin, specifically, can be 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, wherein, especially preferably novolac epoxy resin or cresol-novolac epoxy resin.In addition, as α, β-unsaturated monocarboxylic specifically, can be for example (methyl) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid or citraconic acid.Wherein, preferred especially (methyl) acrylic acid.In addition, as multi-hydroxy carboxy acid or its acid anhydrides, specifically, can be 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 its acid anhydrides, wherein preferably maleic anhydride, tetrahydrophthalic anhydride or hexahydro phthalic anhydride, especially preferably tetrahydrophthalic anhydride.

Comprise in the epoxy resin of unsaturated group and carboxyl, consider photosensitive composite sensitivity, resolution performance and with the adhesion property of substrate, especially preferably wherein epoxy resin is novolac epoxy resin or cresol-novolac epoxy resin, α, β-unsaturated monocarboxylic is (methyl) acrylic acid, and multi-hydroxy carboxy acid or its acid anhydrides are tetrahydro terephthalic acid (TPA) or its acid anhydrides.In addition, preferably this acid number that comprises the epoxy resin of unsaturated group and carboxyl is that 20 to 200mg KOH/g and weight-average molecular weight are 2000 to 200000.

For blue-violet laser photosensitive composition of the present invention, based on negative photosensitive composition N ₁Total amount, negative photosensitive composition N ₁In the content of the alkali soluble resins that comprised be preferably 0～80 weight %, preferred especially 10～70 weight %.

In addition, negative photosensitive composition N of the present invention ₁Can further comprise polymerization accelerator, and the preferred polymeric accelerator is the polymerization accelerator that comprises amino acid whose ester or dipole ion compound.As amino acid whose ester or dipole ion compound, the compound that is preferably following general formula (VIIa) or (VIIb) represents:

(general formula (VIIa) and (VIIb) in, R ¹⁴And R ¹⁵Represent selectivity to have that substituent alkyl, selectivity have substituent aryl, selectivity has substituent heterocyclic radical or hydrogen atom, R separately independently of one another ¹⁶And R ¹⁷Represent selectivity to have substituent alkyl or hydrogen atom, R separately independently of one another ¹⁸Represent that selectivity has substituent alkyl, selectivity has substituent thiazolinyl or selectivity has substituent aryl, R ¹⁹Represent that selectivity has substituent alkyl, selectivity has substituent aryl or selectivity has substituent heterocyclic radical, p is 0 to 10 integer.)

General formula (VIIa) and (VIIb) in, alkyl R ¹⁴, R ¹⁵, R ¹⁶, R ¹⁷, R ¹⁸And R ¹⁹Carbon number be preferably 1 to 8, more preferably 1 to 4.In addition, as thiazolinyl R ¹⁸, can be for example vinyl, allyl or isopropenyl; As aryl R ¹⁴, R ¹⁵, R ¹⁸And R ¹⁹, can be phenyl or naphthyl for example; As heterocyclic radical R ¹⁴, R ¹⁵And R ¹⁹, can be for example furyl, furan alkyls (FUranyl), pyrrole radicals or pyridine radicals.

As the substituting group in described alkyl and the thiazolinyl, can be for example alkoxy, alkoxy carbonyl group, alkene oxygen base, allyloxycarbonyl, phenyl or halogen atom; As the substituting group in described aryl and the heterocyclic radical, can be for example for example further to have substituting group such as alkoxy or phenyl or do not have substituent following group: alkyl, alkoxy, thiazolinyl, alkene oxygen base acyl group, acyloxy, alkoxy carbonyl group, phenoxy group, alkylthio group or alkyl sulphonyl; Perhaps, aldehyde radical, carboxyl, hydroxyl, sulfo group, nitro, cyano group or halogen atom.

In the present invention, in above-mentioned general formula (VIIa) and amino acid whose ester that (VIIb) provides and the dipole ion compound, preferably: the amino-acid ester shown in the general formula (VIIa), wherein, R ¹⁴And R ¹⁵In one be hydrogen atom, another is that selectivity has substituent phenyl, R ¹⁶And R ¹⁷All be hydrogen atom, R ¹⁸Be that selectivity has substituent alkyl or selectivity has substituent phenyl, p is 0,1 or 2; Or the amino acid dipole ion compound shown in the general formula (VIIb), wherein, R ¹⁴And R ¹⁵All be hydrogen atom, or one of them is that selectivity has substituent alkyl, R ¹⁶And R ¹⁷All be hydrogen atom, R ¹⁹Be that selectivity has substituent alkyl or selectivity has substituent phenyl, p is 0,1 or 2.Particularly preferably be the ester of the N-phenylglycine shown in the above-mentioned general formula (VIIa), wherein, p is 0, R ¹⁴And R ¹⁵In one be hydrogen atom, another is a phenyl, R ¹⁶And R ¹⁷All be hydrogen atom, N-phenylglycine benzyl esters particularly, wherein, R ¹⁸It is benzyl; Or the dipole ion compound of the N-phenylglycine shown in the above-mentioned general formula (VIIb), wherein, p is 0, R ¹⁴, R ¹⁵, R ¹⁶And R ¹⁷All be hydrogen atom, R ¹⁹Be phenyl).

In addition, as polymerization accelerator, also can be amines.This amines can be any in fatty amine, aliphatic cyclic amine and the aromatic amine, and this amines is not limited to monoamine, and can be for example diamines or triamine of polyamine, and can be in primary amine, secondary amine and the tertiary amine any.Yet preferably pKb is at most 7 amines.As described amines, specifically, can be for example fatty amine that replaced by hydroxyl or phenyl of selectivity, for example butylamine, dibutylamine, tri-n-butylamine, amylamine, diamylamine, triamylamine, hexylamine, dihexylamine, trihexylamine, allylamine, diallylamine, triallylamine, triethanolamine, benzyl amine, dibenzylamine or tribenzylamine.Wherein, in the present invention, preferred especially tribenzylamine.

In addition, as polymerization accelerator, can be: the compound that for example contains sulfydryl, as 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 3-sulfydryl-1,2,4-triazole, 2-sulfydryl-4 (3H)-quinazoline, β-mercaptonaphthalene, ethylene glycol bisthioglycolate thiopropionate, trimethylolpropane tris thiopropionate or pentaerythrite tetrathio propionic ester; Multi-functional thiol's compound, for example hexane two mercaptan, trimethylolpropane tris sulfo-gluconate or pentaerythrite tetrathio propionic ester, N, N-dialkyl amido benzoic ether or have the amino acid or derivatives thereof of aromatic rings, for example N-phenylglycine or derivatives thereof for example its salt (for example its ammonium salt or sodium salt) or its ester of its salt (for example its ammonium salt or sodium salt) or phenylalanine or derivatives thereof for example.Wherein, in the present invention, particularly preferably be the compound that contains sulfydryl, or N-phenylglycine or derivatives thereof its salt (for example its ammonium salt or sodium salt) for example.

For blue-violet laser photosensitive composition of the present invention, based on negative photosensitive composition N ₁Total amount, negative photosensitive composition N ₁In the content of the polymerization accelerator that comprises be preferably 30 weight % at the most, especially preferred 20 weight % at the most.

In addition, negative photosensitive composition N of the present invention ₁Can further comprise nonionic, anionic, cationic, amphoteric, fluorine type or other surfactant, so that improve for example coating performance on substrate and the developing performance of photosensitive composite layer when forming the photosensitive composite layer.Specifically, as non-ionics, can be for example polyoxyethylene alkyl ether, polyoxyethylene polyoxy-propylene, polyoxyethylene alkyl phenyl ether, polyxyethylated ester, polyoxyethylene fatty acid ester, glycerine fatty acid ester, polyoxyethylene glycerine fatty acid ester, pentaerythritol fatty ester, polyoxyethylene pentaerythritol fatty acid ester, sorbitan aliphatic ester, polyoxyethylene sorbitan aliphatic ester, D-sorbite fatty acid ester or polyoxyethylene sorbitol fatty acid ester; As anionic surfactant, can be for example alkyl sulfonate, alkyl benzene sulfonate, alkylnaphthalene sulfonate, polyoxyethylene alkyl ether sulfonate, alkyl sulfate, alkyl sodium sulfate ester, higher alcohol sulfate, aliphatic alcohol sulfate, polyoxyethylene alkyl ether sulfuric ester, polyoxyethylene alkyl phenyl ether sulfuric ester, alkylphosphonate, polyoxyethylene alkyl ether phosphate or polyoxyethylene alkyl phenyl ether phosphate; As cationic surfactant, can be for example quaternary ammonium salt, imidazolidine derivatives or amine salt; As amphoteric surfactant, can be for example betaine type compound, imidazole salts, imidazoline or amino acid.

For blue-violet laser photosensitive composition of the present invention, based on negative photosensitive composition N ₁Total amount, negative photosensitive composition N ₁In the content of the above-mentioned surfactant that comprises be preferably 10 weight % at the most, especially preferred 5 weight % at the most.

In addition, negative photosensitive composition N of the present invention ₁Can comprise: the antioxidant of 2 weight % at the most, for example 2,6 di t butyl phenol, 2,6 ditertiary butyl p cresol, 2,4,6-tri-butyl-phenol or 4,4 '-di-2-ethylhexylphosphine oxide (2,6 di t butyl phenol); 20 weight %'s comprises colorant organic or inorganic dyestuff or pigment at the most; The plastifier of 40 weight % at the most, for example dioctyl phthalate, the two dodecyl esters of phthalic acid or tricresyl phosphate; The sensory characteristic improver of 10 weight %, for example tertiary amine or mercaptan at the most; Or the dyestuff former of 30 weight % at the most, each consumption is based on negative photosensitive composition N ₁The consumption of total amount.

In addition, in the blue-violet laser photosensitive composition of the present invention,, can be for example to comprise above-mentioned sensitizer and be the negative photosensitive composition N of basic composition with alkali soluble resins, the crosslinking chemical that is used for described resin and light acid producing agent as negative photosensitive composition ₂

{ negative photosensitive composition N ₂}

In the present invention, negative photosensitive composition N ₂In alkali soluble resins be resin as described below: during with this photosensitive composite of active light beam irradiates, this resin makes the light acid producing agent of the following stated produce acid under the effect of above-mentioned sensitizer and forms cross-linked structure by the crosslinking chemical of the following stated by acid.As described alkali soluble resins, can be the resin or the carboxylic vinyl-type resin of for example phenolic hydroxy group.Negative photosensitive composition N ₂In, the preferably resin of phenolic hydroxy group, for example polyvinylphenol resin; Phenol resin, for example linear phenol-aldehyde resin or resol; Have phenolic hydroxyl group acrylic acid derivative copolymer resin or have the polyvinyl acetal resin of phenolic hydroxyl group.Wherein, be more preferably polyvinylphenol resin or for example phenol resin such as linear phenol-aldehyde resin or resol, especially preferably polyvinylphenol resin or linear phenol-aldehyde resin.

The polyvinylphenol resin can be the polyvinylphenol resin that for example obtains by polymerization or one or more hydroxyls of copolymerization (Alpha-Methyl) styrene in the presence of radical polymerization initiator or cationic polymerization initiators, described hydroxyl (Alpha-Methyl) styrene be for example adjacent hydroxyl (Alpha-Methyl) styrene (here, " (Alpha-Methyl) styrene " is meant " styrene " and/or " α-Jia Jibenyixi ", below identical), between hydroxyl (Alpha-Methyl) styrene, to hydroxyl (Alpha-Methyl) styrene, dihydroxy (Alpha-Methyl) styrene, trihydroxy (Alpha-Methyl) styrene, tetrahydroxy (Alpha-Methyl) styrene and penta hydroxy group (Alpha-Methyl) styrene; Or the polyvinylphenol resin that further obtains by hydroxyl (Alpha-Methyl) styrene with another vinyl-type compound copolymerization, described another vinyl-type compound be for example (Alpha-Methyl) styrene, have (Alpha-Methyl) styrene, (methyl) acrylic acid, (methyl) acrylate, maleic acid or the maleimide of the substituting group (for example alkoxy, acyl group, acyloxy, allyloxy, aryloxy group or halogen atom) that is different from hydroxyl; Or, dissociate this protecting group and the polyvinylphenol resin that obtains by after making the shielded styrene derivative of the cinnamic hydroxyl of hydroxyl (Alpha-Methyl) that similar polymerization or copolymerization take place.

As linear phenol-aldehyde resin, can be phenolics in the presence of acidic catalyst for example by at least a phenol and at least a aldehydes or ketones polycondensation are obtained, described phenol is phenol for example, 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 diphenol, bisphenol-A, catechol, resorcinol, p-dihydroxy-benzene, 1,2,3,-thrihydroxy-benzene, 1,2,4-benzenetriol or phloroglucin; Described aldehyde is for example formaldehyde, paraformaldehyde, acetaldehyde, paraldehyde, propionic aldehyde, benzaldehyde or furfural; Described ketone is for example acetone, methyl ethyl ketone or methylisobutylketone; As resol, can be for example to obtain by the identical polycondensation that is used for above-mentioned linear phenol-aldehyde resin, difference is to use base catalyst rather than acidic catalyst.

The resin of this phenolic hydroxy group has preferred 1500 to 50000 weight-average molecular weight.

Negative photosensitive composition N ₂In, crosslinking chemical is the compound that can form cross-linked structure during with active light beam irradiates photosensitive composite on above-mentioned alkali soluble resins, as crosslinking chemical, usually can be amino-compound etc., this amino-compound for example has two or more methylols as functional group, or has alkoxy methyl that the pure condensation and modification by methylol obtains or acetoxy-methyl as functional group.Specifically, can be the modified resin that the pure polycondensation modification of for example melamine resin by melamine and formaldehyde condensation polymer are obtained, the benzoguanamine resin by benzoguanamine and formaldehyde condensation polymer are obtained, the glycoluril resin by glycoluril and formaldehyde condensation polymer are obtained, the carbamide resin by urea and formaldehyde condensation polymer are obtained, the resin that obtains by two or more and the formaldehyde condensation copolymerization that makes in melamine, benzoguanamine, glycoluril, the urea etc. or the methylol by this resin obtains.They are sold with trade name " CYMEL " and " NIKALAC ", and it is respectively by Mitsui CytecLtd. and Sanwa Chemical Co., and Ltd. produces.

In addition, as described crosslinking chemical, it can also be the compound that contains epoxy radicals, contain the compound of epoxy radicals as this, it is the constitutive character repetitive of so-called epoxy resin, can be that low-molecular-weight is to high-molecular weight compounds, for example by the poly epihydric alcohol ether compound that the reaction of polyol and chloropropylene oxide is obtained, the poly epihydric alcohol ester compounds by the reaction of polybasic carboxylic acid compound and chloropropylene oxide is obtained, the poly epihydric alcohol ylamine compounds by the reaction of polyamine compounds and chloropropylene oxide is obtained.

As this poly epihydric alcohol ether compound, specifically, diglycidyl ether-type epoxy, line style phenolic epoxy or the cresols-line style phenol aldehyde type epoxy resin of the bisphenol-A of the oxirane that can be the diglycidyl ether-type epoxy of diglycidyl ether-type epoxy, tetramethyl bisphenol-A of diglycidyl ether-type epoxy, the bisphenol-A of diglycidyl ether-type epoxy, the Bisphenol F of the diglycidyl ether-type epoxy of the diglycidyl ether-type epoxy of for example polyglycol, two (4-hydroxy phenyls), two (3,5-dimethyl-4-hydroxy phenyl) or addition.For this poly epihydric alcohol ether compound, the compound of acid anhydrides or divalent acid can react to introduce carboxyl with residual hydroxyl.In addition, as for the poly epihydric alcohol ester compounds, particularly, can be the glycidyl ester type epoxy resin of for example hexahydro-phthalic acid or the glycidyl ester type epoxy resin of phthalic acid; As for the poly epihydric alcohol amines, particularly, can be the glycidyl amine type epoxy resin of for example two (4-aminophenyl) methane or the three-glycidyl amine type epoxy resin of isocyanuric acid.

In addition, in the present invention, negative photosensitive composition N ₂In the light acid producing agent be the reactive compound that when with active light beam irradiates photosensitive composite, produces under the effect at above-mentioned sensitizer as the acid of spike.As the light acid producing agent, can be for example halogen-containing compound, as the alkane of halogen replacement or Striazine derivative, salt or the sulphones of halogenated methylation, wherein preferably produce the sulphones of sulfonic acid especially.

As the halogenated paraffin and the halomethylation Striazine derivative of halogen contained compound, can be and above-mentioned negative photosensitive composition N ₁Described in the identical compound of Photoepolymerizationinitiater initiater.

In addition, as salt, can be ammonium salt for example, as 4 bromide or tetraethylammonium bromide; Salt compounded of iodine, for example diphenyl hexafluoroarsenate iodine, diphenyl tetrafluoro boric acid iodine, diphenyl p-toluenesulfonic acid iodine, diphenyl camphorsulfonic acid iodine, dicyclohexyl hexafluoroarsenate iodine, dicyclohexyl tetrafluoro boric acid iodine, dicyclohexyl p-toluenesulfonic acid iodine or dicyclohexyl camphorsulfonic acid iodine; Or sulfonium salt, for example triphenyl hexafluoroarsenate sulfonium, triphenyl tetrafluoro boric acid sulfonium, triphenyl p-toluenesulfonic acid sulfonium, triphenyl camphorsulfonic acid sulfonium, thricyclohexyl hexafluoroarsenate sulfonium, thricyclohexyl tetrafluoro boric acid sulfonium, thricyclohexyl p-toluenesulfonic acid sulfonium or thricyclohexyl camphorsulfonic acid sulfonium.

As sulphones, specifically, can be for example two (sulfonyl) methane compounds, as two (benzenesulfonyl) methane, two (para hydroxybenzene sulfonyl) methane, two (to the methoxy benzenesulfonyl) methane, two (Alpha-Naphthyl sulfonyl) methane, two (betanaphthyl sulfonyl) methane, two (cyclohexyl sulfonyl) methane, two (tert-butyl group sulfonyl) methane or benzenesulfonyl (cyclohexyl sulfonyl) methane; Carbonyl (sulfonyl) methane compounds, for example phenylcarbonyl group (benzenesulfonyl) methane, naphthyl carbonyl (benzenesulfonyl) methane, phenylcarbonyl group (naphthalene sulfonyl base) methane, cyclohexyl-carbonyl (benzenesulfonyl) methane, tert-butyl group carbonyl (benzenesulfonyl) methane, phenylcarbonyl group (cyclohexyl sulfonyl) methane or phenylcarbonyl group (tert-butyl group carbonyl) methane; Two (sulfonyl) diazomethane compound, for example two (benzenesulfonyl) diazomethanes, 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) diazomethane; Or carbonyl (sulfonyl) diazomethane compound, for example phenylcarbonyl group (benzenesulfonyl) diazomethane, naphthyl carbonyl (benzenesulfonyl) diazomethane, phenylcarbonyl group (naphthalene sulfonyl base) diazomethane, cyclohexyl-carbonyl (benzenesulfonyl) diazomethane, tert-butyl group carbonyl (benzenesulfonyl) diazomethane, phenylcarbonyl group (cyclohexyl sulfonyl) diazomethane or phenylcarbonyl group (tert-butyl group carbonyl) diazomethane.

In the blue-violet laser photosensitive composition of the present invention, as negative photosensitive composition N ₂In the content of above-mentioned sensitizer, alkali soluble resins, crosslinking chemical and light acid producing agent, based on the above-mentioned alkali soluble resins of 100 weight portions, preferred sensitizer is 0.1 to 30 weight portion, crosslinking chemical is 1 to 80 weight portion, the light acid producing agent is 0.001 to 30 weight portion, preferred especially sensitizer is 0.5 to 20 weight portion, and crosslinking chemical is 5 to 60 weight portions, and the light acid producing agent is 0.005 to 10 weight portion.

In addition, in the blue-violet laser photosensitive composition of the present invention,, can be for example to comprise above-mentioned sensitizer and with the resin that contains sour crosslinkable groups and light acid producing agent negative photosensitive composition N as basic composition as negative photosensitive composition ₃

{ negative photosensitive composition N ₃}

Among the present invention, negative photosensitive composition N ₃In the resin that contains sour crosslinkable groups be during with active light beam irradiates photosensitive composite hereinafter the effect of described smooth acid producing agent form the resin of cross-linked structure down.As sour crosslinkable groups, specifically, can be for example hydroxymethyl, alkoxy methyl, vinyl ether or epoxy radicals.Comprising containing of this acid crosslinkable groups sour crosslinkable groups resin is not particularly limited, as long as it is the resin that per molecule has at least two sour crosslinkable groups, specifically, can be: for example, the resin that obtains by following method: the resin that is obtained to introduce above-mentioned sour crosslinkable groups by etherificate or esterification to the small part phenolic hydroxyl group in the phenolic hydroxy group resin, described phenolic hydroxy group resin is a phenol resin for example, as phenolics or resol, or the polyvinylphenol resin, described phenolic hydroxy group resin is used for above-mentioned negative photosensitive composition N as alkali soluble resins ₂The resin that obtains by following method: in the carboxylic vinyl-type resin to the esterified resin that obtains to introduce above-mentioned acid cross-linked group of small part carboxyl, described carboxylic vinyl-type resin is used for above-mentioned negative photosensitive composition N as alkali soluble resins ₁Or the polymerization or the copolymerization of the vinyl-type monomer by having above-mentioned sour crosslinkable groups, introduce above-mentioned sour crosslinkable groups and the resin that obtains.Wherein, preferably with linear phenol-aldehyde resin or polyvinylphenol resin resin, special preferably with the resin of linear phenol-aldehyde resin as matrix as matrix.The resin that contains sour crosslinkable groups comprises the potpourri that the resin of introducing sour crosslinkable groups and the resin of not introducing sour crosslinkable groups form.

In addition, among the present invention, as negative photosensitive composition N ₃In the light acid producing agent, can be and above-mentioned negative photosensitive composition N ₂The identical compound of described smooth acid producing agent.

As blue-violet laser photosensitive composition of the present invention, for negative photosensitive composition N ₃In above-mentioned sensitizer, contain the content of sour crosslinking group resin and light acid producing agent, based on the above-mentioned resin that contains sour crosslinkable groups of 100 weight portions, preferred sensitizer is 0.1 to 30 weight portion, the light acid producing agent is 0.001 to 30 weight portion, preferred especially sensitizer is 0.5 to 20 weight portion, and the light acid producing agent is 0.005 to 10 weight portion.

According to circumstances need the above-mentioned negative photosensitive composition N of the present invention ₁, above-mentioned negative photosensitive composition N ₂With above-mentioned negative photosensitive composition N ₃Can further comprise the various adjuvants that are usually used in photosensitive composite, for example coating performance improver, bond properties improver, sensitivity improving agent, lipid sensitizer (lipid sensitizer), colorant and developing performance improver.

{ physical property except that above-mentioned of described photosensitive composite }

Blue-violet laser photosensitive composition of the present invention preferably has the peak-peak of spectrum sensitivity in the wavelength coverage of 390～430nm, more preferably have the peak-peak of spectrum sensitivity in the wavelength coverage of 400～420nm.When its wavelength coverage at peak-peak place of spectrum sensitivity during less than above-mentioned scope, as photosensitive composite, it is often relatively poor to the sensitivity of the laser beam of wavelength 390～430nm, if and it has peak-peak in surpassing the wavelength coverage of above-mentioned scope, then lack the safety light performance under the amber light.

Among the present invention, the peak-peak of spectrum sensitivity is the peak-peak in the spectral response curve, described spectral response curve obtains by the following method: by using the spectrum sensitivity surveying instrument, will be from the light beam split of for example light source such as xenon lamp or tungsten lamp, make exposure wavelength linear change on horizontal axis, and exposure intensity is the logarithm variation on vertical axis, with the irradiate light of beam split comprise substrate and the photonasty image formation component sample of the photosensitive composite layer that on this substrate surface, forms to expose, carry out the image of development treatment subsequently with the sensitivity that obtains corresponding each exposure wavelength, calculate the exposure energy that can form image according to picture altitude, with the wavelength is transverse axis, and be that the longitudinal axis obtains chart with the inverse of exposure energy, this method for example is disclosed in " photopolymer technology (Photopolymer Technology) " (inferior husband of hillock, Nikkan Kogyo Shimbun publishes, 1988, the 262 pages).

In addition, blue-violet laser photosensitive composition of the present invention can form the minimum exposure amount (S of image at wavelength 410nm place ₄₁₀) with the minimum exposure amount (S that can form image at wavelength 450nm place ₄₅₀(mJ/cm ²)) ratio (S ₄₁₀/ S ₄₅₀) preferred maximum 0.1, more preferably maximum 0.05.If ratio (S ₄₁₀/ S ₄₅₀) surpass above-mentioned scope, often be difficult to obtain simultaneously the sensitivity of satisfied blue-violet laser and the safety light performance under amber light.

As the exposure energy that can form image, can form the minimum exposure amount (S of image at wavelength 410nm place ₄₁₀) and can form the minimum exposure amount (S of image at wavelength 450nm place ₄₅₀) be to calculate according to the picture altitude that in the above-mentioned spectrum sensitivity peak-peak of measuring with the spectrum sensitivity surveying instrument, obtains, they are meant the minimum exposure amount that can form image under the best development conditions of determining by development conditions such as Change Example such as developer type, development temperature and development times.As best development conditions, usually adopt 25 ℃, have 0.5～3 minute this condition of dipping said composition in 11 to 14pH the alkaline developer.

{ Image forming material (A) and image formation component (B) }

Negative blue-violet laser photosensitive composition of the present invention can be used to form negative blue-violet laser bearing member, image of the present invention and form material (A) (abbreviating Image forming material (A) hereinafter sometimes as).Image forming material (A) forms usually by the following method: be coated with interim supporting film with having the coating fluid that dissolves or be dispersed in the above-mentioned various components of suitable solvent, subsequent drying, and according to circumstances need, cover the surface of formed photosensitive composite layer with coverlay.As this Image forming material (A), can be dry film erosion resistant for example.

In addition, above-mentioned Image forming material (A) can be further used for forming negative blue-violet laser bearing member, image of the present invention and form element (B) (abbreviating image formation component (B) hereinafter sometimes as).Usually there are two kinds of methods to prepare image formation component (B).A kind of method is, Image forming material (A) is laminated to photosensitive composite layer one side of processed substrate, if this side has covered coverlay, then after peeling off this coverlay, Image forming material (A) is laminated to photosensitive composite layer one side of processed substrate.Another kind method is to implement according to following operation (1)～(3).(1) will be used for each components dissolved of above-mentioned negative blue-violet laser photosensitive composition or be dispersed in suitable solvent with the preparation coating fluid; (2) directly on processed substrate, be coated with described coating fluid, subsequent drying; (3) on processed substrate, form the negative blue-violet laser photosensitive composition layer.

Image formation component (B) is applicable to following map formation method.That is,, make image developing by development treatment subsequently with the expose photosensitive composite layer of this image formation component (B) of the laser beam flying of wavelength 390～430nm.

When Image forming material (A) during as dry film erosion resistant for example, interim supporting film adopts known in the past film, for example polyethylene terephthalate film, polyimide film, polyamidoimide film, polypropylene screen or polystyrene film.In this case, when required solvent resistance, thermotolerance etc., can directly be coated with the photosensitive composite coating fluid on interim supporting film when this film has preparation Image forming material (A), subsequent drying is to prepare Image forming material of the present invention (A).In addition, if this film has low solvent resistance, low heat resistant etc., at first for example form the photosensitive composite layer on the poly tetrafluoroethylene or on the releasable film at film with release property, the interim supporting film that low solvent resistance, low heat resistant etc. are arranged at above-mentioned layer upper strata pressing element then, peel off described film then, thereby can make Image forming material of the present invention (A) with release property.Requiring under the extra high situation of resolution, the mist value of interim supporting film is preferably 0.01%～1.8%, and the thickness of interim supporting film is 10～30 μ m preferably.

The solvent that is used for coating fluid is not particularly limited, as long as it has enough solubleness to employed component, and provides good filming property to get final product.For example, can be the cellosolve kind solvent, for example methyl cellosolve, ethyl cellosolve, methylcellosolve acetate or ethyl cellosolve acetate; Propandiols solvent, for example propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol single-butyl ether, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol single-butyl ether acetic acid esters or dipropylene glycol dimethyl ether; Esters solvent is butyl acetate, pentyl acetate, ethyl butyrate, butyl butyrate, diethy-aceto oxalate, ethyl pyruvate, 2-hydroxybutyric acid ethyl ester, ethyl acetoacetate, methyl lactate, ethyl lactate or 3-methoxypropionic acid methyl ester for example; Alcohols solvent, for example enanthol, hexanol, diacetone alcohol or furfuryl alcohol; Ketones solvent is cyclohexanone or 2-heptanone for example; High polar solvent, for example dimethyl formamide, dimethyl acetamide or N-Methyl pyrrolidone; Or their mixed solvent, or has the solvent of the aromatic hydrocarbon that adds described solvent.The ratio of solvent ratio is by weight calculated about 1 times～about 20 times that are generally the photosensitive composite general assembly (TW).

In addition, as coating process, can be known in the past method, for example rotary coating, the excellent coating that winds the line, spraying, dip-coating, airblade coating, print roll coating, blade coating, silk screen are coated with or curtain coating.As coating weight, consider that for example described hereinafter image forms and the processing characteristics with after etching or plating the time, this build is at least 0.1 μ m, more preferably be at least 10 μ m, consider for example sensitivity, it is maximum 200 μ m preferably, more preferably maximum 100 μ m.Baking temperature for example is about 30 ℃ to about 150 ℃, and preferred about 40 ℃ to about 110 ℃, for example be about 5 seconds to 60 minutes drying time, preferred about 10 seconds to about 30 minutes.In requiring the extra high situation of resolution, as on the coverlay with the preferred maximum 0.15 μ m of the surface roughness Ra on the plane that contacts of photosensitive composite, R _MaxPreferred maximum 1.5 μ m, the preferred maximum 5/m of the quantity of the flake of the diameter at least 80 μ m that comprise in the coverlay ²

In addition, when Image forming material (A) during as dry film erosion resistant for example, preferably before Image forming material (A) being laminated on the processed substrate during this period of time, cover the surface of formed photosensitive composite layer with coverlay always, as this coverlay, can adopt known in the past film, for example polyethylene film, polypropylene screen or poly tetrafluoroethylene.

By heating, pressurization etc., photosensitive composite layer one side of above-mentioned Image forming material (A) is laminated on the processed substrate, if this photosensitive composite layer one side is coated with coverlay, then peel off above-mentioned coverlay, subsequently by heating, pressurization etc., photosensitive composite layer one side of Image forming material (A) is laminated on the processed substrate; Perhaps, on processed substrate, directly be coated with above-mentioned photosensitive composite coating fluid, carry out drying subsequently, thereby make image formation component of the present invention (B).By with the photosensitive composite layer that forms on this substrate of laser beam lithography for example, carry out development treatment subsequently, with the minus image that developed as resist, by for example etching or electroplate and on this substrate surface, form for example circuit or electrode pattern.Described processed substrate itself can be a sheet metal, for example copper, aluminium, gold, silver, chromium, zinc, tin, lead or nickel.Usually, the preferred clad laminate that adopts, this clad laminate comprises on the insulating support substrate of the about 0.01mm of thickness～about 10mm and this support surface the about 1 μ m of formed thickness to the conductive layer of about 100 μ m, this insulating support substrate is made by following material: resin, thermoset resin for example is as epoxy resin, polyimide resin, bimaleimide resin, unsaturated polyester resin, phenol resin or melamine resin; Or thermoplastic resin, for example saturated polyester resin, polycarbonate resin, polysulfone resin, acryl resin, polyamide, polystyrene resin, Corvic, polyolefin resin or fluororesin; Paper; Glass; Inorganic material, for example aluminium oxide, silicon dioxide, barium sulphate or lime carbonate; Or compound substance, for example glass fabric base material epoxy resin, glass adhesive-bonded fabric base material epoxy resin, paper base material epoxy resin or paper base material phenol resin; Described conductive layer is formed by following method: with the metal forming heating of above-mentioned metal or metal oxide (for example the tin oxide that mixes of indium oxide, tin oxide, indium oxide etc.) or by contacting the bonding lamination that comes, or with metal sputtering, gas deposition or plating etc.

When preparing image formation component (B) by above-mentioned photosensitive composite coating fluid of direct coating and subsequent drying, can on formed photosensitive composite layer on the above-mentioned processed substrate, form for example oxygen barrier layers of protective seam, in case block gas is to the inhibition of photosensitive composite; Or light transmission adjustment layer, to adjust the wavelength coverage of sensitivity.

The material that constitutes oxygen barrier layers is a kind of water-soluble polymers, this water-soluble polymers water soluble, or water soluble and organic solvent that can the miscible water mixed solvent that forms of alcohol or tetrahydrofuran for example, specifically can be for example polyvinyl alcohol (PVA) or derivatives thereof, for example product of polyvinyl alcohol (PVA) part acetalation, cation-modified product that forms by for example quaternary ammonium salt and polyvinyl alcohol (PVA) or the anion-modified product that forms by polyvinyl alcohol (PVA) and for example sodium sulfonate, polyvinyl pyrrolidone, polyoxyethylene, methylcellulose, carboxymethyl cellulose, hydroxyethyl cellulose or hydroxypropyl cellulose.Wherein, consider for example oxygen barrier properties, preferably polyethylene alcohol or derivatives thereof is for example considered the bond properties with the photosensitive composite layer, preferred vinyl pyrrolidone type polymkeric substance, for example polyvinyl pyrrolidone or vinyl pyrrolidone/vinyl acetate co-polymer.As oxygen barrier layers, preferred use following potpourri: with respect to the polyvinyl alcohol (PVA) or derivatives thereof of 100 weight portions, this potpourri preferably comprises 1 to 20 weight portion, the more preferably polyvinyl pyrrolidone type polymkeric substance of 3 to 15 weight portions.

Consider and give storage stability, oxygen barrier layers preferably comprises organic acid, for example succinic acid; Or acylate, for example ethylenediamine tetraacetic acid.It can also comprise non-ionics, for example polyoxyethylene alkyl phenyl ether; Anionic surfactant, for example neopelex; Cationic surfactant, for example alkyl trimethyl ammonium chloride; Defoamer, dyestuff, plastifier, pH regulator agent etc.Their total content is 10 weight % at the most preferably, more preferably 5 weight % at the most.

The mixed solvent solution that adopts aqueous solution or water and organic solvent that can miscible water to form forms oxygen barrier layers by the method identical with the used coating process of above-mentioned photosensitive composite layer, and coating weight is according to dry thickness calculating 1～10g/m preferably ², 1.5～7g/m more preferably ²

In addition, adjusting the material of layer as constituting light transmission, can be the material that the light absorptive dyestuff by will absorbing visible light ray for example obtains in the coumarin type dyestuff adding polymeric binder material.By adopting polyvinyl alcohol (PVA) or derivatives thereof or polyvinyl pyrrolidone type polymkeric substance to be used for above-mentioned oxygen barrier layers, can obtain having the protective seam of oxygen barrier properties and light transmission adjustment performance as polymeric binder material.

The image formation component of the present invention (B) of preparation as mentioned above as having the blue-violet laser photosensitive composition layer of the present invention that is formed on the processed substrate preferably has by above-mentioned negative photosensitive composition N ₁The image formation component of the photosensitive composite layer that constitutes.In this case, in order effectively to obtain above-mentioned film residual rate/exposure characteristic or above-mentioned developing powder/exposure characteristic, constitute the negative photosensitive composition N of photosensitive composite layer ₁Middle level of inhibitor is 5～60ppm preferably, and the lower limit of preferred especially level of inhibitor is 10ppm, and the upper limit is 50ppm.

{ image forming method }

For having the invention described above image formation component (B) that is formed at the blue-violet laser photosensitive composition layer of the present invention on the processed substrate; when forming the photosensitive composite layer by above-mentioned Image forming material (A); after peeling off interim supporting film; maybe when being dried again subsequently by direct coating photosensitive composite coating fluid with formation photosensitive composite layer; when having above-mentioned protective seam etc.; after peeling off protective seam etc.; adopt laser beam to come this photosensitive composite layer of scan exposure as exposure light source; carry out development treatment subsequently, thereby on processed substrate, form the minus image.

As lasing light emitter, can be for example helium-neon laser, Argon ion laser, yttrium-aluminum garnet laser, HeCd laser instrument, semiconductor laser or ruby laser, the special preferably light source of the livid purple region generating laser beam in 390～430nm wavelength coverage.Although it is not particularly limited, specifically, can be the InGaN semiconductor laser of 410nm laser beam of for example vibrating.

In addition, using the scanning exposure method of lasing light emitter to be not particularly limited, can be for example flat scanning exposure method, external drum scanning exposure method or interior bulging scanning exposure method.Preferred laser output light intensity is 1～100mW when carrying out scan exposure, more preferably 3～70mW, oscillation wavelength is preferably 390～430nm, more preferably 400～420nm, beam spot diameter, is preferably 0.5～30 μ m, more preferably 1～20 μ m, sweep velocity is preferably 50～500m/ second, more preferably 100～400m/ second, scanning density is 2000dpi (point/inch) at least preferably, more preferably 4000dpi at least.

Development treatment behind the laser scanning exposure is preferably undertaken by the water developer that use comprises alkaline components and surfactant.Alkaline components can be an inorganic base salts for example, 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, ammonium phosphate, sodium borate, potassium borate or ammonium borate; Or organic amine compound, for example single methylamine, dimethylamine, trimethylamine, mono aminoethane, diethylamine, triethylamine, single isopropylamine, diisopropylamine, dibutyl amine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine or diisopropanolamine, described alkaline components uses with the concentration of about 0.1 weight %～about 5 weight %.

In addition, as surfactant, can be the surfactant identical with the surfactant that is used for above-mentioned photosensitive composite, wherein, preferably nonionic, negative ion or amphoteric surfactant, especially preferably amphoteric surfactant, especially preferably betaine type compound.Surfactant preferably uses with the concentration of 0.0001 weight %～20 weight %, and more preferably concentration is 0.0005 weight %～10 weight %, preferred especially 0.001 weight %～5 weight %.

In addition, according to circumstances need, can in developer, add organic solvent, as isopropyl alcohol, phenmethylol, ethyl cellosolve, butyl cellosolve, ethylene glycol monophenyl ether, propylene glycol or diacetone alcohol.In addition, the pH of developer is preferably 9 to 14, and more preferably 11 to 14.

Described development is carried out with following known developing method usually: for example, under preferred about 10 ℃～about 50 ℃, more preferably from about 15 ℃～about 45 ℃ temperature, with about 5 seconds to about 10 minutes time, dipping image formation component or be sprayed on the image formation component in above-mentioned developer with above-mentioned developer.In addition, after the development treatment, for example can use light source irradiation such as high-pressure mercury-vapor lamp to handle formed minus image and/or to about 160 ℃ temperature, this minus image is heat-treated, thereby can improve it as the chemical resistance of resist etc. at about 140 ℃.

Embodiment

Now, reference example is further described the present invention.Yet in the scope that does not exceed main idea, the present invention is in no way limited to the following example.

Embodiment

1 and 2 and Comparative Examples 1

In the mixed solvent of the methyl ethyl ketone/isopropyl alcohol (weight ratio 8/2) of 100 weight portions, press the prescription shown in the table 1 and add sensitizer (1) to (6), alefinically unsaturated compounds (1), Photoepolymerizationinitiater initiater (1), alkali soluble resins (1) and (2) and other component (1), at room temperature stir subsequently to prepare coating fluid to (3).Go up the use spreader in polyethylene terephthalate film (thickness 19 μ m) and be every kind of coating fluid of amount coating of 20 μ m with dry thickness as interim supporting film, dry in 90 ℃ baking oven subsequently.The negative photosensitive composition N that is forming ₁On the layer, lamination forms material (A) as the polyethylene film (thickness 25 μ m) of coverlay with preparation negative blue-violet laser bearing member, image.

{ sensitizer }

(1) following compounds (absorption maximum 365nm, the compound that comprises in the prescription (I))

(2) following compounds (absorption maximum 386nm, the compound that comprises in the prescription (III))

(3) following compounds (absorption maximum 389nm, the compound that comprises in the prescription (XI))

(4) following compounds (absorption maximum 378nm, the compound that comprises in the prescription (XII))

(5) following compounds (absorption maximum 414nm, the compound that comprises in the prescription (XII))

(6) following compounds (absorption maximum 365nm, the compound that comprises in the prescription (XII))

{ alefinically unsaturated compounds }

(1) following compounds (comprise 250ppm to mequinol as polymerization inhibitor, " BPE-500 " produced by Xin Zhong village chemistry society.)

{ Photoepolymerizationinitiater initiater }

(1) 2,2 '-two (Chloro-O-Phenyl)-4,4 ', 5,5 '-tetraphenyl diimidazole (172 ℃ of fusing points locate to have the maximum diffraction peak for 21.16 ° at Bragg angle (2 θ ± 0.2 °) in the X-ray diffraction spectrum of 1.54 angstroms wavelengths)

{ alkali soluble resins }

(1) styrene/methacrylic acid methyl esters/n-BMA/2-ethylhexyl acrylate/methacrylic acid 2-hydroxyl ethyl ester/methacrylic acid copolymer (molar ratio 10/35/10/10/15/20, acid number 144KOHmg/g, weight-average molecular weight 62300 does not add polymerization inhibitor)

(2) identical multipolymer (add 500ppm to mequinol as polymerization inhibitor)

{ other component }

(1) leuco crystal violet

(2) crystal violet

(3) to mequinol (adding in addition)

In addition, by use " Scotch-Brite SF " (producing) by SUMITOMO 3M Limited with polishing roll will comprise polyimide resin and thickness be 35 μ m and with copper-clad laminated substrate (the thickness 1.5mm of the Copper Foil of this resin-bonding, size 250mm x 200mm) polishing of copper foil surface, wash with water and with the airflow drying with smooth its surface.In baking oven, substrate is preheated to 60 ℃, use the laminate speed of hand roll laminating machine then with the roll-in of 100 ℃ roller temperature, 0.3MPa, 1.5m/ minute, the above-mentioned negative blue-violet laser bearing member, image that obtains is formed the release surface that material (A) peelled off behind the polyethylene film to be laminated on the Copper Foil of described copper-clad laminate, form element (B), the negative photosensitive composition N that this element comprises the copper-clad laminated substrate and forms to produce the negative blue-violet laser bearing member, image on this substrate ₁Layer.

For the photosensitive composite layer of the negative blue-violet laser bearing member, image formation element (B) that obtains,, the results are shown in table 1 by the content of gas chromatography according to following method measurement polymerization inhibitor.

{ measurement level of inhibitor }

Under following condition, make analytic curve according to measured value to the acetone standard solution of mequinol (0,1,3,10,20,50ppm) by gas chromatography.On the other hand, the optical polymerism composition layer of dissolving image formation component against corrosion (B) is measured according to the measured value of described solution by gas chromatography under following condition to prepare 10 weight % solution in acetone.

{ condition }

Post: HP-5 (0.32mm internal diameter * 30m d.f. (the immobile liquid net thickness of carrier) 0.25 μ m)

Carrier: He 2.0mL/ minute

Split ratio: 1/10

Injector temperature: 250 ℃

320 ℃ of detecting device: FID (flame ionization detector)

Baking oven: 50 ℃～20 ℃/minute-300 ℃ (10 minutes)

Injection volume: the 10 weight % acetone solns of 2.0 μ L

In addition,, measure described breakpoint and make the film residual rate become at least 90% minimum exposure amount, the results are shown in table 1 with following method for the photosensitive composite layer of the negative blue-violet laser bearing member, image formation element (B) that obtains.

{ breakpoint }

Spray as developer photosensitive composite layer to unexposed gained image formation component under 0.15MPa with 25 ℃ 0.7 weight % aqueous sodium carbonates, and measurement is until the time of complete dissolved composition layer.

{ minimum exposure amount }

Use has the lasing light emitter (" NLHV500C " of 405nm centre wavelength and 5mW laser output power, inferior chemical industry society produces by day) with the beam spot diameter, of the image illumination of 2mW, 20 μ m the photosensitive composite layer of the image formation component (B) of gained is carried out scan exposure, transformation beam sweep spacing simultaneously and sweep velocity.Then, 0.7 weight % aqueous sodium carbonate with 25 ℃ is sprayed to the photosensitive composite layer under 0.15MPa as developer, and carry out spray development so that the image developing on the spot of 0.5mm * 0.5mm with 1.5 times breakpoint time, make the film residual rate become 90% exposure according to the THICKNESS CALCULATION that under each condition of scanning, records by " Alpha-Step500 " (producing) by KLA Tencor Corporation.

In addition, calculate γ value in the above-mentioned prescription (1) and the α value in the above-mentioned prescription (2), the results are shown in table 1 according to the above-mentioned exposure that obtains and film residual rate.

{ γ value, α value }

According to above-mentioned exposure that obtains and film residual rate, with the logarithm (logE (mJ/cm of film residual rate (t (%)) to exposure ²)) mapping, thereby making film residual rate/exposure curve, 15% and 80% point of junctional membrane residual rate calculate the γ value according to formula t=γ logE+ δ (Fig. 1).In addition, by calculating dissolving film rate (100-t (%)) from the above-mentioned film residual rate that obtains, with developing powder (s={100-t}/T (%/the second)) mapping that obtains divided by development time (T (second)) by this dissolving film rate, make developing powder/exposure curve, 80% and 20% point connecting maximum developing powder, according to formula s=-α logE+ β (Fig. 2) alpha value calculated, the results are shown in table 1.

In addition, for the photosensitive composite layer of the image formation component that obtains (B), with following method respectively evaluate spectra sensitivity peak-peak, can form the minimum exposure amount (S of image at wavelength 410nm place ₄₁₀(mJ/cm ²)) with the minimum exposure amount (S that can form image at wavelength 450nm place ₄₅₀(mJ/cm ²)) ratio (S ₄₁₀/ S ₄₅₀) and the safety light performance under amber light, the results are shown in table 1.

{ peak-peak of spectrum sensitivity }

With adopting xenon lamp (" UI-501C ", produce by USHIO INC.) as the diffraction spectrum irradiation unit (" RM-23 " of light source, produce by Narumi K.K.) expose and be cut into the sample that 50mm * the 60mm size obtains by image formation component (B), its Exposure mode is, with by the rayed sample of the spectrum in beam split to 350～650nm wavelength coverage 10 seconds, so that exposure wavelength is changing linearly on the X direction and making exposure intensity logarithm variation on y direction.Then, under 0.15MPa, sample is sprayed as developer with 25 ℃ 0.7 weight % aqueous sodium carbonates, and in the time of 1.5 times of breakpoints, carry out spray development to obtain image corresponding to each exposure wavelength sensitivity.Calculate according to picture altitude and can form the exposure energy of image, and be respectively transverse axis with the wavelength, be longitudinal axis mapping with the exposure energy inverse of this wavelength, to obtain spectral response curve, read peak-peak from it.

{(S ₄₁₀/S ₄₅₀)}

When exposing when developing subsequently with method same as described above, obtain to form the minimum exposure amount (S of image at wavelength 410nm place by in 350～650nm wavelength coverage, changing wavelength ₄₁₀(mJ/cm ²)) and can form the minimum exposure amount (S of image at wavelength 450nm place ₄₅₀(mJ/cm ²)), calculate its ratio (S ₄₁₀/ S ₄₅₀), and assess according to following standard.

A:S ₄₁₀/ S ₄₅₀Be 0.03 to the maximum.

B:S ₄₁₀/ S ₄₅₀Greater than 0.03, be 0.05 to the maximum.

C:S ₄₁₀/ S ₄₅₀Greater than 0.05, be 0.1 to the maximum.

D:S ₄₁₀/ S ₄₅₀Surpass 0.1.

{ the safety light performance under amber light }

Under amber light (under the wavelength condition that the light of about 470nm is blocked at the most), image formation component (B) was left standstill 1 minute, 2 minutes, 5 minutes, 10 minutes, 20 minutes or 30 minutes, carry out scan exposure and development treatment with method same as described above then, obtaining until comparing the time of repose of image before changing, and assess based on following standard with above-mentioned.

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.

In addition, for the photosensitive composite layer of the image formation component that obtains (B),, the results are shown in table 1 with following method assessment resolution performance and rectangle performance.

{ resolution performance }

Use has the lasing light emitter (" NLHV500C " of 405nm centre wavelength and 5mW laser output power, inferior chemical industry society produces by day) with the beam spot diameter, of the image illumination of 2mW and 20 μ m the photosensitive composite layer of the image formation component (B) that obtains is carried out scan exposure, change beam flying simultaneously at interval and sweep velocity.Then, 0.7 weight % aqueous sodium carbonate with 25 ℃ is sprayed to the photosensitive composite layer under 0.15MPa as developer, and in the time of 1.5 times of breakpoints, carry out spray development so that with the be arranged in parallel image developing of lines of 20 width, 20 μ m, length 0.2cm of 20 μ m spacings, and according to the reappearance of following criterion evaluation image live width.

O: the live width of reproducing 20 μ m.

*: live width is wideer or narrow than 20 μ m.

{ rectangle performance }

Make image developing with the method identical with 20 lines that be arranged in parallel with spacing 20 μ m, width 20 μ m, length 0.2cm with the resolution Performance Evaluation, and according to the sharpness of following criterion evaluation image lines.

O: the edge is sharp keen rectangle, and does not have ruffle.

*: the edge is plentiful trapezoidal or be footing shape.

Comparative Examples 2 and 3

Commercially available by adopting by the dry film erosion resistant (high sensitivity type) of the A of company production and the dry film erosion resistant of producing by the B of company (high resolving power type), produce image formation component against corrosion (B) with method same as described above, with the same manner assessment, the results are shown in table 1.

Industrial applicibility

Negative blue-violet laser photosensitive composition of the present invention and adopt its Image forming material (A), image formation component (B) and image forming method to be used for as etch resistant coating or anti-plate layer, form as for example conducting channel in printed-wiring board (PWB), liquid crystal display cells, Plasma Display, large scale integrated circuit, thin film transistor (TFT), semiconductor packages, color filter or the organic electroluminescent body or electrode substrate processing being used for, and be particularly suitable for the direct record of blue-violet laser Shu Jinhang with wavelength coverage 390～430nm.

The present invention is based on Japanese patent application No. 2003-332626 (submission on September 25th, 2003) and Japanese patent application No. 2003-344636 (submission on October 2nd, 2003), its full content is incorporated herein with the form of reference.

Claims

1. a negative blue-violet laser photosensitive composition is characterized in that, described composition is negative photosensitive composition N ₁, described negative photosensitive composition N ₁Be with alefinically unsaturated compounds and Photoepolymerizationinitiater initiater negative photosensitive composition, described negative photosensitive composition N as basic composition ₁With the described compound that in the wavelength coverage of 330～450nm, has absorption maximum as sensitizer, described alefinically unsaturated compounds is have two or more than the compound of two ethylenic unsaturated bond, based on described negative photosensitive composition N that comprise ester that unsaturated carboxylic acid and polyol form ₁The described sensitizer of total amount be 0.05～20 weight %, described alefinically unsaturated compounds is 10～90 weight %, described Photoepolymerizationinitiater initiater is 0.5～50 weight %, and described sensitizer is at least a type in the sensitizer of following general formula (XI) to (XII) representative:

General formula (XI) and (XII) in, have four or in the molecule more than four phenyl ring, ring A～E has phenyl ring as basic framework, in the general formula (XII), linking group L represent to comprise two or more than two phenyl ring, have that this phenyl ring directly connects or this phenyl ring passes through C _1-3The linking group of the structure that alkylene connects, linking group L and N connect by described phenyl ring key, n is 2～5 integer, phenyl ring and linking group L selectivity have substituting group, described substituting group is selected from alkyl and has the thiazolinyl of aryl substituent, described composition is when being exposed to the blue-violet laser bundle, and making the film residual rate reach at least 90% minimum exposure amount is 1mJ/cm ²To 20mJ/cm ²And in the film residual rate/exposure curve that the logH logE of blue-violet laser bundle mapping is obtained with the film residual rate t on the exposed portion, the γ value of straight line that connects 15% of described film residual rate and following formula (1) at 80% is 4.0 * 10 ²To 1.0 * 10 ⁴, wherein t represents with %, the unit of E is mJ/cm ²:

t＝γlogE+δ(1)。

2. a negative blue-violet laser photosensitive composition is characterized in that, described composition is negative photosensitive composition N ₁, described negative photosensitive composition N ₁Be with alefinically unsaturated compounds and Photoepolymerizationinitiater initiater negative photosensitive composition, described negative photosensitive composition N as basic composition ₁With the described compound that in the wavelength coverage of 330～450nm, has absorption maximum as sensitizer, described alefinically unsaturated compounds is have two or more than the compound of two ethylenic unsaturated bond, based on described negative photosensitive composition N that comprise ester that unsaturated carboxylic acid and polyol form ₁The described sensitizer of total amount be 0.05～20 weight %, described alefinically unsaturated compounds is 10～90 weight %, described Photoepolymerizationinitiater initiater is 0.5～50 weight %, and described sensitizer is at least a type in the sensitizer of following general formula (XI) to (XII) representative:

General formula (XI) and (XII) in, have four or in the molecule more than four phenyl ring, ring A～E has phenyl ring as basic framework, in the general formula (XII), linking group L represent to comprise two or more than two phenyl ring, have that this phenyl ring directly connects or this phenyl ring passes through C _1-3The linking group of the structure that alkylene connects, linking group L and N connect by described phenyl ring key, n is 2～5 integer, phenyl ring and linking group L selectivity have substituting group, described substituting group is selected from alkyl and has the thiazolinyl of aryl substituent, described composition is when being exposed to the blue-violet laser bundle, and making the film residual rate reach at least 90% minimum exposure amount is 1mJ/cm ²To 20mJ/cm ²And, after calculating dissolving film rate 100-t by the film residual rate t at exposed portion place, in developing powder/exposure curve that the developing powder s={100-t}/T that obtains divided by development time T with this dissolving film rate (100-t) obtains the logH logE of blue-violet laser bundle mapping, the α value of straight line that connects 80% of maximum developing powder and following formula (2) at 20% is 12 to 100, wherein t represents with %, the unit of T is second, the unit of s is %/second, and the unit of E is mJ/cm ²:

s＝-αlogE+β(2)。

3. negative blue-violet laser photosensitive composition as claimed in claim 1 or 2, wherein, described negative photosensitive composition N ₁Comprise polymerization inhibitor, the content of described polymerization inhibitor is 5 to 60ppm.

4. negative blue-violet laser photosensitive composition as claimed in claim 3, wherein, described polymerization inhibitor is the hydroquinone derivative.

5. negative blue-violet laser photosensitive composition as claimed in claim 1 or 2, wherein said negative photosensitive composition N ₁With Hexaarylbiimidazole type compound as Photoepolymerizationinitiater initiater.

6. negative blue-violet laser photosensitive composition as claimed in claim 1 or 2, wherein said negative photosensitive composition N ₁Further comprise alkali soluble resins.

7. negative blue-violet laser photosensitive composition as claimed in claim 6, wherein, described negative photosensitive composition N ₁In the described alkali soluble resins that comprised comprise multipolymer with following constitutive character repetitive, described constitutive character repetitive is derived from following various monomers: styrene type monomer, acrylate and/or methacrylate monomers, acrylic acid and/or methacrylic acid monomer.

8. a negative blue-violet laser bearing member, image forms material, it is characterized in that, forms the layer of each described negative blue-violet laser photosensitive composition of claim 1～7 on interim supporting film.

9. a negative blue-violet laser bearing member, image forms element, it is characterized in that, negative blue-violet laser photosensitive composition layer one side that the described negative blue-violet laser bearing member, image of claim 8 is formed material is laminated on the processed substrate.

10. negative blue-violet laser bearing member, image as claimed in claim 9 forms element, wherein, be laminated to the thickness that negative blue-violet laser bearing member, image on the described processed substrate forms the negative blue-violet laser photosensitive composition layer in the material and be at least 10 μ m.

11. image forming method, it is characterized in that, the laser beam that with wavelength is 390～430nm is carried out scan exposure to the negative blue-violet laser photosensitive composition layer that claim 9 or 10 described negative blue-violet laser bearing member, images form elements, subsequently with its development treatment so that image developing.