TWI354864B - - Google Patents

Description

1354864 (1) IX. Description of the Invention [Technical Fields of the Invention] The present invention relates to the use of a printed wiring board, a liquid crystal display element, a plasma display, a large scale integrated circuit, a thin transistor, a semiconductor package, a color filter. 'Negative blue-violet laser photosensitive composition such as etching of a conductor circuit or an electrode processing substrate such as an organic electroluminescence element, or an electro-mineral photoresist, etc.' is particularly suitable for direct use of blue-violet laser light having a wavelength of 390 to 430 nm. A negative blue-violet laser photosensitive composition and an image forming material, an image forming material, and an image forming method using the set of φ·products. - [Prior Art] Conventionally, a conductor circuit or an electrode processing substrate which forms a printed wiring board, a liquid crystal display element, a plasma display, a large scale integrated circuit, a thin transistor, a semiconductor package, a color filter, an organic electroluminescence element, or the like There are two types of photosensitive compositions. In other words, the representative of the negative photosensitive composition is composed of, for example, an ethylenically unsaturated compound, a photopolymerization initiator, and an alkali-soluble resin containing a carboxyl group-containing resin, and is polymerized and cured by photopolymerization of an ethylenically unsaturated compound. Composition insoluble in alkali imaging liquid * Resin containing phenolic hydroxy resin such as polyvinyl phenol resin and crosslinking agent of the resin _ or acid-crosslinking group-containing resin such as epoxy group-containing phenol resin and halomethyl group A photoacid generator such as an s-triazine derivative is known, and it is known that a light generated by a photoacid generator is crosslinked by light irradiation to form a composition insoluble in an alkali developing solution. Representative examples of the positive photosensitive composition include an acid-soluble base resin such as a polyvinylphenol resin containing an acid-decomposable group such as an alkoxy group, and a halomethyl-5-(2) 1354864 s-triazine derivative. It is known that the photoacid generator is formed by crosslinking the acid generated by the light irradiation generating agent to be insoluble in the alkali developing solution. When a conductor circuit, an electrode processing substrate, or the like is formed, a layer composed of these photosensitive compositions is formed on the film (1), and then the surface of the photo-component layer is separated by a dry film photoresist which is covered with a film, and is processed. The photosensitive image forming layer is formed on the substrate by laminating the image forming material or the processed substrate, and if necessary, a protective layer is provided thereon, and the photosensitive composition layer is image-exposed by drawing a circuit or an electric photomask film. . (2) When the photomask film (3) is provided with a dummy support film or a protective layer, the protective layer or the like (4) is a non-image portion of the negative type, and the non-image portion of the positive type is made of a base. The liquid is dissolved and removed to form light corresponding to the circuit pattern. (5) using the photoresist image as a mask, performing work or electroplating on the substrate to be processed, and then removing the photoresist image, and forming a lithography on the circuit or electrode pattern of the mask film on the substrate to be processed. The law has been applied. In addition, in recent years, laser light has been used to expose light sources without using light. Lasers that can directly form images by digital information such as computers can directly improve the productivity, resolution, and positional accuracy. If the filming method is not as good as the use of laser light. The Ray has various light sources known as ultraviolet light to infrared light, but can be exposed to laser light from argon ion laser, cesium ion laser, YAG laser and semiconductor from output, stability, photographic ability and cost. The photoacid composition falsely supports stripping the sensation to the direct image polar pattern. Stripped. Exposure resistance image etching and plate shape is widely used to cover the film, the purpose, because of the light, for example, the image point of view, laser, etc. (3) (3) 1354864 light generated from the visible light to the infrared field. For example, an argon ion laser having a wavelength of 488 nm has been used, and a lithography method of FD-YAG laser having a wavelength of 532 nm has been put into practical use, and a material of 3 65 nm UV laser for printed wiring substrate has been sold. However, in the conventional direct-drawing method of the photosensitive composition, the sensitivity is still insufficient, and it can be seen that the safety light under the yellow light of the photosensitive composition under the laser light must be operated in a dark room environment of red illumination. However, in recent years, laser technology has made remarkable progress, and a semiconductor laser that can operate in a bright environment illuminated by yellow light and that can stably oscillate in the blue-violet field is used. However, since the output force is lower than that of other visible light fields, and there is still room for improvement in the sensitivity of the photosensitive composition, in particular, the photoresist material used in a state where the thickness of the photosensitive composition layer is not thick is not obtained. The high resolution, the rectangularity, etc. of the image that can be obtained, and even the direct drawing method and the lithography method cannot be put to practical use. The photosensitive composition is, for example, intended to mention the sensitivity of the blue-violet field, etc., and proposes a compound having at least one vinyl group in which at least one of its ortho and para positions is substituted with a sulfur atom as a sensitizer and a polymerization initiator. A photopolymerizable composition for a lithographic printing plate in which a combination of a titanium compound is used (for example, see JP-A-2002-169282). However, the photoresist of the photosensitive composition is particularly thicker than ημηι in the photosensitive composition layer formed on the substrate to be processed via the dry film resist. In the plating step of the manufacturing steps of a printed circuit wiring board or the like, in recent years, a thicker plating thickness is required as the wiring line width is smaller, and there is still room for improvement in sensitivity in the blue-violet field. In addition, there is also a high-sensitivity yellow light under the -7- (4) (4) 1354864 * reduced problem. Further, it has been attempted to use the material corresponding to the above-described UV laser for blue-violet laser light, but the image obtained by the high-sensitivity type is inferior in resolution and shape, and the sensitivity of the high-resolution type is poor. [Disclosure of the Invention] The present invention has been made in view of the prior art, and an object of the present invention is to provide a high sensitivity to laser light in the blue-violet field, and an excellent safety lamp under a yellow lamp, and at the same time, the obtained image It is excellent in resolution and rectangularity, and can be used as a photosensitive layer of dry film photoresist, and is suitable for blue-violet laser photosensitive composition which is directly depicted by blue-violet light. Further, an object of the present invention is to provide an image forming material, an image forming material and an image forming method using the composition. In order to solve the above problems, the inventors of the present invention have found that the exposure amount of blue-violet laser light and the residual film ratio or the photosensitive composition having a specific relationship with the exposure amount and the development speed can achieve the aforementioned object, and the present invention has been completed. 〇 In other words, the main technical feature of the present invention is a negative blue-violet laser photosensitive composition characterized by exposure of blue-violet laser light, so that the residual film rate becomes 90% or more, and the minimum exposure amount is 4 〇mJ. /cm2 or less, the residual film ratio of the exposed portion [t(%)] to the logarithm of the exposure amount of the blue-violet laser light [logE ( nuT/cm2 )], and the residual film rate of the exposure amount curve is 15 The line of the following formula (〗) where the % point is connected to the 80% point (5) The γ値 of 1354864 is 4.0M02 or more, and t = ylogE + 5 (1). In addition, the main technical feature of the present invention is that a negative blue photosensitive composition is characterized in that the exposure rate of the blue-violet laser light is 90% or more, and the minimum exposure amount is 4 〇mJ/cm2. Membrane rate [t(%)] Calculated dissolved membrane rate. %)] Divided by imaging time [T ( sec )]. Imaging speed. Ο71" ( % /sec )] exposure to blue-violet laser light The point of the development speed (mJ/cm2) is 80% of the speed of the exposure curve and 20% of the point is connected to the following equation (: α値 is 1 2 or more, s=-alogE +p (2) The photosensitive composition is a negative photosensitive composition having a basic composition of an ethylenically unsaturated compound initiator (the following photopolymerizable composition), and the polymerization inhibitor in the composition is The amount is more preferably used as a sensitizer in a specific absorption wavelength range to achieve the object of the present invention. In other words, the preferred embodiment is that the photosensitive composition is based on an ethylenic material and a photopolymerization initiator. In the negative form of the composition, the photosensitive polymerization inhibitor is contained in an amount of 5 to 60 ppm. The photosensitive composition having a preferred shape contains a compound having a maximum absorption in the range of 340 to 450 nm as a sensitizer. The photopolymerizable composition is an ethylenically unsaturated compound contained in the photopolymerizable composition. Preventing polymerization or purple laser light during manufacture, so that the line is exposed by exposure [100-t ([s={]00-number [logE maximum development]) and photopolymerization is sometimes called a specific reduction. The state of the saturated composition of the present invention is a polymerization inhibitor of the product of the above-mentioned wavelength range, which is a component of the product of the above-mentioned wavelength range, and a polymer which is capable of forming a photopolymerizable layer. In the case of the bonding material, a polymerization inhibitor may be added at the time of manufacture, in order to prevent thermal polymerization or polymerization over time of the photopolymerizable composition, and to be added to the polymerization inhibitor of the ethylenically unsaturated compound or the polymer binder. The amount of the polymerization inhibitor to be added to the composition is usually 100 ppm or more, and the polymerization in the photopolymerizable composition is ensured. Controlling the amount of the inhibitor in a small amount is contrary to the common knowledge of those skilled in the art. The main technical feature of the present invention is a negative blue-violet thunder which forms a layer of the aforementioned negative blue-violet laser photosensitive composition on the pseudo-support film. And irradiating the photosensitive image forming material on the substrate to be processed, and laminating the negative blue-violet laser photosensitive image forming material on the side of the negative blue-violet laser photosensitive composition layer and the negative blue-violet The negative blue-violet laser photosensitive composition layer of the laser photosensitive image forming material is subjected to development processing by laser light having a wavelength of 3 90 to 430 nm, and an image forming method for generating an image is performed. EFFECT OF THE INVENTION The present invention provides high sensitivity to laser light in the blue-violet field, excellent safety light under a yellow lamp, and excellent image resolution and rectangularity. In particular, it can be used as a photosensitive layer of a dry film photoresist material, and is suitable for a blue-violet laser photosensitive composition directly painted by blue-violet laser light, and an image forming material, an image forming material, and a drawing using the same. Like the formation method. (7) (1) 1354864 Best Mode for Carrying Out the Invention <Minimum Exposure Amount> The negative blue-violet laser photosensitive composition of the present invention (hereinafter, the negative blue-violet laser photosensitive composition of the present invention has When it is only called blue-violet laser photosensitive composition), it is exposed by blue-violet laser light, and the residual film rate is 90% or more. The minimum exposure amount is 40 mJ/crn2 or less, and the minimum exposure amount is 20 mJ/ It is preferably cm2 or less, and more preferably 1 omj/cm2 or less. The minimum exposure amount at which the residual film ratio is 90% or more is a photosensitive composition layer having a thickness of 0.5 cm x 〇 5 cm formed on a support of 5 to 100 μm by a wavelength of 400 to 4 1 On m. The blue-violet laser light/exposure amount is tentatively exposed, and the unexposed photosensitive composition layer is sprayed at 0.15 Mpa using a 5% 7% aqueous sodium carbonate solution at 25 ° C. When the development reaches 1.5 times of the time (end point) of complete dissolution, the residual film rate becomes the minimum exposure amount of 90% or more. The minimum exposure amount is not particularly limited, but the lower the better, but it is usually lmJ/cm2 or more. <Residual film rate-exposure amount curve and γ値> The blue-violet laser photosensitive composition of the present invention has a residual film ratio of 90% or more and a minimum exposure amount of 40 mJ/cm 2 or less, and a residual film of the exposed portion Rate [t(%)] is the logarithm of the residual film rate of the residual film rate and exposure curve plotted on the logarithm of the blue-violet laser light [i〇gE ( m J / c m2 )] The γ 直线 of the straight line of the following formula (1) to which 80% of the points are connected must be 4.0 X 1 02 or more.値 値 is ideally 4.5 X 1 〇 2 or more, particularly preferably -11 - (8) (8) I354864 5 . Ο χ 1 Ο 2 or more, and most preferably γ 値 must be 5. 5 χ 1 Ο 2 or more. In the straight line of the following formula (1), when l 〇 gE = 0, δ t of t is an unintended number in the present invention. t = γ1〇 g Ε + 6 (1). When γ値 does not reach the above range, the resolution and shape of the obtained image may be inferior. The larger the γ値, the better the resolution and the squareness of the image, but the upper limit is usually 1.0x1 〇4. The residual film rate-exposure amount curve of the residual film ratio [t(%)] of the exposed portion to the logarithm of the exposure amount of the blue-violet laser light [logE (mJ/cm2)] is desirably in the field of insufficient exposure amount. The residual film ratio shows a certain enthalpy which is close to 〇%, and the residual film ratio in the field where the residual film ratio is 90% or more of the minimum exposure amount shows almost 90% or more, and the amount of the intermediate exposure amount is more than 90%. When the residual film ratio forms an image, it is still insufficient. However, in the field where the critical exposure amount of a certain residual film ratio is more than or equal, the inclination of the upper right straight line is displayed. In the present invention, the inclination of the straight line in the middle exposure amount field of the residual film rate/exposure amount curve is the slope γ of the straight line of the above formula (1) in which the residual film rate is 15% and the point of 80% is connected, and Limited to a specific 値 or more. In other words, the portion adjacent to the exposure portion is irradiated with a plurality of leaked light, which is of course less than the minimum exposure amount, and the critical exposure amount or more, and the portion which should not be exposed originally forms a film, which deteriorates the squareness, but is adjacent to the exposure portion. The portion of the intermediate exposure amount which is irradiated with the leak light of the critical exposure amount or less is reduced, and the leak light forming film of the portion adjacent to the exposed portion can be suppressed. <Development speed-exposure curve and α値> -12-(9) (9) 1354486 The blue-violet laser photosensitive composition of the present invention has a residual film rate of 90% or more and a minimum exposure amount of 40 mJ. /cm2 or less, and the dissolution rate (1〇〇_ t (%)) calculated from the residual film rate [t (%)] of the exposed portion is divided by the development time [T (sec)]. s = { 1 〇〇 · t} / τ ( % /sec )] The maximum resolution of the imaging speed-exposure curve plotted against the logarithm of the exposure of the blue-violet laser light [丨〇gE( mJ/cm2 )] The α値 of the straight line of the following formula (2) to which the point of 80% of the image speed is connected to the point of 20% is required to be 12 or more, preferably 13 or more, and more preferably 14 or more. The β値 of 5 in the straight line of the following formula (2) when 'logE = 0' is an unintended number in the present invention. s = -alogE + P (2) When a 値 does not reach the above range, the resolution and shape of the resulting image may be poor. The larger the a値, the better the resolution and the squareness of the image, but the upper limit is usually 100. The dissolution rate [100-t (%)] calculated from the residual film rate [t(%)] of the exposed portion is divided by the development time [T (sec)] by the development speed [5={100-1} / D (%/5^)] The imaging speed-exposure curve plotted against the logarithm of the exposure of blue-violet laser light [logE (mJ/cm2)], ideally the dissolved film rate in the field of insufficient exposure Almost 1%, the development speed is a high level of certain enthalpy, and the dissolution rate is less than I 〇 % of the exposure amount, and the development speed is a low level. The dissolution rate was 10 ° /. The following is still insufficient ‘but the slope of the lower right line is shown in the field above the critical exposure amount of the dissolved film rate to some extent. In the present invention, the inclination of the straight line in the intermediate exposure amount field of the development speed-exposure amount curve is the maximum dissolution rate (the following -13 - 1354864 do). When the image is developed, the dissolution film rate [100-t (%)] The slope α of the straight line of the above formula (2) in which the point of 80% of the development speed of =0 is 20% of the point is limited to a specific 値 or more. The maximum dissolution rate is the development speed when the film rate is [100-t (%)] = 100% when the image is developed under the following conditions. The residual film rate-exposure amount curve and the developing speed-exposure amount curve were produced as follows. (!) 感光.5cmx〇_5cm, film thickness 5~ ΐΟΟμπι photosensitive composition layer by blue-violet laser light with a wavelength of 400 to 410nm, changing the exposure amount for tentative exposure. (2) Then, using a 0.7% by weight aqueous sodium carbonate solution of the developing solution to spray at 25 ° C, 〇15 Mpa, the time when the unexposed photosensitive composition layer is completely dissolved (*) in the same condition. At a time of 1.5 times the time of development, the residual film rate was measured. (3-1) Residual film rate-exposure amount curve is a plot of the residual film rate [t (%)] of the exposed portion with respect to the exposure amount [l〇gE (mJ/cm2)]. Or (3-2) development speed and exposure amount curve depicting the dissolution film rate [100-t (%)] calculated from the residual film rate [t (%)] of the exposed portion by the development time [T (sec) )] In addition to the development speed [s={100-t}/T(%/Sec)] versus the logarithm of the exposure amount (logE(mJ/cm2)]. <sensitizer> Blue-violet thunder of the present invention In the case where the photosensitive composition has the residual film rate-exposure amount characteristic, the development speed and the exposure amount characteristic, and the minimum exposure amount, when the photosensitive composition receives the irradiation of the active light, the photoexcitation energy is transmitted to the later description. Activating photo-polymerization initiator, photo-acid generator, etc. -14-(11) (11)1354864, which is decomposed by the active compound, and has a sensitizing agent which generates a sensitizing function of an active species such as a radical or an acid. For example, a compound having a maximum absorption in the wavelength range of 3 30 to 4 5 Onm is preferred. The sensitizer is, for example, the following formula: (i) Japanese Patent Laid-Open Publication No. 2000-10277, Japanese Patent Application No. 2002-362326, and the like. The basic formula is a basic skeleton, a diaminobenzophenone compound, and (ii) Japanese Patent Laid-Open Publication No. 2004-198446. The sulfonylimine-based compound of the basic skeleton, such as the aminophenyl benzoimidazole/benzoxazole/benzothiazole-based compound, (iii) the specification of the Japanese Patent Application No. 2004-424180, (iv) The following formula of the specification of the Japanese Patent Publication No. 2003-3 92404 is an amino group D-quino compound of the basic skeleton, (v) Japanese Patent Laid-Open Publication No. 2002-169282, and JP-A No. 20〇4" 9 1 93 8 The following formula is a part of the basic skeleton, a cyanine-based compound, and (vi) the following formula, such as the specification of JP-A-2002-2682 39, which is a basic skeleton of a thiazolone-based compound, (vii) a wish 2003- The following formula in the specification of No. 606, No. 606, is a basic skeleton quinone imine compound, (viii) an aminophenyl phenyl-benzimidazole/benzobisazole/benzothiazole compound having the following basic formula; (ix) a triazole-based compound having a basic skeleton, (X) a cyanostyrene compound having a basic skeleton, and (xi) an anthracene compound having a basic skeleton and (xii) The oxadiazole/thiadiazole compound of the basic skeleton, (xiii) is a pyrazoline system of the basic skeleton (Xiv) The following formula in which the following formula is a basic skeleton coumarin compound, (χν) Patent No. 2004-2189, No. 5, etc., is a basic skeleton triphenylamine compound, (xvi) The fluorenone compound of the basic skeleton, etc. -15- (12) 1354864 In the following formula, X and Z are each independently a nitrogen atom, an oxygen atom, a sulfur atom or CR, and Y is an arbitrary linking group, and η is An integer of 0 or more, and a compound of the following formula representing a basic skeleton may have, for example, an alkyl group, a ring-based group, an alkenyl group, a cycloalkenyl group, an alkoxy group, an alkylthio group, an aryl group, or an aryloxy group. Base, alkenyloxy, olefinylthio, fluorenyl, decyloxy, amine, decylamino, carboxy 'carboxylate, urethane, aminomethyl decyl, amine ore, Substituents such as a sulfonate group, a saturated or unsaturated heterocyclic group, and the like may further have a substituent, and a plurality of substituents may be bonded to each other to form a cyclic structure. (ii (iv) (v)

^ / Ν, ΝΗ 2 (ix) yNeY"(*Nx (ii) h2n

0 II HS—N=CH2 O

H2n X fj o

*N N /η (X) (xi)

CH=CH~CN <Q)-ch=ch-^〇) (xii)

N-N

X <Q^

CH=CH—CH II X (xiii) (vi) (xiv)

H 〇 -16- (13) 1354864

(viii)

The sensitizer of the photosensitive composition of the present invention is preferably a dialkylamino benzene compound having a dialkylamino benzene structure and a triphenylamine compound having a triphenyl structure in the structure. In particular, the former has, for example, a dialkylamino benzene-based compound, a dialkylamino benzene compound having a substituent of a heterocyclic group in the carbon atom of the phenyl ring at the para position, and an amine group on the benzene ring. a dialkylamino benzene-based compound having a sulfonyl imine group-containing substituent and a dialkylamino benzene-based compound forming a quinol skeleton, wherein the carbon atom of the para-position has a mercapto-based carbene-based compound The general formula (I) is represented.

[In the formula (I), 'R1, R2, R5 and R6 are each independently an alkyl group which may have a substituent, and R3, R4, R7 and R8 each independently may have a substituent group or a hydrogen atom, and R1 and R2, respectively. , R5 and R6, R1 and -17-(14) (14) 1354864 R4, R5 and R7, and R6 and R8 are independently capable of forming a nitrogen-containing heterocyclic ring, respectively, R1, ^2 in the formula (I) ! The carbon number of the alkyl group of ^5 and R6 and the carbon number when R3, R4, R7 and R8 are alkyl groups are preferably from 1 to 6. When a nitrogen-containing heterocyclic ring is formed, it is preferably a 5- or 6-membered ring' and R1 and R3' R2 and R4, R5 and R7, or R6 and R8 form a 6-membered ring of a tetrahydroporphyrin ring, preferably 'R1, R2, R3, R4 or/and R5, R6, R7 and R8 are more preferably azatricyclo. Particularly preferred is a tetrahydrogenated 11 quinoline ring having an alkyl substituent at the 2-position or an azatricyclic ring containing the ruthenium quinolate ring. Specific examples of the compound represented by the general formula (I) are 4' 4'-bis(dimethylamino)benzophenone, 4' 4,_bis(diethylamino)benzhydrazide and the following Structure of the compound. -18 · (15)1354864

Further, the heterocyclic group of the dialkylamino benzene compound having a substituent on the benzene ring and having a substituent of the heterocyclic group at the carbon atom of the para position has, for example, a nitrogen atom, an oxygen atom or a sulfur atom 5 or The 6-member ring is particularly preferably a 5-membered ring having a condensed benzene ring, which is represented by the following general formula (11).

(II) [In the formula (II), 'R| and R2 are each independently an alkyl group which may have a substituent, and R and R4 each independently may have a substituent alkyl group or a hydrogen atom-19-(16) (16) 1354864, R1 and R2, R1 and R3, R2 and R4 are each independently capable of forming a nitrogen-containing heterocyclic ring, and X is an oxygen atom, a sulfur atom, a dialkylmethyl group, an imido group or an alkylimine group. The benzene ring of the ring may have a substituent]. The carbon number of the alkyl group of R1 and R2 in the formula (Π) and the carbon number in the case where R3 and R4 are an alkyl group are preferably from 1 to 6. When a nitrogen-containing heterocyclic ring is formed, it is preferably a 5- or 6-membered ring, and R1 and R3, R2 and R4, R5 and R7, or R6 and Rs form a 6-membered ring of tetrahydrofuran quinoline ring, R1, R2. R3, R4 or/and R5, R6, R7 and R8 are more preferably aza-tricyclic. Particularly preferred is a tetrahydroquinoline ring having an alkyl substituent at the 2-position or an azatricyclic ring containing the tetrahydroporphyrin ring. The alkyl group in the case where X is a dialkylmethyl group has a carbon number of preferably from 5 to 6, and the alkyl group of the alkyl imino group preferably has a carbon number of from 1 to 6. Specific examples of the compound represented by the above general formula (II) are, for example, 2-(p-dimethylaminophenyl)benzoxazole, 2-(p-diethylaminophenyl)benzoxazole ' 2 - (pair) Dimethylaminophenyl)benzo[4,5]benzoxazole, 2 · (p-dimethylaminophenyl)benzo[6,7]benzoxazole, 2-(p-dimethyl Aminophenyl)benzothiazole, 2-(p-diethylaminophenyl)benzothiazole, 2-(p-dimethylaminophenyl)benzimidazole, 2-(p-diethylamine) Benzimidazole, 2-(p-dimethylaminophenyl)-3,3-dimethyl-3H-D, 2-(p-diethylaminophenyl)-3 , 3-dimethyl-3H-indole and a compound of the following structure. -20- (17) 1354864

The dialkylamino benzene compound other than the compound represented by the above general formula (Ic) for the substituent of the amino group on the phenyl ring having a heterocyclic group at the carbon atom of the para position has, for example, 2-(p-dimethylene) Aminophenyl)pyridine, 2-(p-diethylaminophenyl)pyridine, 2-(p-dimethylaminophenyl)porphyrin, 2-(p-diethylaminophenyl)quinoline Porphyrin, 2-(p-dimethylaminophenyl)pyrimidine, 2-(p-diethylaminophenyl)pyrimidine, 2,5-bis(p-diethylaminophenyl)-1' 3, 4. Oxadiazole, 2,5-bis(p-diethylaminophenyl)-1,3,4-oxadiazole and the like. Further, the dialkylamino benzene-based compound having a sulfonium imide group-containing substituent on the carbon atom at the para position, for example, has the following general formula (m).

0 11 C=N—S—R10 (III)

I II R9 〇-21 - (18) 1354864 [In the formula (III), R1 and R2 are each independently an alkyl group which may have a substituent, and R3 and R4 are each independently an alkyl group or a hydrogen atom which may have a substituent, R1 And R2, R1 and R3, and R2 and R4 are each independently capable of forming a nitrogen-containing heterocyclic ring, R9 is a monovalent group or a hydrogen atom, and R1Q is a monovalent group. The carbon number of the alkyl group of R1 and R2 in the formula (III) and the carbon number when R3 and R4 are a fluorenyl group are preferably from 1 to 6. When a nitrogen-containing heterocyclic ring is formed, it is preferably a 5- or 6-membered ring, and R3 and R4 are preferably a hydrogen atom. R9 and rig are monovalent groups 'for example, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkoxy, alkenyloxy, decyl, decyloxy, aryl, aryloxy, aralkyl, Aralkenyl, hydroxy, methionyl, carboxy, carboxylate, aminomethyl decyl, amine, decylamino, urethane, sulfonyl, sulfonate, sulfonate a group, an amine sulfonyl group, an alkylthio group, an imido group 'cyano group, a heterocyclic group, and the like. Among these, R9 is preferably a hydrogen atom, and R1() is an aryl group.

Shape IV

Example 1 column \-/下 (IV has C such as the compound phenyl group [in the formula (IV), 'R, R2 and R11 are each independently an alkyl group which may have a substituent, and R3 and R4 are each independently capable of having a substituent or an alkyl group or a hydrogen atom, R1 and R2, W and R3 and R2 and R4 each independently form a nitrogen-containing heterocyclic ring, R12 is a substituent group, and may have a substituent of aryl-22- ( 19) 1354486 or a hydrogen atom. The carbon number of the alkyl group of R^R2 and Ri1 in the formula (IV) and the carbon number when R3, R4 and R11 are an alkyl group are preferably from 1 to 6. The ring is preferably a 5 or 6 membered ring and R3 and R4 are preferably a hydrogen atom. R12 is preferably a phenyl group.

Among the sensitizers composed of the above dialkylamino benzene-based compounds, 'the preferred one is the dialkylamino benzophenone-based compound represented by the above general formula (I), and the above general formula (III) An amine group on a benzene ring, a dialkylamino benzophenone compound having a sulfonium imino group-containing substituent on a carbon atom at a para position, or the above general formula (IV) ) represents a dialkylamino benzene compound which forms a quinol skeleton. The sensitizer of the present invention is preferably a compound having a structure in which at least two aromatic rings are bonded to a nitrogen atom represented by the following general formulas (XI) to (XIII) (the general formula (XI) contains the aforementioned triphenylamine compound. ).

...(XI)

-23- (20)1354864

.••(ΧΙΕ) (In the above general formula (XI)~(XIII), the ring Α~G series are independent of an aromatic hydrocarbon ring or an aromatic heterocyclic ring as the basic skeleton, and ring A and ring B, ring D The ring E' ring F and the ring G are bonded to each other to form a bond ring containing n. In the general formula (XII), the link group L represents a linker group containing an aromatic hydrocarbon ring and/or an aromatic hetero ring, and is linked. The group L and the N are an aromatic hydrocarbon ring or an aromatic heterocyclic bond 'n' which is an integer of 2 or more. In the general formula (ΧΙΠ), 'R is an alkyl group which may have a substituent, and the ring a to G and the linking group L There may be a substituent 'these substituents may be bonded to each other to form a ring). In the above general formulae (XI) to (XIII), the aromatic hydrocarbon ring represented by the rings A to G may, for example, be a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, an anthracene ring, an anthracene ring, a terpene ring or an anthracene ring. The aromatic heterocyclic ring represented by the ring A to G is, for example, a furan ring, a thiophene ring, a pyrrole ring, an oxazole ring, an isoxazole ring, a thiazole ring, an isothiazole ring, an imidazole ring, a pyrazole ring, a furazan ring, and a triazole. Ring, pyran ring, thiadiazole ring, oxadiazole ring, pyridine ring, pyridazine ring, pyrimidine ring and pyrazine ring, and the like. Preferred among the aromatic hydrocarbon rings represented by the rings A to G are a benzene ring 'naphthalene ring, an anthracene ring, and more preferably a benzene ring. Preferred among the aromatic heterocyclic rings represented by the rings A to G are a furan ring, a thiophene ring, a pyrrole ring, a pyridine ring, an oxazole ring, and a thiazole ring, and more preferably a furan ring, a thiophene ring or a pyrrole ring. Rings A, Ring B, Ring D, Ring E, Ring F, Ring G, and the ring contained in the linking group L are bonded to each other to form a condensed ring containing N atoms. In this case, for example, -24-(21) 1354864 is formed to contain each A carbazole ring of a ring-bonded N atom. When the carbazole ring is formed, any of the rings of a to G may be an acyclic structure, and may be any substituent, and is preferably an alkyl group having a substituent. The rings A to G may have a substituent at any position, and these substituents may bond to each other to form a ring. In the above general formula (XII), the linking group L contains a linking group of one or two or more aromatic hydrocarbon rings and/or an aromatic heterocyclic ring, and N is an aromatic hydrocarbon ring which directly bonds the linking group or Aromatic heterocycle. The aromatic hydrocarbon ring and the aromatic hetero ring contained in the linking group L are the same as those exemplified as the aromatic hydrocarbon ring of the ring A to G and the aromatic hetero ring. The aromatic hydrocarbon ring contained in the linking group L is preferably a benzene ring, a naphthalene ring or an anthracene ring, and more preferably a benzene ring. Preferred among the aromatic heterocyclic rings contained in the linking group L are a furan ring, a thiophene ring, a pyrrole ring, a pyridine ring, an oxazole ring, a thiazole ring, a thiadiazole ring, an oxadiazole ring, and more preferably a furan group. Ring, thiophene ring, pyrrole ring. When the linking group L contains two or more aromatic hydrocarbon rings and/or aromatic heterocyclic rings, these rings may be directly linked or via a linking group having two or more valences (the linking group is not limited to a base of two or more valences) and may contain two valences. The above atoms) are bonded. In this case, a linking group having a valence of two or more is known, for example, an alkyl group of the following formula, 3C = C^; m , (m is an integer of 1 or more), an amine group, a ruthenium atom, an s atom, a ketone group, a thioketone. Base, -c(=o)o-25-(22) (22)1354864, amidino group, Se, Te' P, As, Sb, Si, B, etc., a metal atom, an aromatic hydrocarbon ring group, aromatic A heterocyclic group (unsaturated heterocyclic group), a non-aromatic heterocyclic group (saturated heterocyclic group), a combination thereof, and the like. The linking group interposed between the aromatic hydrocarbon ring and/or the aromatic hetero ring contained in the linking group L is, for example, an alkyl group having the following formula, (m is an integer of 1 or more), an amine group, a germanium atom, an S atom, More preferably, keto group, -C ( =0 ) ortho, decylamino, aromatic hydrocarbon ring group, aromatic heterocyclic group, -C = N-, -C = NN=, saturated or unsaturated heterocyclic group It is an alkylene group having a carbon number of 1 to 3, -OCH2, -OCH2CH2, -o, keto, phenylcyclo, furanyl, thiophene, or pyrrole. In the above general formula (XII), η is preferably from 2 to 5. The linking group L is preferably a compound having a large absorption and an appropriate absorption in the wavelength range of 350 to 430 nm by adjusting an aromatic hydrocarbon ring or a combination of an aromatic hetero ring and an unsaturated linking group. The ring of the linking group L and the linking group of the linking ring may have any substituent at any position. These substituents are bonded to each other to form a ring. The ring A to G and the linking group L may have any substituent such as a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom 'iodine atom; a hydroxyl group; a nitro group; a cyano group; a monovalent organic group. The monovalent organic group is, for example, the following. Methyl 'ethyl, n-propyl' isopropyl, n-butyl, isobutyl, -26-(23) (23)1354864 tributyl, pentyl, tert-pentyl, n-hexyl, n-glycol a linear or branched alkyl group having 1 to 18 carbon atoms such as a group, an n-octyl group or a third octyl group; a carbon number of 3 to 18 such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group or an adamantyl group; a cycloalkyl group; a linear or branched alkenyl group having 2 to 18 carbon atoms such as a vinyl group, a propenyl group or a hexenyl group; a cyclic alkene having 3 to 18 carbon atoms such as a cyclopentenyl group and a cyclohexenyl group; Methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, second butoxy, tert-butoxy, pentyloxy, third pentyloxy, n-hexyloxy a straight or branched alkoxy group having 1 to 18 carbon atoms such as n-heptyloxy, n-octyloxy or trioctyloxy: methylthio, ethylthio, n-propylthio, isopropylthio Carbon number such as n-butylthio 'second butylthio group, third butyl thio group, pentylthio group, third pentylthio group, n-hexylthio group, n-heptylthio group, n-octylthio group and third octylthio group a linear or branched alkylthio group of 1 to 18; a carbon number of 6 or more such as a phenyl group, a tolyl group, a xylyl group or a fluorenyl group; An aryl group of 18; an aralkyl group having 7 to 18 carbon atoms such as a benzyl group or a phenethyl group; a linear or branched olefin having 2 to 18 carbon atoms such as a vinyloxy group, a propyleneoxy group or a hexenyloxy group; Oxyl; a linear or branched alkenethio group having 2 to 18 carbon atoms such as an ethylenethio group, a propylenethio group or a hexenylthio group; a fluorenyl group represented by -COR21; a carboxyl group; a methoxy group represented by -OCOR21. An amine group represented by -NR23R24; a mercaptoamine group represented by -NHCOR25; a urethane group represented by -NHCOOR26; an aminocarbenyl group represented by -CONR27R28; a sulfonic acid represented by -S〇2R32; Ester group; -C = group represented by NR33; -C=N-NR34R35; 2-thiol, 2-pyridyl, furyl, oxazolyl, benzoxazolyl, thiazolyl, A saturated or unsaturated heterocyclic group such as a benzothiazolyl, morpholinyl, pyrrolidinyl or tetrahydrothiophene dioxide group. R21 to R35 are independently a hydrogen atom, a substituent which may be substituted, a dilute group which may be substituted with -27-(24) 1354864, an aryl group which may be substituted, or an aralkyl group which may be substituted. In the above substituent group, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkoxy group, an alkylthio group, a aryl group, an aralkyl group, a aryl group or an aryl group may be further substituted with a substituent. The substitution positions of the rings A to G and the linking group L of these substituents are not particularly limited. When a plurality of substituents are present, these may be the same or different. Rings A to G, a linking group are unsubstituted, or a substituent such as a halogen atom, a cyano group, an alkyl group which may be substituted, a cycloalkyl group which may be substituted, an alkenyl group which may be substituted, an alkyl group which may be substituted An oxy group, an aryl group which may be substituted, a aryl group which may be substituted, an alkenyl group which may be substituted, an alkenyl group which may be substituted, an amine group which may be substituted, a fluorenyl group which may be substituted , _. =City 33, the base of -C=N-NR34R35 is succulent _ corpse lamp base is replaced by a saturated or unsaturated heterocyclic group, when it has a substituent, the east w is opposite to you _ 吏The substituents are a halogen atom, a cyano group, an alkyl group which may be substituted, a cycloalkyl group which may be substituted, a substituted alkoxy group, an aryl group which may be substituted, an amine group which may be substituted '_C = an alkenyl group which may be substituted by a group represented by NR33, a aryl group substituted by a cocoa group, a group represented by -C=N_NR34r35, a saturated or unsaturated heterocyclic group. Rings A to G and linking _ L may have the above-mentioned substituents 尙 which may be substituted by any (tetra) group. The substituent is preferably methoxy, ethoxy, n-, isopropoxy or n-butoxy. Carbon number of the group, the second butoxy group, the third butoxy group, etc.] to the k-oxy group of & t _: methoxymethoxy, ethoxymethoxy, propoxymethoxy 'z oxygen a ethoxylated alkoxy group having a carbon number of 2 to a methoxy alkoxy group; a methoxymethoxymethoxy group; a methoxymethyl group TMZ-fc *. Ethyl ethoxy, methoxyethoxymethoxy, ethoxy-28 - (25) (25) 1354486 methoxy methoxy, ethoxyethoxy methoxy and other carbon number 3 An alkoxyalkoxy alkoxy group to ι 5; an aryl group having 6 to 12 carbon atoms such as a phenyl group, a tolyl group or a xylyl group (these may be further substituted by a substituent); a phenoxy group, a tolyloxy group, and a second group; a aryloxy group having 6 to 12 carbon atoms such as a tolyloxy group or a naphthyloxy group; an alkenyloxy group having 2 to 12 carbon atoms such as a vinyloxy group or a propyleneoxy group; an anthracenyl group such as an ethyl fluorenyl group; a propyl fluorenyl group; Nitro; hydroxy; tetrahydrofuranyl; amine; N,N-dimethylamino, N,N- Alkyl sulfonamide having a carbon number of 1 to 6 such as a diethylamino group and the like having a carbon number of from 10 to 10: a methylsulfonic acid amine group, an ethyl sulfonylamino group, a n-propyl alanine group a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom; an alkoxy group having 2 to 7 carbon atoms such as a methoxycarbonyl group, an ethoxycarbonyl group, a n-propoxycarbonyl group, an isopropoxycarbonyl group or a n-butoxycarbonyl group; a carbonyl group having 2 to 7 carbon atoms such as a methylcarbonyloxy group, an ethylcarbonyloxy group, a n-propylcarbonyloxy group, an isopropylcarbonyloxy group or a n-butyloxy group; Carbonic groups 2 to 7 such as an aryloxy group, an ethoxycarbonyloxy group, a n-propoxycarbonyloxy group, an isopropoxycarbonyloxy group, a n-butoxycarbonyloxy group, a third butoxycarbonyloxy group Alkoxycarbonyloxy; a linear or branched alkenyl group having 2 to 18 carbon atoms such as a vinyl group, a propenyl group or a hexenyl group; The sensitizer represented by the above general formulas (XI) to (XIII) used in the present invention has a moderate absorption in the wavelength range of 3 90 to 43 Oiim, and thus is in the wavelength range of 330 to 450 nm, more preferably 350 to 430 nm. Has a great absorption. Therefore, it is preferable that the molecule contains four or more aromatic hydrocarbon rings and/or aromatic heterocyclic rings, and it is more preferable to contain five or more aromatic hydrocarbon rings and/or aromatic heterocyclic rings. Specific examples of the sensitizer represented by the above general formulas (XI) to (xm) -29-(26) 1354864 are as follows, but are not limited thereto. Example (XI-a) of the above sensitizer of general formula (XI) ύ

(Xl-b). (XI-c) H3c (XI-d) ch3 Η3〇-©>- 0^ P V= N-Nfe> (Xl-e)

OCH, (XI-f) •30- (27)1354864

-31 - (28) 1354864 R41 Repair N Hair R42 (XI — 1)

R 43 r R·4' R42 R43 are each independently a group below.

N

9 M

CH3

NS —NO ch3 -ch3 -ch2ch3 —ch ch3 H〇) V.

J

(XI -m) -32- (29)1354864

CH CH

/- (ΧΠ-a) (ΧΠ-b)

CH, x. ch3

(ΧΠ-c) (XD-d)

-33- (30) 1354864

Vw H3c ch3

(ΧΠ-e)

Ch3 h3c ch3 h3c

(ΧΠ-f)

-CH = CH -CH = CH V. (ΧΠ-g) (In the above (XII _ g ), the bonding position is at the end of the two phenyl groups or two of the two toluene groups at the end of the benzene ring Above.) (ΧΠ-h) 6 φ

CH=CH-CH=CH

CH = CH-CH=CH -34- (31) 1354864

R51, R52, and R53 are each independently independent of the base. /0>/0> A N — N X (X^CHg. F. Cl. Br) Pu /□>

N

X (x2=h. ch3)

P

CH, (ΧΠ-k) 35- (32)1354864

CH, CH3 H3C N CHi (χπ-ΐ) (ΧΠ-m) h3c-^^-

Ch3 N

CH3 N CH3 (ΧΠ-η)

H, C

Ch3 N

CH,

CH/ (ΧΠ-ο) CH' ch3

(ΧΠ-ρ) 6 6 Example of the sensitizer of the above general formula (ΧΠΙ) -36- (33) 1354486

(ΧΙΠ-a) (ΧΠ-b) (XI-e) (X melon-c) (Xm-d) -37- (34) 1354864 <Polymerization inhibitor> The negative blue-violet refinement of the present invention As described later, a negative photosensitive composition having an ethylenically unsaturated composition (having the aforementioned residual film ratio-exposure amount and the minimum exposure amount as described above, such as a compound which is absorbed as a sensitizer, the content of the inhibitor is 5~) 60 ppm is preferably 50 ppm, and the lower limit is desirably, in other words, in the case of the photo-ethylenically unsaturated compound, a polymer-bonding polymerization inhibitor used for polymerization formation or the like may be added in order to prevent photopolymerization and the like. In addition to the addition of the ethylene non-polymerization inhibitor, the content of the composition is usually 100 ppm or more, and the content of the inhibitor is determined when the composition is prepared. When the negative photosensitive composition is small, the manufacturing drawing will be described later. If the formation stability of the formed material is not good, the thermal polymerization or the polymerization of the gel-forming layer is generated, and the pattern of the photoresist image obtained is a detailed compound of the composition of the photosensitive composition and the photopolymerization initiator. For the basic N,) is better. In particular, in order to be effective or the aforementioned developing speed-exposure amount characteristic, it is described that it is extremely useful in a specific wavelength range, and polymerization of a photosensitive composition is preferable. The upper limit of the content of the polymerization inhibitor is 10 p p m ° The essential component in the polymerizable composition is formed to prevent polymerization or to impart a protective agent to the product. In the case of imparting a photopolymerizable layer, a thermal polymerization or a mixture of a polysaturated compound and a photopolymerization initiator may be added as needed in the production, and a polymerization inhibitor may be added to ensure a photopolymerizable composition. In a preferred embodiment of the present invention, the photosensitive composition coating liquid is reduced when the content of the polymerization inhibitor of poly(N?) is too large, or the negative photosensitive group is not easily prevented. When the content of the polymerization inhibitor is too large, the shape of the bottom is not good, and the shape of the bottom is not good, and the phenomenon of pulling the bottom -38 - (35) 1354864 is generated, and the resolution is poor. In the present invention, when the polymerization of the photosensitive composition is controlled within the above range, for example, (i) a method for suppressing the content of the polymerization inhibitor contained in the ethylene compound or using the unsaturated unsaturated compound or the like, Ii) a method of suppressing the content of the polymerization inhibitor contained therein or using the content of the coating material or the like, and (iii) drying conditions for producing the photoresist image-formable photo-coating composition, for example, a high temperature, a polymerization inhibitor Method (iv) A method of producing a photoresist image by a step of consuming a polymerization inhibitor by heating or the like, and avoiding denaturation and productivity of the photopolymerizable composition, and the method of (ii). In the present invention, the polymerization inhibitor is, for example, generally used as a polymerization inhibitor in light, and is not particularly limited, and has phenol 'methyl hydroquinone, t-butyl hydroquinone, 2-base hydroquinone, P-benzoquinone derivatives such as p-methoxyphenol and the like, p-benzoquinone, methyl p-benzoquinone, 2,5-diphenyl-p-benzoquinone, etc. Among them, the preferred one is hydroquinone, which is preferably p-methoxyphenol. In the present invention, the polymerization inhibitor of the photosensitive composition is applied to a nail-supporting substrate by a coating liquid of a calibration composition prepared by using an acetone standard solution by gas chromatography, and the photosensitive composition layer of the image-forming material is dried. 〗 〖When the content of the oxidizing inhibitor is 0% by weight, the amount of the olefinic unsaturation is less than that of the polymer-bonding material having a small amount of the ethylene polymer binder. Among them, S (I) or a polymerizable composition is considered to have a structure of p-phenylene-5-di-tert-butyl hydroquinone and a derivative of a tert-butyl-p-benzoquinone structure, and the content is based on The measurement enthalpy obtained by gas chromatography-39-(36) (36) 1354864 of the photosensitizing photoresist is quantified. The negative blue-violet laser photosensitive composition of the present invention is preferably a negative photosensitive composition containing the above-mentioned compound as a sensitizer. The negative photosensitive composition has, for example, the following (N , ) to (N3 ) ' The preferred one is (N , ) < negative photosensitive composition (Νι ) > In the negative blue-violet laser photosensitive composition of the present invention, the negative photosensitive composition contains, for example, a sensitizer The above compound is a negative photosensitive composition (N) having an ethylenically unsaturated compound and a photopolymerization initiator as a basic composition. In the present invention, the ethylenically unsaturated compound constituting the negative photosensitive composition (N) is added by a photopolymerization initiator containing a photopolymerization initiator to be described later when the photosensitive composition is irradiated with active light. A compound which polymerizes at least one crosslinked and hardened radically polymerizable ethylenically unsaturated bond in the molecule. The ethylenically unsaturated compound of the present invention is a compound having one ethylenically unsaturated bond in the molecule, and specifically, for example, (meth)acrylic acid [in the present invention, '(meth)acrylic acid) means "acrylic acid Or / and [methacrylic acid]], crotonic acid, isocrotonic acid, maleic acid, itaconic acid, citraconic acid and other unsaturated residual acid and its vinegar, (meth)acrylonitrile, (methyl) Acrylamide styrene and the like. Among them, two or more ethylenic unsaturations are contained in the molecule from the viewpoints of the polymerizability, the crosslinkability, and the difference in the solubility of the developing solution between the exposed portion and the non-exposed portion due to the polymerizability and the paternity. It is preferred that the bond is a compound of -40(37)(37)1354864, and it is particularly preferred that the unsaturated bond is an acrylate compound derived from a (meth) acryloyloxy group. Representative examples of compounds having two or more ethylenically unsaturated bonds in the molecule include esters of unsaturated carboxylic acids and polyhydroxy compounds, (meth) acryloxy phosphates, and hydroxy (meth) acrylates. A urethane (meth) acrylate of a compound and a polyisocyanate compound, an (meth)acrylic acid or a hydroxy (meth) acrylate compound, and an epoxy (meth) acrylate of a polyepoxide. Specific examples of the ester include the aforementioned unsaturated carboxylic acid, ethylene glycol, polyethylene glycol (addition number 2 to 14), propylene glycol, polypropylene glycol (addition number 2 to 14), propylene glycol, butanediol, and neopentyl Glycol, hexanediol, decanediol, Sanjing Methylamine, Sijing Methylamine, Sanjing Methylamine, glycerol 'pentaerythritol, dipentaerythritol' sorbitol and its ethylene oxide A reactant of an aliphatic polyhydroxy compound such as an adduct, a propylene oxide adduct, diethanolamine or triethanolamine, and a specific example thereof is ethylene glycol di(meth)acrylate 'diethylene glycol di(methyl) Acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, nonaethylene glycol di(meth)acrylate 'propylene glycol di(meth)acrylate, tripropylene glycol Di(meth)acrylate, butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, hexanediol di(meth)acrylate, decanediol di(methyl) Acrylate, trimethylolethane tri(meth)acrylate, tetramethylolethane tris(methyl) Acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane ethylene oxide tri(meth)acrylate, C Triol-41 - (38) (38) 1354864 di(meth) acrylate, glycerol tri(meth) acrylate, addition glycerol propylene oxide tris (meth) acrylate, pentaerythritol II (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (a) Base) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, sorbitol tri (meth) acrylate, sorbitol tetra (meth) acrylate, sorbitol Penta(meth)acrylate, sorbitol hexa(meth)acrylate, and the like, and the same crotonate, isocrotate, maleate, itaconate, citraconate, and the like. Examples of the ester include an aromatic polyhydroxy compound such as the above unsaturated carboxylic acid and 'hydroquinone, resorcinol' pyrophenol, bisphenol F, and bisphenol A, or an ethylene oxide adduct thereof. The reactant containing the epoxy propyl compound adduct, specifically, for example, hydroquinone di(meth)acrylate, resorcinol di(meth)acrylate, pyrogallol tri(meth)acrylate , bisphenol A di(meth) acrylate, bisphenol A bis [hydroxyethylene (meth) acrylate], bisphenol A bis [trihydroxy ethylene (meth) acrylate], bisphenol A bis [five Hydroxyethylene (meth) acrylate], bisphenol A bis [hexahydroxyethylene (meth) acrylate], bisphenol A bis [epoxy propyl ether (meth) acrylate], etc. a reaction product of a carboxylic acid and a heterocyclic polyhydroxy compound such as tris(2-hydroxyethyl)isocyanate, specifically, for example, a di(meth)acrylate di(meth)acrylate of tris(2-hydroxyethyl)isocyanate Acid vinegar, di(methyl) propylene sulphuric acid vinegar, etc., unsaturated acid, multi-acid and polyhydroxy compound reactants, specific For example, there are (meth)acrylic acid-42-(39) (39) 1354864, a condensate of phthalic acid and ethylene glycol, a (meth) acrylate, a condensate of maleic acid and diethylene glycol, (A) a condensate of acrylate, terephthalic acid and pentaerythritol, a condensate of (meth)acrylic acid, adipic acid, butanediol and glycerin, and the like. The (meth) acryloxy group-containing phosphate is not particularly limited as long as it is a (meth) acryloxy group-containing phosphate compound, and the compound represented by the following general formula (Va) or (Vb) is good. R13o ο

r I II N II

[CH2 = C—C—〇—(CHZ) n —〇] m —P— (OH) 3-„ (Va) r13o o

r I II II CCHa =CC-〇-(CH2 CH2 O) n ] m -P- (OH) 3-^ (Vb) [In the formula (Va) or (Vb), 'R13 is a hydrogen atom or a methyl group, n Is an integer from 1 to 25, and m is 1, 2 or 3]. π is 1 to 1 Torr, preferably 1 to 4, and specific examples thereof are (meth) acryloxyethyl phosphate, bis[(meth) propylene methoxyethyl] phosphate, (methyl) Ethylene oxyethylene glycol phosphate or the like, which may be used singly or in the form of a mixture. Specific examples of the urethane (meth) acrylate are hydroxymethyl (meth) acrylate 'hydroxyethyl (meth) acrylate, glycerol di (methyl) di (meth) acrylate, pentaerythritol III a hydroxy (meth) acrylate compound such as (meth) acrylate or tetramethylol ethane tri(meth) acrylate, hexamethylene diisocyanate, 2,4,4-trimethyl hexamethylene diisocyanate, Methyl lysine diisocyanate, decyl decyl triisocyanate, polyacid diisocyanate, 1,6,11-^-alkyl triisocyanate,], -43- (40) (40) 1354864 3 '6-hexamethylene triisocyanate, 1,8 diisocyanate-4 • Aliphatic polyphthalocyanate such as isocyanate methyl octyl, cyclohexane diisocyanate, dimethylcyclohexyl diisinate, 4, 4,-Methylene bis(cyclohexyl isocyanate), isophorol diisocyanate, dicycloheptane triisocyanate, etc. alicyclic polyisocyanate 'p-phenylene diisocyanate, 2,4-toluene diisocyanate, 2, 6-toluene diisocyanate, benzodimethyl diisocyanate, tetramethyl benzene dimethyl Sour vinegar, 4,4'-diphenylmethane diisocyanate, tolidine diiso-acid ' I ' 5-naphthalene diisocyanate, tris(isocyanate phenylmethane) ' 异 (isocyanate phenyl) thiophosphate A urea compound (meth) acrylate such as a reaction product of an aromatic polyisocyanate such as an ester or a polycyanate compound such as a heterocyclic polyisocyanate preferably has four or more urethane bonds in one molecule [_NH_C adjacent And a compound of four or more acryloxy groups. This compound is, for example, a compound having four or more hydroxyl groups in one molecule such as pentaerythritol or polyglycerin, and a diisocyanate such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate or benzodimethyl diisocyanate. Compound (1-]) ' obtained by compound reaction or a compound having two or more hydroxyl groups in one molecule such as ethylene glycol, and "Duranate 24A-100", "Duranate 22A-75PXj, "D ura nat e 2 1 by Asahi Kasei Kogyo Co., Ltd. S- 7 5 E", "D uranate 1 8 H - 7 0 B" and other biuret types, "Duranate P-30" - 75Ej, "Duranate E-402-90T", "Duranate E-405-80T", etc. a compound obtained by reacting a compound having three or more isocyanate groups in one molecule, such as a compound, or a polymerization or copolymerization of an isocyanate ethyl (meth) acrylate - 44- (41) (41) 1354864 A compound having four or more molecules, such as a compound (1-3), and a compound having an isocyanate group of 6 or more, etc., and a specific example of "Duranate ME20-100" (i) and pentaerythritol II (see: AOpen Chemical Industries, Ltd.) methyl) Acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate A compound (ii) having one or more hydroxyl groups and two or more, preferably three or more (meth) propylene fluorenyloxy groups, is obtained by reacting one molecule of the ester or the like. The weight average molecular weight of the aforementioned compound (i) is preferably from 500 to 200,000, more preferably from 1,000 to 150, Å. The weight average molecular weight of the aforementioned urethane (meth) acrylate is preferably from 600 to 150,000. It is preferable to have 6 or more urethane bonds, more preferably 8 or more, and 6 or more and more preferably 8 or more (meth) acryloxy groups. For example, the above-mentioned compound (i) and the aforementioned compound (ii) can be used in an organic solvent such as toluene or ethyl acetate, and the former isocyanate group and the latter hydroxyl group. The ratio is 1/1〇~1〇/] 'If necessary, use a catalyst such as n-butyltin dilaurate to 1〇~15〇. (The reaction is carried out by a method of 5 minutes to 3 hours. In the present invention, the urethane (meth) acrylate is preferably represented by the following general formula (VI).

Ra -fRb--Rd (10)

-X [In the formula (VI), the Ra group has a weight of -45-(42) 1354864 covering an alkoxy group or an aryloxy group, and has 4 to 20 hydroxyl groups bonded to Rb, Ra and Each of the alkyl groups having an independent carbon number of 1 to 10, the Rd has an organic residue of 1 to 10 methyl) acryloxy groups, and Ra, Rb, Rc and Rd may have a substituent 'x 4 to 20 An integer, y is an integer from 0 to 15, and z is an integer of 1 1 5]. The repetitive structure of the alkoxy group of Ra in the formula (VI) is, for example, glycerol, glycerin or pentaerythritol, and the repetitive structure of the extended aryloxy group is derived from pyrogallol, 1, 3, 5 - Benzene alcohol and the like. The carbon number of the alkylene of Rb and Rc is desirably 1 to 5, the carbon number of the (meth)acrylomethoxy group of Rd is 1 to 7, X is 4 to 15, y is 1 to 10, and z is 1 to 5. 10.

Ra is preferably a formula (wherein k is an integer of 2 to 10), and Ra Rb is independently a methyl group, a monomethyldimethyl group or a trisyl group, and Rd is preferably the following Type.

Ra 0

I 0 ch2 fH2 9

Q

Rb (with white as the base and a

fH2 CH2 <p-CH2- 0-Q CH2 〇 ch2 π V Q V Q

Rd : 2 o-ch2-ch—(ch2~o~q) (However, Q is -c-ch=ch2 -46 - (43) (43)1354864 Specific examples of the epoxy (meth) acrylate There is (meth)propionic acid' or the above hydroxy (meth) acrylate compound and (poly)ethylene glycol polyglycidyl ether, (poly) propylene glycol polyglycidyl ether, (poly) tetramethyl diol polyglycidyl Ether, (poly)pentamethylglycol polyglycidyl ether, (poly) neopentyl glycol polyglycidyl ether, (poly) hexamethylene glycol polyglycidyl acid, (poly) trimethylolpropane polyglycidyl ether, (poly) glycerol polyglycidyl ether ' (poly) sorbitol polyglycidyl ether and other aliphatic polyepoxy compounds, phenol novolac lacquer polyepoxides brominated phenol phenolic enamel lacquer polyepoxide, (oigh, Inter-, p-phenol phenolic enamel enamel polyepoxide, bisphenol A polyepoxy compound, bisphenol F polyepoxy compound and other aromatic polyepoxides, sorbitan polyglycidyl ether, triglycidyl Polyepoxy such as heterocyclic polyepoxide such as isocyanurate or triglycidyl tris(2-hydroxyethyl)isocyanuric acid In addition to the above, the other ethylenically unsaturated compound may be, for example, an ethyl methacrylate such as ethylene bis(meth) acrylamide or a propylene acrylate such as diallyl phthalate. A vinyl-containing compound such as an ester or a divinyl phthalate. The above ethylenically unsaturated compound may be used singly or in combination of two or more kinds. The ethylenically unsaturated compound is preferably an ester in the present invention. (Methyl) acrylates, (meth) propylene oxy oxyphosphates, or urethane (meth) acrylates, more preferably ester (meth) acrylates, the ester (A) More preferably, the acrylate group is a polyoxyalkylene group containing polyethylene glycol, polypropylene glycol or a polyethylene oxide adduct of bisphenol A, and contains two or more (meth) propylene oxides. In the present invention, the photopolymerization initiator constituting the negative photosensitive composition (Ν) is co-presented by the sensitizer or the like. When light is irradiated, the light of the sensitizer is excited to generate energy, and the active species are produced. An active compound which causes polymerization of the above ethylenically unsaturated compound, for example, a hexaarylbiimidazole compound, a titanocene compound, a halogenated hydrocarbon derivative, an iodine salt, an organic borate, etc. The sensitization of the composition, the adhesion to the substrate, the preservation stability, and the like are preferably a hexaarylbiimidazole compound, a titanocene compound, and an organic borate, and a safety lamp from a yellow lamp. In terms of the aspect, a particularly preferred one is a hexaarylbiimidazole compound. Specific examples of the hexaarylbiimidazole compound are 2,2,_bis(o-chlorophenyl)-4' 4'' 5 . 5'-tetraphenyl-bi-dimidine, 2,2,-bis(o-chlorophenyl)-4' 4',5,5,-tetra(p-methylphenyl)biimidazole, 2,2 Bis(o-chlorophenyl)-4,4,,5' 5,-tetrakis(p-methoxyphenyl)biimidazole, 2,2'-bis(o-,p-dichlorophenyl)_4,4, ,5,tetrakis(p-methoxyphenyl)biimidazole, 2,2,-bis(o-chlorophenyl)_4,4,,5 '5'-tetra(p-ethoxyphenyl) Mi, 2, 2, - double o-Chlorophenyl)·4,4′,5,5′-tetra(p-chlorophenyl)biimidazole, 2, 2,·bis(p-dichlorophenyl)bi-di-n-chlorophenyl)-4 , 4',5,5,-tetra (o-azole, 2,2,-bis(o-, p-dichlorophenyl)·4, 4, , 5,5,_tetra(o-, p-dichlorophenyl) Bis-imidazole, 2,2,_bis(o-chlorophenyl)_4,4,,^ ' 5'-tetra(p-fluorophenyl)biimidazole, 2,2,·bis(o-chlorophenyl)^ , 4',5,5'-tetra(o-,p-dibromophenyl)-diimidine, 2,2,_bis(o-bromophenyl)-4 ' 4, ' 5,5,_ four ( O-, p-dichlorophenyl)-dialdehyde-48-(45) (45)1354864 oxazole, 2,2'-bis(o-bromophenyl)-4,4,,5,5,-tetra(p-iodine Phenyl) diimidazole, 2, 2, bis(o-bromophenyl)_4,4,5,5,-tetrakis (o-chloro-p-methoxyphenyl)-biimidazole, 2,2,-double (o-chlorophenyl)-4, 4,, 5' 5'-tetra(p-chloronaphthyl)biimidazole and the like. Among them, a hexaphenylbiimidazole compound is preferred, and the ortho position of the benzene ring bonded to the 2,2,_ position on the imidazole ring is preferably substituted by a halogen atom, particularly 4' bonded to the imidazole ring. The benzene ring at the 4', 5, 5'-position is preferably unsubstituted or substituted by a halogen atom or an alkoxycarbonyl group. A conventional hexaaryl disaccharide-based compound which is a photopolymerization initiator of a photosensitive composition has a melting point of 丨9〇 〇c or more, for example, 丨96 to 2〇2. 〇 ′ and the X-ray refractive spectrum of the wavelength I54 A, the Bragg angle (2Θ±0.2.) 9 · 9 2 5 has the largest refractive peak. The hexadecandyl-melamine compound of the present invention preferably has a melting point of 180, from the viewpoints of solubility in a coating solvent and dispersion stability in a photosensitive composition. {: The following, more preferably, the Bragg angle (2θ ± 〇 2 , Λ ) 21.16 having the maximum refractive peak in the X-ray refractive spectrum of the wavelength of 1.54 A. The best hexaaryl^-melt compound is, for example, 2' 2,-bis(o-chlorophenyl)_4,4,5 tetraphenylbiimidazole, 2,2,·bis (o-, p-pair) Chlorophenyl)-4 4 5 , tetraphenyldiimidazole, 2,2,bis(o-bromophenyl)_4, 4 5 S'-tetraphenylbiimidazole, 2,2,-double (neighbor) , p-dichlorophenyl) 4 4 '5'5'-tetrakis(p-methoxyphenyl)biimidazole, etc., preferably by gastric sputum, is '2' 2' bis (o-chlorophenyl) )-4, 4,,5, 5,_tetraphenylbiimidazole, q 2,2, bis(o-, p-dichlorophenyl)·4, 4,5,5,tetra(p-methoxy) Phenyl) diimidazole. -49- (46) (46) 1354864 Specific examples of the above titanocene-based compound include dicyclopentadienyl titanium dichloride, dipentadienyl titanium biphenyl, and dicyclopentadienyl titanium bis (2, 4-difluorophenyl), dicyclopentadienyl titanium bis(2,6-difluorophenyl), dicyclopentadienyl titanium bis(2,4,6-trifluorophenyl), bicyclo Pentadienyl titanium bis(2,3,5,6-tetrafluorophenyl), dicyclopentadienyl titanium bis(2,3,4,5,6-pentafluorophenyl), di(methyl) Cyclopentadienyl)titanium bis(2,6-difluorophenyl), bis(methylcyclopentadienyl)titanium bis(2,3,4,5,6-pentafluorophenyl), bicyclo Pentadienyl titanium bis[2,6-difluoro-3-(1-indolyl)phenyl] and the like. Further, it is preferred that the titanium compound having a dicyclopentadienyl structure and a biphenyl structure is substituted by a halogen atom at the ortho position of the biphenyl ring. The halogenated hydrocarbon derivative such as a halogenated alkane 'halomethyl group S-triazine derivatives and halomethylation] 3,4-oxadiazole derivatives, etc., specific examples of the halogenated alkane are dichloromethane, chloroform, 1,2-dichloroethane, 1,2-dibromoethane, and the like. Specific examples of the halomethylated s-triazine derivative are, for example, 2,4,6-tris(monochloromethyl)-s-triazine, 2' 4,6-tris(dichloromethyl)-s_ Sansui, 2,4,6-tris(trichloromethyl)-s-diazine, 2-methyl-4,6-bis(trichloromethyl)-s-tris-Q,2-n-propyl -4,6·bis(dichloromethyl)_s_triazine' 2_(α,α,β-trichloroethyl)-4,6·bis(trichloromethyl)_s_trisole, 2_phenyl -4,6-bis(trichloromethyl)-s-triazine' 2·(p-methoxyphenyl)_ 4' 6-bis(trichloromethyl)-s-triazine, 2-(3 ,4-epoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2·(p-chlorophenyl)6·bis(trichloromethyl)-s-triazine '2 - [1-(p-methoxyphenyl)_2,4·butadiene•50-(47) (47)1354864 base]-4,6-bis(trichloromethyl)-s-triazine, 2 -styryl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxystyryl)-4,6-bis(trichloromethyl)triazine, 2- (p-methoxy-m-hydroxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-isopropoxy styryl)-4,6-bis ( Trichloromethyl)-s-triazine ' 2-(p-tolyl) -4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(pair Ethoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl)-s- Triazine, 2-phenylthio-4,6-bis(trichloromethyl)-s-triazine, 2-benzylsulfonyl-4,6-bis(trichloromethyl)-s-triazine, 2,4,6-tris(dibromomethyl)-s-triazine, 2,4,6-tris(tribromomethyl)-s-triazine, 2-methyl-4,6-bis (three Bromomethyl)-s-triazine, 2,methoxy-4,6-bis(tribromomethyl)-s-triazine, and the like. Among them, bis(trihalomethyl)-s-triazine is preferred, 2-methyl-4,6-bis(trichloromethyl)-s-triazine, 2-phenyl-4,6-bis ( Trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(3,4-epoxyphenyl -4,6-bis(trichloromethyl)-s-triazine, 2-[1-(p-methoxyphenyl)-2,4-butadienyl]-4,6-bis (three) Chloromethyl)-s-triazine' 2-(p-methoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxy-m-hydroxybenzene Vinyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-isopropoxystyryl)-4,6-bis(trichloromethyl)-s-triazine Better. Specific examples of the halomethylated 1,3,4-oxadiazole derivative are 2-(p-methoxyphenyl)-5-trichloromethyl-1,3,4-oxadiazole, 2-( P-methoxystyryl)-5-trichloromethyl-1,3,4-oxadiazole, 2-(o-benzofuran-51-(48) 1354864 yl)-5-trichloromethyl -1,3,4-oxadiazole, 2-[β-(o-phenylpyranyl)vinyl]-5-trichloromethyl-], 3,4-oxadiazole and the like. Further, the iodonium salt is, for example, a diphenyl iodine hexafluoroarsenate, a diiodo mirror tetrafluoroborate, a diphenyl iodine p-toluenesulfonate or a diphenylsulfonium sulfonate. Key salt, dicyclohexyl iodide hexafluoroarsenate cyclohexyl iodide tetrafluoroborate, dicyclohexyl iodide p-toluenesulfonate cyclohexyl iodide sulfonate, etc. Among them, a diaryl iodine salt is preferred. Organoborates such as organoboron ammonium complexes, organoboron miscible organoboron oxime complexes, organoboron hydroxy hydrazine complexes, organoboron iodine guns, organoboron transition metal coordination complexes, and the like. The organoboron anion is n-butyltriphenylboron anion, n-butyltris(2,4,6-trimethyl)boron anion, n-butyltris(p-methoxyphenyl)boranium anion butyl tri P-fluorophenyl)boron anion, n-butyltris(m-fluorophenyl anion, n-butyltris(3-fluoro-4-methylphenyl)boron anion, n-tris(2,6-difluorophenyl)boron Anionic 'n-butyl tris(2,4,6-phenyl)boron anion, n-butyl tris(2,3,4,5,6-pentafluorophenylboron anion, n-butyl tris(p-chlorophenyl) An alkyltriphenylboron such as a boron anion, n-butyl 2,6-difluoro-3.pyrrolylphenyl)boron anion, and a cation such as a saddle cation '铙 cation, a mirror cation iodine gun cation, etc. The compound, which is preferably an ammonium cation such as a tetraalkylammonium or the like. The negative blue-violet laser photosensitive composition of the present invention constitutes the sensitizer of the photosensitive composition (Ν,), and the ethylenicity is not Sodium hydride is a substance, misfit such as phenyl, n-borobutyl trifluoro) III (anion, organic negative and -52- (49) 13 When the total amount of the composition of the photopolymerization initiator is 54864, the former %, the ethylenically unsaturated photopolymerization initiator contains 0.5 to 50, 0.1 to 10% by weight, and 70% by weight of the light. The polymerization initiation of the negative photosensitive group of the present invention, the ethylenically unsaturated compound and the photosensitive composition layer are preferably an alkali-soluble resin in the substrate, and the alkali-soluble resin and the carboxyl group-containing styrene resin are preferably carboxyl group-containing styrene. a carboxyl group-containing styrene resin having stolic acid, isocrotonic acid, maleic acid, an unsaturated carboxylic acid, and styrene, α-based (meth) acrylate, ethyl acrylate, butyl (methyl) Ethyl ester, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hydroxyethyl (meth) acrylate, benzyl (methyl) propyl (meth) acrylate Ν·( ) acrylonitrile, (meth) acrylamide, Ν ' Ν-dimethyl (methyl) content ratios for negative photosensitive sensitizers containing 〇. 〇 5~20 weights 10 to 90% by weight, the aforementioned weight %, more ideal In addition to the sensitizer and the photopolymerization initiator, the sensitizer ethylenically unsaturated compound is contained in an amount of from 1 to 30% by weight, in addition to the sensitizer and the photopolymerization initiator. The hydrazine-soluble resin has, for example, a phenolic hydroxyl group-containing, such a negative photosensitive composition (such as a resin such as (meth)acrylic acid, palmitic anhydride, itaconic acid, citraconic acid, etc. , hydroxystyrene, methyl (meth) acrylate, propyl (meth) acrylate, pentyl (methyl) propionate, dodecyl (meth) propylene acrylate, hydroxymethyl (methyl) Acrylate, epoxypropyl (meth) acrylate, hydrazine, N-dimethylaminoethylmethyl propylene hydrazinomorph, (methylamine, N-hydroxymethyl (meth) propylene propylene Amidoxime, anthracene, N-dimethylamino-53-(50) (50) 1354864 A copolymer of other vinyl compounds such as ethyl (meth) acrylamide or vinyl acetate. The carboxyl group-containing vinyl resin is preferably from 30 to 250 KOH.g/g, more preferably from 1 Torr to 250 KOH. mg/g. Further, the polystyrene-converted weight average molecular weight is 10,000 to 200,000, more preferably 20,000 to 〇〇, 〇〇〇. Among them, the soluble resin contained in the negative photosensitive composition (N,) of the present invention preferably contains a styrene monomer, a (meth) acrylate monomer, and a (meth) acrylic acid. The composition of each monomer is a unit of repeating copolymer. The copolymer contains 3 to 3 mol%, preferably 5 to 25 mol%, and (meth)acrylate monomer 1 to 80 mol% from the styrene monomer. 2 〇 to 6 〇 mol % and (meth)acrylic acid 1 〇 to 60 mol % 'preferably 15 to 55 mol % of each monomer constitutes a repetitive position. Specific examples of the styrene monomer of the above copolymer include α-substituted alkylstyrene such as styrene 'α-methylbenzidine and α-ethylstyrene; o-methylphenylacetone-methyl-ethylene and para-methyl Styrene, 2,5-dimethylstyrene 4-nuclear substituted alkylstyrene; o-hydroxystyrene, m-hydroxystyrene, p-hydroxy-p-ethylene, monohydroxy-p-ethylene, etc. ^ Substituting halogenated styrene with nuclear such as Mobibi and dibromostyrene. Further, specific examples of the 'acrylic acid vinegar monomer are methyl (meth) acrylate, benzyl (meth) acrylate, propyl (meth) acrylate butyl butyl acrylate) Acetate butyl (methyl) propyl succinic acid ketone (A two-field acid vinegar '2-ethylhexyl (methyl) propylene vinegar, octyl (meth) acrylate, etc. (A) acrylic acid is preferred It is a carbon number of 1 to 12, more -54 - (51) (51) 1354864. It is preferably an alkyl ester having 1 to 8 carbon atoms and a methylol (meth) acrylate, a hydroxyethyl (meth) acrylate, or a ring. Substituted alkane such as oxypropyl (meth) acrylate, benzyl (meth) acrylate, amine ethyl (meth) acrylate, hydrazine, hydrazine monomethylaminoethyl (meth) acrylate a base ester or the like. The copolymer of the above-mentioned styrene-based monomer, (meth)acrylic acid-based monomer, and (meth)acrylic acid may be contained in a repeating unit. Unsaturated carboxylic acid such as acid, isocrotonic acid, maleic acid, maleic acid ST 'itaconic acid, citraconic acid or (meth)acrylonitrile, (meth)acrylamide, hydrazine-hydroxymethyl group base (meth)acrylic acid derivatives such as acrylamide, hydrazine, hydrazine-dimethyl(meth) acrylamide, hydrazine, hydrazine-dimethylaminoethyl (meth) propyl amide, and vinyl acetate, A repeating unit of another monomer copolymerizable with an ethylene compound such as vinyl chloride, and the content of the repeating unit derived from these other monomers is preferably 1% by mole or less based on the total amount of the copolymer. The resin is, for example, a carboxyl group-containing vinyl resin having an ethylenically unsaturated bond in a branched chain. The carboxyl group-containing vinyl resin is specifically, for example, '5 to 90 moles of a carboxyl group of a carboxyl group-containing polymer and a carboxyl group-containing polymer. %, preferably 30 to 70 mol% of allyl glycidic acid, glycidyl (meth) acrylate, α-ethyl glycidyl (meth) acrylate, glycidyl crotonate, Glycidyl isobar ugly vinegar, ugly thioglycidyl ether, itaconic acid single hospital based monoglycidyl vinegar, fumaric acid monoalkyl monoglycidyl ester, maleic acid monoalkyl monoglycid vinegar, etc. Aliphatic epoxy-containing unsaturated compounds, or 3 ,4·epoxycyclohexylmethyl(methyl)propoxylate vinegar '2' 3-epoxycyclopentylmethyl (methyl-55-(52) (52)1354864) acrylate, 7,8- Epoxy [tricyclo[5.2.1.0]non-2-yl]oxymethyl (meth) acrylate and other alicyclic epoxy-containing unsaturated compounds produce a reaction product obtained by the reaction' and an allyl group (A) Acrylate, 3-allyloxy-2-hydroxypropyl (meth) acrylate, cinnamyl (meth) acrylate, crotonyl (meth) acrylate, methallyl ( a compound having two or more kinds of unsaturated groups such as methyl acrylate or N ' N-diallyl (meth) acrylamide, or a vinyl (meth) acrylate or a fluorene-chlorovinyl group (methyl) ) acrylate '2-phenylvinyl (meth) acrylate, 1-propenyl (meth) acrylate, 2-phenyl crotonate, vinyl (meth) allylimine, etc. The compound of the above unsaturated group, 10 to 90 mol%, preferably 30 to 80 mol% of the unsaturated carboxylic acid or unsaturated carboxylic acid such as (meth)acrylic acid, of the entire compound having an unsaturated group. The resulting ester to produce a reaction product of the copolymerization. The other carboxyl group-containing vinyl resin is, for example, an epoxy resin containing an unsaturated group and a carboxyl group, which is a polyvalent carboxylic acid or an acid anhydride thereof, which is added to an α,β-unsaturated monocarboxylic acid adduct of an epoxy resin. Specific examples of the epoxy group containing an unsaturated group and a carboxyl group, for example, ring-opening on the epoxy group of the epoxy resin, and addition of a carboxyl group of the α,β-unsaturated monocarboxylic acid to form an ester bond (-COO-) A group in which an ethylenically unsaturated bond is added and a hydroxyl group formed is reacted with a carboxyl group of a polyvalent carboxylic acid or an anhydride thereof to form a residual carboxyl group via an ester bond. Specific examples of the epoxy resin include bisphenol oxime epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, phenol novolac lacquer epoxy resin, cresol novolac lacquer epoxy resin trisphenol epoxy Resin, etc., in which phenol novolac lacquer epoxy resin or cresol novolac lacquer epoxy resin is preferred. Specific examples of the α,β-unsaturated-56-(53)(53)1354864 and the monocarboxylic acid include (meth)acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, and the like. . Of these, preferred is (meth)acrylic acid. Specific examples of the polycarboxylic acid or its anhydride include succinic acid 'maleic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, and terminal methyltetrahydrophthalic acid. Methyl end extension methyltetrahydrophthalic acid, hexahydrophthalic acid, methyl hexahydrophthalic acid and these anhydrides, among which maleic anhydride, tetrahydrophthalic anhydride or hexahydrophthalic anhydride Preferably, it is more preferably tetrahydrophthalic anhydride. Among these epoxy resins containing an unsaturated group and a carboxyl group, the epoxy resin is preferably a phenol novolac lacquer epoxy resin or the like from the viewpoints of sensitivity, resolution, and adhesion to a substrate of the photosensitive composition. Cresol novolac lacquer epoxy resin '(X,β-unsaturated carboxylic acid is (meth)acrylic acid, and polybasic carboxylic acid or its anhydride is desirably tetrahydro phthalic anhydride. The acid bismuth is 20 to 200 mg. The KOH/g and the weight average molecular weight are preferably 2,000 to 200,000. In the negative blue-violet laser photosensitive composition of the present invention, the ratio of the alkali-soluble resin contained in the negative photosensitive composition (N) is The total amount of the negative photosensitive composition (N,) is 0 to 80% by weight, preferably 10 to 70% by weight. The negative photosensitive composition (N,) of the present invention may contain a polymerization accelerator. The polymerization accelerator preferably contains an amino acid ester or a bipolar ion compound. The amino acid ester or bipolar ion compound has, for example, the following general formula (Vila) or (Vllb): -57- ( 54) 1354486

O II R14 R1( (Vila) N——c- (CH2 ) p -C-O-R1 LI.,

R R14 R1 19-iV - C- (CH2 ) 〇II -CO' (vilb) [In the formulae (Vila) and (Vllb), R14 and R15 each independently may have a substituent alkyl group, and may have a substituent An aryl group which may have a heterocyclic group or a hydrogen atom of a substituent, R16 and R17 each independently an alkyl group or a hydrogen atom which may have a substituent, R18 may be an alkyl group which may have a substituent, and an alkenyl group which may have a substituent Or an aryl group which may have a substituent, or a heterocyclic group which may have a substituent, and P is an integer of 0 to 10. The alkyl groups of R14, R15, RU, Ri7, Ris and R19 in the formulas (Vila) and (Vllb) preferably have a carbon number of from 1 to 8, more preferably from 丨 to 4. The alkenyl group of r]* is, for example, a vinyl group, an allyl group or an isopropenyl group, and the aryl group of Rm, R18 and R19 is, for example, a phenyl group or a naphthyl group, and the heterocyclic group of r14 and rM is, for example, a furyl group. Pyrrolyl, pyridyl and the like. Examples of the substituent of the alkyl group and the alkenyl group include an alkoxy group, an alkoxycarbonyl group, an alkenyloxy group, an alkenyloxycarbonyl group, a phenyl group, a halogen atom and the like. The substituents of these aryl groups and heterocyclic groups may have, for example, an alkoxy group. An alkyl group, an alkoxy group, an alkenyl group, a oxy group, a decyl group, a decyloxy group, a oxo group, a phenoxy group, an alkylthio group, an alkylsulfonyl group and an aldehyde group a carboxyl group, a hydroxyl group, a sulfo group, a nitro group, a cyano group, a halogen atom or the like. In the present invention, the above general formula (Vila) or (Vllb) represents an amino acid ester or a bipolar ion compound of -58 - (55) (55) 1354486, and Rm and Rh in the formula (Vila) One is a hydrogen atom, the other is a phenyl group which may have a substituent, R16 and R17 are a hydrogen atom, R18 is an alkyl group which may have a substituent, or a phenyl group which may have a substituent, and P is 0, 1 or 2 The amino acid ester, or R14 and R15 in the formula (VIIb) are a hydrogen atom, or one of them is an alkyl group which may have a substituent, Rh and R17 are a hydrogen atom, R19 is an alkyl group which may have a substituent, or A phenyl group having a substituent, and p is an amino acid bipolar ion compound of 0, 1, or 2. In the above general formula (Vila), p is 0, R14 and R15 are each a hydrogen atom, the other is a phenyl group, R16 and R17 are hydrogen atoms of N-phenylglycine, and R18 is a benzyl group. In the benzyl N-phenylglycine or the above formula (VIIb), p is hydrazine, R14, R15, R16 and R1, wherein - the hydrogen atom 'R19 is a phenyl group N-phenylgan Bipolar ionic compound of aminic acid. The polymerization accelerator is, for example, an amine compound, and the amine compound may be an aliphatic, alicyclic or aromatic amine, and is not limited to a monoamine, and may be a polyamine such as a diamine or a triamine, or may be a first amine or a second. An amine or a third amine, but preferably having a pKb of 7 or less. Specific examples of the amine compound are butylamine, dibutylamine, tributylamine 'penta-, penta makeup, diamylamine, hexylamine, dihexylamine, trihexylamine, alanine, diallylamine, triallylamine. An aliphatic amine which may be substituted with a hydroxyl group or a phenyl group such as triethanolamine, benzylamine or diphenylmethylamine 'tritylamine. Among them, among the present invention, triphenylmethylamine is particularly desirable. The polymerization accelerator is, for example, 2-mercaptobenzothiazole, 2-mercaptobenzimidazole '2-mercaptobenzoxazole, 3 毓 丨 丨, 2,4 · triazole, 2 锍 _ _ 4 ( 3 η )-D quinoxaline, β-mercaptophthalene, ethylene glycol dithiopropionate, trimethylolpropane-59- (56) (56) 1354864 trithiopropionate, pentaerythritol tetrathiopropionate And other thiol-containing compounds; dimethyldithiolan, trimethylolpropane tridecyl acetate, pentaerythritol tetramercaptopropionate and other polyfunctional thiophene compounds; N,N-dialkylamino benzene An amine group having an aromatic ring such as a salt of a formate or N-phenylglycine or a salt thereof such as an ammonium or a sodium salt, a salt of a phenylalanine acid or an ammonium or a sodium salt thereof, or a derivative thereof. An acid or a derivative thereof. The present invention is preferably a derivative containing a mercapto compound and N-phenylglycine or a salt thereof such as an ammonium salt or a sodium salt. In the blue-violet laser photosensitive composition of the present invention, the ratio of the polymerization accelerator contained in the negative photosensitive composition (N!) is 30% by weight for the total amount of the negative photosensitive composition (N,). % or less, more preferably 20% by weight or less. The negative photosensitive composition (N i ) of the present invention may contain nonionic and anionic properties in order to improve coating properties when forming a photosensitive composition layer on a substrate and development of a photosensitive photoresist layer. a surfactant such as a cationic, amphoteric or fluorine-based surfactant, specifically, for example, the nonionic surfactant is, for example, a polyethylene oxide alkyl ether, a polyethylene oxide polypropylene oxide alkyl ether, or a poly Ethylene oxide alkylphenyl ethers, polyethylene oxide alkyl esters, polyethylene oxide fatty acid esters, glycerin fatty acid esters, polyethylene oxide glycerin fatty acid esters, pentaerythritol fatty acid esters, Polyethylene oxide pentaerythritol fatty acid esters, sorbitan fatty acid esters, polyethylene oxide sorbitan fatty acid esters, sorbitol fatty acid esters, polyethylene oxide sorbitol fatty acid esters, etc. The anionic surfactants are, for example, alkyl sulfonates, alkyl benzene sulfonates, alkyl naphthalene sulfonates, polyethylene oxide alkyl ether sulfonates, alkyl sulfates, Alkyl sulfate salts, higher alcohols -60- (57) 1354864 Acid esters, aliphatic alcohol sulfates, 'polyethylene oxide alkyl ether salts', polyethylene oxide alkyl phenyl ether sulfates, alkyl phosphates, polyethylene oxide alkyl ethers Examples of the 'cationic surfactants such as phosphates and polyethylene oxide alkylphenylates include quaternary ammonium salts, porphyrin derivatives, amine salts, etc., and amphoteric surfactants such as beet compounds. , imidazole mirror salts, imidazolines, amino acids and the like. In the blue-violet laser photosensitive composition of the present invention, the ratio of the surfactant contained in the negative photosensitive material (N) is a negative optical composition (when the total amount of Nd is 1% by weight or less) 5% by weight or less. The negative photosensitive composition (N,) of the present invention may contain 2% by weight or less of the total amount of the negative photosensitive composition (N,). Antioxidants such as phenol, 2,6-di-t-butyl-p-cresol, 2,4-tris-tert-butylphenol, 4,4'-methylene bis (2,6-di-t-butylbenzene, etc. It may contain 20% by weight or less of a coloring agent composed of organic or non-pigmenting, and may contain 40% by weight or less of dioctyl dicarboxylate, behenyl phthalate or tricresol phosphate plasticizer. The dye precursor may be contained in an amount of 30% by weight or less. In the blue-violet laser photosensitive composition of the present invention, the negative-sensitive composition may contain, for example, the sensitizer, an alkali-soluble resin, the crosslinking agent, and light. The acid generator is a negative photosensitive composition of the basic composition N2). <Negative photosensitive composition (N2) > Sulfate ether phosphoimidazole basic type feeling is better, such as 2,6-phenol) Machine-dyed benzene and other light resin (-61 - (58) (58) 1354864 In the present invention, the alkali-soluble resin constituting the negative photosensitive composition (N 2 ) is produced by the action of the sensitizer when the photosensitive composition is irradiated with active light. The agent generates an acid, and a resin having a crosslinked structure is formed by using a crosslinking agent described later, and the alkali-soluble resin is, for example, a phenol-containing warp-based resin and a residue-containing ethylenic resin, etc. The negative photosensitive composition ( In the case of N2), for example, a phenol resin such as a polyvinyl phenol resin, a phenol resin, a resol resin, a copolymer resin such as a phenolic hydroxyl group-containing acrylic acid derivative, or a polyvinyl acetal resin having a phenolic hydroxyl group; The hydroxy resin is preferably a polyvinyl phenol resin, a phenol resin such as a phenol resin or a resol resin, and particularly preferably a polyvinyl phenol resin and a phenol resin. The polyvinyl phenol resin has, for example, an o-hydroxy group (α). Methyl)styrene ["(α-methyl)styrene" means "styrene" or / and ra_methylstyrene" the same as below], m-hydroxy (a-methyl)styrene, p-hydroxyl (α-methyl)styrene, dihydroxy(α-methyl)styrene, trihydroxy(α-methyl)styrene, tetrahydroxy(α-methyl)styrene, pentahydroxy(α-methyl)benzene One or more of hydroxy (α-methyl)styrenes such as ethylene or (α-methyl)styrene, having an alkoxy 'fluorenyl group, a decyloxy group, a propyleneoxy group, an aryloxy group, a halogen atom Other amino-based compounds such as (α-methyl) styrene, (meth)acrylic acid, (meth) acrylate, maleic acid, and yttrium imide, other than a hydroxyl group, in free radicals Polymerization or copolymerization is carried out in the presence of a polymerization initiator or a cationic polymerization initiator, or these styrene derivatives protected by a hydroxy group of a methyl group styrene are polymerized or copolymerized, and then the protecting group is removed. -62- (59) (59)1354864 The phenolic resin is, for example, phenol, o-cresol, m-cresol, p-formamidine, 2,5-xylenol, 3,5-xylenol, o-ethylphenol, M-ethyl benzoquinone, p-ethyl benzene, propyl benzoquinone, n-butyl phenyl hydrazine, tert-butyl phenol, 1-naphthoquinone, 2-caffeene, 4' 4:-biphenyl diol, double At least one of 酣a, pyrophyllin, isophthalic acid, hydroquinone, pyrogallol, 1,2,4-benzenetriol, fluorosorbate, etc. under acid catalyst, and for example Awake, aldehydes such as formaldehyde, acetaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, aldaldehyde, or at least one of ketones such as propyl ketone, methyl ethyl ketone, methyl isobutyl ketone, etc. Further, the resol phenol resin is subjected to polycondensation in the same manner, for example, by using an alkali catalyst instead of an acid catalyst. The weight average molecular weight of these phenol-containing hydroxy resins is from 10 to 5 Å, and 0 0 0. In the negative photosensitive composition (N2), when the crosslinking agent-based photosensitive composition is irradiated with active light, the alkali-soluble resin is formed into a crosslinked structure. The representative of the crosslinking agent has at least two The functional group is a methylol group, an alkoxymethyl group such as an alkoxymethyl group obtained by condensation-modifying an alcohol, or the like. Specifically, for example, a melamine resin in which melamine is condensed with formaldehyde, a benzoguanamine resin in which benzoguanamine is condensed with formaldehyde, a glycoluril resin which is polycondensed with glycoluril and formaldehyde, and a urea which is condensed with urea and formaldehyde. Two kinds of resins, such as resin, melamine, benzoguanamine, glycoluril or urea, which are copolymerized and condensed with toluene and a modified resin in which the methylol group of these resins is modified by alcohol condensation. These are sold, for example, under the trade names of "Sytech" by Mitsui Scitech, and "Nikalac" by ChemicaI. -63- (60) 1354864 The crosslinking agent also contains an epoxy group-containing polyglycidyl ether compound obtained by reacting a polyhydroxy compound constituting a repeating unit of a so-called epoxy resin with propane, and a polycarboxylate. A polyglycidylamine compound obtained by the reaction of an acidified chloropropane and a polyglycidylamine compound obtained by reacting polyamined epichlorohydrin, and the like, from a compound to a high molecular weight compound. Specific examples of such polyglycidyl ether compounds are polyethylene glycol glyceryl ether type epoxy, bis(4-hydroxyphenyl) diglycidyl ether 'bis(3,5-dimethyl-4-phenyl) ) bis glycidyl ether type bisphenol F diglycidyl ether type epoxy, bisphenol A diglycidyl epoxy, tetramethyl bisphenol A bis glycidyl ether type epoxy, additional alkane bisphenol A Diglycidyl ether type epoxy, phenol novolac lacquer, and the like. Among these polyglycidyl ether compounds, a carboxyl group obtained by reacting a residual hydroxyl group or a divalent oxygen compound can be introduced. Specific examples of the polyglycidyl esterification include a diglycidyl ester type epoxy of hexahydrophthalic acid, an oligoglycidyl type epoxy of an acid, and the like, and a polyglycidylamine compound is bis(4-aminophenyl). Methane diglycidylamine type cycloglycolic acid triglycidylamine type epoxy or the like. In the present invention, when the photoreceptor photosensitive composition constituting the negative photosensitive composition (N 2 ) is irradiated with active light, an active compound of an active species is generated by the above-mentioned action, and the photoacid generator halogen-substituted chain A halogen-containing key salt such as an alkane or a halomethylated S-triazine derivative, and a compound such as a sulfonate are preferable. For example, an epoxy and diacid generating sensitizer of an epoxy compound and a condensate and a low molecular weight diepoxy epoxy, an oleyl ether epoxy epoxy resin and an acid anhydride compound. For example, there is a substance, a compound of -64 - (61) (61) 1354864. The halogen-substituted alkane of the halogen-containing compound and the tooth-methylated S-tri-D-Qin derivative are, for example, the aforementioned negative photosensitive composition (N). ,) The photopolymerization initiator is the same as listed. The gun salt is, for example, an ammonium salt such as tetramethylammonium bromide or tetraethylammonium bromide; diphenyliodonium hexafluoroarsenate, diphenyl iodine tetrafluoroborate, diphenyl iodine gun toluene Sulfonate, diphenyl iodide sulfonate, dicyclohexyl iodide hexafluoroarsenate, dicyclohexyl iodide tetrafluoroborate, dicyclohexyl iodide p-toluenesulfonate, dicyclohexyl iodide Iodine gun salt such as sulfonate sulfonate; triphenylsulfonium hexafluoroarsenate, triphenylsulfonium tetrafluoroborate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium sulfonate, tricyclic Hexyl hexafluoroarsenate, tricyclohexyl fluorene tetrafluoroborate, tricyclohexyl fluorene p-toluene sulfonate, tricyclohexyl sulfonium sulfonate and the like. Specific examples of the compound include bis(phenylsulfonyl)methane, bis(p-hydroxyphenylsulfonyl)methane, bis(p-methoxyphenylsulfonyl)methane, and bis(α-naphthylsulfonate). Mercapto) methane, bis(β-naphthylsulfonyl)methane, bis(cyclohexylsulfonyl)methane, bis(t-butylsulfonyl)methane, phenylsulfonyl (cyclohexylsulfonyl) a bis(sulfonyl)methane compound such as methane; phenylcarbonyl(phenylsulfonyl)methane, naphthylcarbonyl(phenylsulfonyl)methane, phenylcarbonyl(naphthylsulfonyl)methane' cyclohexyl a carbonyl group such as carbonyl (phenylsulfonyl)methane, tert-butylcarbonyl (phenylsulfonyl)methane, phenylcarbonyl (cyclohexylsulfonyl)methane, phenylcarbonyl (t-butylcarbonyl)methane ( Sulfhydryl)methane compound; bis(phenylsulfonyl)diazomethane, bis(p-hydroxyphenylsulfonyl)diazomethane, bis(p-methoxyphenylsulfonyl)diazomethane, double (α-naphthylsulfonyl-65-(62) (62)1354864) Diazomethane, bis(β·naphthylsulfonyl)diazomethane, bis(cyclohexyl) Sulfhydryl)diazomethane, bis(t-butylsulfonyl)diazomethane, phenylsulfonyl (cyclohexylsulfonyl)diazomethane, bis(sulfonyl)diazomethane compound; benzene Carbonyl (phenylsulfonyl) diazomethane, naphthylcarbonyl (phenylsulfonyl) diazomethane, phenylcarbonyl (naphthylsulfonyl) diazomethane, cyclohexylcarbonyl (phenylsulfonyl) a carbonyl group such as diazomethane, tert-butylcarbonyl (phenylsulfonyl)diazomethane, phenylcarbonyl (cyclohexylsulfonyl)diazomethane, phenylcarbonyl (t-butylcarbonyl)diazomethane (sulfonyl) diazomethane compounds and the like. In the negative blue-violet laser photosensitive composition of the present invention, the content ratio of the sensitizer, the alkali-soluble resin, the crosslinking agent, and the photo-acid generator constituting the negative photosensitive composition (N2) In the case of 100 parts by mass of the alkali-soluble resin, the sensitizer is contained in an amount of 0.1 to 30% by weight, the crosslinking agent is contained in an amount of 1 to 80% by weight, and the photoacid generator is contained in an amount of 0.001 to 30% by weight, more preferably The sensitizer contains 0.5 to 20% by weight, the crosslinking agent contains 5 to 60% by weight, and the photoacid generator contains 0.005 to 10% by weight. In the blue-violet laser photosensitive composition of the present invention, the negative photosensitive composition contains, for example, the negative sensitizing agent containing an acid crosslinkable group resin and a photoacid generator as a basic composition. (N3). <Negative photosensitive composition (N 3 ) > In the present invention, the acid-containing crosslinkable resin constituting the negative photosensitive composition (N3) is obtained by irradiating the photosensitive composition with active light. Pre-66- (63) (63) 1354486 The use of a photoacid generator forms a resin having a crosslinked structure. The acid crosslinkable group may, for example, be a methylol group, an alkoxymethyl group, a vinyl ether group or an epoxy group. The acid-crosslinkable group-containing resin containing the acid-crosslinkable group is not particularly limited as long as it contains two or more of these acid-crosslinkable groups in the molecule, and specifically, for example, the above-mentioned negative-type photosensitive composition The phenolic resin such as a phenol resin such as a soluble resin, a phenol resin such as a resol resin, and a phenolic hydroxyl group of a phenolic hydroxyl group-containing resin such as a polyvinyl phenol resin, which are listed in (N 2 ), are etherified or esterified. The resin of the acid crosslinkable group and at least a part of the carboxyl group of the carboxyl group-containing vinyl resin of the alkali-soluble resin exemplified as the negative photosensitive composition (N j ) are esterified, and the acid crosslinkable group is introduced. A resin or a resin obtained by polymerizing or copolymerizing the vinyl monomer having an acid crosslinkable group and introducing the acid crosslinkable group. Among them, preferred are phenolic resins or polyvinyl phenol resins, and it is particularly preferred to be based on phenolic resins. The resin containing an acid crosslinkable group means a resin containing an acid crosslinkable group and a resin having no acid crosslinkable group introduced therein. In the present invention, the photoacid generator constituting the negative photosensitive composition (N3) is, for example, the same as the photoacid generator exemplified for the negative photosensitive composition (N2). In the blue-violet laser photosensitive composition of the present invention, the content ratio of the sensitizer, the acid-crosslinkable group-containing resin, and the photoacid generator constituting the negative photosensitive composition (n3) is as described above. When the acid-crosslinkable group-containing resin is 100 parts by mass, the sensitizer is contained in an amount of 0.1 to 30% by weight, and the photoacid generator is contained in an amount of 0.001 to 30% by weight, more preferably the sensitizer is contained in an amount of 0.5 to 20% by weight. % and the above photoacid generator contain 0.005 to 10 weight-67-(64) 1354864% by volume. The negative photosensitive composition (Ν), the negative composition (N2), and the negative photosensitive composition (N3) of the present invention may contain, for example, a coating property improver, an adhesion improver, and Sensitively, various additives such as a photosensitive composition such as a lipid stabilizer, a colorant, and a development improver. The blue-violet laser photosensitive composition of the present invention has a maximum peak of spectral sensitivity in a wavelength range of 3 90 to 90, more preferably a maximum peak having a spectral sensitivity in a wavelength range of 420 nm, and has a spectral range in the aforementioned wavelength range. At the time of the maximum peak of the sensitivity, the sensitivity of the sensed light to the laser light having a wavelength of 390 to 43 Onm is lowered, and the characteristic of the safety lamp under the maximum peak color lamp having the spectral sensitivity exceeding the above-mentioned wavelength range tends to be lowered. In the present invention, the maximum peak of the spectral sensitivity is a photosensitive image of the photosensitive composition layer on the substrate, as described in, for example, "PhotoPolymer technology" (issued by Yamaoka Yasushi, published by Industrial News, Inc., p. 262). The material sample is formed, and the light split by the light source such as a xenon lamp or a tungsten lamp is linearly changed to the exposure wavelength by the minute measuring device, and the exposure intensity is normalized in the vertical axis direction. After the exposure, the development process is performed to obtain a corresponding image. The image of each exposure waviness is calculated from the height of the image to form an image whose horizontal axis of exposure is the wavelength, and the vertical axis is the maximum peak of the sub-curve of the exposure energy. The blue-violet laser photosensitive composition of the present invention has a wavelength of 41 and is preferably a good agent, and a commonly used 4 3 0 n m is 400. In the tendency of the unlighted group, the yellow year 曰 形成 形成 形成 形成 形成 形成 形成 形成 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 68 68 68 68 68 68 68 68 68 68 68 68 68 68 68 68 68 68 68 68 68 68 68 The ratio [S41c/S45()] of [S41〇(mJ/cm2)] to the minimum exposure amount [S450 (mJ/cm2)] of the image formable wavelength of 450 nm is 0.1 or less, more preferably 0.05 or less. When the above [S4l〇/S 4 5 0] exceeds the above range, it is difficult to have both a blue-violet laser sensitivity and a safety lamp characteristic under a yellow lamp. The minimum exposure amount [S41Q] at which the image can be formed at a wavelength of 410 nm and the minimum exposure amount at which the image can be formed at a wavelength of 450 nm [S45C] is the maximum peak in which the spectral sensitivity is measured by the spectroscopic sensitivity measuring device, and the image height is Calculating the exposure energy of the image that can be formed, and changing the minimum exposure amount when the image can be formed under the most appropriate development conditions determined by the development conditions such as the type of the developing liquid, the imaging temperature, and the development time. The most suitable development conditions are generally the use of an alkali photographic solution of Ρ Η 1 1 to 14 at a temperature of 25. (: Conditions of immersion for 0.5 to 3 minutes. <Image Forming Material (A) and Image Forming Material (Β)> The negative blue-violet laser photosensitive composition of the present invention can be used to form the negative blue-violet laser photosensitive image forming material of the present invention. (A) (hereinafter sometimes referred to simply as image forming material (A)). The image forming material (a) is usually obtained by dissolving or dispersing the above-mentioned respective components in a coating liquid of a suitable solvent, and then applying it on the dummy support film, after drying, if necessary, covering with a coating film to form a photosensitive property. Formed on the surface of the composition layer. Such an image forming material (A) is, for example, a dry film resist material or the like. The above image forming material (A) can be used to form the negative blue-violet laser-sensitive image forming material (B) of the present invention (hereinafter sometimes referred to simply as image-69-(66) 1354864 forming material (B) ). The image forming material (B) usually has two types of methods. When the photosensitive composition of the image forming material (A) is covered with a coating film, the coating film is peeled off and laminated to be processed. The other system is produced in the following order (1) to (3). 1) The components of the negative blue-violet laser photosensitive composition are dispersed in a suitable solvent to form a coating liquid. (2) Directly coated on a substrate and then dried. (3) A layer of the present-type blue-violet laser photosensitive composition is formed on the substrate to be processed. The image forming material (B) is applied to the following image forming mode. The image forming material (B) is subjected to scanning exposure at a wavelength of 390 to 43 Onm, and subjected to development processing to form an image. As the image forming material (A) of a dry film photoresist material or the like, the pseudo support film is, for example, a polyethylene terephthalate film, a poly(ethylene terephthalamide film), a polypropylene film, or a polystyrene film. When it is known that these have the required agent properties or heat resistance when the image forming material (A) is produced, the photosensitive composition can be directly applied onto the dummy support film. Image shape of the invention (A) 'The solvent resistance or heat resistance of these films is poor, and the layer can be formed on a film-forming composition layer having a release property such as a polytetrafluoroethylene film or a release film. A false support film such as solvent resistance or heat resistance is laminated thereon. Thereafter, the release film is peeled off to form an image forming material (A). In addition, the high resolution is particularly sought to support the film haze (Haze) 値 ideally 〇. 〇1~].8%, and the false thickness is ideally 10~30μπι. The fabrication layer is made on the substrate side. (Soluble method of dissolving or being processed by the negative method. The amine film and film for laser light replacement) are coated with a solution, for example, when the invention is poorly sensitized, the false support film -70-(67)(67)1354864 The solvent to be used in the coating liquid is not particularly limited as long as it has sufficient solubility for the component to be used and can impart good coating properties, and examples thereof include methyl cellosolve, ethyl solvent, and methyl cellosolve. Soluble solvent such as acetate, ethyl cellosolve acetate; propylene glycol monomethyl ether, propylene glycol monoacetic acid, propylene glycol monobutyl ether 'propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol single Propylene glycol solvent such as butyl ether acetate or dipropylene glycol dimethyl ether; butyl acetate, amyl acetate, ethyl butyrate, butyl butyrate, dimethyl oxalate, ethyl pyruvate, ethyl-2 - an ester solvent such as hydroxybutyrate, ethyl acetoacetate, methyl lactate, ethyl lactate or methyl 3-methoxypropionate; an alcohol such as heptanol, hexanol 'diacetone alcohol or decyl alcohol Solvent; ketone solvent such as cyclohexanone or methylpentanone; dimethylformamide, dimethyl a highly polar solvent such as acetamide or N-methylpyrrolidone or a mixed solvent thereof, and an aromatic hydrocarbon may be added to these solvents, etc. The amount of the solvent used is usually from 1 to 20 by weight based on the total amount of the photosensitive composition. The coating method may be a known method, such as rotary coating, steel brush coating, spray coating, dip coating, air force coating, roller coating, blade coating, sieve coating, and the like. A method of coating a curtain, etc. The coating amount is preferably from the viewpoint of image formation described later and subsequent processing such as etching or plating, and the dry thickness is preferably Ο.ίμηι or more 'more preferably lOpm or more, and From the viewpoint of sensitivity, it is preferably 200 μm or less, more preferably 1 〇〇μηι or less. The temperature of the drying medium used at this time is, for example, 30 to 150 ° C, preferably 40 to 110 ° C, The drying time is, for example, 5 seconds to 60 minutes, preferably 1 second to 3 minutes. In addition, when the resolution is obtained, the surface roughness of the coating film and the contact surface of the photosensitive composition are Ra 〇" 5μιη Hereinafter, Rmax is -71 - (68) 1354864, and the diameter of the coating film is 80 μm. The above /m2 or less is preferable. It can be used as an image test of a dry film photoresist material or the like, and the image forming material (A) is laminated on the surface of the photosensitive composition layer to be covered with a coating film to be polyethylene. When the film, the polypropylene film, and the polytetrafluoroethylene film are covered with the photosensitive film of the image forming material (A), the coating film is peeled off, and the photosensitive composition coating liquid is directly applied or dried. The substrate to be processed (B) is subjected to exposure by exposure of a photosensitive composition layer of Ray, and a developed image is used as a photoresist, and a pattern such as a circuit or an electrode is formed by etching or plating, for example, Copper 'zinc, tin, lead, nickel and other metal plates. Generally can be made of polyimide resin, bismaleimide resin, non-phenol resin, melamine resin and other thermosetting resin; carbonate resin 'poly resin, acrylic Resin, vinyl resin, polyvinyl chloride resin, polyolefin resin resin, etc.; inorganic materials such as paper, glass, alumina, and calcium carbonate; or glass cloth substrate epoxy resin, paper substrate epoxy resin Paper-based materials The thickness is 0.02 to 10 mm, and the metal foil such as the metal or the metal oxide such as indium oxide or tin oxide is heated or laminated, or the number of fish eyes used is 5 pieces of material (A). Preferably, the film is formed, and the film can be made into a known film. The side of the composition layer is laminated by pressurization or the like, and the process of forming the above-described light of the present invention is performed, and the resulting negative-form work can be used on its surface, inscriptions, gold, silver, and for example, rings. Composite materials such as oxy-resin, saturated polyester resin, benzene saturated polyester resin, polyacrylamide resin, polyphenylene, fluororesin, etc., on the surface of composite support such as thermoplastic yttrium oxide, barium sulfate, grease, glass non-woven phenol resin Tin, indium oxide doped oxygen sputtering, evaporation, electroplating -72- (69) (69) I354864 and other methods for treating metals, etc., forming a metal laminate of a conductive layer having a thickness of 1 to 100 μm. When the photosensitive composition coating liquid is directly applied and dried to produce the image forming material of the present invention, the photosensitive composition layer formed on the substrate to be processed can be formed to prevent the cause An oxygen blocking layer for suppressing polymerization of oxygen of the photosensitive composition, or a protective layer for adjusting a light transmittance adjusting layer such as a wavelength range of sensitivity. The oxygen blocking layer which is constituting the oxygen barrier layer, for example, is soluble in water or a mixed solvent of water and a water-miscible organic solvent such as an alcohol or tetrahydrofuran, and specifically, for example, polyvinyl alcohol and a part thereof acetalized product thereof a cationically modified product such as a quaternary ammonium salt or a derivative such as an anionic modified product such as sodium sulfonate, such as polyvinylpyrrolidone, polyethylene oxide, methylcellulose, carboxymethylcellulose, or hydroxyethylcellulose. , hydroxypropyl cellulose, and the like. Among them, polyvinyl alcohol and its derivatives are preferred from the viewpoints of oxygen barrier properties, etc., and from the viewpoint of adhesion to a photosensitive composition, etc., polyvinylpyrrolidone or vinylpyrrolidone-vinyl acetate copolymerization is preferred. A vinylpyrrolidone polymer such as a substance. The oxygen barrier layer is preferably a mixture of 1 to 20 parts by weight, preferably 3 to 15 parts by weight, based on the weight of the polyvinyl alcohol or its derivative, of the polyvinylpyrrolidone polymer. The oxygen barrier layer preferably contains an organic acid such as succinic acid or an organic acid salt such as ethylene-amine tetraacetic acid, and may contain a nonionic such as polyethylene oxide alkyl phenyl ether or the like. A surfactant such as an anionic or alkyltrimethylammonium chloride such as an alkylbenzenesulfonate, a defoaming agent, a coloring matter, a plasticizer, a cerium adjusting agent, or the like. These total contents are preferably -73 - (70) (70) 1,354,864% by weight or less, more preferably 5% by weight or less. The oxygen barrier layer is formed by the same coating method as the above-mentioned photosensitive photo-composition layer in the form of a solution of water or a mixed solvent of water and a mixed organic solvent, and the coating amount is a dry film thickness of 1 to L〇g/m2, more preferably 1.5 to 7 g/m2. In the light-transmitting property-adjusting layer, the polymer binder contains a light-absorbing pigment in the visible light region such as a coumarin dye, and in this case, the polymer binder is polyvinyl alcohol exemplified as the oxygen barrier layer or The derivative or the polyvinylpyrrolidone polymer can form a protective layer having oxygen blocking energy and light transmittance adjusting energy. The image forming material (B) having the blue-violet laser photosensitive composition layer of the present invention on the substrate to be processed has a photosensitive composition layer composed of the negative photosensitive composition (N!) In this case, in order to have a residual film ratio-exposure amount characteristic or the above-described developing speed-exposure amount characteristic, a polymerization inhibitor of the negative photosensitive composition (N i ) constituting the photosensitive composition layer is used. The content is preferably from 5 to 60 ppm, and the lower limit of the polymerization inhibitor content is preferably 10 ppm and the upper limit is 50 ppm. <Image Forming Method> The image forming material (B) of the present invention having the blue-violet laser photosensitive composition layer of the present invention on the substrate to be processed is formed by the image forming material (A) In the case of constituting the material layer, after the dummy support film is peeled off, or the photosensitive composition coating liquid is directly applied, and the photosensitive composition layer is dried to form a photosensitive composition layer, when the protective layer is removed, the protective layer is peeled off. Sense-74-(71) (71)1354864 The optical composition layer is subjected to scanning exposure by using laser light as an exposure light source, and then subjected to development processing to form a negative image on the substrate to be processed. The laser exposure light source is, for example, a HeNe laser, an argon ion laser, a YAG laser, a HeCd laser, a semiconductor laser, a ruby laser, etc., and is particularly preferably a laser light that generates a blue-violet range of a wavelength range of 390 to 430 nm. The light source 'is not particularly limited, and is specifically, for example, an indium gallium nitride semiconductor laser which generates a vibration edge of 4 10 nm. The scanning exposure method of the laser light source is not particularly limited, for example, a plane scanning exposure mode, an outer drum scanning exposure mode, an inner drum scanning exposure mode, etc., and the laser output light intensity is preferably 1 to 100 mW. More preferably, it is 3 to 70 mW, and the oscillation wavelength is preferably 3 90 to 430 nm, more preferably 400 to 420 nm, and the electron beam spot diameter is preferably 〇5 to 30 μm, more preferably 1 to 20 μm, and the scanning speed is better. The scanning density is 50 to 500 m/sec, more preferably 1 to 400 m/sec, and the scanning density is preferably 2,000 dpi or more, more preferably 4,000 dpi or more. The development processing after the above laser scanning exposure is preferably carried out using an aqueous developing solution containing a base component and a surfactant. The alkali component is, for example, sodium citrate, potassium citrate, lithium niobate, ammonium citrate, sodium metasilicate, potassium metasilicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, sodium hydrogencarbonate, Inorganic alkali salt such as potassium carbonate, sodium diphosphate, sodium tripolyphosphate, second o-acid, third peat, sodium borate, potassium borate, ammonium borate; monomethylamine, dimethylamine, trimethylamine, single Organic amine compounds such as ethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, monobutylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, etc. The concentration used is 0.1 to 5 -75- (72) (72) 1354864% by weight. The above surfactant is, for example, the same surfactant as that of the above-mentioned photosensitive composition. Among them, a nonionic, anionic or amphoteric surfactant is preferred, and a betaine-type compound of an amphoteric surfactant is particularly preferred. The surfactant is preferably used in a concentration of 0.0001 to 20% by weight, more preferably 0.0005 to 10% by weight, particularly preferably 0.001 to 5% by weight. If necessary, the developing solution may contain, for example, isopropanol or benzyl alcohol. , ethyl cellosolve, butyl cellosolve 'phenyl cellosolve, two diol, diacetone alcohol and other organic solvents. Further, the pH of the developing liquid is preferably from 9 to 14 , more preferably from 1 1 to 14. The development is generally performed by immersing the image forming material in the above-described developing solution or spraying the developing liquid onto the image forming material, such as from 1 Torr to 50 ° C, more preferably The temperature is 15 to 4 5 °c for 5 seconds to 10 minutes. After the development process, the negative image formed is irradiated with a light source such as a high pressure mercury lamp or/and heat-treated at a temperature of, for example, 140 to 160 ° C to improve the resistance of the photoresist. [Embodiment] [Embodiment] Hereinafter, the present invention will be more specifically described by way of Examples, and the present invention is not limited to the embodiments described below. Example 1 to 2, Comparative Example 1 -76- (73) (73) 1354864 The following sensitizers (1) to (6) 'ethylenically unsaturated compound (1), photopolymerization initiator (1), The alkali-soluble resin (1) to (2) and the other components (1) to (3) are added to 100 parts by weight of a mixed solvent of methyl ethyl ketone/isopropanol (weight ratio: 8/2) according to the formulation of Table 1. The coating liquid was prepared by mixing at room temperature. The coating liquid was applied onto a pseudo support film of polyethylene terephthalate (thickness: 19 μm) in an amount of 20 μm by using an applicator, and dried in an oven at 90 °C. A negative blue-violet laser-sensitive image forming material was prepared by forming a negative-type photosensitive composition (N!) layer of a polyethylene film (thickness 25 μmη) of the laminated film (><sensitizer> (1) The following compounds (maximum absorption of 3 6 5 nm / compound contained in the former # stomach)) (2) Compounds of the following compounds (maximum absorption of 3 86 nm / contained in the aforementioned θ ΙΠ) (3) The following compounds (maximum absorption of 3 89 nm / compound contained in the aforementioned stomach XI)) (4) The following compounds (maximum absorption of 3 78 nm / compound contained in the aforementioned gastric fistula) (5) The following compounds ( Maximum absorption of 4l4nm / compound contained in the former ruthenium) (6) The following compounds (maximum absorption of 3 65nm / compound contained in the former stomach XII) -77- (74)1354864

/C2H5 N , C2H5

-78- 1354864

-79-(76)1354864 &lt;Ethylene unsaturated compound&gt; Pair (1) The following compound (containing 2500 ppm of polymerization inhibitor methoxyphenol, Xinzhongcun Chemical Pharmaceuticals r BPE-500) (1) CH2 =CJ-〇(cH2CH20^<^~|—^^~C&gt;|CH2CH2〇)^-i=CH2 0 CH3 0 π^η=10 &lt;Photopolymerization Initiator&gt; Base, at (1) 2 , 2,-bis(o-chlorophenyl)-4,4,5,5,-tetraphenyldiimidazole (melting point 172 ° C, wavelength 1 · 5 4 Α X-ray refractive spectrum in the Bragg angle ( 20±〇.2°) 21.16. with maximum refraction peak) &lt;alkali-soluble resin&gt; (1) styrene/(meth)acrylate/n-butylmethylpropene/2- Ethylhexyl acrylate/2-hydroxyethyl methacrylate/methyl propylene copolymer (Morby 10/35/10/10/15/20, acid value 144 KOH·, weight average molecular weight 62,300, no Add polymerization inhibitor). (2) Copolymer as above (but polymerization of 500 MPa is added to inhibit p-methoxyphenol) &lt;Others&gt; (1) Colorless crystal violet reagent (2) Crystal violet reagent (3) p-methoxyphenol (additional portion) -80- (77) (77)1354864 In addition, the surface of the copper foil of the copper-clad laminate (thickness 1.5 mm, size 250 mm x 200 mm) of the polyimide foil coated with a 35 μm thick copper foil was used by Sumitomo 3M Co., Ltd. "Scotch" Blide SF" is polished by a sanding shaft and washed with water to dry the air stream and finish the surface. Then, after preheating in the oven of 60, the polyethylene film of the negative blue-violet laser photosensitive image forming material (A) produced above was peeled off, and the peeling surface was lightly used using a manual roller laminator. The film was laminated on the copper foil of the copper-clad laminate by a temperature of 100 ° C, a light pressure of 0.3 MPa, and a lamination speed of 1.5 m/min to produce a negative photosensitive composition (N,) on the copper-clad laminate substrate. A negative blue-violet laser photosensitive image forming material (B) of the layer. The content of the polymerization inhibitor of the photosensitive composition (N) layer of each of the negative blue-violet laser-sensitized image-forming material (B) obtained was determined by gas chromatography as follows. Table 1 shows. &lt;Measurement of Content of Polymerization Inhibitor&gt; The acetone standard solution of p-methoxyphenol (each 〇, 1, 3, 0' 2 0, 50 ppm) was determined by gas chromatography of the following conditions. Check line. Further, the photosensitive composition layer of the resist image forming material (B) was dissolved in acetone, and the prepared 10 wt% solution was quantified by gas chromatography as described below under the following conditions. &lt;conditions&gt;

Clumn: HP-5 (0.32mmI.D.x30m d_f.0.25pm) carrier; He 2.0mL/min -81 - (78) 1354864

Separation ratio; 1 /1 Ο injection inlet; 2 5 0 °C detector; FID 320 °C supply phase, 5〇C-2〇C/rnin-300°C ( lOrnin) injection amount; 10% by weight acetone solution The photosensitive composition layer of each of the obtained negative blue-violet laser photosensitivity patterns ') was measured for the minimum exposure amount of the end point J 9 0 % or more by the following method, and the results are shown in Table 1. &lt;End point&gt; The photosensitive composition layer of the image forming material obtained was measured at 25 ° C for spraying a developing solution at M15 Mpa. The sodium aqueous solution was until the composition layer was completely dissolved. Time &lt;minimum exposure amount&gt; The center wavelength is 4〇5 nm, the laser output force is 5 mW ("NLHV500C" manufactured by Nichia Corporation), 2 mW, electron beam spot diameter 20 μηι, and the electron beam donating speed is changed, The obtained image forming material (Β) is scanned and exposed. Then, using 二.1 5Mpa to spray the developing solution with a 2% by weight sodium carbonate aqueous solution, and taking the end point of 1.5 times, the test image of 〇.5mmx〇.5mm was generated. Each scan was calculated using Keteretencol. "The residual film ratio of the Alpha-Step film thickness is 90% of the exposure amount. : The formed material (B residual film rate becomes 7.5% by weight of the laser light source in the exposure state, and the scanning interval is scanned by the image illuminance: The composition layer is 0.7 at 25 ° C. § Under the conditions of spray display, 5 〇〇 测定 - 82 - (79) (79) U54864 From the above-mentioned exposure amount and residual film rate, calculate the above formula ( 1) γ 値 and α 値 of the above formula (2), and the results are shown in Table 1. &lt; γ 値, α 値 > The residual film rate was obtained from the exposure amount and residual film ratio obtained above [t (% } The residual film rate-exposure curve plotted against the logarithm of the exposure amount [l〇gE (mJ/cm2)] is defined by the point connecting the residual film rate of 15% and the 80% point ^γ1ο8Ε + δ (refer to Fig. 1) Calculate γ 値. The dissolution rate (1 〇〇 - t ( % )) calculated from the residual film ratio obtained above is divided by the development time [T ( sec )] [s={100-t}/T (% /sec)] The development speed-exposure curve of the plot, the point connecting the maximum imaging speed of 80% and the point of 2〇% s = -alogE+p The result of calculating the α値' by the formula (see Fig. 2) is shown in Table 1. In addition, the photosensitive composition layer of the obtained image forming material (Β) was evaluated by the following method for the maximum peak of the spectral sensitivity and the wavelength of 410 nm. The ratio of the minimum exposure amount of the image [S4io(mJ/cm2)] to the minimum exposure amount of the image at 450 nm [S450 (mJ/cm2)] [S410/S450] and the safety light under the yellow lamp The results are as shown in Table 1. &lt;Maximum peak of spectral sensitivity&gt; The image forming material (B) was cut into a sample of 50 mm x 60 mm, and a refracting spectroscopic irradiation device ("RM-23" manufactured by Narumy Co., Ltd.) was used. ("UI-50〗 C" manufactured by Niumei Electric Co., Ltd.) is a light source, and the light split by the wavelength range of 305 to 650 nm is set to be linear in the horizontal axis. -83-(80) (80)^354864 For the longitudinal direction, the exposure intensity is logarithmicly changed, and the exposure is irradiated by 1 〇 second. Then, the sodium sulphate of 0.7% by weight at 25 ° C is sprayed with 〇.15 Mpa. The aqueous solution is spray-developed at a time of 1.5 times, and an image corresponding to the sensitivity of each exposure wavelength can be obtained. The exposure energy of the image can be calculated from the height of the image, and the horizontal axis is read as the wavelength. The vertical axis is the maximum peak of the spectral sensitivity curve obtained by the reciprocal of the exposure energy. &lt;[S41〇/S45〇]&gt; With the above method, the wavelength is changed in the wavelength range of 350 to 650 nm, and the minimum exposure amount of the image which can be formed at the wavelength of 4 1 〇 nm at the time of exposure and development [ The minimum exposure amount [S45〇(mJ/cm2)] of S41〇(mJ/cm2)] and the wavelength of 450nm can be formed, and the ratio [S41G/S45()] is calculated and evaluated by the following criteria. A: S410/S45Q is 〇.〇3 or less. B: S410/S450 exceeds 〇·〇3 and is 0.05 or less. C: S410/S450 is more than 〇_〇5 and less than 0.1. D: S410/S45Q exceeds 〇·1. &lt;Safety under yellow light> The image forming material (Β) is placed in a yellow light (conditions for blocking wavelength light of about 47 nm or less) for 1 minute, 2 minutes, 5 minutes, 10 minutes, After 20 minutes and 30 minutes, scanning exposure and development processing were performed as described above, and the time until the image was changed was compared with the above, and evaluated by the following criteria. -84- (81) (81) 1354864 A: 20 minutes or more. B: 10 minutes or more, less than 20 minutes. C: 1 minute or more, less than 10 minutes. D: Less than 1 minute. With respect to the photosensitive composition layer of the obtained image-forming material (B), the resolution and the squareness were evaluated by the following methods, and the results are shown in Table 1. &lt;Resolving property&gt; A laser light source ("NLHV500C" manufactured by Nichia Chemical Industry Co., Ltd.) having a center wavelength of 405 nm' laser output of 5 mW was used, and the image illuminance was 2 mW, the electron beam spot diameter was 20 μm, and the electrons were changed. The beam scanning interval and the scanning speed 'scan and expose the photosensitive composition layer of the obtained image forming material (Β). Then, a 0.7% by weight sodium carbonate aqueous solution at 25 ° C for 15 ° C was sprayed with 〇.15 Mpa, and spray development was performed at a time point of 1.5 times, so that a line having a width of 20 μm and a length of 0.2 cm was formed at intervals of 20 μm. The 20 arranged images, at which time the reproducibility of the image line width is evaluated by the following criteria. 〇: The line width of 20μηι can be reproduced. X: The line width is greater than 20 μm or less than 20 μm. &lt;Rectangularity&gt; As with the resolution, an image having a line width of 20 μm and a length of 0.2 cm arranged at intervals of 20 μΐ is generated, and the sharpness of the image line at this time is evaluated by the following criteria. 〇: A sharp angled rectangle with no pull. -85- (82) 1354864 x: The angle is slightly rounded, or trapezoidal, or has a pull-up phenomenon. Comparative Examples 2 to 3 Using a commercially available dry film resist material (high sensitivity type) manufactured by Company A and a dry film resist material (high resolution type) manufactured by Company B, the photoresist image forming material (B) was produced in the same manner as described above. The same assessment is shown in Table 1. -86- 1354864

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Inch&quot;5F 〇〇VV ς〇 inch ί·ιζ I SICNI —Ml OIOJI SQOI so § 〇〇VV 〇Q inch m 11.9 1^1 inch·e un ΟΙΟΌ i § 〇〇VV ΙΟΟΙ6ΙΓΟΙ Q.el 9//inch Un L-9 Qlcsl ΟΙΟΌ so es i— § 0 inch 〇〇VV I.6T nm un L-9 QS ΙΟΟΌ SO § § Βΐϋΐ Η Ν /-\ /·&quot;-\ /-&quot;-Ν /·* &quot;·\ Η OJ CO inch νο fi®^^ 1M _1 _Mongo ii-lM lgls〕/F§I (su)螌驾1-KI围 ηνιμιτ§1ι^ι1φι g} iphNISK (loll X) IMNSml (Shame Moving Qjfm) 1 _·1· §__)(0 §_s)e (φ}_ϋ)ω_Stupid §_βδι laigxl) ^1—a lallgwlXI) 粼lIrLnlKnl Acid Zhu M m -87- (84) (84 1354486 Industrial Applicability The negative blue-violet laser photosensitive composition of the present invention and the image forming material (A), the image forming material (B) and the image forming method using the same can be used for forming printing Etching or electroplating photoresist of a conductor circuit, an electrode processing substrate, or the like of a wiring board, a liquid crystal display element, a plasma display, a large-scale integrated circuit, a thin transistor, a semiconductor package, a color filter, an organic electroluminescence element, or the like, particular It is a direct depiction of blue-violet laser light with a wavelength of 3 90 to 4 30 nm. The disclosure of the specification of the present invention is based on the entire contents of the Japanese Patent Application No. 2003-332626 (filed on September 25, 2003) and Japanese Patent No. 2003-344636 (filed on October 2, 2003). The contents of the manual. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a graph showing the residual film ratio-exposure amount of the blue-violet laser photosensitive compositions of Examples 1 to 2 and Comparative Examples 1 to 3 of the present invention. Fig. 2 is a graph showing the development speed-exposure amount of the blue-violet laser photosensitive compositions of Examples 1 to 2 and Comparative Examples 1 to 3 of the present invention. -88-

Claims (1)

1354864 Announcement this too. V: '&quot;2~2~1 Cui Wei 曰 Amendment I I Patent No. 093128914 Patent application Chinese patent application scope amendments Amendment of September 22, 100, the patent application scope 1. A negative The blue-violet laser photosensitive composition is characterized in that the minimum exposure amount of the residual film rate of 90% or more is 40 mJ/cm 2 or less by exposure of blue-violet laser light, and the residual film ratio of the exposed portion [t (%) )] The logarithm of the exposure amount of blue-violet laser light [logE (mJ/cm2)] is plotted as follows: the residual film rate-exposure curve is 15% of the residual film rate and the 80% point is connected to the following The γ 直线 of the straight line of the formula (1) is 4. ΟχΙΟ 2 or more, wherein the sensitizer is a sensitizer represented by at least the following general formula (XII), t = 7 logE + 6 ( 1 ) (In the general formula (XII), the rings D and E are each independently an aromatic hydrocarbon ring or an aromatic heterocyclic ring, and the ring D and the ring E are bonded to each other to form a N-containing bonding ring. In the general formula (XII), the linking group L represents a linking group containing an aromatic hydrocarbon ring and/or an aromatic hetero ring, and the linking group L and the N group are bonded by the aromatic hydrocarbon ring or the aromatic heterocyclic ring, and η represents An integer of 2 or more, the ring D Ε and the linking group L may have a substituent which may be bonded to each other to form a ring). 2. A negative blue-violet laser photosensitive composition characterized by exposure of blue-violet laser light, so that the residual film rate becomes 90% or more, and the minimum exposure of 1354486 is 4〇mJ/cm2 or less. The residual film rate of the part [t(%)] is calculated by dividing the dissolution rate [1〇〇·t(%)] by the development time [T(sec)] [s={100-t} /T(%/sec)] Point to 20% of the maximum development speed in the development speed and exposure curve of the logarithm of the exposure amount of blue-violet laser light [logE (mJ/cm2)] and 20% The α値 of the straight line of the following formula (2) to which the point is connected is 12 or more, wherein the sensitizer is a sensitizer represented by at least the following general formula (XII), s = -alogE + p (2) (In the general formula (X11), the rings D and E are each independently an aromatic hydrocarbon ring or an aromatic heterocyclic ring as a basic skeleton, and the ring D and the ring E are bonded to each other to form a N-containing bonding ring. In the general formula (XII), the linking group L represents a linking group containing an aromatic hydrocarbon ring and/or an aromatic hetero ring, and the linking group L and the N group are bonded by the aromatic hydrocarbon ring or the aromatic heterocyclic ring, n An integer of 2 or more is represented, and the ring D Ε and the linking group L may have a substituent which may be bonded to each other to form a ring). 3. The negative blue-violet laser photosensitive composition according to claim 1 or 2, wherein the photosensitive composition contains a compound having a maximum absorption in a wavelength range of 330 to 450 nm as a sensitizer. 4. A negative blue-violet laser photosensitive composition according to claim 3, wherein the 1354864 compound having a maximum absorption in the wavelength range of 330 to 450 nm is a dialkylamino benzene compound. 5·$α string Please refer to the negative blue-violet laser photosensitive composition of item 3 of the patent range 'The compounds having a maximum absorption in the wavelength range of 330 to 45 Onm are represented by the following general formulas (XI) and (χπΙ) At least one of the sensitizers, (xm) (In the general formulae (XI) and (XIII), the rings A, B, C, F, and G are each independently an aromatic hydrocarbon ring or an aromatic heterocyclic ring as the basic skeleton' ring A and ring. 8. The ring F and the ring g are bonded to each other to form a N-containing bond ring. In the general formula (XIII), R is an alkyl group which may have a substituent, and the rings A, B, C, F, G may have a substitution. The substituents may be bonded to each other to form a ring). 6. The negative blue-violet laser photosensitive composition 'in which ring 1' and the E system are independently selected from the group consisting of a benzene ring, a naphthalene ring, an anthracene ring, a sin ring, a mo ring, and the like, respectively. An aromatic hydrocarbon ring of an anthracene ring, a terpene ring and an anthracene ring, or a furan ring, a thiophene ring, a pyrrole ring, an oxazole ring, an isoxazole ring 'thia-3- 1354864 azole ring, an isothiazole ring, an imidazole ring The pyrazole ring, the furazolium ring, the triazole ring, the pyran ring, the thiadiazole ring, the oxadiazole ring, the pyridine ring, the pyridazine ring, the pyrimidine ring and the aromatic heterocyclic ring of the pyrazine ring are basic skeletons. The linking group L contains one or two or more rings selected from the above aromatic hydrocarbon ring and aromatic hetero ring, and when two or more such rings are contained, these ring systems are directly bonded or bonded via a valence of two or more valences. Come to the key. ' 7. The negative blue-violet laser photosensitive group φ of the fifth aspect of the patent application, wherein the rings A to G are independently selected from the group consisting of a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a ring. An aromatic hydrocarbon ring of an anthracene ring, a terpene ring and an anthracene ring, or a furan ring, a thiophene ring, a pyrrole ring, an oxazole ring, an isoxazole ring, a thiazole ring, an isothiazole ring, an imidazole ring, a pyrazole ring, The aromatic heterocyclic ring of the furazan ring, the triazole ring, the pyran ring, the thiadiazole ring, the oxadiazole ring, the pyridine ring, the pyridazine ring, the pyrimidine ring and the pyrazine ring is a basic skeleton, and the linking group L contains 1 When two or more rings selected from the above aromatic hydrocarbon ring and aromatic hetero ring contain two or more such rings, these rings are directly bonded or bonded via a divalent or higher linking group φ. 8. The negative blue-violet laser photosensitive composition according to claim 1 or 2, wherein the ring D and E and the linking group L may have a substituent selected from a halogen atom; a hydroxyl group; a nitro group; Carboxyl; alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkoxy, alkylthio, aryl, aralkyl, alkenyloxy, arylthio, decyl, decyloxy groups which may be substituted , amine, mercaptoamine, urethane, aminocarbyl, carboxylate, amidoxime, sulfonate, group represented by -C = N, -C = NN a group represented by a saturated or unsaturated heterocyclic group. -4 - 1354864 9. The negative blue-violet laser photosensitive composition of claim 5, wherein the ring A to G and the linking group L may have a substituent selected from a halogen atom; a hydroxyl group; a nitro group; Cyano; carboxy; alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkoxy, alkylthio, aryl, aralkyl, alkenyloxy, arylthio, anthracenyl, anthracene Oxy group, amine group, mercaptoamine group, urethane group, aminomercapto group, carboxylate group, amidoxime group, sulfonate group, group represented by -C=N, -C a group represented by =NN, a saturated or unsaturated heterocyclic group. 10. The negative blue-violet laser photosensitive composition of claim 6, wherein the ring A to G and the linking group L may have a substituent selected from a halogen atom; a hydroxyl group; a nitro group; a cyano group; Alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkoxy, alkylthio, aryl, aralkyl, alkenyloxy, arylthio, decyl, decyloxy, amine a group represented by a group, a mercaptoamine group, a urethane group, an aminocarbamyl group, a carboxylate group, an aminesulfonyl group, a sulfonate group, and -C=N' -C = NN a group, a saturated or unsaturated heterocyclic group. The negative blue-violet laser photosensitive composition according to claim 1 or 2, wherein the photosensitive composition is a negative type mainly composed of an ethylenically unsaturated compound and a photopolymerization initiator. A negative blue-violet laser photosensitive composition according to claim 1 or 2, wherein the polymerization inhibitor is contained in an amount of 5 to 60 ppm. A negative blue-violet laser photosensitive composition according to claim 12, wherein the polymerization inhibitor is a hydroquinone derivative. 14. The negative blue-violet laser photosensitive -5 - 1354864 composition according to the nth aspect of the patent application, wherein the photopolymerization initiator contains a hexaarylbiimidazole compound. 15. The negative blue-violet laser photosensitive composition of claim 3, wherein the cerium contains an alkali-soluble resin. 16. The negative blue-violet laser photosensitive composition according to claim 15, wherein the alkali-soluble resin contains a content derived from a styrene monomer, a (meth) acrylate monomer, and a (meth) acrylic acid. The copolymer of each monomer constitutes a repeating unit. #17—a negative blue-violet laser photosensitive image forming material (A) characterized in that a negative blue-violet laser is formed on the dummy support film as in any one of claims 1 to 16. A layer of a photosensitive composition is formed. 18. A negative blue-violet laser photosensitive image forming material (B) characterized by being laminated on a substrate to be processed on the side of a negative blue-violet laser photosensitive composition layer as claimed in the patent application A 17-negative blue-violet laser photosensitive image forming material (A). 19. The negative-type blue-violet laser-sensitized φ image-forming material (B) according to claim 18, wherein the negative-type blue-violet laser-sensitive image forming material laminated on the substrate to be processed ( The thickness of the negative blue-violet laser photosensitive composition layer of A) is more than the above. 20. An image forming method which is characterized by a negative blue-violet laser photosensitive composition layer of a negative blue-violet laser photosensitive image forming material (B) as claimed in claim 18 or 19. 'Image scanning is performed by laser light exposure with a wavelength of 390 to 43 Onm to generate an image.