KR20080011351A - Image forming material having bluish-violet laser-photosensitive resist material layer and resist image forming method therefor - Google Patents

Abstract

An image forming material having a bluish-violet laser-photosensitive resist material layer highly sensitive to a laser beam in a bluish-violet region and free from a decrease in sensitivity even a film thickness is increased. An image forming material comprising a bluish-violet laser- photosensitive resist material layer formed on a substrate to be worked, wherein the photosensitive resist material layer has a bluish-violet laser-photosensitive resist material layer having a film thickness of at least 10 mum and an absorbance at a wavelength of 405 nm of up to 0. 3 per film thickness of 1 mum; and a resist image forming method of scanning and exposing the photosensitive resist material layer of the image forming material by a laser beam having a wavelength of 320-450 nm, and then developing the resultant material.

Description

IMAGE FORMING MATERIAL HAVING BLUISH-VIOLET LASER-PHOTOSENSITIVE RESIST MATERIAL LAYER AND RESIST IMAGE FORMING METHOD THEREFOR}

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image forming material having a blue violet laser photosensitive resist material layer capable of resist image formation by exposure with blue violet laser light and development processing, and a resist image forming method thereof, and in particular, by blue violet laser light. An image forming material having a blue-violet laser photosensitive resist material layer, which is useful for forming microelectronic circuits such as printed wiring boards, wiring boards for plasma displays, wiring boards for liquid crystal displays, large-scale integrated circuits, thin transistors, and semiconductor packages by direct drawing. , Flat plate) and a resist image forming method thereof.

Background Art Conventionally, for forming fine electronic circuits such as printed wiring boards, wiring boards for plasma displays, wiring boards for liquid crystal displays, large-scale integrated circuits, thin transistors, and semiconductor packages, for example, a photosensitive resist material layer is provided on a substrate to be processed, If necessary, the photosensitive resist material layer of the image forming material having a protective layer thereon is irradiated with ultraviolet rays through a mask film to be exposed, and then the mask film is peeled off, and when the protective layer is provided thereon, the protective layer is peeled off. A lithography in which a pattern is formed by developing using a difference in solubility in a developer of an exposed part and a non-exposed part, and then a circuit pattern is formed on the processed substrate by performing an etching process or the like on the substrate using the pattern layer as a mask. Law is widely used.

In addition, by using laser light as an exposure light source in recent years, the laser direct drawing method of directly forming an image from digital information such as a computer without using a mask film can improve not only productivity but also resolution and position accuracy. Attention has come to the fore, and along with it, a method of using a laser beam in the lithography method has been actively studied.

On the other hand, various types of light sources from ultraviolet to infrared are known, but as laser light that can be used for image exposure, argon ion laser, helium neon laser, YAG laser in terms of output, stability, photosensitivity, and cost, etc. It is considered to emit light in the infrared region from the visible light such as, and a semiconductor laser. For example, the lithographic method using an argon ion laser having a wavelength of 488 nm and an FD-YAG laser having a wavelength of 532 nm has already been put to practical use. .

However, the image forming method using such a visible laser light is inferior in the safety of yellow light, and requires a work in a dark room environment such as red light illumination. This makes it possible to use a semiconductor laser capable of stably oscillating in the blue-violet region, which is capable of working in a bright environment such as yellow light illumination, but the output is sometimes lower than that of other visible regions. The sensitivity is not necessarily sufficient, and the reality is that the practical drawing method has not reached the level that can be used not only in the direct drawing method but also in the lithography method.

On the other hand, European Patent Application Publication No. 1148387 discloses a photopolymerizable photosensitive composition having a maximum peak of spectral sensitivity in a wavelength region of 390 to 430 nm and having a minimum exposure amount capable of forming an image at wavelengths of 410 nm and 450 nm. Although the photosensitive flatbed printing plate which has the layer of on a support body is disclosed, the film thickness of the photosensitive composition layer is only about 2 micrometers.

However, even as these photosensitive compositions, as a photosensitive resist material, especially in the photosensitive resist material layer formed on the to-be-processed substrate through a dry film resist material, a film thickness is 10 micrometers or more, and it is a manufacturing process, such as a printed wiring board. In the plating process, it is sometimes required to increase the plating thickness in accordance with the recent miniaturization of the wiring line width, and the sensitivity in the blue-violet region still had room for improvement. In addition, in the case of the photosensitive layer using a laser in the infrared region in the visible light of the conventional method described above, when the film thickness is increased, the sensitivity is lowered, and a sensitivity is found that balances both the thickness and the sensitivity requirements. It was hard to do.

SUMMARY OF THE INVENTION The present invention has been made in view of the above-described prior art, and accordingly, the present invention has high sensitivity to laser light in a blue-violet region, and image formation having a blue-violet laser photosensitive resist material layer whose sensitivity does not decrease even when the film thickness is increased. It is an object of the present invention to provide a ash and a resist image forming method thereof.

In the case of using a violet laser, the inventors of the present invention can form an image forming material having a thick film thickness of the resist material layer, since the sensitivity does not decrease even if the film thickness of the resist material layer is thick, especially when the resist material layer has a specific absorbance. The thing which can be obtained, and the image forming material, found that it is advantageously obtained by using the photosensitive composition containing a specific sensitizer, and discovered this invention.

That is, the summary of this invention is an image forming material which has a blue-violet laser photosensitive resist material layer on a to-be-processed board | substrate, The photosensitive resist material layer is 10 micrometers or more in film thickness, and the light absorbency in wavelength 405nm is 1 film thickness. An image forming material having a blue violet laser photosensitive resist material layer, characterized in that it is 0.3 or less per micrometer, and a dry film resist material, wherein a layer of the photosensitive composition constituting the blue violet laser photosensitive resist material layer is formed on a temporary support film. And a photosensitive resist material layer of the image forming material is scanned and exposed to light with a laser beam having a wavelength of 320 to 450 nm, followed by development.

Moreover, the preferable photosensitive composition which comprises the blue-violet laser photosensitive resist material of the said image forming material is a novel photosensitive composition which has a characteristic in a sensitizer. That is, another gist of the present invention is a photosensitive composition containing an active compound which generates a radical or an acid by interacting with a sensitizer and an exposed sensitizer, wherein the sensitizer is molar absorption at a wavelength of 405 nm. Compound which is a dialkylaminobenzene compound represented by the following general formula (Ia) or (Ib) whose coefficient ((epsilon)) is 100 or more and 100,000 or less, and has a alkyl group as a substituent in the 2-position of this tetrahydroquinoline ring, and sulfonyl imide represented by the following general formula (II) It is a no-group containing compound, the 2-naphthylidedione type compound or 2-quinolone type compound represented by following formula (III), or the indolin type compound represented by following formula (IV), The photosensitive composition characterized by the above-mentioned.

And this invention is a photosensitive composition for electronic circuit creation,

(1) The film thickness (D) of the photosensitive resist material layer which consists of this composition, and the photosensitive resist material layer of this film thickness (D) can be resolved by carrying out image development process after scanning exposure by the laser beam of wavelength 390-430 nm. The maximum value of the ratio (D / L) to the minimum line width (L) is 1.0 or more, and

(2) The minimum exposure amount [S ₄₁₀ (μJ / cm 2)] capable of forming an image at a wavelength of 410 nm of the photosensitive resist material layer is 10,000 μJ / cm 2 or less.

It exists in the photosensitive composition for electronic circuit creation.

Moreover, this invention is a photosensitive composition for electronic circuit creation,

(1) The film thickness (D) of the photosensitive resist material layer which consists of this composition, and the photosensitive resist material layer of this film thickness (D) can be resolved by carrying out the scanning exposure after laser exposure of wavelength 390-430 nm, and developing. The maximum value of the ratio (D / L) to the minimum line width (L) is 1.0 or more, and

(2) The exposure amount which achieves the D / L is 20 mJ / cm 2 or less,

It exists in the photosensitive composition for electronic circuit creation.

And this invention is the dry film which has an image forming material which has a photosensitive resist material layer which consists of said photosensitive composition for electronic circuit creation on a to-be-processed substrate, and the photosensitive resist material layer which consists of the photosensitive composition for electronic circuit creation on a temporary support body. It is in the resist material.

The present invention can provide an image forming material having a blue-violet laser photosensitive resist material layer which is highly sensitive to laser light in the blue-violet region, and whose sensitivity does not decrease even when the film thickness is increased, and the resist image forming method thereof.

Implement the invention  Form for

The image forming material having the blue violet laser photosensitive resist material layer of the present invention has a blue violet laser photosensitive resist material layer on a substrate to be processed, and the photosensitive resist material layer has a maximum peak of spectral sensitivity in a wavelength region of 320 to 450 nm, and 390. It is preferable to have the maximum peak of a spectral sensitivity in the wavelength range of -430 nm. When the maximum peak of the spectral sensitivity is in the wavelength range below the above range, the sensitivity to laser light having a wavelength of 320 to 450 nm is inferior as the photosensitive resist material layer. Safety is poor.

On the other hand, in the present invention, the maximum peak of the spectral sensitivity is, for example, as described in detail in "photopolymer technology" (by Yamaoka Aoto, 1983, published in 1983, page 262). In the photosensitive image forming material sample having the photosensitive layer formed on the surface, light spectroscopy from a light source such as a xenon lamp or a tungsten lamp was used for a photosensitive image forming material sample, and the exposure wavelength was changed linearly in the horizontal axis direction, By setting the exposure wavelength to change logarithmically, irradiating and exposing and developing, an image corresponding to the sensitivity of each exposure wavelength is obtained, and an exposure energy that can be imaged is calculated from the image height, and the exposure is performed on the horizontal axis and the vertical axis. The maximum peak in the spectral sensitivity curve obtained by plotting the inverse of the energy is indicated.

Moreover, when the photosensitive resist material layer in the image forming material which has the blue-violet laser photosensitive resist material layer of this invention has a protective layer on this photosensitive resist material layer, the minimum exposure amount [ _S410 ] which can form an image at wavelength _410nm is 10,000 It is preferable that it is μJ / cm 2 or less, 200 μJ / cm 2 or less, more preferably 100 μJ / cm 2 or less, and particularly preferably 50 μJ / cm 2 or less. When this minimum exposure amount [ _S410 ] exceeds the said range, although it changes also with the exposure intensity of a laser light source, exposure time will become long and practicality will fall.

Moreover, when the photosensitive resist material layer in the image forming material which has the blue-violet laser photosensitive resist material layer of this invention does not have a protective layer on the photosensitive resist material layer, the minimum exposure amount [ _S410 ] which can be image-formed at the wavelength of _410nm is It is preferable that it is 10,000 microJ / cm <2> or less, 5,000 microJ / cm <2> or less, and it is more preferable that it is 2,000 microJ / cm <2> or less. When this minimum exposure amount [ _S410 ] exceeds the said range, it will also change with the exposure intensity of a laser light source, but exposure time will become long and practicality will fall.

On the other hand, although the minimum of this minimum exposure amount [ _S410 ] is so small that it is small, it is normally 1 microJ / cm <2> or more, and practically it is 2.5 microJ / cm <2> or more, with or without a protective layer on the photosensitive resist material layer. .

Further, the photosensitive resist material layer in the image forming material having the blue violet laser photosensitive resist material layer of the present invention has a minimum exposure amount [S ₄₅₀ (μJ / cm 2)] at which the image can be formed at a wavelength of 450 nm of the above [S ₄₁₀ ]. It is preferable that ratio with respect to [ _S410 / _S450 ] is 0.1 or less, and it is more preferable that it is 0.05 or less. When this ratio [S ₄₁₀ / S ₄₅₀ ] exceeds the above range, it becomes difficult to achieve both blue-violet laser photosensitivity and safety light under yellow light.

Moreover, the photosensitive resist material layer in the image forming material which has the blue-violet laser photosensitive resist material layer of this invention is the minimum exposure amount which can be image-formed in each wavelength of more than wavelength 450nm and 650nm or less [S _450-650 ( _microJ / cm <2>). It is preferable that the ratio [S _450-650 / S ₄₅₀ ] to the minimum exposure amount [S ₄₅₀ (μJ / cm 2)] that can be formed at a wavelength of 450 nm of)] is greater than 1. If this ratio [S _450-650 / S ₄₅₀ ] is less than the said range, it will become difficult to make blue light laser photosensitivity and safety light under yellow light compatible.

And the minimum exposure amount [S ₄₁₀ ] that can form an image at the wavelength 410 nm, the minimum exposure amount [S ₄₅₀ ] that can form an image at a wavelength 450 nm, and the image formation at each wavelength greater than the wavelength of 450 nm and 650 nm or less. The minimum possible exposure dose [S _450-650 ] is obtained as the _imageable exposure energy calculated from the image height obtained in the measurement of the maximum peak of the spectral sensitivity using the above-described spectral sensitivity measuring device, and the It means the minimum exposure amount that can form an image under the optimum development conditions determined by changing the development conditions such as type, development temperature, development time, and the like. As the optimum development conditions, the temperature is usually 25 ° C. in an alkaline developer having a pH of 11-14. 0.5 to 3 minutes soaking conditions are employed.

In addition, the image forming material having the blue violet laser photosensitive resist material layer of the present invention has a blue violet laser photosensitive resist material layer on a substrate to be processed, and the film thickness of the photosensitive resist material layer is 10 µm or more, 15 µm or more, and 200 µm. Hereinafter, it is preferable that it is 100 micrometers or less, respectively. When the film thickness of the photosensitive resist material layer is less than 10 µm, plating or etching of a sufficient thickness is not performed on the substrate to be processed, and on the other hand, when the film thickness of the photosensitive resist material layer becomes thicker than the preferred range, the sensitivity of the resist is increased. It tends to be lowered.

Conventionally, in the case of a photosensitive layer using a laser in the infrared region from visible light, when the film thickness is made thicker, the sensitivity is lowered and it is difficult to find a material having a balance that satisfies both the film thickness and the sensitivity requirements. The resist material layer which has is not put into practical use. In the case of using a violet laser, the inventors of the present invention form an image forming material having a thick film thickness of the resist material layer, since the sensitivity does not decrease even if the film thickness of the resist material layer is thick, especially when the resist material layer has a specific absorbance. I found it possible.

That is, the absorbance at the wavelength of 405 nm of the photosensitive resist material layer is 0.3 or less per 1 micrometer of film thickness, Preferably it is 0.25 or less, Especially 0.1 or less is good. The lower limit is 0.001 or more and 0.005 or more per 1 micrometer of film thickness.

Generally, when the film thickness of the photosensitive resist material layer becomes thick, the sensitivity of the resist is lowered, but the degree of sensitivity change due to the film thickness is preferably smaller in terms of throughput of substrate processing. That is, it is preferable that S2 / S1 is 1 or more and 5 or less, when the sensitivity at the film thickness of 10 micrometers is set to S1 at the exposure wavelength of the photosensitive resist material layer, and the sensitivity at the film thickness of 20 micrometers is set to S2. It is especially 2 or less, and a minimum is 1 or more. Since S2 / S1 is within the above range, the sensitivity change due to the variation in the film thickness is reduced, so that even if there is a step on the substrate to be processed, good image formation is possible. In the present invention, the sensitivity of the resist is defined as the minimum exposure amount that provides a residual film ratio of 90% or more of the thickness of the resist coating film when the photosensitive layer is exposed and developed by a blue violet laser.

The photosensitive composition which forms the photosensitive resist material layer in this invention,

(1) The film thickness (D) of the photosensitive resist material layer which consists of this composition, and the photosensitive resist material layer of this film thickness (D) can be resolved by carrying out image development process after scanning exposure by the laser beam of wavelength 390-430 nm. The maximum value of the ratio (D / L) to the minimum line width (L) is 1.0 or more, and

(2) The minimum exposure amount [S ₄₁₀ (μJ / cm 2)] capable of forming an image at a wavelength of 410 nm of the photosensitive resist material layer is 10,000 μJ / cm 2 or less.

It is preferable. The minimum line width L that can be resolved varies depending on the film thickness of the photosensitive resist material layer. Therefore, the said maximum value means the maximum value of several D / L obtained by changing the film thickness of the photosensitive resist material layer, measuring the minimum line width L, and obtaining D / L. The said maximum value becomes like this. Preferably it is 1.3 or more, More preferably, it is 2.0 or more. Although D / L is so preferable that it is high, it is 10 or less normally. The preferred range of _{[S 410 (μJ / ㎠)} ] are as defined above.

The photosensitive composition which forms the photosensitive resist material layer in this invention,

(1) The film thickness (D) of the photosensitive resist material layer which consists of this composition, and the photosensitive resist material layer of this film thickness (D) can be resolved by carrying out image development process after scanning exposure by the laser beam of wavelength 390-430 nm. The maximum value of the ratio (D / L) to the minimum line width (L) is 1.0 or more, and

(2) The exposure amount which achieves the D / L is 20 mJ / cm 2 or less,

It is also preferable.

The preferable range of D / L is as above-mentioned. Moreover, the exposure amount which achieves the D / L becomes like this. Preferably it is 10 mJ / cm <2> or less. Although the minimum of the exposure amount which achieves this D / L is so preferable that it is small, it is 1 microJ / cm <2> or more normally, and it is 2.5 microJ / cm <2> or more practically.

The composition of the photosensitive composition constituting the photosensitive resist material layer in the image forming material having the blue violet laser photosensitive resist material layer of the present invention is not particularly limited as long as it satisfies the above-described spectral sensitivity characteristics or film thickness, and is negative and positive type. All is possible. As a negative type, Preferably a photopolymerizable negative photosensitive composition (N1) and a chemically amplified negative photosensitive composition (N2), As a positive type, Preferably a chemically amplified positive photosensitive composition (P1) is mentioned, respectively. have.

N1. Photopolymerizable negative photosensitive composition]

As a photopolymerizable negative type, what consists of a photopolymerizable photosensitive composition containing the following (N1-1), (N1-2), and (N1-3) component is preferable.

(N1-1) ethylenically unsaturated compounds

(N1-2) sensitizer

(N1-3) photopolymerization initiator

The ethylenically unsaturated compound which is the (N1-1) component which comprises the photopolymerizable negative photosensitive composition (N1) in this invention is a component (N1-3) mentioned later, when the photosensitive composition receives irradiation of actinic light. It is a compound which has at least 1 radically polymerizable ethylenic unsaturated bond in a molecule | numerator which is addition-polymerized by the action of the photoinitiator containing a phosphorus photoinitiator, and bridge | crosslinking and hardening as needed.

As an ethylenically unsaturated compound in this invention, the compound which has one ethylenically unsaturated bond in a molecule | numerator, specifically, it is (meth) acrylic acid [Meanwhile, in this invention, "(meth) acryl" And "acrylic" or / and "methacryl"; unsaturated carboxylic acids such as crotonic acid, isocrotonic acid, maleic acid, itaconic acid, citraconic acid, and alkyl esters thereof, and (meth) acrylonitrile , (Meth) acrylamide, styrene, etc. may be used. However, two ethylenically unsaturated bonds may be incorporated into the molecule in that the difference in polymerizability, crosslinkability, and the solubility of the developer in the exposed portion and the non-exposed portion can be widened. It is preferable that it is a compound which has the above, and the acrylate compound whose unsaturated bond originates in a (meth) acryloyloxy group is especially preferable.

Typical examples of the compound having two or more ethylenically unsaturated bonds in the molecule include esters of unsaturated carboxylic acids and polyhydroxy compounds, (meth) acryloyloxy group-containing phosphates, and hydroxy (meth) acrylate compounds. Urethane (meth) acrylates with a polyisocyanate compound, and epoxy (meth) acrylates with a (meth) acrylic acid or a hydroxy (meth) acrylate compound and a polyepoxy compound, etc. are mentioned.

Specific examples of the esters include the above-mentioned unsaturated carboxylic acids, ethylene glycol, polyethylene glycol (additional number 2 to 14), propylene glycol, polypropylene glycol (additional number 2 to 14), and trimethylene glycol , Tetramethylene glycol, neopentyl glycol, hexamethylene glycol, nonamethylene glycol, trimethylolethane, tetramethylolethane, trimethylolpropane, glycerol, pentaerythritol, dipentaerythritol, sorbitol, and their ethylene oxide adducts, propylene oxide Reaction products with aliphatic polyhydroxy compounds, such as an adduct, diethanolamine, and triethanolamine, Specifically, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol Di (meth) acrylate, tetraethylene glycol di (meth) acrylate, nonaethylene glycol di (meth) arc Rate, propylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetramethylene glycoldi (meth) acrylate, neopentyl glycoldi (meth) acrylate, hexamethylene glycoldi (meth) acrylate , Nonamethylene glycol di (meth) acrylate, trimethylol ethane tri (meth) acrylate, tetramethylolethane tri (meth) acrylate, trimethylolpropanedi (meth) acrylate, trimethylolpropane tri (meth) acrylic Rate, trimethylolpropane ethylene oxide addition tri (meth) acrylate, glycerol di (meth) acrylate, glycerol tri (meth) acrylate, glycerol propylene oxide addition tri (meth) acrylate, pentaerythritol di (meth) acrylate To pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipenta Listhritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) 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, isocrotonate, maleate, itaconate And citraconate.

And as esters thereof, the above-mentioned unsaturated carboxylic acid and aromatic polyhydroxy compounds such as hydroquinone, resorcin, pyrogallol, bisphenol F, bisphenol A, or their ethylene oxide adducts and glycidyl group-containing compound adducts The reactants, specifically, hydroquinone di (meth) acrylate, resorcindi (meth) acrylate, pyrogallol tri (meth) acrylate, bisphenol A di (meth) acrylate, bisphenol A bis [oxy Ethylene (meth) acrylate], bisphenol A bis [trioxyethylene (meth) acrylate], bisphenol A bis [pentaoxyethylene (meth) acrylate], bisphenol A bis [hexaoxyethylene (meth) acrylate], Bisphenol A bis [glycidyl ether (meth) acrylate], such as the above-mentioned unsaturated carboxylic acid, tris (2-hydroxyethyl) isocyanurate, etc. The reactant with a monocyclic polyhydroxy compound, specifically, di (meth) acrylate, tri (meth) acrylate, such as tris (2-hydroxyethyl) isocyanurate, and unsaturated carboxylic acid Reactants of polyhydric carboxylic acids with polyhydroxy compounds, specifically, for example, condensates of (meth) acrylic acid with phthalic acid and ethylene glycol, condensates of (meth) acrylic acid with maleic acid and diethylene glycol, ( And condensates of methacrylic acid, terephthalic acid and pentaerythritol, and condensates of (meth) acrylic acid, adipic acid, butanediol, and glycerin.

And as the (meth) acryloyloxy group-containing phosphates, specifically (meth) acryloyloxyethyl phosphate, bis [(meth) acryloyloxyethyl] phosphate, (meth) Acryloyloxyethylene glycol phosphate etc. are mentioned, These may be used individually or respectively as a mixture.

Specific examples of the urethane (meth) acrylates include hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycerol di (meth) acrylate, and pentaerythritol tri (meth). Hydroxy (meth) acrylate compounds such as acrylate and tetramethylol ethane tri (meth) acrylate, hexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine methyl ester diisocyanate and lysine Aliphatic polyisocyanates such as methyl ester triisocyanate, dimer acid diisocyanate, 1,6,11-undecatri isocyanate, 1,3,6-hexamethylene triisocyanate, 1,8-diisocyanate-4-isocyanate methyl octane, cyclohexane Diisocyanate, dimethylcyclohexanediisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), isofo Alicyclic polyisocyanates such as diisocyanate and bicycloheptane triisocyanate, p-phenylenedi isocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, 4 Heterocyclic type, such as aromatic polyisocyanate, such as 4'- diphenylmethane diisocyanate, tolidine diisocyanate, 1, 5- naphthalene diisocyanate, tris (isocyanate phenylmethane), and tris (isocyanate phenyl) thiophosphate, and isocyanurate The reactant with polyisocyanate compounds, such as polyisocyanate, etc. are mentioned.

Specific examples of the epoxy (meth) acrylates include (meth) acrylic acid or the above-described hydroxy (meth) acrylate compound, (poly) ethylene glycol polyglycidyl ether, and (poly) ) Propylene glycol polyglycidyl ether, (poly) tetramethylene glycol polyglycidyl ether, (poly) pentamethylene glycol polyglycidyl ether, (poly) neopentyl glycol polyglycidyl ether, (poly) hexamethylene Aliphatic polyepoxy compounds, such as glycol polyglycidyl ether, (poly) trimethylol propane polyglycidyl ether, (poly) glycerol polyglycidyl ether, and (poly) sorbitol polyglycidyl ether, and phenol novolak polyepoxy Aromatic polys, such as a compound, a brominated phenol novolak polyepoxy compound, (o-, m-, p-) cresol novolak polyepoxy compound, a bisphenol A polyepoxy compound, a bisphenol F polyepoxy compound Reactants with polyepoxy compounds such as heterocyclic polyepoxy compounds such as cation compounds, sorbitan polyglycidyl ether, triglycidyl isocyanurate, and triglycidyl tris (2-hydroxyethyl) isocyanurate Can be mentioned.

Other ethylenically unsaturated compounds, in addition to the above, for example, (meth) acrylamides such as ethylenebis (meth) acrylamide, allyl esters such as diallyl phthalate and vinyl group-containing compounds such as divinyl phthalate Etc. can be mentioned. Each of the above ethylenically unsaturated compounds may be used alone or in combination of two or more thereof.

As the ethylenically unsaturated compound which is the above (N1-1) component, in this invention, ester (meth) acrylates, (meth) acryloyloxy-group containing phosphate, or urethane (meth) acrylates are preferable. And ester (meth) acrylates are particularly preferable, and among these ester (meth) acrylates, they have polyoxyalkylene groups such as polyethylene glycol, polypropylene glycol, or polyethylene oxide adducts of bisphenol A, and (meth) Especially preferred are ester (meth) acrylates having two or more acryloyloxy groups.

The sensitizer which is the (N1-2) component which comprises the photopolymerizable negative photosensitive composition (N1) in this invention efficiently absorbs the light of the blue-violet region of wavelength 320-450 nm, and has a wavelength of 405 nm. The molar extinction coefficient (ε) is 100 or more, preferably 1,000 or more, more preferably 10,000 or more, and 100,000 or less, while transferring the photoexcitation energy to a photopolymerization initiator, which is a component (N1-3) described later, the photopolymerization initiator. The light absorption pigment | dye which has a sensitization function which decomposes | disassembles and produces | generates the active radical which organically superposes | polymerizes the said ethylenically unsaturated compound which is (N1-1) component is preferable.

As a light absorption pigment | dye as a sensitizer which is (N1-2) component in this invention, a dialkylamino benzene-type compound is mentioned, Especially, with respect to a dialkylamino benzophenone type compound and the amino group on a benzene ring The dialkylaminobenzene type compound which has a heterocyclic group as a substituent at the carbon atom of a p-position is preferable.

As this dialkylamino benzophenone type compound, what is represented by following General formula (Ia) is preferable.

Formula Ia

[In formula Ia, R <^1> , R <^2> , R <^3> and R <^4> represent an alkyl group each independently, R <^5> , R <^6> , R <^7> and R <^8> respectively independently represent an alkyl group or a hydrogen atom , R ¹ and R ² , R ³ and R ⁴ , R ¹ and R ⁵ , R ² and R ⁶ , R ³ and R ⁷ , and R ⁴ and R ⁸ each independently form a nitrogen-containing heterocycle do.]

Here, it is preferable that carbon number of the alkyl groups of R <^1> , R <^2> , R <^3> and R <^4> in general formula (Ia) and carbon number when R <^5> , R <^6> , R <^7> and R <^8> is an alkyl group is 1-6, Moreover, when forming a nitrogen-containing heterocycle, it is preferable that it is a 5 or 6 membered ring, and a 6 membered ring is especially preferable. In this invention, the compound which forms the nitrogen-containing heterocycle is especially preferable.

As a specific example of the thing which does not form the nitrogen containing heterocycle among the compounds represented by the said Formula (Ia), For example, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino ) Benzophenone, etc. are mentioned.

Among the compounds represented by the above formula (Ia), as the nitrogen-containing heterocycle, the compound forming the tetrahydroquinoline ring is preferable, and the compound represented by the following formula (Ib) is more preferable.

Formula Ib

[In Formula Ib, R <^2> and R <^4> respectively independently represents the alkyl group which may have a substituent, R <^6> and R <^8> respectively independently represents the alkyl group which may have a substituent, or a hydrogen atom, and R <^2> and R ⁶ and R ⁴ and R ⁸ may each independently form a nitrogen-containing heterocycle, and the two tetrahydroquinoline rings may have a substituent.]

Herein, in the formula (Ib), the carbon number of the alkyl groups of R ² and R ⁴ and the carbon number when R ⁶ and R ⁸ are alkyl groups are preferably 1 to ⁶ , and R ² and R ⁶ , and R ⁴ and R ^{When 8} forms a nitrogen-containing heterocycle, it is preferably a 5 or 6 membered ring, more preferably a 6 membered ring, and R ² and R ⁶ are It is especially preferable that the tetrahydroquinoline ring, and R <^4> and R <^{8> form} the tetrahydroquinoline ring and a julolidine ring, respectively.

In addition, as a substituent in the alkyl group of R <^2> , R <^4> , R <^6> and R <^8> in general formula (Ib), an alkoxy group, an acyl group, an acyloxy group, an alkyloxycarbonyl group, an aryl group, an aryloxy group, and an alkylthio group And an arylthio group, an amino group, a hydroxyl group, a halogen atom and the like, and examples of the substituent in both tetrahydroquinoline rings include, for example, an alkyl group, an alkoxy group, an acyl group, an acyloxy group and an alkyloxy group. A carbonyl group, an aryl group, an aryloxy group, an alkylthio group, an arylthio group, an amino group, a hydroxyl group, a halogen atom, etc. are mentioned. In that case, both benzene rings are carbon atoms in o-position relative to the carbonyl group, An imino group, an alkylimino group, an oxygen atom, or a sulfur atom may be bonded to each other to form a ring structure.

As a specific example of the compound represented by the said general formula (Ib), the compound of the following structure is mentioned.

Among the compounds represented by the above formula (Ib), compounds in which both tetrahydroquinoline rings have an alkyl group as a substituent at the 2-position are particularly preferable, and the alkyl group preferably has 1 to 10 carbon atoms, and particularly preferably 1 to 6 carbon atoms. In the specific example, when the alkyl group of 2-position is set to R <^9> and R <^10> , and the benzene ring in the said Formula (Ib) does not form the ring structure of carbon atoms of o-position with respect to a carbonyl group, a substituent When Ra to Rl are attached to a carbon atom having the structure represented by the following general formula (Ib1), and the benzene ring in the above general formula (Ib) forms an intervening group when the carbon atoms in the o-position form a ring structure with respect to the carbonyl group, It is set as Y, and it attaches Ra-Rl to the carbon atom which has a substituent, and is represented by following formula (Ib2), and is shown in following Table 1.

Formula Ib1

Formula Ib2

TABLE 1-1

TABLE 1-2

Moreover, as a heterocyclic group in the dialkylaminobenzene type compound which has a heterocyclic group as a substituent at the carbon atom of a p-position with respect to the amino group on a benzene ring, the 5 or 6 membered ring containing a nitrogen atom, an oxygen atom, or a sulfur atom A 5-membered ring having a condensed benzene ring is particularly preferable, and the dialkylaminobenzene compound is particularly preferably represented by the following general formula (Ic).

Formula Ic

[In formula Ic, R <^1> and R <^2> respectively independently represents an alkyl group, R <^5> and R <^6> respectively independently represent an alkyl group or a hydrogen atom, R <^1> and R <^2> , R <^1> and R <^5> , And R ² and R ⁶ may each independently form a nitrogen-containing heterocycle. X represents an oxygen atom, a sulfur atom, a dialkylmethylene group, an imino group, or an alkylimino group, and ring A represents an aromatic ring which may have a substituent.]

Here, it is preferable that carbon number of the alkyl group of R <^1> and R <^2> in general formula (Ic), and carbon number when R <^5> and R <^6> is an alkyl group are 1-6, and when forming a nitrogen containing heterocycle, it is 5 or 6 It is preferable that it is a ring, and 6-membered ring is especially preferable. In this invention, the compound which forms the nitrogen-containing heterocycle is especially preferable. Moreover, it is preferable that carbon number of the alkyl group when X is a dialkyl methylene group is 1-6, and it is preferable that carbon number of the alkyl group when an alkylimino group is 1-6. And as ring A, a benzene ring is preferable.

As a specific example of the thing which does not form the nitrogen-containing heterocycle among the compounds represented by the said Formula (Ic), for example, 2- (p-dimethylaminophenyl) benzoxazole and 2- (p-diethylaminophenyl) Benzoxazole, 2- (p-dimethylaminophenyl) benzo [4,5] benzoxazole, 2- (p-dimethylaminophenyl) benzo [6,7] benzoxazole, 2- (p-dimethylaminophenyl ) Benzothiazole, 2- (p-diethylaminophenyl) benzothiazole, 2- (p-dimethylaminophenyl) benzoimidazole, 2- (p-diethylaminophenyl) benzoimidazole, 2- (p -Dimethylaminophenyl) -3,3-dimethyl-3H-indole, 2- (p-diethylaminophenyl) -3,3-dimethyl-3H-indole, and the like.

Moreover, in the dialkylaminobenzene type compound which has a heterocyclic group as a substituent at the carbon atom of p-position with respect to the amino group on a benzene ring other than the compound represented by the said Formula (Ic), it does not form the nitrogen containing heterocycle, For example, 2- (p-dimethylaminophenyl) pyridine, 2- (p-diethylaminophenyl) pyridine, 2- (p-dimethylaminophenyl) quinoline, 2- (p-diethylaminophenyl) quinoline, 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-thiadiazole and the like.

Among the compounds represented by the general formula (Ic), as the nitrogen-containing heterocycle, the compound forming the tetrahydroquinoline ring is preferable, and the compound represented by the following general formula (Id) is more preferable.

Formula Id

[In formula Id, R <^2> represents the alkyl group which may have a substituent, R <^6> represents the alkyl group which may have a substituent, or a hydrogen atom, and R <^2> and R <^6> may form the nitrogen containing heterocycle. X represents a dialkylmethylene group, an imino group or an alkylimino group, an oxygen atom, or a sulfur atom, ring A represents an aromatic ring which may have a substituent, and the tetrahydroquinoline ring may have a substituent else do.]

Here, it is preferable that carbon number of the alkyl group of R <^2> in general formula (Id) and carbon number when R <^6> is an alkyl group are 1-6, and when R <^2> and R <^6> form a nitrogen-containing heterocycle, it is 5 or 6 It is preferable that it is a ring, It is further more preferable that it is a 6-membered ring, It is especially preferable that R <^2> and R <^{6> form} the tetrahydroquinoline ring and the julolidine ring. Moreover, it is preferable that carbon number of the alkyl group when X is a dialkyl methylene group or an alkylimino group is 1-6. Moreover, as ring A, a benzene ring is preferable.

And as a substituent in the alkyl group of R <^2> and R <^6> in general formula (Id), an alkoxy group, an acyl group, an acyloxy group, an alkyloxycarbonyl group, an aryl group, an aryloxy group, an alkylthio group, an arylthio group, an amino group, A hydroxyl group, a halogen atom, etc. are mentioned, As another substituent in a tetrahydroquinoline ring, an alkyl group, an alkoxy group, an acyl group, an acyloxy group, an alkyloxycarbonyl group, an aryl group, an aryloxy group, for example. , Alkylthio group, arylthio group, amino group, hydroxyl group, halogen atom and the like.

As a specific example of the compound represented by the said general formula (Id), the compound of the following structure is mentioned.

Among the compounds represented by the above formula (Id), compounds in which the tetrahydroquinoline ring has an alkyl group at the 2-position as a substituent are particularly preferable, and the alkyl group preferably has 1 to 10 carbon atoms, and particularly preferably 1 to 6 carbon atoms. . The specific example is set to the alkyl group of 2-position as R <^9> , Rc-Rf is attached to the carbon atom which has a substituent, and is represented by following formula (Id1), and is shown in following Table 2.

Formula Id1

TABLE 2

Moreover, as a light-absorbing dye as a sensitizer which is (N1-2) component in this invention, the compound which has a sulfonyl imino group is mentioned, Especially, it is preferable to represent with following formula (II).

[Formula II]

[In formula II, R <^11> and R <^12> respectively independently represents a hydrogen atom or arbitrary substituents, and R <^13> represents arbitrary substituents.]

Preferable groups as R ¹¹ and R ¹² in the general formula (II) include a hydrogen atom; Linear or branched alkyl groups having 1 to 18 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group and n-heptyl group; Cycloalkyl groups having 3 to 18 carbon atoms such as cyclopropyl group, cyclopentyl group, cyclohexyl group, and adamantyl group; C2-C18 linear or branched alkenyl groups, such as a vinyl group, a propenyl group, and a hexenyl group; Cycloalkenyl groups having 3 to 18 carbon atoms such as a cyclopentenyl group and a cyclohexenyl group; 1-phenylvinyl group, 2-phenylvinyl group, 2-phenylpropenyl group, 1- (α-naphthyl) vinyl group, 2- (α-naphthyl) vinyl group, 1- (β-naphthyl) vinyl group C8-C18 aryl alkenyl groups, such as a 2-((beta) -naphthyl) vinyl group; Saturated or unsaturated heterocyclic groups such as 2-thienyl group, 2-pyridyl group, furyl group, thiazolyl group, benzothiazolyl group, morpholino group, pyrrolidinyl group, and tetradrathiothiophene dioxide group; C6-C18 aryl groups, such as a phenyl group, a tolyl group, a xylyl group, and a mesityl group; C7-C20 aralkyl groups, such as a benzyl group and a phenethyl group; C2-C18 linear or branched acyl groups, such as an acetyl group, a propionyl group, butyryl group, an isobutyryl group, a valeryl group, and an isovaleryl group; Linear or branched alkoxy groups having 1 to 18 carbon atoms such as methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group and tert-butoxy group; Linear or branched alkenyloxy groups having 3 to 18 carbon atoms such as propenyloxy group, butenyloxy group, and pentenyloxy group; Linear or branched alkylthio groups having 1 to 18 carbon atoms such as methylthio group, ethylthio group, n-propylthio group, n-butylthio group, sec-butylthio group and tert-butylthio group; Cyano group; Hydroxyl group; Formyl group; Sulfonic acid groups; Carboxyl groups; Acyloxy group represented by -OCOR; Amino group represented by -NRR '; Acylamino group represented by -NHCOR; Carbamate groups represented by -NHCOOR; Sulfonamide groups represented by -NHSOOR; Carboxylic acid ester group represented by -COOR; Carbamoyl group represented by -CONRR '; Sulfamoyl group represented by -SOONRR '; -SO and the like sulfonic acid ester group represented by OR _2, Further, preferred groups as R ¹³ is, in addition to these groups, and the like imino group represented by -N = CRR '.

In addition, as R and R 'in these groups, C1-C1-, such as a methyl group, an ethyl group, a propyl group, isopropyl group, n-butyl group, sec-butyl group, tert- butyl group, n-heptyl group, etc. are preferable. 18 linear or branched alkyl groups; Cycloalkyl groups having 3 to 18 carbon atoms such as cyclopropyl group, cyclopentyl group, cyclohexyl group, and adamantyl group; C2-C18 linear or branched alkenyl groups, such as a vinyl group, a propenyl group, and a hexenyl group; Cycloalkenyl groups having 3 to 18 carbon atoms such as a cyclopentenyl group and a cyclohexenyl group; Saturated or unsaturated heterocyclic groups such as 2-thienyl group, 2-pyridyl group, furyl group, thiazolyl group, benzothiazolyl group, morpholino group, pyrrolidinyl group and tetrahydrothiophene dioxide group; C6-C18 aryl groups, such as a phenyl group, a tolyl group, a xylyl group, and a mesityl group, etc. are mentioned.

In addition, the alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, heterocyclic group, aryl group, etc. which are contained in the group represented by R <^11> -R <^13> may further be a methoxy group, an ethoxy group, n-propoxy group, isopropoxy. An alkoxy group having 1 to 10 carbon atoms such as a time group, an n-butoxy group, a sec-butoxy group, and a tert-butoxy group; Alkoxyalkoxy groups having 2 to 12 carbon atoms such as methoxymethoxy group, ethoxymethoxy group, propoxymethoxy group, ethoxyethoxy group, propoxyethoxy group and methoxybutoxy group; An alkoxyalkoxyalkoxy group having 3 to 15 carbon atoms, such as a methoxy methoxy methoxy group, a methoxy methoxy ethoxy group, a methoxy ethoxy methoxy group, and an ethoxy ethoxy methoxy group; Allyloxy group; C6-C12 aryl groups, such as a phenyl group, a tolyl group, and a xylyl group (these may be substituted by the substituent further); C6-C12 aryloxy groups, such as a phenoxy group, a tolyloxy group, a xylyloxy group, and a naphthyloxy group; Acyl groups, such as an acetyl group and a propionyl group; Cyano group; Nitro group; Hydroxyl group; Tetrahydrofuryl group; Amino group; Alkylamino groups having 1 to 10 carbon atoms such as N, N-dimethylamino group and N, N-diethylamino group; Alkylsulfonylamino groups having 1 to 6 carbon atoms such as methylsulfonylamino group, ethylsulfonylamino group and n-propylsulfonylamino group; Halogen atoms such as fluorine atom, chlorine atom and bromine atom; An alkoxycarbonyl group having 2 to 7 carbon atoms such as a methoxycarbonyl group, an ethoxycarbonyl group, and an n-butoxycarbonyl group; Alkylcarbonyloxy groups having 2 to 7 carbon atoms such as methylcarbonyloxy group, ethylcarbonyloxy group, n-propylcarbonyloxy group, isopropylcarbonyloxy group and n-butylcarbonyloxy group; C2-C7 alkoxycarbonyl jade, such as a methoxycarbonyloxy group, an ethoxycarbonyloxy group, n-propoxycarbonyloxy group, isopropoxycarbonyloxy group, n-butoxycarbonyloxy group, etc. You may have time etc. as a substituent.

In these substituents, the preferable substituent in the case where R ¹¹ to R ¹³ is an alkyl group, a cycloalkyl group or a cycloalkenyl group is an alkoxy group or an alkoxyalkoxy group, and when R ¹¹ to R ¹³ are an alkenyl group, a heterocyclic group or an aryl group. Preferable substituents are an alkoxy group, an alkoxyalkoxy group, an aryl group, an amino group, an alkylamino group, a cyano group, or a hydroxyl group.

As the compound represented by the above formula (II), a compound in which at least one of R ¹¹ , R ¹² , and R ¹³ is an alkenyl group, a cycloalkenyl group, an aryl alkenyl group, a heterocyclic group, an aryl group, or an acyl group is preferable, and R is More preferable are compounds in which at least one of ¹¹ , R ¹² , and R ¹³ is an unsaturated heterocyclic group which may have a substituent or an aryl group which may be substituted, R ¹¹ is a hydrogen atom, and R ¹² and R ¹³ are each Independently, the compound which is an unsaturated heterocyclic group which may have a substituent or the aryl group which may be substituted is especially preferable, and the phenyl group which has an amino group which R <^12> may be substituted by the alkyl group etc. is especially preferable.

The molecular weight of the compound represented by the above formula (II) is usually 200 or more, preferably 2,000 or less, and more preferably 1,000 or less. Specific examples of the compound represented by the formula (II) include the following ones.

Moreover, as a light-absorbing dye as a sensitizer which is (N1-2) component in this invention, a 2-naphthylidedione type compound or a 2-quinolone type compound is mentioned, Especially, it is represented by following General formula (III) It is preferable.

[Formula III]

Wherein III, Z represents a nitrogen atom or ^{CR 21, R 14, R 15} , R 16, R 17, R 18, R 19, R 20, and R ²¹ are, each independently, a hydrogen atom, or an optionally R ¹⁸ and R ¹⁹ , R ¹⁹ and R ²⁰ , and R ²⁰ and R ²¹ may each independently form a nitrogen-containing heterocycle, and R ¹⁵ to R ¹⁸ may be adjacent to each other. May combine to form a ring.]

Here, in the general formula (III), preferred groups as R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , and R ²¹ include a hydrogen atom; Linear or branched alkyl groups having 1 to 18 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group and n-heptyl group; Cycloalkyl groups having 3 to 18 carbon atoms such as cyclopropyl group, cyclopentyl group, cyclohexyl group, and adamantyl group; C2-C18 linear or branched alkenyl groups, such as a vinyl group, a propenyl group, and a hexenyl group; Cycloalkenyl groups having 3 to 18 carbon atoms such as a cyclopentenyl group and a cyclohexenyl group; Saturated or unsaturated heterocyclic groups such as 2-thienyl group, 2-pyridyl group, furyl group, thiazolyl group, benzothiazolyl group, morpholino group, pyrrolidinyl group and tetrahydrothiophene dioxide group; C6-C18 aryl groups, such as a phenyl group, a tolyl group, a xylyl group, and a mesityl group; C7-C20 aralkyl groups, such as a benzyl group and a phenethyl group; C2-C18 linear or branched acyl groups, such as an acetyl group, a propionyl group, butyryl group, an isobutyryl group, a valeryl group, and an isovaleryl group; Linear or branched alkoxy groups having 1 to 18 carbon atoms such as methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group and tert-butoxy group; Linear or branched alkenyloxy groups having 3 to 18 carbon atoms such as propenyloxy group, butenyloxy group, and pentenyloxy group; Linear or branched alkylthio groups having 1 to 18 carbon atoms such as methylthio group, ethylthio group, n-propylthio group, n-butylthio group, sec-butylthio group and tert-butylthio group; Halogen atoms such as fluorine atom, chlorine atom and bromine atom; Nitro group; Cyano group; Hydroxyl group; Formyl group; Sulfonic acid groups; Carboxyl groups; Acyloxy group represented by -OCOR; Amino group represented by -NRR '; Acylamino group represented by -NHCOR; Carbamate groups represented by -NHCOOR; Sulfonamide groups represented by -NHSOOR; Carboxylic acid ester group represented by -COOR; Carbamoyl group represented by -CONRR '; Sulfamoyl group represented by -SOONRR '; And sulfonic acid ester groups represented by -SO ₂ OR.

Moreover, as R and R 'in these groups, C1-C1-, such as a methyl group, an ethyl group, a propyl group, isopropyl group, n-butyl group, sec-butyl group, tert- butyl group, n-heptyl group, etc. are preferable. 18 linear or branched alkyl groups; Cycloalkyl groups having 3 to 18 carbon atoms such as cyclopropyl group, cyclopentyl group, cyclohexyl group, and adamantyl group; C2-C18 linear or branched alkenyl groups, such as a vinyl group, a propenyl group, and a hexenyl group; Cycloalkenyl groups having 3 to 18 carbon atoms such as a cyclopentenyl group and a cyclohexenyl group; Saturated or unsaturated heterocyclic groups such as 2-thienyl group, 2-pyridyl group, furyl group, thiazolyl group, benzothiazolyl group, morpholino group, pyrrolidinyl group and tetrahydrothiophene dioxide group; C6-C18 aryl groups, such as a phenyl group, a tolyl group, a xylyl group, and a mesityl group, etc. are mentioned.

In addition, the alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, heterocyclic group, aryl group, etc. which are contained in the group represented by R <^14> -R <^21> may have a substituent further, and as these substituents, R in said Formula (II) C1-C10 alkoxy groups similar to those exemplified as substituents such as alkyl groups, cycloalkyl groups, alkenyl groups, cycloalkenyl groups, heterocyclic groups, and aryl groups as ¹¹ to R ¹³ ; An alkoxyalkoxy group having 2 to 12 carbon atoms; An alkoxyalkoxyalkoxy group having 3 to 15 carbon atoms; Aryl groups having 6 to 12 carbon atoms; Aryloxy group having 6 to 12 carbon atoms; Acyl group; Cyano group; Nitro group; Hydroxyl group; Tetrahydrofuryl group; Amino group; An alkylamino group having 1 to 10 carbon atoms; An alkylsulfonylamino group having 1 to 6 carbon atoms; Halogen atom; Alkoxycarbonyl group having 2 to 7 carbon atoms; An alkylcarbonyloxy group having 2 to 7 carbon atoms; C2-C7 alkoxycarbonyloxy group etc. are mentioned.

In Formula III, R ¹⁴ , R ¹⁵ , R ¹⁷ , R ¹⁸ , and R ²¹ are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, a heterocyclic group, an aryl group, an aralkyl group, Acyl group, alkoxy group, alkenyloxy group, alkylthio group, halogen atom, nitro group, cyano group, hydroxyl group, formyl group, sulfonic acid group, carboxyl group, amino group, acylamino group, carbamate group, sulfonamide group, carboxylic acid Ester group, carbamoyl group, sulfamoyl group, sulfonic acid ester group, etc. are preferable, and hydrogen atom, alkyl group, alkenyl group, heterocyclic group, aryl group, aralkyl group, acyl group, alkoxy group, alkylthio group, halogen atom, nitro Groups, cyano groups, hydroxyl groups, carboxyl groups, amino groups, acylamino groups, carbamate groups, sulfonamide groups, carboxylic acid ester groups, carbamoyl groups and the like are more preferable, and hydrogen atoms, alkyl groups having 1 to 6 carbon atoms, and carbon C2-C18 alkenyl group, C6-C18 aryl group, C7-C18 aralkyl group, C2-C15 acyl group, C1-C6 alkoxy group, C1-C6 fluoroalkyl group, C1-C6 Particularly preferred are fluoroalkoxy groups of 1 to 6, fluoroalkylthio groups of 1 to 6 carbon atoms, halogen atoms, nitro groups, cyano groups, substituted amino groups, carboxylic acid ester groups and the like. Adjacent mutually combine these, and may form ring structure.

The R ^14, R ^15, R ^17, R ^18, and R ²¹ roneun, each independently, R ¹⁴ is a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group, a heterocyclic group, an aralkyl group, Or an acyl group, R ¹⁵ and R ¹⁸ are any of the groups described above, and R ¹⁷ and R ²¹ are most preferably hydrogen atoms.

In addition, R ¹⁶ , R ¹⁹ , and R ²⁰ are preferably any substituents in order to have an absorption spectrum that is increased or decreased by light in the violet region, and as R ¹⁶ , an alkyl group, a cycloalkyl group, an alkenyl group, and a cycloalkenyl group , Heterocyclic group, aryl group, aralkyl group, alkoxy group, alkenyloxy group, alkylthio group, halogen atom, nitro group, cyano group, hydroxyl group, formyl group, sulfonic acid group, carboxyl group, amino group, acylamino group, carbamate group, a sulfonamide group, a carboxylic acid ester group, a carbamoyl group, a sulfamoyl group, a sulfonic acid ester group, etc. are preferred, and an alkyl group, an alkenyl group, an aryl group, or an aralkyl group of and more preferably, R ¹⁹ and R ²⁰ a is And -NR ¹⁹ R ²⁰ may be a substituent in which the amino group is an electron-supplying group, and independently of each other, an alkyl group, an alkenyl group, an aralkyl group, or an acyl group is preferable, and R ¹⁶ is alkyl having 1 to 6 carbons. It is especially preferable that it is a C1-C6 alkyl group as R <^19> and R <^20> each independently as a group or a C6-C18 aryl group.

On the other hand, as in the above compounds represented by the above general formula III, R ¹⁸ and R ^19, R ¹⁹ and R ^20, R ²⁰ and R ^21, R ¹⁵ and adjacent to each other are coupled to the ~R ¹⁸ when forming the ring is, Saturated or unsaturated nitrogen-containing heterocycles in which R ¹⁸ and R ¹⁹ , or R ²⁰ and R ²¹ , or adjacent mutual groups of R ¹⁵ to R ¹⁸ are condensed to a quinoline ring or a 1,8-naphthyridine ring, which are basic skeletons, or When forming a hydrocarbon ring, when R ¹⁹ and R ²⁰ are bonded to form a heterocyclic ring such as a nitrogen-containing heterocycle such as a piperidinyl group and a pyrrolidinyl group, or a morpholinyl group further containing an oxygen atom, and , R ¹⁸ and R ¹⁹ , and R ²⁰ and R ²¹ combine to form a zololidine ring. These formed rings may further have a substituent.

As an example which forms such a ring, the following structure is mentioned, for example. Moreover, in the following structures, the formed ring structure may have arbitrary substituents, and the site | part represented by the hydrogen atom among the site | parts corresponded to R <^14> -R <^21> of the said general formula (III) may have arbitrary substituents.

The molecular weight of the compound represented by the general formula (III) is usually 200 or more, preferably 2,000 or less, and more preferably 1,000 or less. Specific examples of the compound represented by the formula (II) include the following ones.

Moreover, an indolin type compound can be mentioned as a light absorption pigment | dye as a sensitizer which is (N1-2) component in this invention, Especially, it is preferable to represent with following formula (IV).

[Formula IV]

[In formula IV, R <^22> , R <^23> , R <^24> , R <^25> , R <^26> , R <^27> , R <^28> , R <^29> , and R <^30> respectively independently represent a hydrogen atom or an arbitrary substituent, and R <^22> and R ^23, and are each independently R ²² and R ^30, and may form a nitrogen containing heterocycle, and, R ²³ ~R ³⁰ is may form a ring by mutual binding adjacent,.;

Here, as a group preferable as R <^22> , R <^23> , R <^24> , R <^25> , R <^26> , R <^27> , R <^28> , R <^29> and R <^30> in general formula (IV), A hydrogen atom; Linear or branched alkyl groups having 1 to 18 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group and n-heptyl group; Cycloalkyl groups having 3 to 18 carbon atoms such as cyclopropyl group, cyclopentyl group, cyclohexyl group, and adamantyl group; C2-C18 linear or branched alkenyl groups, such as a vinyl group, a propenyl group, and a hexenyl group; Cycloalkenyl groups having 3 to 18 carbon atoms such as a cyclopentenyl group and a cyclohexenyl group; Saturated or unsaturated heterocyclic groups such as 2-thienyl group, 2-pyridyl group, furyl group, thiazolyl group, benzothiazolyl group, morpholino group, pyrrolidinyl group and tetrahydrothiophene dioxide group; C6-C18 aryl groups, such as a phenyl group, a tolyl group, a xylyl group, and a mesityl group; C7-C20 aralkyl groups, such as a benzyl group and a phenethyl group; C2-C18 linear or branched acyl groups, such as an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a valeryl group, and an isovaleryl group; Linear or branched alkoxy groups having 1 to 18 carbon atoms such as methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group and tert-butoxy group; Linear or branched alkenyloxy groups having 3 to 18 carbon atoms such as propenyloxy group, butenyloxy group, and pentenyloxy group; Linear or branched alkylthio groups having 1 to 18 carbon atoms such as methylthio group, ethylthio group, n-propylthio group, n-butylthio group, sec-butylthio group and tert-butylthio group; Halogen atoms such as fluorine atom, chlorine atom and bromine atom; Nitro group; Cyano group; Hydroxyl group; Formyl group; Sulfonic acid groups; Carboxyl groups; Acyloxy group represented by -OCOR; Amino group represented by -NRR '; Acylamino group represented by -NHCOR; Carbamate groups represented by -NHCOOR; Sulfonamide groups represented by -NHSOOR; Carboxylic acid ester group represented by -COOR; Carbamoyl group represented by -CONRR '; Sulfamoyl group represented by -SOONRR '; Sulfonic acid ester group represented by -SO ₂ OR, sulfonyl group represented by -SO ₂ R; The group represented by following formula (IV ') etc. are mentioned.

Preferable examples of R and R 'in these groups include the alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, heterocyclic group, aryl group, aralkyl group, acyl group, alkoxy group, alkenyloxy group and alkylthio group described above. And C2-C18 carboxylic acid ester groups such as methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, tert-butoxycarbonyl group, phenoxycarbonyl group and benzyloxycarbonyl group, in addition to the cyano group.

In Formula (IV), R ^{22, which} is a substituent on a nitrogen atom, includes a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, a heterocyclic group, an aryl group, an aralkyl group, an acyl group, a hydroxyl group, a sulfonyl group, and the like. Preferably, a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkenyl group, an aryl group, etc. are more preferable.

In the above formula (IV), R ²³ , R ²⁴ , R ²⁵ , and R ²⁶ which are substituents on a nitrogen-containing 5-membered ring each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, or the like. Preferably, as R <^23> and / or R <^24> , an alkyl group and a cycloalkyl group are more preferable among these.

In Formula (IV), each of R ²⁷ and R ³⁰ , which are substituents on the benzene ring, is independently a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, a heterocyclic group, an aryl group, an aralkyl group, or an aralkyl group. Real group, alkoxy group, alkenyloxy group, alkylthio group, halogen atom, nitro group, hydroxyl group, sulfonic acid group, carboxyl group, amino group, acylamino group, carbamate group, sulfonamide group, carboxylic acid ester group, carbamoyl group, A sulfamoyl group, a sulfonic acid ester group, a sulfonyl group, etc. are preferable, A hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkylthio group, a nitro group, a hydroxyl group, an amino group, etc. are more preferable.

In the above formula (IV), R ²⁸ and R ^{29 which} are substituents on the benzene ring are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, a heterocyclic group, an aryl group, an aralkyl group, or an acyl group. , An alkoxy group, an alkenyloxy group, an alkylthio group, a halogen atom, a nitro group, a hydroxyl group, an amino group, an acylamino group, a group represented by the following general formula (IV '), and the like, and as R ²⁹ , a hydrogen atom, an alkyl group, A cycloalkyl group, an alkoxy group, an alkylthio group, an amino group, an acylamino group, and the like are more preferable, and R ²⁸ is more preferably a group represented by the following formula (IV ').

[Formula IV ']

[In formula IV ', R ³¹ represents a hydrogen atom or an arbitrary substituent, W represents a divalent arbitrary atom or a substituent, and R ³¹ and R ²⁷ , and R ³¹ and R ²⁹ each independently, They may be bonded to each other to form a ring.]

In the general formula (IV '), W preferably includes an oxygen atom, a sulfur atom, a substituted or unsubstituted methylene group, a substituted or unsubstituted imino group, and the like, and an oxygen atom, a substituted or unsubstituted methylene group, and a substituent. Or an unsubstituted imino group or the like is more preferable. Examples of compounds in which W is these oxygen atoms, substituted or unsubstituted methylene groups, or substituted or unsubstituted imino groups include the following general formulas (IVa), (IVb), (IVc), (IVd), and The compound represented by IVe is mentioned.

[Formula IVa]

[Formula IVb]

[Formula IVc]

Formula IVd

[Formula IVe]

[In formula IVa, IVb, IVc, IVd, and IVe, R <^22> , R <^23> , R <^24> , R <^25> , R <^26> , R <^27> , R <^29> and R <^30> are the same as that of said Formula IV, ^R31 , R ³² , R ³³ , R ³⁴ , R ³⁵ , and R ³⁶ represent a hydrogen atom or an optional substituent, V represents an oxygen atom or NR ³⁷ , and R ³⁷ represents a hydrogen atom or any A substituent.]

표시는 바람직한 치환기를, ◎ 는 특히 바람직한 치환기를 각각 나타낸다.In the above general formula [IVa, IVb, IVc, IVd, and ^{IVe R 31, R 32, R} 33, R 34, R 35, and R ^36, and roneun R ³⁷ in IVd, for Formula IV, R ^22, there may be mentioned ^{R 23, R 24, R 25} , R 26, R 27, R 28, R 29, R ³⁰ and preferred groups the same as those exemplified as the. Among them, preferred groups of R ³¹ are different in each of Formulas IVa, IVb, IVc, IVd, or IVe, and are shown in Table 3 below. Meanwhile, in the following table,

The mark represents a preferable substituent, and (?) Represents a particularly preferred substituent.

TABLE 3

(The preferred group of R ³¹ )

(IVa) (IVb) (IVc) (IVd) (IVe) Hydrogen atom ◎ ◎ ◎ ◎ Alkyl group

◎ ◎ ◎ ◎ Cycloalkyl group

◎ ◎ ◎ ◎ Alkenyl groups ◎

Cycloalkenyl group ◎

Heterocyclic ◎

◎ Aryl group ◎ ◎

◎ ◎ Aralkyl group Acyl

◎

Alkoxy group

◎ ◎ ◎ Alkenyloxy group

Alkylthio group

◎

◎ Halogen atom Nitro group Cyanogi Hydroxy lock

Formyl Sulfonic acid group Carboxyl group

Acyloxy group

◎

Amino group

Acylamino group Carbamate Sulfonamide groups Carboxylic Acid Ester Group

Carbamoyl group Sulfa diary Sulfonic acid ester group Sulfonyl groups

표시는 바람직한 치 환기를, ◎ 는 특히 바람직한 치환기를 각각 나타낸다.In addition, in the general formula (IV), as R ³² , R ³³ , R ³⁴ , R ³⁵ , and R ³⁶ in the general formula (IVb), (IVc), (IVd), and (IVe), R ²² , R ²³ , R ²⁴ , R ²⁵ The same as what was illustrated as a preferable group of R <^26> , R <^27> , R <^28> , R <^29> , and R <^30> , Among them, as each preferable group, it is as Table 4 below. Meanwhile, in the following table,

Indication shows preferable tooth restoration, (double-circle) shows especially preferable substituent, respectively.

TABLE 4

(Preferred group of R ³² to R ³⁶ )

(IVb) (IVc) (IVd) (IVe) R ³² R ³³ R ³⁴ R ³⁵ R ³⁶ Hydrogen atom ◎ ◎ ◎ ◎ ◎ Alkyl group ◎ ◎

◎ ◎ Cycloalkyl group ◎ ◎

◎ ◎ Alkenyl groups ◎ ◎ ◎

Cycloalkenyl group ◎ ◎ ◎

Heterocyclic

◎ ◎ Aryl group

◎ ◎ ◎ Aralkyl group

Acyl ◎ ◎

◎

Alkoxy group

◎ Alkenyloxy group

Alkylthio group

Halogen atom

◎ Nitro group Cyanogi ◎ ◎

Hydroxy lock ◎ Formyl Sulfonic acid group

Carboxyl group

◎

Acyloxy group

Amino group

Acylamino group

Carbamate Sulfonamide groups

Carboxylic Acid Ester Group ◎ ◎ ◎

Carbamoyl group Sulfa diary Sulfonic acid ester group

Sulfonyl groups

◎

Further, in the general formula IVd, R ³⁷ roneun preferred when V is NR ³⁷ days, a hydrogen atom; Linear or branched alkyl groups having 1 to 18 carbon atoms; C1-C18 linear or branched acyl group etc. are mentioned, Among these, a hydrogen atom or an alkyl group is especially preferable.

In the above formula (IV), a nitrogen-containing heterocycle in which R ²² and R ²³ , and R ²² and R ³⁰ may be formed, and a ring structure in which adjacent groups of R ²³ to R ³⁰ may be bonded to each other are formed; The specific example of is shown below.

[Example of Forming Ring with R ²² and R ³⁰ ]

[Example of Forming Ring with R ²² and R ²³ ]

[Example of Forming Ring with R ²⁴ and R ²⁵ ]

[Example of Forming Ring with R ²⁶ and R ²⁷ ]

[Example of Forming Ring with R ²⁷ and R ²⁸ ]

[Example of Forming Ring with R ²⁸ and R ²⁹ ]

[Example of Forming Ring With R ²⁹ and R ³⁰ ]

The molecular weight of the compound represented by the above formula (IV) is usually 200 or more, preferably 2,000 or less, and more preferably 1,000 or less. As a specific example of the compound represented by the said general formula (IV), the following compounds are respectively mentioned in said general formula (IVa), IVb, IVc, IVd, and IVe.

[Compound represented by Formula IVa]

[Compound represented by Formula IVb]

[Compound represented by Formula IVc]

[Compound represented by Formula IVd]

[Compound represented by Formula IVe]

In the present invention, when the blue-violet laser photosensitive resist material layer of the image forming material is composed of a photopolymerizable negative photosensitive composition (N1), the dialkylaminobenzene-based compound and the sulfonyl as a sensitizer which is a component (N1-2) By containing an imino-group containing compound, the said 2-naphthylidedione type compound, the 2-quinolone type compound, or the said indolin type compound, even if it is a thick film | membrane, a sensitivity does not fall and a resist image excellent in resolution can be formed. It becomes possible.

When the photoinitiator which is the (N1-3) component which comprises the photopolymerizable negative photosensitive composition (N1) in this invention is light-irradiated under coexistence with the sensitizer etc. which are said (N1-2) components, A hexaarylbiimidazole-based compound, for example, as a radical generator as an active compound that accepts photoexcitation energy of to generate an active radical and leads to polymerization of the ethylenically unsaturated compound as the (N1-1) component. , Titanocene-based compounds, halogenated hydrocarbon derivatives, diaryl iodonium salts, and organic peroxides. Among them, hexaarylbiimidazole-based compounds or titanocene-based compounds are preferable, and hexaarylbiimidazole-based compounds are particularly preferable in view of sensitivity as a photosensitive composition, adhesion to a substrate, storage stability, and the like.

Specifically as the hexaarylbiimidazole-based compound, for example, 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2, 2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetra (p-methylphenyl) biimidazole, 2,2'-bis (o-chlorophenyl) -4,4', 5 , 5'-tetra (p-methoxyphenyl) biimidazole, 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetra (p-ethoxycarbonylphenyl) ratio Imidazole, 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetra (p-chlorophenyl) biimidazole, 2,2'-bis (o-chlorophenyl)- 4,4 ', 5,5'-tetra (o, p-dichlorophenyl) biimidazole, 2,2'-bis (o, p-dichlorophenyl) -4,4', 5,5'-tetra ( o, p-dichlorophenyl) biimidazole, 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetra (p-fluorophenyl) biimidazole, 2,2' -Bis (o-chlorophenyl) -4,4 ', 5,5'-tetra (o, p-dibromophenyl) biimidazole, 2,2'-bis (o-bromophenyl) -4, 4 ', 5,5'-tetra (o, p-dichlorophenyl) biimidazole, 2,2'-bis (o-bromophenyl ) -4,4 ', 5,5'-tetra (p-iodinephenyl) biimidazole, 2,2'-bis (o-bromophenyl) -4,4', 5,5'-tetra (o -Chloro-p-methoxyphenyl) biimidazole, 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetra (p-chloronaphthyl) biimidazole and the like Can be. Especially, a hexaphenyl biimidazole compound is preferable, It is more preferable that the o-position of the benzene ring couple | bonded with the 2,2'-position on the imidazole ring is substituted by the halogen atom, The 4,4 'on the imidazole ring It is particularly preferable that the benzene ring bonded at the, 5,5'-position is unsubstituted or substituted with a halogen atom or an alkoxycarbonyl group. Moreover, these hexaaryl biimidazole type compounds are [Bull. Chem. Soc. Japan; 33, 565 (1960), J. Org. Chem .; 36, 2262 (1971)] may be used in combination with a biimidazole-based compound synthesized by the method disclosed in.

The hexaarylbiimidazole type compound known conventionally as a photoinitiator in a photosensitive composition has a melting point of 190 degreeC or more, for example, about 196-202 degreeC, and Bragg angle in the X-ray-diffraction spectrum of wavelength 1.54 Hz. (X) (Bragg angle) (2θ ± 0.2 °) Although having a maximum diffraction peak at 9.925 °, the hexaarylbiimidazole-based compound in the present invention is soluble in a coating solvent and dispersion stability in a photosensitive composition. From the standpoint of this, the melting point is 180 ° C. or lower, more preferably 175 ° C. or lower, and most preferably has a maximum diffraction peak at a Bragg angle (2θ ± 0.2 °) of 21.16 ° in the X-ray diffraction spectrum with a wavelength of 1.54 Hz. Suitable and suitable hexaarylbiimidazole-based compounds are, for example, 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2, 2'-bis (o, p-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'- Bis (o-bromophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o, p-dichlorophenyl) -4,4', 5,5'- Tetra (p-methoxyphenyl) biimidazole and the like, among which 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2 Particular preference is given to, 2'-bis (o, p-dichlorophenyl) -4,4 ', 5,5'-tetra (p-methoxyphenyl) biimidazole.

As the titanocene-based compound, specifically, for example, dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium bisphenyl, dicyclopentadienyl titanium bis (2,4-difluoro Phenyl), dicyclopentadienyl titanium bis (2,6-difluorophenyl), dicyclopentadienyl titanium bis (2,4,6-trifluorophenyl), dicyclopentadienyl titanium bis (2 , 3,5,6-tetrafluorophenyl), dicyclopentadienyltitaniumbis (2,3,4,5,6-pentafluorophenyl), di (methylcyclopentadienyl) titaniumbis (2, 4-difluorophenyl), di (methylcyclopentadienyl) titaniumbis (2,6-difluorophenyl), di (methylcyclopentadienyl) titaniumbis (2,4,6-trifluorophenyl ), Di (methylcyclopentadienyl) titaniumbis (2,3,5,6-tetrafluorophenyl), di (methylcyclopentadienyl) titaniumbis (2,3,4,5,6-pentafluoro Rophenyl), dicyclopenta Enyl, and the like titanium bis [2,6-difluoro-3- (1-pyrrolyl) phenyl]. Especially, the titanium compound which has a dicyclopentadienyl structure and a biphenyl structure is preferable, and it is especially preferable that the o-position of a biphenyl ring substituted by the halogen atom.

In this invention, the ethylenically unsaturated compound which is the said (N1-1) component in the said photopolymerizable negative photosensitive composition (N1), the sensitizer which is the said (N1-2) component, and said (N1-3) It is preferable that each content rate of the photoinitiator which is a component is 0.05-20 weight part, and, as for the sensitizer which is (N1-2) component with respect to 100 weight part of ethylenically unsaturated compounds which are (N1-1) components, 0.1-10 weight More preferably denial. Moreover, it is preferable that it is 1-60 weight part, and, as for the photoinitiator which is (N1-3) component, it is more preferable that it is 5-40 weight part.

The photopolymerizable negative photosensitive composition (N1) of the present invention is formed as a photosensitive resist material layer on a substrate other than the components (N1-1), (N1-2) and (N1-3). And for the purpose of improvement of developability etc., it is preferable to contain a polymeric binder (N1-4) component further, As this polymeric binder, it is (meth) acrylic acid, (meth) acrylic acid ester, ( Homopolymers or copolymers such as meth) acrylonitrile, (meth) acrylamide, maleic acid, styrene, vinyl acetate, vinylidene chloride, maleimide, and polyamides, polyesters, polyethers, polyurethanes, and polyvinyls Butyral, polyvinyl alcohol, polyvinylpyrrolidone, acetyl cellulose, etc. are mentioned, Among these, a carboxyl group-containing vinyl resin is preferable at the point of alkali developability.

Specific examples of the carboxyl group-containing vinyl resin include unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid, styrene, α-methylstyrene, hydroxystyrene, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate , Dodecyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) Acrylate, N, N-dimethylaminoethyl (meth) acrylate, N- (meth) acryloyl morpholine, (meth) acrylonitrile, (meth) acrylamide, N-methylol (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-dimethylamino And copolymers with vinyl compounds such as methyl (meth) acrylamide, vinyl acetate, and the like. These carboxyl group-containing vinyl resins have an acid value of 30 to 250 KOH · mg / g and a weight average molecular weight in terms of polystyrene. It is preferable that it is 1,000-300,000.

Among these, as a polymeric binder in a negative photosensitive composition (N1), it is a copolymer containing the structural repeating unit derived from each monomer of a styrene type monomer, a (meth) acrylic acid ester monomer, and (meth) acrylic acid. Preferably, as the copolymer, the constituent repeating units derived from each of the monomers of the styrene monomer, the (meth) acrylic acid ester monomer, and the (meth) acrylic acid are respectively 3 to 30 mol%, 10 to 70 mol%, And 10 to 60 mol%, and particularly preferably 5 to 25 mol%, 20 to 60 mol%, and 15 to 55 mol%.

Here, as the styrene monomer in the copolymer, specifically, for example, α-substituted alkyl styrene such as styrene, α-methyl styrene, α-ethyl styrene, o-methyl styrene, m-methyl styrene, Nuclear substituted hydroxy styrene, such as p-methylstyrene, 2, 5- dimethyl styrene, o-hydroxy styrene, m-hydroxy styrene, p-hydroxy styrene, dihydroxy styrene, p- Nuclear-substituted halogenated styrenes, such as chloro styrene, p-bromo styrene, and dibromo styrene, etc. are mentioned, Specifically, as an acrylate ester monomer, For example, methyl (meth) acrylate and ethyl (Meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl ( Of (meth) acrylic acid, such as meth) acrylate, Preferably burnt Alkyl 1-12, More preferably, the alkyl ester of C1-C8, glycidyl (meth) acrylate, benzyl (meth) acrylate, aminoethyl (meth) acrylate, N, N- dimethylaminoethyl Substituted alkyl esters, such as (meth) acrylate, etc. are mentioned.

On the other hand, as said copolymer, in addition to the structural repeating unit derived from the said styrene monomer, the (meth) acrylic acid ester monomer, and each monomer of (meth) acrylic acid, For example, crotonic acid, isocrotonic acid, Unsaturated carboxylic acids such as maleic acid, maleic anhydride, itaconic acid, citraconic acid, (meth) acrylonitrile, (meth) acrylamide, N-methylol (meth) acrylamide, N, N-dimethyl (meth) Even if it contains the structural repeating unit derived from (meth) acrylic acid derivatives, such as acrylamide and N, N- dimethylaminoethyl (meth) acrylamide, and other copolymerizable monomers, such as vinyl compounds, such as vinyl acetate and a vinyl chloride. It is preferable that content of the structural repeating unit derived from these other monomers is 10 mol% or less of the whole copolymer. Moreover, it is preferable that these copolymers have an acid value of 30-250 mg.KOH / g, and the weight average molecular weight of polystyrene conversion is 1,000-300,000.

As other carboxyl group-containing vinyl-type resin, carboxyl group-containing vinyl resin which has an ethylenically unsaturated bond in a side chain is mentioned, As this carboxyl group-containing vinyl resin, specifically, for example, allyl to a carboxyl group-containing polymer Glycidyl ether, glycidyl (meth) acrylate, α-ethylglycidyl (meth) acrylate, glycidyl crotonate, glycidyl isoctonate, crotonyl glycidyl ether, itaconic acid Aliphatic epoxy group-containing unsaturated compounds such as monoalkyl monoglycidyl esters, monoalkyl monoglycidyl esters of fumaric acid, and monoalkyl monoglycidyl esters of maleic acid, or 3,4-epoxycyclohexylmethyl (meth) acrylates; Alicyclic epoxy group containing fluorine, such as 2, 3- epoxycyclopentyl methyl (meth) acrylate and 7,8-epoxy [tricyclo [5.2.1.0] dec-2-yl] oxymethyl (meth) acrylate 5 to 90 mol%, preferably about 30 to 70 mol%, of the carboxyl group of the carboxyl group-containing polymer, the reaction product obtained, and allyl (meth) acrylate, 3-allyloxy-2-hydride 2 or more types of unsaturated groups, such as oxypropyl (meth) acrylate, cinnamil (meth) acrylate, crotonyl (meth) acrylate, a metalyl (meth) acrylate, and N, N- diallyl (meth) acrylamide Compound which has, or vinyl (meth) acrylate, 1-chlorovinyl (meth) acrylate, 2-phenylvinyl (meth) acrylate, 1-propenyl (meth) acrylate, vinyl crotonate, vinyl (meth 10-90 mol% of the compound which has 2 or more types of unsaturated groups, such as acrylamide, unsaturated carboxylic acid, such as (meth) acrylic acid, or more unsaturated carboxylic acid ester in the whole compound which has an unsaturated group which is an electron is preferable. There may be mentioned a reaction product such as obtained by copolymerization so that the degree of 30~80 mol%.

Moreover, as another carboxyl group-containing vinyl-type resin, the unsaturated group and carboxyl group-containing epoxy resin which polyhydric carboxylic acid or its anhydride was added to the (alpha), (beta)-unsaturated monocarboxylic acid adduct of an epoxy resin are mentioned.

Specifically, the unsaturated group and the carboxyl group-containing epoxy resin have an ethylenically unsaturated bond added to the epoxy group of the epoxy resin via an ester bond (-COO-) formed by ring-opening addition of a carboxyl group of α, β-unsaturated monocarboxylic acid. At the same time, the carboxyl group remaining through the ester bond formed by the reaction of the carboxyl group of a polyvalent carboxylic acid or its anhydride with the resulting hydroxyl group is added.

Here, as this epoxy resin, a bisphenol A epoxy resin, a bisphenol F epoxy resin, a bisphenol S epoxy resin, a phenol novolak epoxy resin, a cresol novolak epoxy resin, a trisphenol epoxy resin etc. are specifically mentioned here, for example. Among them, phenol novolac epoxy resin or cresol novolac epoxy resin is particularly preferred. Moreover, as the (alpha), (beta)-unsaturated monocarboxylic acid, (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, a citraconic acid etc. are mentioned specifically, Meth) acrylic acid is particularly preferred. Moreover, as the polyhydric carboxylic acid or its anhydride, for example, succinic acid, maleic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, endomethylenetetrahydrophthalic acid, and methylendomethylenetetra Hydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, and their anhydrides, and the like, among which maleic anhydride, tetrahydrophthalic anhydride, or hexahydrophthalic anhydride is preferred, and tetrahydrophthalic anhydride is particularly preferred. .

Among these unsaturated groups and carboxyl group-containing epoxy resins, epoxy resins are phenol novolac epoxy resins or cresol novolac epoxy resins in terms of sensitivity, resolution, and adhesion to substrates as photosensitive compositions, and α, β- It is especially preferable that unsaturated monocarboxylic acid is (meth) acrylic acid, and polyhydric carboxylic acid or its anhydride is tetrahydrophthalic anhydride. Moreover, it is preferable that acid value is 20-200 mgKOH / g, and the weight average molecular weight is 2,000-200,000.

In this invention, the content rate of the polymeric binder which is the said (N1-4) component in the said photopolymerizable negative photosensitive composition (N1) is with respect to 100 weight part of ethylenically unsaturated compounds which are (N1-1) components, It is preferable that it is 50-500 weight part, and it is more preferable that it is 70-200 weight part.

Moreover, it is preferable that the said photopolymerizable negative photosensitive composition (N1) in this invention contains a hydrogen supply compound (N1-5) component further for the purpose of the improvement of a photoinitiation capability, etc., As this hydrogen supply compound, 2-mercaptobenzothiazole, 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, 3-mercapto-1,2,4-triazole, Mercapto group containing, such as 2-mercapto-4 (3H) -quinazolin, (beta) -mercaptonaphthalene, ethylene glycol dithio propionate, trimethylol propane tristyopyropionate, pentaerythritol tetrakistylopyropionate Polyfunctional thiol compounds such as compounds, hexanedithiol, trimethylolpropane tristhioglyconate, pentaerythritol tetrakistiopriopionate, N, N-dialkylaminobenzoic acid esters, N-phenylglycine, or esters thereof; That ammonium Or amino acids having aromatic rings such as salts such as sodium salts, derivatives such as dipole compounds, phenylalanine or esters thereof, salts such as ammonium and sodium salts, derivatives such as dipole compounds, and derivatives thereof. Can be mentioned. Among them, mercapto group-containing compounds and amino acids or derivatives thereof are preferred in the present invention.

In this invention, the content rate of the hydrogen supply compound which is the said (N1-5) component in the said photopolymerizable negative photosensitive composition (N1) is 100 weight part of ethylenically unsaturated compounds which are the said (N1-1) components. It is preferable that it is 1-50 weight part with respect to, and it is more preferable that it is 10-40 weight part.

Moreover, it is preferable that the said photopolymerizable negative photosensitive composition (N1) in this invention contains an amine compound (N1-6) component further for the purpose of the improvement of storage stability, etc. as a photosensitive composition, The amine compound may be any aliphatic, cycloaliphatic or aromatic amine, and is not limited to monoamines, and may be polyamines such as diamines and triamines, and both first amines, second amines, and third amines may be used. It is preferable that pKb is 7 or less. As the amine compound, specifically, for example, butylamine, dibutylamine, tributylamine, amylamine, diamylamine, triamylamine, hexylamine, dihexylamine, trihexylamine, allylamine, Aliphatic amines which may be substituted with a hydroxyl group or a phenyl group, such as diallylamine, triallylamine, triethanolamine, benzylamine, dibenzylamine, and tribenzylamine, are mentioned. Among them, in the present invention, tribenzylamine This is preferable.

In this invention, the content rate of the amine compound which is the said (N1-6) component in the said photopolymerizable negative photosensitive composition (N1) is based on 100 weight part of ethylenically unsaturated compounds which are the said (N1-1) components. It is preferable that it is 1-20 weight part, and it is more preferable that it is 5-10 weight part.

Moreover, the said photopolymerizable negative photosensitive composition (N1) in this invention is further aimed at the improvement of the applicability | paintability at the time of forming a photosensitive resist material layer on a board | substrate, developability, etc. of the photosensitive resist material layer, and the like. It is preferable to contain surfactant (N1-7) components, such as nonionic, anionic, cationic, amphoteric, and fluorine-based, and specifically, as the nonionic surfactant, for example, poly Oxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl esters, polyoxyethylene fatty acid esters, glycerin fatty acid esters, polyoxyethylene glycerin fatty acid esters , Pentaerythrite fatty acid esters, polyoxyethylene pentaerythrite fatty acid esters, sorbitan fatty acid esters, poly Reoxyethylene sorbitan fatty acid esters, sorbitol fatty acid esters, polyoxyethylene sorbitol fatty acid esters, and the like, and as the anionic surfactant, alkyl sulfonates, alkylbenzene sulfonates, alkyl naphthalene sulfonates, polyoxy Ethylene alkyl ether sulfonates, alkyl sulfates, alkyl sulfate ester salts, higher alcohol sulfate ester salts, aliphatic alcohol sulfate ester salts, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkylphenyl ether sulfates, alkyl phosphate ester salts, poly Oxyethylene alkyl ether phosphates, polyoxyethylene alkyl phenyl ether phosphates, and the like, and as cationic surfactants, quaternary ammonium salts, imidazoline derivatives, amine salts, and the like, As a betaine type compound, imidazolium salt, imidazoline, amino acid, etc., respectively, Can.

In this invention, the content rate of surfactant which is the said (N1-7) component in the said photopolymerizable negative photosensitive composition (N1) is based on 100 weight part of ethylenically unsaturated compounds which are the said (N1-1) components. It is preferable that it is 0.1-10 weight part, and it is more preferable that it is 1-5 weight part.

Moreover, the said photopolymerizable negative photosensitive composition (N1) in this invention further contains the silane compound (N1-8) component known as a silane coupling agent for the purpose of the improvement of adhesiveness etc. with respect to a board | substrate. You may contain it. Specifically as the silane compound, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, vinyltrichlorosilane, 3-methacryloyloxy Propyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyl Methyldimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane , 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- [N- (2-aminoethyl) amino] propyltrimethoxysilane, 3- [N- (2-aminoethyl) amino ] Propyltriethoxysilane, 3- [N- (2-aminoethyl) amino] propylmethyldimethoxysilane, 3- [N- (2-aminoethyl) amino] propylmethyldiethoxysil , 3- (N-allyl-N-glycidylamino) propyltrimethoxysilane, 3- (N-allyl-N-glycidylamino) propyltriethoxysilane, 3- (N, N-digly Cydylamino) propyltrimethoxysilane, 3- (N, N-diglycidylamino) propyltriethoxysilane, 3- (N-phenylamino) propyltrimethoxysilane, 3- (N-phenylamino ) Propyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, etc., and N- Glycidyl-N, N-bis [3- (trimethoxysilyl) propyl] amine, N-glycidyl-N, N-bis [3- (triethoxysilyl) propyl] amine, N-glycid Di-N, N-bis [3- (methyldimethoxysilyl) propyl] amine, N-glycidyl-N, N-bis [3- (methyldiethoxysilyl) propyl] amine, and the like.

In this invention, the content rate which is the said silane compound (N1-8) component in the said photopolymerizable negative photosensitive composition (N1) is with respect to 100 weight part of ethylenically unsaturated compounds which are the said (N1-1) components, It is preferable that it is 10 weight part or less, and it is more preferable that it is 5 weight part or less.

Moreover, the said photopolymerizable negative photosensitive composition (N1) in this invention further contains various additives, for example, hydroquinone, p-methoxy phenol, 2, 6- di- t-butyl- p- 2 parts by weight or less of a thermal polymerization inhibitor such as cresol, based on 100 parts by weight of the ethylenically unsaturated compound as the (N1-1) component, and 20 parts by weight or less of a colorant composed of an organic or inorganic dye pigment, dioctylphthalate, Similarly, plasticizers such as dodecyl phthalate and tricredyl phosphate may also contain 40 parts by weight or less, a sensitivity characteristic improver such as tertiary amine or thiol, 10 parts by weight or less, and a dye precursor in a proportion of 30 parts by weight or less. .

N2. Chemically amplified negative photosensitive composition]

Moreover, as a photosensitive composition which comprises the photosensitive resist material layer of this invention, the chemically amplified negative photosensitive composition (N2) containing the following (N2-1), (N2-2), and (N2-3) component It is preferable that it consists of.

(N2-1) alkali soluble resin

(N2-2) Crosslinking agent which acts on alkali-soluble resin under acidic conditions

(N2-3) acid generator

As alkali-soluble resin which is the (N2-1) component which comprises the chemically amplified negative photosensitive composition (N2) in this invention, if an unexposed part becomes alkali-soluble at the time of image development, and is eluted to alkaline developing solution, Although it is not limited, Usually, it contains phenol resins, such as a novolak resin and a resol resin, polyvinyl phenol resin, polyacrylic acid, polyvinyl alcohol, styrene maleic anhydride resin, and acrylic acid, vinyl alcohol, or vinylphenol as a monomer unit. Polymers or derivatives thereof. Among these, it is preferable to contain the polymerization unit which has a phenolic hydroxyl group especially, and a novolak resin or polyvinyl phenol resin is preferable.

As a novolak resin, For example, a phenol, o-cresol, m-cresol, p-cresol, 2, 5- xylenol, 3, 5- xylenol, o-ethylphenol, m-ethylphenol, p-ethylphenol, propylphenol, n-butylphenol, t-butylphenol, 1-naphthool, 2-naphthool, 4,4'-biphenyldiol, bisphenol-A, pyrocatechol, resorcinol, hydro At least one of phenols such as quinone, pyrogallol, 1,2,4-benzenetriol, and phloroglucinol is, for example, formaldehyde, paraformaldehyde, acetaldehyde, paraaldehyde, propionaldehyde under an acid catalyst. , Polycondensed with at least one of aldehydes such as benzaldehyde, furfural, or ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and the like as the resol resin for polycondensation of the novolak resin. In addition, the thing polycondensed similarly except using an alkali catalyst instead of an acid catalyst is mentioned, respectively.

As the novolak resin, at least one phenol selected from o-cresol, m-cresol, p-cresol, 2,5-xylenol, 3,5-xylenol, and resorcin is selected from formaldehyde, Resin polycondensed with at least 1 sort (s) chosen from aldehydes, such as acetaldehyde and a propionaldehyde, is preferable, Especially, m-cresol: p-cresol: 2, 5- xylenol: 3, 5- xylenol The novolak resin, which is a polycondensation product of phenols having a mixing ratio of resorcin in a molar ratio of 70 to 100: 0 to 30: 0 to 20: 0 to 20: 0 to 20 and formaldehyde as aldehydes, is particularly preferred. Moreover, it is preferable that the weight average molecular weights (Mw) of polystyrene conversion by a gel permeation chromatography measurement are 1,000-15,000, and it is especially preferable that it is 1,500-10,000.

As a polyvinyl phenol resin, o-hydroxy styrene, m-hydroxy styrene, p-hydroxy styrene, dihydroxy styrene, trihydroxy styrene, tetrahydroxy styrene, pentahydroxy styrene, 2 alone or two or more kinds of hydroxystyrenes such as-(o-hydroxyphenyl) propylene, 2- (m-hydroxyphenyl) propylene, 2- (p-hydroxyphenyl) propylene, or, further, Styrene, (meth) acrylic acid, (meth) acrylic acid ester, maleic acid having a substituent other than hydroxyl groups such as styrene, alkyl group, alkoxy group, acyl group, acyloxy group, allyloxy group, aryloxy group and halogen atom Other vinyl compounds, such as maleic acid imide, are polymerized or copolymerized in the presence of a radical polymerization initiator or a cationic polymerization initiator, or hydroxyl groups of these hydroxystyrenes are t-butoxycarbonyl group, pyranyl group and furanyl group. Protected by a back protector The thing which dissociated the protecting group after superposing | polymerizing or copolymerizing one styrene derivative similarly is mentioned.

As polyvinyl phenol resin, what consists of hydroxy styrenes which do not have substituents other than a hydroxyl group is especially preferable, Moreover, the weight average molecular weight (Mw) of polystyrene conversion by gel permeation chromatography measurement is 1,000-100,000. It is preferable that it is and it is especially preferable that it is 1,500-50,000.

Moreover, the crosslinking agent which acts on alkali-soluble resin under acidic conditions of the (N2-2) component which comprises the chemically amplified negative photosensitive composition (N2) in this invention was that the photosensitive composition was irradiated with actinic light. When forming a crosslinked structure in the said alkali-soluble resin (N2-1) at this time, if it is a compound which causes a crosslinking reaction to the said alkali-soluble resin to be used, it will not specifically limit, Typically, it is a methylol group as a functional group, The amino compound etc. which have at least two alcohol condensation-modified alkoxy methyl group, an acetoxy methyl group, etc. are mentioned, For example, the polycondensation of the melamine resin which polycondensed melamine and formaldehyde, benzoguanamine, and formaldehyde polycondensed Benzoguanamine resin, glycoluril resin polycondensed glycoluril and formaldehyde, urea and formaldehyde The resin which co-condensed 2 or more types, such as urea resin, melamine, benzoguanamine, glycoluril, or urea which polycondensed, and formaldehyde, and the modified resin which carried out alcohol condensation-modification of the methylol group of these resins are mentioned. have.

Specifically, as melamine resin and its modified resin, Mitsui Cytec Co., Ltd. "Cymel" (registered trademark) 300, 301, 303, 350, 736, 738, 370, 771, 325, 327, 703, 701, 266, 267 , 285, 232, 235, 238, 1141, 272, 254, 202, 1156, 1158, and "Nikarak" (registered trademark) E-2151, MW-100LM, MX-750LM from Sangwa Chemical Co., Ltd. As guanamine resin and its modified resin, "Cymel" (registered trademark) 1123, 1125, 1128, Moreover, as glycol uril resin and its modified resin, "Cymel" (registered trademark) 1170, 1171, 1174, 1172, and , "Nikarak" (registered trademark) MX-270, "UFR" (registered trademark) 65, 300, and "Nikarak" (registered trademark) MX-290 from Mitsui Cytec Co., Ltd. as urea resins and modified resins thereof. Can be mentioned.

As a crosslinking agent, an epoxy group containing compound can also be mentioned, As this epoxy group containing compound, the polyglycidyl ether compound and poly which are obtained by making the polyhydroxy compound and epichlorohydrin which comprise the repeating unit of what is called an epoxy resin react, Polyglycidyl ester compounds obtained by reacting a carboxylic acid compound with epichlorohydrin, and polyglycidylamine compounds obtained by reacting a polyamine compound with epichlorohydrin. Can be mentioned.

Specifically as these polyglycidyl ether compounds, For example, the diglycidyl ether type epoxy of polyethyleneglycol, the diglycidyl ether type epoxy of bis (4-hydroxyphenyl), bis (3,5) -Dimethyl-4-hydroxyphenyl) diglycidyl ether type epoxy, bisphenol F diglycidyl ether type epoxy, bisphenol A diglycidyl ether type epoxy, tetramethyl bisphenol A diglycidyl ether Diglycidyl ether type epoxy, phenol novolak type epoxy, cresol novolak type epoxy, etc. of ethylene oxide addition bisphenol A, etc. are mentioned to these polyglycidyl ether compounds. An acid anhydride or a divalent acid compound may be made to react and a carboxyl group may be introduce | transduced. As the polyglycidyl ester compound, specifically, for example, a diglycidyl ester epoxy of hexahydrophthalic acid, a diglycidyl ester epoxy of phthalic acid, or the like, and a polyglycidyl amine compound As a specific example, the diglycidyl amine type epoxy of bis (4-aminophenyl) methane, the triglycidyl amine type epoxy of isocyanuric acid, etc. are mentioned, for example.

As the epoxy group-containing compound, specifically, "YDP N-638, 701, 702, 703, 704" manufactured by Toto Kasei Co., Ltd., "YH-434" also, "Epicoat 825, 826, 827, manufactured by Japan Epoxy Resin Co., Ltd." 828, 1001, 1002, 1003, 1055, 1004, 1007, 1009, 1010 ”and the like.

In this invention, in these crosslinking agents, a melamine resin or urea resin is preferable. Moreover, the acid generator which is the (N2-3) component which comprises the chemically amplified negative photosensitive composition (N2) in this invention is an active compound which produces an acid when the photosensitive composition is irradiated with actinic light. Examples of the photoacid generator include halogen-containing compounds such as halogen-substituted alkanes and halomethylated s-triazine derivatives, onium salts, sulfone compounds, and the like. Among them, in the present invention, Halomethylated s-triazine derivatives or sulfone compounds are particularly preferred.

Here, as the halogen-substituted alkanes among the halogen-containing compounds, for example, dichloromethane, trichloromethane, 1,2-dichloroethane, 1,2-dibromoethane and the like can be mentioned.

In addition, as the halomethylated s-triazine derivative in the halogen-containing compounds, specifically, for example, 2,4,6-tris (monochloromethyl) -s-triazine, 2,4,6- Tris (dichloromethyl) -s-triazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2 -n-propyl-4,6-bis (trichloromethyl) -s-triazine, 2- (α, α, β-trichloroethyl) -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- (p-chlorophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2 -[1- (p-methoxyphenyl) -2,4-butadienyl] -4,6-bis (trichloromethyl) -s-triazine, 2-styryl-4,6-bis (trichloro Methyl) -s-triazine, 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) -s- Lysine, 2- (p-methoxy-m-hydroxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (pi-propyloxystyryl) -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- (p-ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-ethoxycarbonylnaph Tyl) -4,6-bis (trichloromethyl) -s-triazine, 2-phenylthio-4,6-bis (trichloromethyl) -s-triazine, 2-benzylthio-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 (tribromomethyl) -s-triazine, 2-methoxy-4,6-bis (tribromomethyl) -s-triazine, etc. are mentioned, Among them, Bis (trihalomethyl) -s-triazine is preferred, and 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 (trichloromethyl) -s-triazine, 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxy-m-hydric Oxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (pi-propyloxystyryl) -4,6-bis (trichloromethyl) -s-triazine and the like desirable.

Moreover, as the onium salt, ammonium salts, such as tetramethylammonium bromide and tetraethylammonium bromide, diphenyl iodonium hexafluoro arsenate, diphenyl iodonium tetrafluoro borate, and diphenyl iodonium p-toluene sulfonate , Diphenyl iodonium camphor sulfonate, dicyclohexyl iodonium hexafluoroacenate, dicyclohexyl iodonium tetrafluoroborate, dicyclohexyl iodonium p-toluenesulfonate, dicyclohexyl iodonium camphor sulfonate Iodonium salts, triphenylsulfonium hexafluoroarsenate, triphenylsulfonium tetrafluoroborate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium camphorsulfonate, tricyclohexylsulfonium hexafluoro Loarsenate, tricyclohexylsulfonium tetrafluoroborate, tricyclohexylsulfonium p-tolu Sulfonate, sulfonium salts, etc. may be mentioned, such as tricyclohexylphosphine sulfonyl nyumkam formate sulfonate.

Moreover, specifically, as sulfone compounds, bis (phenylsulfonyl) methane, bis (p-hydroxyphenyl sulfonyl) methane, bis (p-methoxyphenylsulfonyl) methane, bis ( bis such as α-naphthylsulfonyl) methane, bis (β-naphthylsulfonyl) methane, bis (cyclohexylsulfonyl) methane, bis (t-butylsulfonyl) methane, phenylsulfonyl (cyclohexylsulfonyl) methane (Sulfonyl) methane compound, phenylcarbonyl (phenylsulfonyl) methane, naphthylcarbonyl (phenylsulfonyl) methane, phenylcarbonyl (naphthylsulfonyl) methane, cyclohexylcarbonyl (phenylsulfonyl) methane, t Carbonyl (sulfonyl) methane compounds, such as butylcarbonyl (phenylsulfonyl) methane, phenylcarbonyl (cyclohexylsulfonyl) methane, and phenylcarbonyl (t-butylcarbonyl) methane, bis (phenylsulfonyl) Diazomethane, bis (p-hydroxyphenylsulfonyl) diazomethane, bis (p-methoxyphenylsulfonyl) diazomethane, bis (α-naphthylsulfonyl) diazomethane, bis ( β-naphthylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (t-butylsulfonyl) diazomethane, phenylsulfonyl (cyclohexylsulfonyl) diazomethane, bis (sulfonyl Diazomethane compound, phenylcarbonyl (phenylsulfonyl) diazomethane, naphthylcarbonyl (phenylsulfonyl) diazomethane, phenylcarbonyl (naphthylsulfonyl) diazomethane, cyclohexylcarbonyl (phenylsulfonyl) Carbonyl, such as fonyl) diazomethane, t-butylcarbonyl (phenylsulfonyl) diazomethane, phenylcarbonyl (cyclohexylsulfonyl) diazomethane, and phenylcarbonyl (t-butylcarbonyl) diazomethane (Sulfonyl) diazomethane compounds and those represented by the following formulas Va and Vb are mentioned.

[Formula Va]

[Formula Vb]

[In formula Va and Vb, R <^38> , R <^39> , R <^41> and R <^42> respectively independently represent a hydrogen atom or arbitrary substituent, R <^40> and R <^43> respectively independently represent an arbitrary substituent, and are R ⁴¹ and R ⁴² in Vb may form a nitrogen-containing heterocycle.]

Preferable groups as R ³⁸ , R ⁴¹ , and R ⁴² include a hydrogen atom; Linear or branched alkyl groups having 1 to 18 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group and n-heptyl group; Cycloalkyl groups having 3 to 18 carbon atoms such as cyclopropyl group, cyclopentyl group, cyclohexyl group, and adamantyl group; C2-C18 linear or branched alkenyl groups, such as a vinyl group, a propenyl group, and a hexenyl group; Cycloalkenyl groups having 3 to 18 carbon atoms such as a cyclopentenyl group and a cyclohexenyl group; Saturated or unsaturated heterocyclic groups such as 2-thienyl group, 2-pyridyl group, furyl group, thiazolyl group, benzothiazolyl group, morpholino group, pyrrolidinyl group and tetrahydrothiophene dioxide group; C6-C18 aryl groups, such as a phenyl group, a tolyl group, a xylyl group, and a mesityl group; C7-C20 aralkyl groups, such as a benzyl group and a phenethyl group; C2-C18 linear or branched acyl groups, such as an acetyl group, a propionyl group, butyryl group, an isobutyryl group, a valeryl group, and an isovaleryl group; C1-C18 linear or branched alkoxy groups such as methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group and tert-butoxy group: propenyloxy group C3-C18 linear or branched alkenyloxy group, such as a butenyloxy group and a pentenyloxy group; Linear or branched alkylthio groups having 1 to 18 carbon atoms such as methylthio group, ethylthio group, n-propylthio group, n-butylthio group, sec-butylthio group and tert-butylthio group; Halogen atoms such as fluorine atom, chlorine atom and bromine atom; Nitro group; Cyano group; Hydroxyl group; Formyl group; Sulfonic acid groups; Carboxyl groups; Acyloxy group represented by -OCOR; Amino group represented by -NRR '; Acylamino group represented by -NHCOR; Carbamate groups represented by -NHCOOR; Sulfonamide groups represented by -NHSOOR; Carboxylic acid ester group represented by -COOR; Carbamoyl group represented by -CONRR '; Sulfamoyl group represented by -SOONRR '; -SO the like can be mentioned sulfonic acid ester group represented by OR ₂ (and, in which, R, R 'is an alkyl group.).

In addition, R ⁴¹ and R ⁴² may form a nitrogen-containing heterocycle, and the nitrogen-containing heterocycle may be further condensed with a saturated or unsaturated hydrocarbon ring or a heterocycle.

Moreover, as a group preferable as R <^39> , A hydrogen atom; Linear or branched alkyl groups; Cycloalkyl group; Linear or branched alkenyl groups; Cycloalkenyl group; Aryl group; Aralkyl group; Acyl group; Acyloxy group; Alkyloxycarbonyl group; Aryloxycarbonyl group; Nitro group; Cyano group; A carboxyl group etc. are mentioned, These may further have a substituent. Among these, acyl group, alkyloxycarbonyl group, nitro group and cyano group are more preferable, and alkyloxycarbonyl group and cyano group are particularly preferable.

In addition, preferred groups as R ⁴⁰ and R ⁴³ is straight or branched chain alkyl group; Cycloalkyl group; Linear or branched alkenyl groups: cycloalkenyl groups; Heterocyclic group; Aryl group; Aralkyl group; A camphor group etc. are mentioned, The hydrogen atom in these groups may be substituted by the fluorine atom, and may have another substituent.

R ³⁸ ~R with a substituent in the above group, and R ⁴¹ and the nitrogen-containing heterocyclic ring which R ⁴² is the formation of ⁴³ is a methoxy group, an ethoxy group, n- propoxy group, isopropoxy group, n- butoxy group an alkoxy group having 1 to 10 carbon atoms such as a sec-butoxy group and a tert-butoxy group; Alkoxyalkoxy groups having 2 to 12 carbon atoms such as methoxymethoxy group, ethoxymethoxy group, propoxymethoxy group, ethoxyethoxy group, propoxyethoxy group and methoxybutoxy group; An alkoxyalkoxyalkoxy group having 3 to 15 carbon atoms, such as a methoxy methoxy methoxy group, a methoxy methoxy ethoxy group, a methoxy ethoxy methoxy group, and an ethoxy ethoxy methoxy group; Allyloxy group; C6-C12 aryl groups, such as a phenyl group, a tolyl group, and a xylyl group (these may be substituted by the substituent further); C6-C12 aryloxy groups, such as a phenoxy group, a tolyloxy group, a xylyloxy group, and a naphthyloxy group; Acyl groups, such as an acetyl group and a propionyl group; Cyano group; Nitro group; Hydroxyl group; Tetrahydrofuryl group; Amino group; Alkylamino groups having 1 to 10 carbon atoms such as N, N-dimethylamino group and N, N-diethylamino group; Alkylsulfonylamino groups having 1 to 6 carbon atoms such as methylsulfonylamino group, ethylsulfonylamino group and n-propylsulfonylamino group; Halogen atoms such as fluorine atom, chlorine atom and bromine atom; An alkoxycarbonyl group having 2 to 7 carbon atoms such as a methoxycarbonyl group, an ethoxycarbonyl group, and an n-butoxycarbonyl group; Alkylcarbonyloxy groups having 2 to 7 carbon atoms such as methylcarbonyloxy group, ethylcarbonyloxy group, n-propylcarbonyloxy group, isopropylcarbonyloxy group and n-butylcarbonyloxy group; C2-C7 alkoxycarbonyl jade, such as a methoxycarbonyloxy group, an ethoxycarbonyloxy group, n-propoxycarbonyloxy group, isopropoxycarbonyloxy group, n-butoxycarbonyloxy group, etc. The time period etc. are mentioned, The hydrogen atom in these groups may be substituted by the fluorine atom.

Among the sulfone compounds represented by the above formulas Va and Vb, specific examples of the compound in which R ⁴¹ and R ⁴² form a nitrogen-containing heterocycle are shown below.

In this invention, alkali-soluble resin which is the said (N2-1) component in the said chemically amplified negative photosensitive composition (N2), the crosslinking agent which is the said (N2-2) component, and the said (N2-3) component It is preferable that each content rate of a phosphorus photoacid generator is 1-80 weight part with respect to 100 weight part of alkali-soluble resin which is (N2-1) component, and it is 5-60 weight part More preferably, the photoacid generator as the (N2-3) component is preferably 0.001 to 30 parts by weight, and more preferably 0.005 to 10 parts by weight.

In addition, the chemically amplified negative photosensitive composition (N2) according to the present invention may be used in addition to the (N2-1), (N2-2), and (N2-3) components, such as sensitivity as a photosensitive resist material layer. It is preferable to contain a sensitizer (N2-4) component for the purpose of an improvement. The sensitizer (N2-4) component efficiently absorbs light in a blue-violet region having a wavelength of 320 to 450 nm, and transmits the photoexcitation energy to the photoacid generator as the (N2-3) component. The light absorption pigment | dye which has a sensitization function which decomposes a generator and produces | generates the acid which induces the bridge | crosslinking of alkali-soluble resin which is (N2-1) component by the said crosslinking agent which is (N2-2) component, The light absorption As a pigment | dye, the thing similar to the light absorption pigment | dye illustrated as a sensitizer which is (N1-2) component of the said photopolymerizable negative photosensitive composition (N1) is mentioned. These light-absorbing dyes can suppress the sensitivity from being lowered even when the photosensitive resist material layer composed of the chemically amplified negative photosensitive composition (N2) is a thick film, and can obtain a resist image excellent in resolution. Let's do it.

In this invention, the content rate of the sensitizer which is said (N2-4) component in the said chemically amplified negative photosensitive composition (N2) is based on 100 weight part of alkali-soluble resins which are (N2-1) components. It is preferable that it is 0.1-30 weight part, and it is especially preferable that it is 0.5-20 weight part.

And in the said chemically amplified negative photosensitive composition (N2) in this invention, if necessary, further, for example, a coating property improving agent, an adhesive improvement agent, a sensitivity improvement agent, a sensing agent, a coloring agent, a developability improvement agent, etc. The various additives normally used for the photosensitive composition of may contain.

[P1. Chemically amplified positive photosensitive composition]

As a photosensitive composition which comprises the photosensitive resist material layer of this invention, it is preferable to consist of chemically amplified positive photosensitive composition (P1) containing the following (P1-1) and (P1-2) component.

(P1-1) Acid Degradable Group-Containing Resin

(P1-2) Acid Generator

Acid-decomposable group containing resin which is (P1-1) component which comprises the chemically amplified positive type photosensitive composition (P1) in this invention is mentioned later, when the photosensitive composition receives irradiation of actinic light (P1-2). Is a resin having an acid-decomposable group which is decomposed by an acid generated by the photoacid generator as a component and gives alkali solubility to the resin itself, and specific examples of the acid-decomposable group include, for example, methoxy group, ethoxy group, i Alkoxy groups having 1 to 15 carbon atoms such as propoxy group and t-butoxy group, methoxymethoxy group, dimethoxymethoxy group, ethoxymethoxy group, 1-methoxyethoxy group, 1-ethoxyethoxy group, Ether type, such as a C2-C15 alkoxyalkoxy group, such as a 1-propoxyoxy group, a 1-t-butoxyethoxy group, a 1-cyclohexyloxyethoxy group, and 1-ethoxy propoxy group Oxycarbonyloxy group, ethoxycarbonyloxy group, n-propoxycarbonyloxy group, i- 2-15 alkoxycarbonyloxy groups, ethoxycarbonyloxymethoxy group, n-propoxycarbonyl, such as a looxycarbonyloxy group, n-butoxycarbonyloxy group, and t-butoxycarbonyloxy group Carbonates, such as a C2-C15 alkoxycarbonyloxyalkoxy group, such as an oxymethoxy group, i-propoxycarbonyloxymethoxy group, n-butoxycarbonyloxymethoxy group, and t-butoxycarbonyloxymethoxy group Groups which have an alkoxy group, a siloxy group, etc. at least at the terminal, such as a type | mold and silyl ether types, such as siloxy groups, such as a trimethyl siloxy group and a trimethoxy siloxy group, are mentioned, An ether type is preferable in it.

Moreover, as resin containing these acid-decomposable groups, the furnace similar to what was illustrated as alkali-soluble resin as (N2-1) component in the said chemically amplified negative photosensitive composition (N2) specifically, is mentioned, for example. Phenolic resins, such as a phenol resin and a resol resin, and resin which introduce | transduced the said acid-decomposable group by etherifying or esterifying at least one part of phenolic hydroxyl group of phenolic hydroxyl group containing resin, such as polyvinyl phenol resin, are mentioned as a preferable thing, Especially, in this invention, resin which introduce | transduced the said acid-decomposable group into the novolak resin or polyvinyl phenol resin is more preferable, and resin which introduce | transduced the said acid-decomposable group into polyvinyl phenol resin is especially preferable. Here, the acid-decomposable group-containing resin also includes a mixture of a resin into which an acid-decomposable group is introduced and an unintroduced resin.

Moreover, as resin containing an acid-decomposable group, the resin which introduce | transduced the said acid-decomposable group by esterifying at least one part of the carboxyl group of carboxyl group-containing vinyl resin is mentioned as a preferable thing, for example. Examples of the carboxyl group-containing vinyl resin include the same carboxyl group-containing vinyl resins as those exemplified as the polymer binder as the (N1-4) component in the photopolymerizable negative photosensitive composition (N1).

Moreover, the photo-acid generator which is (P1-2) component which comprises the chemically amplified positive type photosensitive composition (P1) in this invention is a compound which produces | generates an acid when a photosensitive composition is irradiated with actinic light, Examples of the photoacid generator include the same compounds as those exemplified as the photoacid generator as the (N2-3) component in the chemically amplified negative photosensitive composition (N2). Among them, halomethylation in the present invention. Especially preferred are s-triazine derivatives or sulfone compounds.

In this invention, each content ratio of the acid-decomposable group containing resin which is said (P1-1) component in the said chemically amplified positive type photosensitive composition (P1), and the said photoacid generator which is said (P1-2) component It is preferable that it is 0.1-50 weight part with respect to 100 weight part of acid-decomposable group containing resin which is (P1-1) component, and it is more preferable that it is 0.5-20 weight part. .

Moreover, the positive type photosensitive composition (P1) of the said chemically amplified type in this invention is sensitized for the purpose of improvement, such as the sensitivity as a photosensitive resist material layer other than the said (P1-1) and (P1-2) components. It is preferable to contain the (P1-3) component. The sensitizer (P1-3) component efficiently absorbs light in the blue violet region having a wavelength of 320 to 450 nm, and transmits the photoexcitation energy to the photoacid generator as the (P1-2) component. A light absorbing dye having a sensitizing function of decomposing a generator to generate an acid that induces decomposition of an acid-decomposable group-containing resin as a component (P1-1) is preferable. As the light absorbing dye, the photopolymerizable negative type The same thing as the light absorption pigment | dye illustrated as a sensitizer which is (N1-2) component of the photosensitive composition (N1) is mentioned. These light-absorbing dyes prevent the sensitivity from being lowered even when the photosensitive resist material layer composed of the chemically amplified positive photosensitive composition (P1) is made into a thick film, and further, obtaining a resist image excellent in resolution. Make it possible.

In this invention, the content rate of the sensitizer which is said (P1-3) component in the said chemically amplified positive photosensitive composition (P1) is 100 weight of acid-decomposable group containing resin which is the said (P1-1) component. It is preferable that it is 1-30 weight part with respect to a part, and it is especially preferable that it is 5-20 weight part.

Moreover, the said chemically amplified positive photosensitive composition (P1) in this invention aims at the improvement of the applicability | paintability at the time of forming a photosensitive resist material layer on a board | substrate, developability, etc. of a photosensitive resist material layer, Furthermore, you may contain surfactant (P1-4) components, such as a nonionic, anionic, cationic, amphoteric, and fluorine system, and as this surfactant, in the said photopolymerizable negative photosensitive composition (N1), The same thing as what was illustrated as surfactant as (N1-7) component is mentioned, The content rate is 0.1-10 weight part with respect to 100 weight part of acid-decomposable group containing resin which is said (P1-1) component. It is preferable and it is more preferable that it is 1-5 weight part.

On the other hand, in the chemically amplified positive photosensitive composition (P1) according to the present invention, if necessary, photosensitivity such as a coatability improver, an adhesive improver, a sensitivity improver, a sensing agent, a colorant, and a developer improver, for example. Various additives commonly used in the composition may be contained.

As mentioned above, although the photosensitive composition which comprises the resist material layer of the image forming material of this invention was demonstrated, the compound which has an alkyl group as a substituent at the 2-position of a tetrahydroquinoline ring as a compound represented by the said general formula (Ib) or (Id) as a sensitizer among these was mentioned above. When using a compound selected from the group consisting of a compound represented by the formula (II), a compound represented by the formula (III), and a compound represented by the formula (IV), even if the film thickness of the resist material layer is 10 μm or more, the sensitivity does not decrease, An image forming material having a resist material layer having good sex and image shape can be obtained.

In this invention, the said negative type or positive type photosensitive composition is apply | coated on the temporary support film as a coating liquid which melt | dissolved or disperse | distributed each said component normally in a suitable solvent, and it dried, and formed the photosensitive composition layer as needed. By covering the surface with a coating film, a so-called dry film resist material is formed, and when the photosensitive composition layer side of the dry film resist material is covered with the coating film, the coating film is peeled off and then on the substrate to be processed. By laminating or by applying and drying the above-mentioned components in a coating liquid dissolved or dispersed in a suitable solvent directly on the substrate to be processed, an image forming material having a photosensitive resist material layer formed on the substrate to be processed is obtained. Scanning exposure of the photosensitive resist material layer by blue-violet laser light of wavelength 320-450 nm And, it is preferably used in the developing process by using the image forming method of saliency of the image as form.

As a temporary support film in the case of being used as this dry film resist material, conventionally well-known films, such as a polyethylene terephthalate film, a polyimide film, a polyamide imide film, a polypropylene film, a polystyrene film, are used, for example. do. In that case, if these films have solvent resistance, heat resistance, etc., the photosensitive composition coating liquid can be apply | coated and dried directly on these temporary support films, and a dry film resist material can be produced, and these films are solvent resistance, heat resistance, etc. Even if this is low, for example, a photosensitive composition layer is first formed on a film having releasability such as a polytetrafluoroethylene film or a release film, and then a temporary supporting film having low solvent resistance, heat resistance or the like is laminated on the layer. Then, a dry film resist material can also be produced by peeling a film which has mold release property. Moreover, as a coating film, conventionally well-known films, such as a polyethylene film, a polypropylene film, and a polytetrafluoroethylene film, are used.

The solvent used for the coating liquid is not particularly limited as long as it has sufficient solubility in the used component and imparts good coating properties. For example, methyl cellosolve, ethyl cellosolve, methyl cellosolve, etc. Cellosolve solvents such as acetate and ethyl cellosolve acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monobutyl Propylene glycol solvents such as ether acetate and dipropylene glycol dimethyl ether, butyl acetate, amyl acetate, ethyl butyrate, butyl butyrate, diethyl oxalate, ethyl pyruvate, ethyl-2-hydroxybutylate, ethyl acetate acetate, and methyl lactate Such as ethyl lactate and methyl 3-methoxypropionate Alcohol solvents such as ester solvents, heptanol, hexanol, diacetone alcohol, furfuryl alcohol, ketone solvents such as cyclohexanone, methyl amyl ketone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone High polar solvents, such as these, or these mixed solvents, and the thing which added aromatic hydrocarbon to these, etc. are mentioned. The use ratio of a solvent is the range of about 1 to 20 times by weight ratio normally with respect to the total amount of the photosensitive composition.

As the coating method, a conventionally known method such as rotary coating, wire bar coating, spray coating, dip coating, air knife coating, roll coating, blade coating, screen coating, curtain coating and the like can be used. have. It is preferable that it is 10 micrometers or more as a dry film thickness, It is more preferable that it is 15 micrometers or more, It is preferable that it is 200 micrometers or less, It is further more preferable that it is 100 micrometers or less in that case. On the other hand, as the drying temperature at that time, for example, about 30 to 150 ° C, preferably about 40 to 110 ° C, and as the drying time, for example, about 5 seconds to 60 minutes, preferably 10 seconds to About 30 minutes are employed.

In addition, when the photosensitive composition layer side of the said dry film resist material is covered with a coating film, the coating film is peeled off, it heats, presses, etc., it is laminated | stacked, or the said photosensitive composition coating liquid is directly apply | coated and dried, an image The substrate to be processed in the case of forming the forming material is subjected to scanning exposure of the photosensitive resist material layer formed thereon with a blue-violet laser light and developed for processing, thereby performing etching or plating processing on the surface of the exposed image as a resist. A pattern such as an electrode or the like is formed, and may be a metal plate itself such as copper, aluminum, gold, silver, chromium, zinc, tin, lead, nickel, or the like, but typically, for example, an epoxy resin, a polyimide resin, Thermosetting resins such as bismaleimide resins, unsaturated polyester resins, phenol resins, melamine resins, and saturated Resins such as thermoplastic resins such as polyester resins, polycarbonate resins, polysulfone resins, acrylic resins, polyamide resins, polystyrene resins, polyvinyl chloride resins, polyolefin resins, fluorine resins, paper, glass, and alumina, silica, Inorganic materials such as barium sulfate and calcium carbonate, or a composite material such as a glass cloth base epoxy resin, a glass nonwoven fabric base epoxy resin, a paper base epoxy resin, or a paper base phenol resin, and the like. A metal foil such as the metal or metal oxide such as indium oxide, tin oxide, indium-doped tin oxide, or the like on the surface of the insulating support having a thickness of about 0.02 to 10 mm, or sputtering, vapor-depositing, plating the metal, or the like. By this, a laminated plate with a metal on which a conductive layer having a thickness of about 1 to 10 µm is formed is preferably used.

And in this invention, in the image forming material in which the photosensitive resist material layer by the said photopolymerizable negative photosensitive composition was formed, the polymerization inhibitory effect by oxygen of a photopolymerizable composition on the photosensitive resist material layer formed on the said to-be-processed substrate The protective layer, such as an oxygen barrier layer for preventing the damage, or a light transmittance adjusting layer for adjusting the wavelength region of the maximum peak of the spectral sensitivity described above, may be formed.

What constitutes the oxygen barrier layer is a water-soluble polymer soluble in water or a mixed solvent of water and a water-miscible organic solvent such as alcohol or tetrahydrofuran, or a water-insoluble polymer such as polyethylene terephthalate, specifically For example, polyvinyl alcohol, derivatives thereof, such as a cation modified substance thereof by partial acetalide, quaternary ammonium salt, the anion modified substance by sodium sulfonate, etc., polyvinylpyrrolidone, polyethylene oxide, methyl cellulose, Carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose and the like.

Among them, polyvinyl alcohol and derivatives thereof are preferable in terms of oxygen barrier property, and in addition, vinyl such as polyvinylpyrrolidone and vinylpyrrolidone-vinyl acetate copolymer in terms of adhesiveness with the photosensitive resist material layer. Pyrrolidone-based polymers are preferable, and as the oxygen barrier layer in the present invention, the polyvinylpyrrolidone-based polymer is preferably 1 to 20 parts by weight, more preferably to 100 parts by weight of polyvinyl alcohol or its derivatives. It is preferable to use as a mixture which mixed 3-15 weight part.

The oxygen barrier layer preferably contains organic acids such as succinic acid, organic acid salts such as ethylenediaminetetraacetic acid, and the like, and nonionics such as polyoxyethylene alkylphenyl ether, and dode Surfactants, such as anionic, such as sodium benzene sulfonate, and cationics, such as alkyl trimethylammonium chloride, an antifoaming agent, a pigment | dye, a plasticizer, a pH adjuster, etc. may be included, and these total content ratios are 10 weight% or less. It is preferable and it is more preferable that it is 5 weight% or less.

The oxygen barrier layer is a solution of water or a mixed solvent of water and a water-miscible organic solvent, and is formed by the same coating method as the above-described photosensitive resist material layer, and the coating amount is 1 to 10 g / m 2 as a dry film thickness. It is preferable to set it as the range, and it is more preferable to set it as the range of 1.5-7 g / m <2>.

Moreover, what comprises a light-transmitting adjustment layer can mention the thing which contained the light absorption pigment | dye of visible region, such as a coumarin pigment | dye, etc. in a polymeric binder, The polymer binder at that time is made into the said oxygen barrier layer By setting it as the polyvinyl alcohol or its derivative (s) and polyvinylpyrrolidone type polymer which were illustrated in the above, it can be set as the protective layer which has oxygen blocking ability and light transmittance adjustment capability.

And the image forming material which has the blue violet laser photosensitive resist material layer of this invention scan-exposes the photosensitive resist material layer with a laser beam, and develops a resist image by developing.

Here, the laser exposure light source may be, for example, a HeNe laser, an argon ion laser, a YAG laser, a HeCd laser, a semiconductor laser, a ruby laser, or the like, but in particular, a laser light in a blue violet region having a wavelength range of 320 to 450 nm. The light source which generate | occur | produces is preferable, It does not specifically limit, Specifically, the indium gallium nitride semiconductor laser etc. which oscillate at 410 nm are mentioned, for example.

Moreover, the scanning exposure method is not specifically limited, For example, a planar scanning exposure system, an outer-surface drum scanning exposure system, an inner-surface drum scanning exposure system, etc. are mentioned, The output light intensity of the laser in a plate surface is preferable. 100 nW to 100 mW, more preferably 1 μW to 70 mW, oscillation wavelength is preferably 320 to 450 nm, more preferably 390 to 430 nm, particularly preferably 400 to 420 nm, and the beam spot diameter is preferably Is 0.5 to 30 µm, more preferably 1 to 20 µm, and a scanning speed is preferably 50 to 500 m / sec, more preferably 100 to 400 m / sec, and a scanning density is preferably 2,000 dpi or more. Preferably it is 4,000 dpi or more, and scanning exposure is carried out.

Moreover, the developing process after the said laser scanning exposure, Preferably, it can carry out using the aqueous developing solution containing an alkali component and surfactant. As the alkali component, for example, sodium silicate, potassium silicate, lithium silicate, ammonium silicate, sodium metasilicate, potassium metasilicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, diphosphate Inorganic alkali salts such as sodium, trisodium phosphate, diammonium phosphate, triammonium phosphate, sodium borate, potassium borate and ammonium borate, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, tri Organic amine compounds such as ethylamine, monoisopropylamine, diisopropylamine, monobutylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, and the like. It is used at a concentration of about% by weight.

Moreover, as surfactant, surfactant illustrated in the said photopolymerizable negative photosensitive composition is mentioned, Among these, a nonionic, anionic, or amphoteric surfactant is preferable, Especially an amphoteric surfactant, especially a betaine type Compounds are 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.

The developer can be contained, for example, according to organic solvents such as isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol and diacetone alcohol. Moreover, as for pH of a developing solution, it is preferable to set it as 9-14, and it is more preferable to set it as 11-14.

On the other hand, the image development is usually carried out by a known developing method such as immersing the image forming material after exposure in the developer or spraying the developer on the image forming material after exposure, preferably about 10 to 50 ° C, more preferably. Preferably it is made at the temperature of about 15-45 degreeC in the time of 5 second-about 10 minutes. In that case, the said protective layer may be previously removed by water etc., and may be removed at the time of image development.

Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to a following example, unless the summary is exceeded. In addition, the evaluation method as an image forming material in a following example and a comparative example is shown below.

<Absorbance>

About the photosensitive resist material layer of 10 micrometers of dry film thicknesses formed on the glass substrate, the absorbance in wavelength 405nm was measured using the spectrophotometer ("UV-3100 PC" by Shimadzu Corporation), and the measured value The absorbance per micrometer was computed by dividing by the film thickness.

<Maximum peak of spectral sensitivity>

The sample which cut out the image forming material into the size of 50x60 mm was made into the light source using the xenon lamp (Ushio Denko Co., Ltd. "UI-501C") as a light source using the diffraction spectrophotometer (RM-23 by Narumi). After irradiating and exposing light spectroscopically to the wavelength region of 650 nm for 10 second, the exposure wavelength is changed linearly in the horizontal axis direction, and the exposure intensity is changed algebraically in the vertical axis direction, and then developed conditions described in each Example. In the spectral sensitivity curve obtained by obtaining an image according to the sensitivity of each exposure wavelength, calculating the exposure energy that can be formed from the image height, and plotting the wavelength on the horizontal axis and the inverse of the exposure energy on the vertical axis. The maximum peak was read.

<[S ₄₁₀ / S ₄₅₀ ], [S _450-650 / S ₄₅₀ ]>

Minimum exposure amount at which the image can be formed at a wavelength of 410 nm when exposure is performed by changing the wavelength in the wavelength region of 320 to 650 nm by the same method as described in the above <Maximum Peak of Spectral Sensitivity> [S ₄₁₀ (mJ / cm 2)] and the minimum exposure amount [S ₄₅₀ (mJ / cm 2)] that can form an image at a wavelength of 450 nm, and the minimum exposure amount that can be formed at each wavelength of more than 450 nm and 650 nm or less [ S _450-650 (mJ / cm 2)] were obtained, respectively, and the ratios [S ₄₁₀ / S ₄₅₀ ] and [S _450-650 / S ₄₅₀ ] were calculated and evaluated according to the following criteria.

<Evaluation Criteria for S ₄₁₀ / S ₄₅₀ >

A: S ₄₁₀ / S ₄₅₀ is 0.03 or less.

B: S ₄₁₀ / S ₄₅₀ is more than 0.03 and not more than 0.05.

C: _S410 / _S450 is greater than 0.05 and less than or equal to 0.1.

D: S ₄₁₀ / S ₄₅₀ is greater than 0.1.

<Evaluation Criteria for S _450-650 / S ₄₅₀ >

A: S _450-650 / S ₄₅₀ is _greater than 10.

B: S _450-650 / S ₄₅₀ is more than 5 and less than 10.

C: S _450-650 / S ₄₅₀ is more than 1 and not more than 5.

D: S _450-650 / S ₄₅₀ is 1 or less.

<D / L>

Instead of the resist film thickness D, the laser scanning exposure is carried out in the same manner as in the above <Exposure Sensitivity> method to display an image, and the minimum line width L resolved in each resist film thickness is obtained. (D / L) was calculated. In addition, the sensitivity at the time of providing the maximum value of D / L calculated | required in this way was set to S3.

<Exposure Sensitivity>

The photosensitive resist material layer of an image forming material uses a laser light source ("NLHV500C" manufactured by Nichiagaku Kogyo Co., Ltd.) with a center wavelength of 405 nm and a laser output of 5 mW, and has an image plane roughness of 2 µW and a beam spot diameter of 2.5 µm, and the beam scanning interval. And scanning exposure while changing the scanning speed, and then developing under the developing conditions described in each example to display an image, and then obtaining the minimum exposure amount necessary for reproducing a line width of 10 µm for the image obtained at that time. And sensitivity.

Moreover, the said sensitivity (S1) when the film thickness is 10 micrometers, and the said sensitivity (S2) when the film thickness is 20 micrometers was measured, and the ratio (S2 / S1) was computed.

<Safety property under yellow light>

The image forming material was left to stand for 1 minute, 2 minutes, 5 minutes, 10 minutes, 20 minutes, and 30 minutes under yellow light illumination (a condition of blocking light having a wavelength of about 470 nm or less), and then scanned in the same manner as described above. The exposure time and image development process were performed, the leaving time until a change generate | occur | produces in an image compared with the above was calculated | required, and the following references | standards evaluated.

A: 20 minutes or more

B: 10 minutes or more but less than 20 minutes

C: 1 minute or more but less than 10 minutes

D: less than 1 minute

<Resist image>

About the obtained resist image, the reproducible line width and pattern shape in the film thickness shown in the table were observed, and the value of "film thickness (micrometer) / reproducible line width (micrometer)" as a reference of the resolution was measured. Calculated.

<Storage stability of the photosensitive composition coating liquid>

After storing the photosensitive composition coating liquid for 7 days at 25 degreeC in the dark, a resist image was formed, and the presence or absence of a crystalline precipitate was observed with the scanning electron microscope about the resist image, and the following references | standards evaluated.

A: A precipitate is not recognized at all and there is no change in the sensitivity and image before and after storage.

B: Precipitates are not recognized, but the sensitivity after storage is slightly reduced.

C: A trace amount of precipitate is recognized, and the sensitivity after storage decreases.

Example 1-1

As a photopolymerizable negative photosensitive composition (N1), the following each component was added to the mixed solvent of 740 weight part of methyl ethyl ketones, and 400 weight part of methyl cellosolves, and it stirred at room temperature, and prepared the coating liquid on the glass substrate. Using a coater, the dry film thickness was applied in an amount of 10 μm or 20 μm, and then dried at 170 ° C. for 2 minutes to form a photosensitive resist material layer, on which polyvinyl alcohol and polyvinylpyrrolidone were mixed. An aqueous solution (polyvinyl alcohol: polyvinylpyrrolidone = 95% by weight: 5% by weight) was applied in an amount such that the dry film thickness was 3 μm using a bar coater, and dried at 50 ° C. for 3 minutes to protect the protective layer (oxygen). By forming a barrier layer), a photosensitive image forming material was produced.

<(N1-1) ethylenically unsaturated compound>

(N1-1a) the following compound; 10 parts by weight

(N1-1b) the following compound; 5 parts by weight

(N1-1c) the following compound; 8 parts by weight

(N1-1d) dipentaerythritol hexaacrylate; 22 parts by weight

<(N1-2) sensitizer>

(N1-2a) 4,4'-bis (diethylamino) benzophenone (molar extinction coefficient at wavelength 404 nm 14,540); 9 parts by weight

<(N1-3) photoinitiator>

(N1-3a) 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole (Bragg angle in the X-ray diffraction spectrum of melting point 196 ° C and wavelength 1.54 GHz) (2θ ± 0.2 °) having the largest diffraction peak at 9.925 °); 15 parts by weight

<(N1-4) Polymer Binder>

(N1-4a) Reaction product obtained by making 3, 4- epoxycyclohexyl methyl acrylate react with styrene / (alpha) -methylstyrene / acrylic acid copolymer (molar ratio 55/15/30) (50 mol% of an acrylic acid component is an epoxy group And reaction); 45 parts by weight

<(N1-5) hydrogen supply compound>

(N1-5a) 2-mercaptobenzothiazole; 5 parts by weight

(N1-5b) N-phenylglycine benzyl ester; 10 parts by weight

<(N1-6) amine compound>

(N1-6a) tribenzylamine; 10 parts by weight

<(N1-7) surfactant>

(N1-7a) nonionic surfactant ("Emargen 104P" by the Kao Corporation); 2 parts by weight

(N1-7b) Fluorine-type surfactant ("S-381" by Asahi Glass Co., Ltd.); 0.3 parts by weight

<Others>

Copper phthalocyanine pigments (visualizing agents); 4 parts by weight

Dispersing agent ("Disperbyk 161" manufactured by Vikchem Co., Ltd.); 2 parts by weight

After scanning and exposing the photosensitive resist material layer of the obtained photosensitive image forming material to the conditions described in the above-mentioned evaluation method of exposure sensitivity, the oxygen barrier layer was washed with water and peeled off, followed by 0.1% by weight of sodium carbonate and anionic surfactant (Khao After being immersed at 26 degreeC for 60 second in the aqueous solution containing 0.1 weight% of "Perex NBL" manufactured by Corporation, it was rubbed 5 times with a sponge, and the to-be-processed substrate in which the resist image was formed on the surface was obtained. The absorbance of the photosensitive resist material layer at that time, the maximum peak of the spectral sensitivity, the exposure sensitivity, [S ₄₁₀ / S ₄₅₀ ] and [S _450-650 / S ₄₅₀ ], the safety property under yellow light, and the obtained resist image mentioned above Evaluation by the method, the results are shown in Table 5. In addition, S ₄₁₀ was 0.1 mJ / cm 2.

Example 1-2

As the chemically amplified negative photosensitive composition (N2), the following respective components were added to 300 parts by weight of propylene glycol monomethyl ether acetate, and the coating liquid prepared by stirring at room temperature was prepared on a glass substrate with a dry film thickness of 10 µm or 20 After spin-coating in an amount of µm, the photosensitive image forming material was produced by drying at 90 ° C. for 10 minutes to form a photosensitive resist material layer.

<(N2-1) alkali-soluble resin>

(N2-1a) poly (p-hydroxystyrene) (weight average molecular weight 5,000); 100 parts by weight

<(N2-2) crosslinking agent>

(N2-2a) methoxymethylated melamine ("Nicarak E-2151" manufactured by Sangwa Chemical Co., Ltd.); 50 parts by weight

<(N2-3) mine generator>

(N2-3a) 2- (p-carboxyacetyloxyethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine; 1 part by weight

After scanning-exposing the photosensitive resist material layer of the obtained photosensitive image forming material on the conditions described in the said exposure sensitivity evaluation method, it post-heat-processes in 100 degreeC for 10 minutes in oven, Then, it is 20 degreeC in 1weight% of potassium hydroxide aqueous solution. The substrate was immersed for 90 seconds and developed to obtain a processed substrate having a resist image formed on its surface. Hereinafter, it evaluated by the same method. S ₄₁₀ was 4 mJ / cm 2. In addition, when the resist film thickness D was 20 micrometers, the resolved minimum line width L was 10 micrometers, and the maximum value of D / L was 2.0. Moreover, the sensitivity S3 at this time was 7 mJ / cm <2>.

Example 1-3

(N2-3) Except having changed the photo-acid generator into what was mentioned below, the photosensitive image forming material was produced in the same manner as Example 1-2, and the to-be-processed substrate in which the resist image was formed in the surface was obtained. Hereinafter, it evaluated by the same method. S ₄₁₀ was 4 mJ / cm 2. In addition, when the resist film thickness D was 20 micrometers, the resolved minimum line width L was 10 micrometers, and the maximum value of D / L was 2.0. Moreover, the sensitivity S3 at this time was 11 mJ / cm <2>.

(N2-3b) 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine

Example 1-4

A photosensitive image forming material was fabricated in the same manner as in Example 1-2 except that a processed substrate having 1 µm thick copper plating on a silicon substrate was used in place of the glass substrate to form a resist image on the surface. A processed substrate was obtained. Hereinafter, it evaluated by the same method.

Example 1-5

A photosensitive image forming material was fabricated in the same manner as in Example 1-3 except that a substrate having a 1 µm-thick copper plating was used on a silicon substrate in place of the glass substrate, and the workpiece having a resist image formed thereon. A substrate was obtained. Hereinafter, it evaluated by the same method.

Example 1-6

As the chemically amplified positive photosensitive composition (P1), each of the following components was added to a mixed solvent of 640 parts by weight of propylene glycol monomethyl ether acetate and 240 parts by weight of methyl cellosolve, and stirred at room temperature to prepare a coating solution. After spin-coating in the amount which a dry film thickness becomes 10 micrometers or 20 micrometers on a glass substrate, it dried at 90 degreeC for 10 minutes, and formed the photosensitive resist material layer, and produced the photosensitive image forming material.

<(P1-1) acid-decomposable group-containing resin>

(P1-1a) an acid-decomposable group-containing resin in which about 45 mol% of the hydroxyl groups of poly (p-hydroxystyrene) are etherified to introduce 1-ethoxyethoxy group as the acid-decomposable group; 100 parts by weight

<(P1-2) Mine Generator

(P1-2a) 2- (p-methoxy-m-hydroxystyryl) -4,6-bis (trichloromethyl) -s-triazine: 2 parts by weight

After scanning photosensitive resist material layer of the obtained photosensitive image forming material on the conditions described in the evaluation method of the said exposure sensitivity, after-heat-processing in oven at 90 degreeC for 2 minutes, Then, it is 20 degreeC in 2weight% of potassium hydroxide aqueous solution. The substrate was immersed for 90 seconds and developed to obtain a processed substrate having a resist image formed on its surface. Hereinafter, it evaluated by the same method. S ₄₁₀ was 15 mJ / cm 2. In addition, when the resist film thickness D was 20 micrometers, the resolved minimum line width L was 10 micrometers, and the maximum value of D / L was 2.0. Moreover, the sensitivity S3 at this time was 20 mJ / cm <2>.

Example 1-7

A photosensitive image forming material was fabricated in the same manner as in Example 1-6, except that a substrate having a 1 µm-thick copper plating on the silicon substrate was used in place of the glass substrate, and the workpiece having a resist image formed thereon. A substrate was obtained. Hereinafter, it evaluated by the same method.

Example 2-1

As a photopolymerizable negative photosensitive composition (N1), the following each component is added to 100 weight part of mixed solvents of methyl ethyl ketone / isopropanol (weight ratio 8/2), and the coating liquid which prepared by stirring and preparing at room temperature is a temporary support film. On the polyethylene terephthalate film (thickness 19㎛) as a coating film on the photosensitive composition layer formed by using an applicator in an amount such that the dry film thickness is 10㎛ or 20㎛, dried for 5 minutes in an oven at 90 ℃. The dry film resist material was produced by laminating | stacking polyethylene film (thickness 25micrometer) as 1 day and leaving to stand for 1 day.

<(N1-1) ethylenically unsaturated compound

(N1-1e) the following compound; 15 parts by weight

(N1-lf) the following compound; 30 parts by weight

<(N1-2) sensitizer>

(N1-2b) the following compound (molar extinction coefficient (ε) 1,200 at wavelength 405 nm); 0.2 parts by weight

<(N1-3) photoinitiator>

(N1-3a) 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole (Bragg angle in the X-ray diffraction spectrum of melting point 196 ° C and wavelength 1.54 GHz) (2θ ± 0.2 °) having the largest diffraction peak at 9.925 °); 15 parts by weight

<(N1-4) Polymer Binder>

(N1-4b) Obtained by reacting methyl methacrylate / n-butylacrylate / methacrylic acid copolymer (molar ratio 45/15/40, weight average molecular weight 70,000) with 3,4-epoxycyclohexylmethylacrylate Reaction product (37.5 mol% of the carboxyl groups of the methacrylic acid component react with the epoxy groups); 48 parts by weight

<(N1-5) hydrogen supply compound>

(N1-5b) N-phenylglycine benzyl ester; 3 parts by weight

(N1-5c) bipolar ionic compounds of N-phenylglycine; 2 parts by weight

Separately, a copper foil surface of a copper-clad laminated substrate (thickness 1.5 mm, size 250 mm x 200 mm) of a polyimide resin with a copper foil having a thickness of 35 µm was buffed using "Scotchbright SF" manufactured by Sumitomo 3M Co., Ltd. After polishing, washing with water, drying by air flow to even the surface, and then preheating it to 60 ° C. in an oven, the dry film resist obtained above on the copper foil of the copper-clad laminate. The photosensitive resist material layer was laminated on a copper-clad laminated substrate by laminating an ash at a roll temperature of 100 ° C., a roll pressure of 0.3 MPa, and a lamination speed of 1.5 m / min, using a hand roll laminator on the peeling surface while peeling off the polyethylene film. This formed photosensitive image forming material was produced.

After scanning-exposing the photosensitive resist material layer of the obtained photosensitive image forming material on the conditions described in the evaluation method of the said exposure sensitivity, the polyethylene terephthalate film was peeled off, Then, 0.15 Mpa of 32 degreeC sodium carbonate 1weight% aqueous solution is used as a developing solution. By spraying and spray-developing so that it might become, the to-be-processed board | substrate with which the resist image was formed in the surface was obtained. The absorbance of the photosensitive resist material layer at that time, the maximum peak of the spectral sensitivity, the exposure sensitivity, [S ₄₁₀ / S ₄₅₀ ] and [S _450-650 / S ₄₅₀ ], the safety property under yellow light, and the obtained resist image mentioned above Evaluation by the method, the results are shown in Table 5. In addition, S is _410, was 1.1 mJ / ㎠. In addition, when the resist film thickness D was 25 micrometers, the resolved minimum line width L was 10 micrometers, and the maximum value of D / L was 2.5. Moreover, the sensitivity S3 at this time was 0.9 mJ / cm <2>.

Example 2-2

A photosensitive image forming material was produced in the same manner as in Example 2-1 except that the (N1-4) polymer binder was changed to the following, to obtain a processed substrate having a resist image formed on its surface. Hereinafter, it evaluated by the same method. S ₄₁₀ was 1.0 mJ / cm 2. In addition, when the resist film thickness D was 25 micrometers, the resolved minimum line width L was 10 micrometers, and the maximum value of D / L was 2.5. Moreover, the sensitivity S3 at this time was 0.7 mJ / cm <2>.

(N1-4c) styrene / methyl methacrylate / n-butylacrylate / methacrylic acid copolymer (molar ratio 15/45/15/25, weight average molecular weight 70,000, acid value 140 KOHmg / g)

Example 2-3

(N1-2) Except having changed the sensitizer into the following, the photosensitive image forming material was produced in the same manner as Example 2-1, and the to-be-processed board | substrate with a resist image formed in the surface was obtained. Hereinafter, it evaluated by the same method. S ₄₁₀ was 1.6 mJ / cm 2. In addition, when the resist film thickness D was 25 micrometers, the resolved minimum line width L was 10 micrometers, and the maximum value of D / L was 2.5. Moreover, the sensitivity S3 at this time was 1.0 mJ / cm <2>.

(N1-2c) the following compound (molar extinction coefficient 100 at a wavelength of 405 nm)

Example 2-4

(N1-5) A photosensitive image forming material was prepared in the same manner as in Example 2-2, except that the bipolar ion compound of N-phenylglycinebenzyl ester and N-phenylglycine as a hydrogen supply compound was not used. The processed substrate on which the resist image was formed was obtained. Hereinafter, it evaluated by the same method. S ₄₁₀ was 1.5 mJ / cm 2. In addition, when the resist film thickness D was 25 micrometers, the resolved minimum line width L was 10 micrometers, and the maximum value of D / L was 2.5. Moreover, the sensitivity S3 at this time was 1.0 mJ / cm <2>.

Example 2-5

(N1-3) Except having changed the photoinitiator into what was mentioned below, the photosensitive image forming material was produced in the same manner as Example 2-2, and the to-be-processed board | substrate with a resist image formed on the surface was obtained. Hereinafter, it evaluated by the same method. S ₄₁₀ was 0.6 mJ / cm 2. In addition, when the resist film thickness D was 25 micrometers, the resolved minimum line width L was 10 micrometers, and the maximum value of D / L was 2.5. Moreover, the sensitivity S3 at this time was 0.5 mJ / cm <2>.

(N1-3b) 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole (Bragg angle in the X-ray diffraction spectrum of melting point 172 DEG C, wavelength 1.54 GHz) (2θ ± 0.2 °) with maximum diffraction peak at 21.16 °)

Example 2-6

(N1-2) Except having changed the sensitizer into the following, the photosensitive image forming material was produced in the same manner as Example 2-1, and the to-be-processed board | substrate with a resist image formed in the surface was obtained. Hereinafter, it evaluated by the same method. S ₄₁₀ was 1.8 mJ / cm 2. In addition, when the resist film thickness D was 25 micrometers, the resolved minimum line width L was 10 micrometers, and the maximum value of D / L was 2.5. Moreover, the sensitivity S3 at this time was 1.3 mJ / cm <2>.

(N1-2d) the following compound (molar extinction coefficient (ε) 1,300 at a wavelength of 405 nm)

Example 2-7

(N1-2) Except having changed the sensitizer into the following, the photosensitive image forming material was produced in the same manner as Example 2-1, and the to-be-processed board | substrate with a resist image formed in the surface was obtained. Hereinafter, it evaluated by the same method. S ₄₁₀ was 2.4 mJ / cm 2. Moreover, when the resist film thickness D was 25 micrometers, the resolved minimum line width L was 10 micrometers, and the maximum value of D / L was 2.5. Moreover, the sensitivity S3 at this time was 1.6 mJ / cm <2>.

(N1-2e) the following compound (molar extinction coefficient (ε) 1,300 at a wavelength of 405 nm)

Example 2-8

(N1-2) Except having changed the sensitizer into the following, the photosensitive image forming material was produced in the same manner as Example 2-1, and the to-be-processed board | substrate with a resist image formed in the surface was obtained. Hereinafter, it evaluated by the same method. S ₄₁₀ was 2.0 mJ / cm 2. In addition, when the resist film thickness D was 25 micrometers, the resolved minimum line width L was 10 micrometers, and the maximum value of D / L was 2.5. Moreover, the sensitivity S3 at this time was 1.4 mJ / cm <2>.

(N1-2f) The following compound (molar extinction coefficient (ε) 100 at a wavelength of 405 nm)

Example 3-1

As a chemically amplified negative photosensitive composition (N2), the following each component was added to 290 parts by weight of propylene glycol monomethyl ether acetate, and the coating liquid prepared by stirring at room temperature was prepared on a glass substrate with a dry film thickness of 10 µm or 20 After spin-coating in an amount of µm, the photosensitive image forming material was produced by drying at 90 ° C. for 10 minutes to form a photosensitive resist material layer.

<(N2-1) alkali-soluble resin>

(N2-1a) poly (p-hydroxystyrene) (weight average molecular weight 5,000); 100 parts by weight

<(N2-2) crosslinking agent>

(N2-2a) methoxymethylated melamine ("Nicarak E-2151" manufactured by Sangwa Chemical Co., Ltd.); 50 parts by weight

<(N2-3) photoacid generator

(N2-3c) the following compound; 5 parts by weight

<(N2-4) sensitizer>

(N2-4a) the following compound (molar extinction coefficient at wavelength 405 nm 32,500); 1 part by weight

After scanning and exposing the photosensitive resist material layer of the obtained photosensitive image forming material on the conditions described in the said evaluation method of exposure sensitivity, it post-heat-processes in oven at 100 degreeC for 10 minutes, and then 0.5weight% aqueous solution of potassium hydroxide It immersed for 60 second at 20 degreeC, and developed, and the to-be-processed board | substrate with which the resist image was formed in the surface was obtained. The absorbance of the photosensitive resist material layer at that time, the maximum peak of the spectral sensitivity, the exposure sensitivity, [S ₄₁₀ / S ₄₅₀ ] and [S _450-650 / S ₄₅₀ ], the safety property under yellow light, and the obtained resist image mentioned above Evaluation by the method, the results are shown in Table 5.

Example 3-2

(N2-3) Except having changed the photo-acid generator into what was mentioned below, the photosensitive image forming material was produced in the same manner as Example 3-1, and the to-be-processed substrate in which the resist image was formed in the surface was obtained. Hereinafter, it evaluated by the same method.

(N2-3d) the following compound

Example 3-3

(N2-4) Except having changed the sensitizer as follows, the photosensitive image forming material was produced in the same manner as Example 3-2, and the to-be-processed board | substrate with a resist image formed in the surface was obtained. Hereinafter, it evaluated by the same method.

(N2-4b) the following compound (molar extinction coefficient 51,600 at a wavelength of 405 nm)

Example 3-4

As a photopolymerizable negative photosensitive composition (N1), the following each component is added to 100 weight part of mixed solvents of methyl ethyl ketone / isopropanol (weight ratio 8/2), and the coating liquid which prepared by stirring and preparing at room temperature is a temporary support film. On the polyethylene terephthalate film (thickness 19㎛) as a coating film on the photosensitive composition layer formed by using an applicator in an amount such that the dry film thickness is 10㎛ or 20㎛, dried for 5 minutes in an oven at 90 ℃. The dry film resist material was produced by laminating | stacking polyethylene film (25 micrometers in thickness) as it and leaving it to stand for 1 day.

<(N1-1) ethylenically unsaturated compound>

(N1-1e) said compound; 11.5 parts by weight

(N1-1g) the following compound: 10 parts by weight

(N1-1h) the following compound; 23.5 parts by weight

<(N1-2) sensitizer>

(N1-2g) the following compound (molar extinction coefficient 7,320 at a wavelength of 405 nm); 0.6 parts by weight

<(N1-3) photoinitiator>

(N1-3a) 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole (Bragg angle in the X-ray diffraction spectrum of melting point 196 ° C and wavelength 1.54 GHz) (2θ ± 0.2 °) having the largest diffraction peak at 9.925 °); 12 parts by weight

<(N1-4) Polymer Binder>

(N1-4c) styrene / methyl methacrylate / 2-hydroxyethyl methacrylate / methacrylic acid copolymer (molar ratio 10/50/20/20, weight average molecular weight 68,000, acid value 129 KOH · mg / g) ; 55 parts by weight

<(N1-5) hydrogen supply compound>

(N1-5c) bipolar ionic compounds of N-phenylglycine; 0.2 parts by weight

<Others>

Leuco crystal violet; 0.4 parts by weight

9-phenylacridine; 0.2 parts by weight

Separately, a copper foil surface of a copper-clad laminated substrate (thickness 1.5 mm, size 250 mm x 200 mm) of a polyimide resin with a copper foil having a thickness of 35 µm was buffed using "Scotchbright SF" manufactured by Sumitomo 3M Co., Ltd. After polishing and washing with water, the resultant was dried by air flow to even out the noodles, and then preheated to 60 ° C. in an oven, and then the dry film resist material obtained above was coated on the copper foil of the copper-clad laminate. The photosensitive resist material layer in which the photosensitive resist material layer was formed on the laminated substrate with copper by peeling the polyethylene film by laminating at a roll temperature of 100 ° C., a roll pressure of 0.3 MPa, and a lamination speed of 1.5 m / min using a hand roll laminator on the peeling surface. An image forming material was produced.

After scanning-exposing the photosensitive resist material layer of the obtained photosensitive image forming material on the conditions described in the evaluation method of the said exposure sensitivity, the polyethylene terephthalate film is peeled off, Then, 0.15 Mpa is used as a developing solution with 0.7 weight% aqueous solution of 30 degreeC sodium carbonate as a developing solution. By spraying and spray-developing so that it might become, the to-be-processed board | substrate with which the resist image was formed in the surface was obtained. Hereinafter, it evaluated by the same method.

Example 4-1

As a chemically amplified negative photosensitive composition (N2), the following respective components were added to 290 parts by weight of propylene glycol monomethyl ether ether acetate, and the coating liquid prepared by stirring at room temperature was prepared on a glass substrate with a dry film thickness of 10 µm or 20 After spin-coating in an amount of µm, the photosensitive image forming material was produced by drying at 90 ° C. for 10 minutes to form a photosensitive resist material layer.

<(N2-1) alkali-soluble resin>

(N2-1a) poly (p-hydroxystyrene) (weight average molecular weight 5,000); 100 parts by weight

<(N2-2) crosslinking agent>

(N2-2a) methoxymethylated melamine ("Nicarak E-2151" manufactured by Sangwa Chemical Co., Ltd.); 50 parts by weight

<(N2-3) mine generator>

(N2-3c) said compound; 5 parts by weight

<(N2-4) sensitizer>

(N2-4c) The following compound (molar extinction coefficient 14,200 in wavelength 405nm): 1 weight part

After scanning-exposing the photosensitive resist material layer of the obtained photosensitive image forming material on the conditions described in the evaluation method of the said exposure sensitivity, it post-heat-processes in oven at 100 degreeC for 10 minutes, and then to 0.5weight% of potassium hydroxide aqueous solution. By immersing and developing at 20 degreeC for 60 second, the to-be-processed board | substrate with which the resist image was formed in the surface was obtained. The absorbance of the photosensitive resist material layer at that time, the maximum peak of the spectral sensitivity, the exposure sensitivity, [S ₄₁₀ / S ₄₅₀ ] and [S _450-650 / S ₄₅₀ ], the safety property under yellow light, and the obtained resist image mentioned above Evaluation by the method, the results are shown in Table 5.

Example 4-2

(N2-3) Except having changed the photo-acid generator into what was mentioned below, the photosensitive image forming material was produced in the same manner as Example 4-1, and the to-be-processed substrate in which the resist image was formed in the surface was obtained. Hereinafter, it evaluated by the same method.

(N2-3d) the compound

Example 4-3

(N2-4) Except having changed the sensitizer into the following, the photosensitive image forming material was produced in the same manner as Example 4-1, and the to-be-processed board | substrate with a resist image formed in the surface was obtained. Hereinafter, it evaluated by the same method.

(N2-4d) the following compound (molar extinction coefficient 4,300 at a wavelength of 405 nm)

Example 4-4

(N2-3) Except having changed the photo-acid generator into what was mentioned below, the photosensitive image forming material was produced in the same manner as Example 4-3, and the to-be-processed substrate in which the resist image was formed in the surface was obtained. Hereinafter, it evaluated by the same method.

(N2-3d) the compound

Example 4-5

(N2-4) Except having changed the sensitizer into the following, the photosensitive image forming material was produced in the same manner as Example 4-1, and the to-be-processed board | substrate with a resist image formed in the surface was obtained. Hereinafter, it evaluated by the same method.

(N2-4e) the following compound (molar extinction coefficient at wavelength 405 nm, 11,200); 1 part by weight

Example 4-6

(N2-3) Except having changed the photo-acid generator into what was mentioned below, the photosensitive image forming material was produced in the same manner as Example 4-5, and the to-be-processed substrate in which the resist image was formed in the surface was obtained. Hereinafter, it evaluated by the same method.

(N2-3d) the compound

Example 4-7

(N2-4) Except having changed the sensitizer into the following, the photosensitive image forming material was produced in the same manner as Example 4-1, and the to-be-processed substrate in which the resist image was formed in the surface was obtained. Hereinafter, it evaluated by the same method.

(N2-4f) The following compound (molar extinction coefficient at wavelength 405 nm 5,300)

Example 4-8

A photosensitive image forming material was produced in the same manner as in Example 4-5, except that a substrate having a thickness of 1 μm copper plating was used on the silicon substrate in place of the glass substrate, whereby a resist image was formed on the surface. A processed substrate was obtained. Hereinafter, it evaluated by the same method.

Example 4-9

As a photopolymerizable negative photosensitive composition (N1), the following each component is added to 100 weight part of mixed solvents of methyl ethyl ketone / isopropanol (weight ratio 8/2), and the coating liquid which prepared by stirring and preparing at room temperature is a temporary support film. On the polyethylene terephthalate film (thickness 19㎛) as a coating film on the photosensitive composition layer formed by using an applicator in an amount such that the dry film thickness is 10㎛ or 20㎛, dried for 5 minutes in an oven at 90 ℃. The dry film resist material was produced by laminating | stacking polyethylene film (thickness 25micrometer) as 1 day and leaving to stand for 1 day.

<(N1-1) ethylenically unsaturated compound>

(N1-1e) said compound; 11.5 parts by weight

(N1-1g) the compound: 10 parts by weight

(N1-1h) said compound; 23.5 parts by weight

<(N1-2) sensitizer>

(N1-2h) the same compound as the above (N2-4e) (molar extinction coefficient at wavelength 405 nm, 11,200); 0.6 parts by weight

<(N1-3) photoinitiator>

(N1-3a) 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole (Bragg angle in the X-ray diffraction spectrum of melting point 196 ° C and wavelength 1.54 GHz) (2θ ± 0.2 °) having the largest diffraction peak at 9.925 °); 12 parts by weight

<(N1-4) Polymer Binder>

(N1-4c) styrene / methyl methacrylate / 2-hydroxyethyl methacrylate / methacrylic acid copolymer (molar ratio 10/50/20/20, weight average molecular weight 68,000, acid value 129 KOH · mg / g) ; 55 parts by weight

<(N1-5) hydrogen supply compound>

(N1-5c) bipolar ionic compounds of N-phenylglycine; 0.2 parts by weight

<Others>

Leuco crystal violet; 0.4 parts by weight

9-phenylacridine; 0.2 parts by weight

Separately, a copper foil surface of a copper-clad laminated substrate (thickness 1.5 mm, size 250 mm x 200 mm) of a polyimide resin with a copper foil having a thickness of 35 µm was buffed using "Scotchbright SF" manufactured by Sumitomo 3M Co., Ltd. After polishing and washing with water, the resultant was dried by air flow to even out the noodles, and then preheated to 60 ° C. in an oven, and then the dry film resist material obtained above was coated on the copper foil of the copper-clad laminate. The photosensitive resist material layer in which the photosensitive resist material layer was formed on the laminated substrate with copper by peeling the polyethylene film by laminating at a roll temperature of 100 ° C., a roll pressure of 0.3 MPa, and a lamination speed of 1.5 m / min using a hand roll laminator on the peeling surface. An image forming material was produced.

After scanning-exposing the photosensitive resist material layer of the obtained photosensitive image forming material on the conditions described in the evaluation method of the said exposure sensitivity, the polyethylene terephthalate film is peeled off, Then, 0.15 Mpa is used as a developing solution with 0.7 weight% aqueous solution of 30 degreeC sodium carbonate as a developing solution. By spraying and spray-developing so that it might become, the to-be-processed board | substrate with which the resist image was formed in the surface was obtained. Hereinafter, it evaluated by the same method.

Example 5-1

As a chemically amplified negative photosensitive composition (N2), the following each component was added to 290 parts by weight of propylene glycol monomethyl ether acetate, and the coating liquid prepared by stirring at room temperature was prepared on a glass substrate with a dry film thickness of 10 µm or 20 After spin-coating in an amount of µm, the photosensitive image forming material was produced by drying at 90 ° C. for 10 minutes to form a photosensitive resist material layer.

<(N2-1) alkali-soluble resin>

(N2-1a) poly (p-hydroxystyrene) (weight average molecular weight 5,000); 100 parts by weight

<(N2-2) crosslinking agent>

(N2-2a) methoxymethylated melamine ("Nicarak E-2151" manufactured by Sangwa Chemical Co., Ltd.); 50 parts by weight

<(N2-3) mine generator>

(N2-3d) said compound; 6 parts by weight

<(N2-4) sensitizer>

(N2-4g) the following compound (molar extinction coefficient 4300 at a wavelength of 405 nm); 1 part by weight

After scanning-exposing the photosensitive resist material layer of the obtained photosensitive image forming material on the conditions described in the evaluation method of the said exposure sensitivity, it post-heat-processes in oven at 100 degreeC for 10 minutes, and then to 0.5weight% of potassium hydroxide aqueous solution. The processing board | substrate with which the resist image was formed in the surface was obtained by immersing and developing at 20 degreeC for 60 second. The absorbance of the photosensitive resist material layer at that time, the maximum peak of the spectral sensitivity, the exposure sensitivity, [S ₄₁₀ / S ₄₅₀ ] and [S _450-650 / S ₄₅₀ ], the safety property under yellow light, and the obtained resist image mentioned above Evaluation by the method, the results are shown in Table 5.

Example 5-2

(N2-4) Except having changed the sensitizer into the following, the photosensitive image forming material was produced in the same manner as Example 5-1, and the to-be-processed board | substrate with a resist image formed in the surface was obtained. Hereinafter, it evaluated by the same method.

(N2-4h) the following compound (molar extinction coefficient 300 at wavelength 405 nm)

Example 5-3

(N2-4) Except having changed the sensitizer into the following, the photosensitive image forming material was produced in the same manner as Example 5-1, and the to-be-processed board | substrate with a resist image formed in the surface was obtained. Hereinafter, it evaluated by the same method.

(N2-4i) the following compound (molar extinction coefficient 120 at wavelength 405 nm)

Example 5-4

As a photopolymerizable negative photosensitive composition (N1), the following each component is added to 100 weight part of mixed solvents of methyl ethyl ketone / isopropanol (weight ratio 8/2), and the coating liquid which prepared by stirring and preparing at room temperature is a temporary support film. On the polyethylene terephthalate film (thickness 19㎛) as a coating film on the photosensitive composition layer formed by using an applicator in an amount such that the dry film thickness is 10㎛ or 20㎛, dried for 5 minutes in an oven at 90 ℃. The dry film resist material was produced by laminating | stacking polyethylene film (25 micrometers in thickness) as it and leaving it to stand for 1 day.

<(N1-1) ethylenically unsaturated compound

(N1-1e) said compound; 15 parts by weight

(N1-1f) said compound; 30 parts by weight

<(N1-2) sensitizer>

(N1-2i) the same compound as the above (N2-4g) (molar extinction coefficient 4,300 at wavelength 405 nm); 0.3 parts by weight

<(N1-3) photoinitiator>

(N1-3b) 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole (Bragg angle in the X-ray diffraction spectrum of melting point 172 DEG C, wavelength 1.54 GHz) (2θ ± 0.2 °) having the largest diffraction peak at 21.16 °); 12 parts by weight

<(N1-4) Polymer Binder>

(N1-4c) Styrene / methyl methacrylate / 2-hydroxyethyl methacrylate / methacrylic acid copolymer (molar ratio 10/50/20/20, weight average molecular weight 68,000, acid value 129 KOHmg / g) ; 55 parts by weight

<(N1-5) hydrogen supply compound>

(N1-5c) bipolar ionic compounds of N-phenylglycine; 0.2 parts by weight

<Others>

Leuco crystal violet; 0.4 parts by weight

9-phenylacridine; 0.2 parts by weight

Separately, a copper foil surface of a copper-clad laminated substrate (thickness 1.5 mm, size 250 mm x 200 mm) of a polyimide resin with a copper foil having a thickness of 35 µm was buffed using "Scotchbright SF" manufactured by Sumitomo 3M Co., Ltd. After polishing and washing with water, the resultant was dried by air flow to even out the noodles, and then preheated to 60 ° C. in an oven, and then the dry film resist material obtained above was coated on the copper foil of the copper-clad laminate. The photosensitive resist material layer in which the photosensitive resist material layer was formed on the laminated substrate with copper by peeling the polyethylene film by laminating at a roll temperature of 100 ° C., a roll pressure of 0.3 MPa, and a lamination speed of 1.5 m / min using a hand roll laminator on the peeling surface. An image forming material was produced.

After scanning-exposing the photosensitive resist material layer of the obtained photosensitive image forming material on the conditions described in the evaluation method of the said exposure sensitivity, the polyethylene terephthalate film was peeled off, Then, it is 0.15 Mpa using 30 degreeC sodium carbonate 1weight% aqueous solution as a developing solution. By spraying and spray-developing so that it might become, the to-be-processed board | substrate with which the resist image was formed in the surface was obtained. The absorbance of the photosensitive resist material layer at that time, the maximum peak of the spectral sensitivity, the exposure sensitivity, [S ₄₁₀ / S ₄₅₀ ] and [S _450-650 / S ₄₅₀ ], the safety property under yellow light, and the obtained resist image mentioned above Evaluation by the method, the results are shown in Table 5.

Comparative Example 1

In the photopolymerizable negative photosensitive composition (N1) of Example 5-4, a photosensitive resist material layer having a film thickness of 10 μm was obtained in the same manner as in Example 5-4 except that no (N1-2) sensitizer was used. As a result of producing an image forming material, scanning exposure and developing, the exposed portions were all dissolved in a developing solution, and no image was formed.

Comparative Example 2

In the photopolymerizable negative photosensitive composition (N1) of Example 5-4, the (N1-2) sensitizer was described below and was changed to 1 part by weight, except that the photosensitive image was obtained in the same manner as in Example 5-4. The formation material was produced and the to-be-processed board | substrate with which the resist image was formed in the surface was obtained. Hereinafter, it evaluated by the same method. The image forming material having the photosensitive resist material layer having a film thickness of 20 µm was subjected to scanning exposure and development, and as a result, all of the exposed portions were dissolved in the developing solution, and no image was formed.

(N1-2j) The following compound (molar extinction coefficient at wavelength 405 nm 82,700)

Comparative Example 3

In the chemically amplified negative photosensitive composition (N2) of Example 3-2, a photosensitive resist material layer having a film thickness of 10 μm was obtained in the same manner as in Example 3-2, except that no (N2-4) sensitizer was used. As a result of producing an image forming material, scanning exposure and developing, the exposed portions were all dissolved in a developing solution, and no image was formed.

Comparative Example 4

In the chemically amplified negative photosensitive composition (N2) of Example 3-2, a photosensitive image forming material was produced in the same manner as in Example 3-2, except that the (N2-4) sensitizer was changed to the following one, The to-be-processed board | substrate with which the resist image was formed in the surface was obtained. Hereinafter, it evaluated by the same method. The image forming material having the photosensitive resist material layer having a film thickness of 20 µm was subjected to scanning exposure and development, and as a result, all of the exposed portions were dissolved in the developing solution, and no image was formed.

(N2-4j) The same compound as the above (N1-2j) (molar extinction coefficient at wavelength 405 nm 82,700)

TABLE 5

TABLE 6

Claims (5)

A photosensitive composition containing an sensitizer and an active compound which generates a radical or an acid by interacting with an exposed sensitizer, wherein the sensitizer comprises (i) a molar extinction coefficient (ε) at a wavelength of 405 nm of 100 or more; 100,000 or less, and (ii) a dialkylaminobenzene compound represented by the following General Formula (Ia) or (Ic), a sulfonylimino group-containing compound represented by the following General Formula (II), and the following General Formula (III) It is at least 1 type or more sensitizer selected from the 2-naphthylidedione type compound or 2-quinolone type compound represented by the following, and the indolin type compound represented by the following general formula (IV). Formula Ia

[In formula Ia, R <^1> , R <^2> , R <^3>. And R ⁴ each independently represent an alkyl group, R ⁵ , R ⁶ , R ⁷ And R ⁸ each independently represents an alkyl group or a hydrogen atom, R ¹ and R ² , R ³ and R ⁴ , R ¹ and R ⁵ , R ² and R ⁶ , R ³ and R ⁷ , and R ⁴ and R ⁸ May each independently form a nitrogen-containing heterocycle.] Formula Ic

[In formula Ic, R ¹ And R ² each independently represent an alkyl group, and R ⁵ And R ⁶ each independently represents an alkyl group or a hydrogen atom, and R ¹ and R ² , R ¹ and R ⁵ , and R ² and R ⁶ Each independently may form a nitrogen-containing heterocycle. X represents an oxygen atom, a sulfur atom, a dialkylmethylene group, an imino group, or an alkylimino group, and ring A represents an aromatic ring which may have a substituent.] [Formula II]

[In Formula II, R <^11> and R <^12> represents a hydrogen atom or arbitrary substituents each independently, and R <^13> represents arbitrary substituents.] [Formula III]

[Wherein, Z represents a nitrogen atom or CR ²¹ , and R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ and R ²¹ each independently represent a hydrogen atom or an optional substituent; R ¹⁸ and R ¹⁹ , R ¹⁹ and R ²⁰ , and R ²⁰ and R ²¹ may each independently form a nitrogen-containing heterocycle, and R ¹⁵ to R ¹⁸ may be bonded to each other adjacent to each other; To form a ring.] [Formula IV]

[In formula IV, R <^22> , R <^23> , R <^24> , R <^25> , R <^26> , R <^27> , R <^28> , R <^29> and R <^30> respectively independently represent a hydrogen atom or an arbitrary substituent, and R <^22> and R ^23, and R ²² and R ³⁰ is may form a nitrogen-containing heterocyclic ring, each independently, and, R ²³ ~R ³⁰ is, by the mutual adjacent bond may form a ring.] The photosensitive composition according to claim 1, which is a photopolymerizable negative photosensitive composition (N1) containing (N1-1) ethylenically unsaturated compound, (N1-2) sensitizer and (N1-3) photoinitiator. Photosensitive composition. The chemically amplified negative type according to claim 1, wherein the photosensitive composition contains (N2-1) alkali-soluble resin, a crosslinking agent which acts on alkali-soluble resin under (N2-2) acidic conditions, and (N2-3) photoacid generator. It is a photosensitive composition (N2), The photosensitive composition characterized by the above-mentioned. The photosensitive composition according to claim 1, wherein the photosensitive composition is a chemically amplified positive type photosensitive composition (P1) containing (P1-1) an acid-decomposable group-containing resin and (P1-2) a photoacid generator. Hardened | cured material formed from the photosensitive composition of any one of Claims 1-4.