JP2007079567A - Image forming material having bluish-violet laser-photosensitive resist material layer and resist image forming method therefor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an image forming material having high sensitivity to a laser beam in a bluish-violet region, excellent in safelight property under a yellow light, and free from a decrease in sensitivity even if a film thickness is increased, and a resist image forming method therefor. <P>SOLUTION: The image forming material has a bluish-violet laser-photosensitive resist material layer on a substrate to be worked, wherein (a) the photosensitive resist material layer has a film thickness of ≥10 μm and an absorbance at an exposure wavelength of ≤0.3 per film thickness of 1 μm, (b) the photosensitive resist material layer satisfies S2/S1≤5, wherein S1 is sensitivity in the case of a film thickness of 10 μm at the exposure wavelength and S2 is sensitivity in the case of a film thickness of 20 μm, (c) the photosensitive resist material layer has a thickness of ≤200 μm, (d) the photosensitive resist material has a maximum peak of spectral sensitivity at a wavelength of 390-430 nm, and (e) the photosensitive resist material layer comprises (N-1) an ethylenically unsaturated compound, (N-2) a sensitizer and (N-3) a photopolymerization initiator. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an image forming material having a blue-violet laser-sensitive resist material layer capable of forming a resist image by exposure and development processing with blue-violet laser light, and a resist image forming method thereof, and more particularly to blue-violet laser light. A blue-violet laser photosensitive resist material layer that is useful for forming fine electronic circuits such as printed wiring boards, plasma display wiring boards, liquid crystal display wiring boards, large-scale integrated circuits, thin transistors, and semiconductor packages by direct drawing. The present invention relates to an image forming material (except for a lithographic printing plate) and a resist image forming method thereof.

  Conventionally, for forming fine electronic circuits such as printed wiring boards, plasma display wiring boards, liquid crystal display wiring boards, large-scale integrated circuits, thin transistors, semiconductor packages, etc., for example, a photosensitive resist material on a substrate to be processed The photosensitive resist material layer of the image forming material having a layer and, if necessary, a protective layer thereon is exposed by irradiating with ultraviolet rays through the mask film, and then the mask film is peeled off and further having a protective layer In some cases, the protective layer is peeled off, and development is performed using the difference in solubility between the exposed portion and the non-exposed portion in the developer to form a pattern, and the substrate to be processed is etched using this pattern layer as a mask. Accordingly, a lithography method for forming a circuit pattern on a substrate to be processed is widely used.

  Furthermore, in recent years, the laser direct drawing method that directly forms an image from digital information such as a computer without using a mask film by using a laser beam as an exposure light source is not only productive, but also resolution and positional accuracy. As a result, the use of laser light has been actively studied in the lithography method.

  On the other hand, various light sources from ultraviolet to infrared are known as laser light. As laser light that can be used for image exposure, an argon ion laser is used from the viewpoint of output, stability, photosensitive ability, and cost. , Helium neon lasers, YAG lasers, semiconductor lasers, etc. that emit light in the visible to infrared region are promising. For example, lithography using an argon ion laser with a wavelength of 488 nm and an FD-YAG laser with a wavelength of 532 nm The law has already been put into practical use.

However, such an image forming method using visible laser light is inferior in safe light property under a yellow light, and has a restriction that it is necessary to work in a dark room environment such as a red light illumination. On the other hand, the remarkable progress in laser technology in recent years has made it possible to use semiconductor lasers that can operate in a bright room environment such as yellow light lighting and can stably oscillate in the blue-violet region. Since the output is low compared to other visible regions, the sensitivity of the photosensitive resist material is not necessarily sufficient, and it has not reached a level that can be put into practical use not only in the direct drawing method but also in the lithography method. Is the current situation.
EP 1148387 discloses a photosensitive lithographic printing plate having a photosensitive layer having a maximum peak of spectral sensitivity at 390 to 430 nm and an image forming exposure amount at 410 nm and 450 nm in a specific range. The thickness of the photosensitive layer is only about 2 μm.
On the other hand, in the plating process, which is a manufacturing process for printed wiring boards and the like, it is required to increase the plating thickness with the recent miniaturization of the wiring line width.

EP1148387

  The present invention has been made in view of the above-described prior art. Therefore, the present invention is highly sensitive to laser light in the blue-violet region, and the sensitivity does not decrease even when the film thickness is increased. It is an object of the present invention to provide an image forming material having a purple laser photosensitive resist material layer and a resist image forming method thereof.

  In the case of a photosensitive layer using a laser in the visible to infrared region of the conventional method described above, the sensitivity decreases as the film thickness is increased, and a photosensitive material that satisfies both the requirements of the film thickness and sensitivity in a well-balanced manner. It was difficult to find.

  In the case of using a violet laser, the present inventors use a resist material layer having a specific absorbance, and the sensitivity does not decrease even when the thickness of the resist material layer is increased. The present inventors have found that an image forming material having a high film thickness can be formed, and have reached the present invention.

That is, the gist of the present invention is an image forming material having a blue-violet laser-sensitive resist material layer on a substrate to be processed,
(A) The film thickness of the resist material layer is 10 μm or more, and the absorbance at the exposure wavelength of the photosensitive resist material layer is 0.3 or less per 1 μm of film thickness,
(B) When the sensitivity when the photosensitive resist material layer has a film thickness of 10 μm at the exposure wavelength is S1, and the sensitivity when the film thickness is 20 μm is S2, S2 / S1 is 5 or less,
(C) The thickness of the photosensitive resist material layer is 200 μm or less,
(D) the photosensitive resist material has a maximum peak in spectral sensitivity at a wavelength of 390 to 430 nm,
(E) The photosensitive resist material layer is composed of a photopolymerizable negative photosensitive composition containing the following components (N-1), (N-2), and (N-3).
(N-1) ethylenically unsaturated compound (N-2) sensitizer (N-3) photopolymerization initiator
Furthermore, another gist of the present invention is a photosensitive composition for creating an electronic circuit,
(1) The photosensitive resist material layer composed of the composition (D), and the photosensitive resist material layer having the thickness (D) are scanned and exposed with a laser beam having a wavelength of 390 to 430 nm and then developed. The maximum value of the ratio (D / L) to the minimum line width (L) that can be resolved by 1.0 is 1.0 or more, and (2) the minimum exposure capable of image formation at a wavelength of 410 nm of the photosensitive resist material layer The amount [S ₄₁₀ (μJ / cm ² )] is 10,000 μJ / cm ² or less,
(3) The photosensitive resist material layer is a photopolymerizable negative photosensitive composition containing the following components (N-1), (N-2), and (N-3).
(N-1) Ethylenically unsaturated compound (N-2) Sensitizer (N-3) Photopolymerization initiator The present invention resides in a photosensitive composition for producing an electronic circuit.

Furthermore, another gist of the present invention is a photosensitive composition for creating an electronic circuit,
(1) The photosensitive resist material layer composed of the composition (D), and the photosensitive resist material layer having the thickness (D) are scanned and exposed with a laser beam having a wavelength of 390 to 430 nm and then developed. The maximum value of the ratio (D / L) to the minimum line width (L) that can be resolved by 1.0 is 1.0 or more,
(2) The exposure amount for achieving the D / L is 20 mJ / cm ² or less,
(3) The photosensitive resist material layer is a photopolymerizable negative photosensitive composition containing the following components (N-1), (N-2), and (N-3).
(N-1) Ethylenically unsaturated compound (N-2) Sensitizer (N-3) A photopolymerization initiator, which is a photosensitive composition for producing an electronic circuit.
Furthermore, the present invention resides in an image forming material having a photosensitive resist material layer made of the photosensitive composition for producing an electronic circuit on a substrate to be processed.
Furthermore, the present invention resides in a resist image forming method characterized in that a photosensitive resist material layer of the image forming material is subjected to scanning exposure with laser light having a wavelength of 390 to 430 nm and then developed.

  The present invention provides an image forming material having a blue-violet laser-sensitive resist material layer that is highly sensitive to laser light in the blue-violet region and does not decrease in sensitivity even when the film thickness is increased, and a resist image forming method thereof Can be provided.

  The image forming material having a blue-violet laser-sensitive resist material layer of the present invention has a blue-violet laser-sensitive resist material layer on a substrate to be processed, and the photosensitive resist material layer has a wavelength of 390 to 430 nm. It is preferable to have a maximum peak of spectral sensitivity in the wavelength range and a maximum peak of spectral sensitivity in the wavelength range of 400 to 420 nm. In the case where the spectral sensitivity has a maximum peak in a wavelength region less than the above range, the sensitivity to laser light having a wavelength of 390 to 430 nm as the photosensitive resist material layer is inferior. The safe light property under the yellow light will be inferior.

  In the present invention, the maximum peak of spectral sensitivity is, for example, described in detail in “Photopolymer Technology” (Ao Yamaoka, published by Nikkan Kogyo Shimbun, 1988, page 262), etc. Light obtained by spectrally separating a photosensitive image-forming material sample having a photosensitive layer formed on the substrate surface from a light source such as a xenon lamp or a tungsten lamp using a spectral sensitivity measuring device is linearly exposed in the vertical direction with a vertical exposure wavelength. The exposure intensity is set so that it changes logarithmically in the axial direction. After exposure and exposure, an image corresponding to the sensitivity of each exposure wavelength can be obtained by developing, and an image can be formed from that image height. The maximum peak in the spectral sensitivity curve obtained by calculating the exposure energy and plotting the wavelength on the horizontal axis and the reciprocal of the exposure energy on the vertical axis.

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 capable of forming an image at a wavelength of 410 nm when a protective layer is provided on the photosensitive resist material layer. the amount [S _410] is at 10,000μJ / cm ² or less, preferably at 200μJ / cm ² or less, more preferably at 100 .mu.J / cm ² or less, particularly preferably at 50μJ / cm ² or less . If this minimum exposure amount [S ₄₁₀ ] exceeds the above range, although depending on the exposure intensity of the laser light source, the exposure time becomes longer and the practicality is lowered.

Further, the photosensitive resist material layer in the image forming material having the blue-violet laser photosensitive resist material layer of the present invention can form an image at a wavelength of 410 nm when no protective layer is provided on the photosensitive resist material layer. minimum exposure amount [S _410] is at 10,000μJ / cm ² or less, preferably at 5,000μJ / cm ² or less, and even more preferably 2,000μJ / cm ² or less. If this minimum exposure amount [S ₄₁₀ ] exceeds the above range, although depending on the exposure intensity of the laser light source, the exposure time becomes longer and the practicality is lowered.

The lower limit of the minimum exposure amount [S ₄₁₀ ] is preferably as small as possible, but it is usually 1 μJ / cm ² or more regardless of whether or not a protective layer is provided on the photosensitive resist material layer. In practice, it is 2.5 μJ / cm ² or more.
In addition, 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 )] capable of forming an image at the wavelength of 450 nm of S _410. The ratio [S ₄₁₀ / S ₄₅₀ ] is preferably 0.1 or less, and more preferably 0.05 or less. If this ratio [S ₄₁₀ / S ₄₅₀ ] exceeds the above range, it becomes difficult to achieve both blue-violet laser sensitivity and safe light performance under a yellow lamp.

Further, the photosensitive resist material layer of the image forming material having a blue-violet laser photosensitive resist material layer of the present invention, the minimum exposure dose capable of forming an image in each of the following wavelengths wavelength 450nm exceeds 650nm [S _450-650 (μJ / cm ^2)] minimum exposure amount capable of forming an image [S ₄₅₀ (μJ / cm ²⁾ ratio] [S _450-650 / S _450] is preferably 1 excess at the wavelength 450nm of. If this ratio [S _450-650 / S ₄₅₀ ] is less than the above range, it tends to be difficult to achieve both blue-violet laser sensitivity and safe light performance under a yellow lamp.

It should be noted that the minimum exposure capable of forming an image at a wavelength of 410 nm [S ₄₁₀ ], the minimum exposure capable of forming an image at a wavelength of 450 nm [S ₄₅₀ ], and the minimum exposure capable of forming an image at a wavelength exceeding 450 nm and not more than 650 nm. The amount [S _450-650 ] is obtained as exposure energy capable of image formation calculated from the obtained image height in the measurement of the maximum peak of spectral sensitivity using the above-described spectral sensitivity measuring apparatus. The minimum exposure amount that can form an image under optimum development conditions determined by changing development conditions such as the type of developer, development temperature, development time, etc., and the optimum development conditions are usually pH 11-14. The condition of immersing in an alkaline developer of 5 to 3 minutes at a temperature of 25 ° C. is employed.

  The image forming material having a blue-violet laser-sensitive resist material layer of the present invention has a blue-violet laser-sensitive resist material layer on a substrate to be processed, and the film thickness of the photosensitive resist material layer is The film thickness is 10 μm or more, preferably 15 μm or more, and the upper limit is usually 200 μm or less, preferably 100 μm or less. When the film thickness of the photosensitive resist material layer is less than 10 μm, a sufficient thickness of plating or etching is not performed on the substrate to be processed, while the film thickness of the photosensitive resist material layer is within a preferable range. As the thickness increases, the sensitivity of the resist tends to decrease.

  Conventionally, in the case of a photosensitive layer using a laser in the visible to infrared region, the sensitivity decreases as the film thickness is increased, and it is difficult to find a light-sensitive material that satisfies both the film thickness and sensitivity requirements in a balanced manner. Yes, a resist material layer having a thickness of 10 μm or more has not been put to practical use. In the case of using a violet laser, the present inventors use a resist material layer having a specific absorbance, and the sensitivity does not decrease even when the thickness of the resist material layer is increased. It was found that an image forming material having a high film thickness can be formed.

That is, the absorbance at the exposure wavelength of the photosensitive resist material layer is 0.3 or less per 1 μm film thickness, more preferably 0.25 or less, and particularly preferably 0.1 or less. The lower limit is 0.001 or more per 1 μm film thickness, and further 0.005 or more.
Generally, as the photosensitive resist material layer becomes thicker, the sensitivity of the resist decreases. However, in terms of substrate processing throughput, it is preferable that the degree of sensitivity change due to the film thickness is small. That is, when the sensitivity of the photosensitive resist material layer when the film thickness is 10 μm at the exposure wavelength is S1, and when the sensitivity when the film thickness is 20 μm is S2, S2 / S1 is preferably 1 or more and 5 or less, more preferably Is particularly 2 or less, and the lower limit is preferably 1 or more. When S2 / S1 is within this range, the sensitivity change due to the film thickness variation is small, so that a good image format is possible even when there is a step on the substrate to be processed. In the present invention, the resist sensitivity is defined as the minimum exposure amount that gives a residual film ratio of 90% or more of the resist coating thickness when the photosensitive layer is exposed and developed with a blue-violet laser.

The photosensitive composition for forming the photosensitive resist material layer in the present invention includes (1) the thickness (D) of the photosensitive resist material layer comprising the composition, and the photosensitive resist material layer having the thickness (D). The maximum value of the ratio (D / L) to the minimum line width (L) that can be resolved by scanning exposure with a laser beam having a wavelength of 390 to 430 nm and then developing 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 preferably 10,000 μJ / cm ² or less. The minimum line width (L) that can be resolved varies depending on the film thickness of the photosensitive resist material layer. Therefore, the maximum value means the maximum value of a plurality of D / Ls obtained by measuring the minimum line width (L) by changing the film thickness of the photosensitive resist material layer and obtaining D / L. The maximum value is preferably 1.3 or more, more preferably 2 or more. D / L is preferably as high as possible, but is usually 10 or less. The preferable range of [S ₄₁₀ (μJ / cm ² )] is as described above.

Moreover, the photosensitive composition which forms the photosensitive resist material layer in this invention is (1) the film thickness (D) of the photosensitive resist material layer which consists of this composition, and the photosensitive resist of this film thickness (D). The maximum value of the ratio (D / L) to the minimum line width (L) that can be resolved by scanning the material layer with a laser beam having a wavelength of 390 to 430 nm and developing it is 1.0 or more, and (2) An exposure amount that achieves the D / L is preferably 20 mJ / cm ² or less.
A preferable range of D / L is as described above. The exposure amount for achieving the D / L is preferably 10 mJ / cm ² or less. The lower limit of the exposure amount for achieving the D / L is preferably as small as possible, but is usually 1 μJ / cm ² or more, and practically 2.5 μJ / cm ² or more.

The composition of 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 the above spectral sensitivity characteristics or film thickness is satisfied. Any type. Examples of the negative type include [A] a photopolymerizable negative type, [B] a chemically amplified negative type, and examples of the positive type include a chemically amplified positive type.
[A. Photopolymerizable negative type]
The negative type is preferably composed of a photopolymerizable photosensitive composition containing the following components (N-1), (N-2), and (N-3).

(N-1) Ethylenically unsaturated compound (N-2) Sensitizer (N-3) Photopolymerization initiator Ethylene of (N-1) component constituting the photopolymerizable photosensitive composition in the present invention When the photosensitive composition is irradiated with actinic rays, the unsaturated compound undergoes addition polymerization by the action of a photopolymerization initiation system containing a photopolymerization initiator of the component (N-3) described later, and in some cases, is crosslinked. It is a compound having at least one radical polymerizable ethylenically unsaturated bond in the molecule that cures.

  As the ethylenically unsaturated compound in the present invention, a compound having one ethylenically unsaturated bond in the molecule, specifically, for example, (meth) acrylic acid [in the present invention, “(meth) acrylic” Means “acrylic” or / and “methacrylic”. ], Unsaturated carboxylic acids such as crotonic acid, isocrotonic acid, maleic acid, itaconic acid, citraconic acid, and alkyl esters thereof, (meth) acrylonitrile, (meth) acrylamide, styrene, etc. In view of the ability to expand the difference in developer solubility between the exposed part and the non-exposed part accompanying crosslinkability, it is preferably a compound having two or more ethylenically unsaturated bonds in the molecule, An acrylate compound whose unsaturated bond is derived from a (meth) acryloyloxy group is particularly preferred.

  The compounds having two or more ethylenically unsaturated bonds are typically esters of unsaturated carboxylic acids and polyhydroxy compounds, (meth) acryloyloxy group-containing phosphates, hydroxy (meth) acrylates. Examples include urethane (meth) acrylates of a compound and a polyisocyanate compound, and epoxy (meth) acrylates of a (meth) acrylic acid or hydroxy (meth) acrylate compound and a polyepoxy compound.

  Specific examples of the esters include unsaturated carboxylic acids as described above, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, tripropylene glycol, trimethylene glycol, tetramethylene glycol, Neopentyl glycol, hexamethylene glycol, nonamethylene glycol, trimethylol ethane, tetramethylol ethane, trimethylol propane, glycerol, pentaerythritol, dipentaerythritol, sorbitol, and their ethylene oxide adduct, propylene oxide adduct, diethanolamine, Reaction products with aliphatic polyhydroxy compounds such as triethanolamine, specifically, for example, ethylene glycol Di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetramethylene Glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, hexamethylene glycol di (meth) acrylate, nonamethylene glycol di (meth) acrylate, trimethylolethanetri (meth) acrylate, tetramethylolethanetri (meth) Acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide Id addition tri (meth) acrylate, glycerol di (meth) acrylate, glycerol tri (meth) acrylate, glycerol propylene oxide addition tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol Tetra (meth) acrylate, dipentaerythritol 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 And sorbitol hexa (meth) acrylate, and similar crotonate, isocrotonate, maleate, itaconate, citraconate and the like.

  Further, as the esters, a reaction product of an unsaturated carboxylic acid as described above with an aromatic polyhydroxy compound such as hydroquinone, resorcin, pyrogallol, bisphenol F, bisphenol A, and the like, specifically, for example, hydroquinone di (meta ) Acrylate, resorcin di (meth) acrylate, pyrogallol tri (meth) acrylate, etc., and a reaction product of an unsaturated carboxylic acid as described above with a heterocyclic polyhydroxy compound such as tris (2-hydroxyethyl) isocyanurate, Specifically, for example, di (meth) acrylate of tris (2-hydroxyethyl) isocyanurate, tri (meth) acrylate, etc., and a reaction product of unsaturated carboxylic acid, polyvalent carboxylic acid and polyhydroxy compound, Specifically, for example, (meth) acrylic acid and phthalic acid Condensate of ethylene glycol, condensate of (meth) acrylic acid, maleic acid and diethylene glycol, condensate of (meth) acrylic acid, terephthalic acid and pentaerythritol, (meth) acrylic acid, adipic acid and butanediol Examples include condensates with glycerin.

  Further, the (meth) acryloyloxy group-containing phosphates are not particularly limited as long as they are phosphate compounds containing a (meth) acryloyloxy group, but are represented by the following general formula (Ia) or (Ib). Those are preferred.

[In the formulas (Ia) and (Ib), R ¹ represents a hydrogen atom or a methyl group, n is an integer of 1 to 25, and m is 1, 2, or 3. ]
Here, n is preferably from 1 to 10, and particularly preferably from 1 to 4, and specific examples thereof include (meth) acryloyloxyethyl phosphate, bis [(meth) acryloyloxyethyl] phosphate, and (meth). Examples include acryloyloxyethylene glycol phosphate, which may be used alone or as a mixture.
Specific examples of urethane (meth) acrylates include hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycerol di (meth) acrylate, pentaerythritol tri (meth) acrylate, and tetramethylol. Hydroxy (meth) acrylate compounds such as ethane tri (meth) acrylate, hexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine methyl ester diisocyanate, lysine methyl ester triisocyanate, dimer acid diisocyanate, 1,6,6 Aliphatic polymers such as 11-undecatriisocyanate, 1,3,6-hexamethylene triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane Cycloaliphatic polyisocyanates such as isocyanate, cyclohexane diisocyanate, dimethylcyclohexane diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), isophorone diisocyanate, bicycloheptane triisocyanate, p-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2, 6-tolylene diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, 4,4′-diphenylmethane diisocyanate, tolidine diisocyanate, 1,5-naphthalene diisocyanate, tris (isocyanate phenylmethane), tris (isocyanate phenyl) thiophosphate, etc. Heterocyclic polyisocyanates such as aromatic polyisocyanates and isocyanurates Examples thereof include reactants with polyisocyanate compounds such as nates.

  Among them, as the urethane (meth) acrylate, a compound having 4 or more urethane bonds [—NH—CO—O—] and 4 or more (meth) acryloyloxy groups in one molecule is preferable. Is obtained, for example, by reacting a compound having four or more hydroxyl groups in one molecule such as pentaerythritol and polyglycerin with a diisocyanate compound such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, and tolylene diisocyanate. Compound (i-1) or a compound having two or more hydroxyl groups in one molecule such as ethylene glycol, “Duranate 24A-100”, “Duranate 22A-75PX”, “Duranate” manufactured by Asahi Kasei Kogyo Co., Ltd. 21S-75E "," Duranai " 18H-70B "and other biuret types," Duranate P-301-75E "," Duranate E-402-90T "," Duranate E-405-80T ", etc. 1 molecule such as a compound (i-2) obtained by reacting a compound having an isocyanate group, or a compound (i-3) obtained by polymerizing or copolymerizing isocyanate ethyl (meth) acrylate or the like Compounds having 4 or more, preferably 6 or more isocyanate groups, such as “Duranate ME20-100” (i) manufactured by Asahi Kasei Kogyo Co., Ltd., pentaerythritol di (meth) acrylate, penta Erythritol tri (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaeryth 1 or more hydroxyl groups and 2 or more, preferably 3 or more (meth) acryloyl per molecule, such as tall tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, etc. It can be obtained by reacting the compound (ii) having an oxy group.

  Here, the molecular weight of the compound (i) is preferably 500 to 200,000, and particularly preferably 1,000 to 150,000. The molecular weight of the urethane (meth) acrylates as described above is preferably 600 to 150,000. Further, it preferably has 6 or more urethane bonds, particularly preferably 8 or more, more preferably 6 or more (meth) acryloyloxy groups, and particularly preferably 8 or more.

In addition, such urethane (meth) acrylates include, for example, the compound (i) and the compound (ii) between the former isocyanate group and the latter hydroxyl group in an organic solvent such as toluene and ethyl acetate. It can be produced by a method of reacting at a molar ratio of 1/10 to 10/1 at 10 to 150 ° C. for about 5 minutes to 3 hours using a catalyst such as n-butyltin dilaurate as necessary. it can.
In the present invention, among the urethane (meth) acrylates, those represented by the following general formula (II) are particularly preferable.

[In the formula (II), Ra represents a group having a repeating structure of an alkyleneoxy group or an aryleneoxy group and having 4 to 20 oxy groups capable of bonding to Rb, and Rb and Rc are each independently carbon. An alkylene group having a number of 1 to 10, Rd represents an organic residue having 1 to 10 (meth) acryloyloxy groups, Ra, Rb, Rc and Rd may have a substituent; x is an integer of 4 to 20, y is an integer of 0 to 15, and z is an integer of 1 to 15. ]
Here, as the repeating structure of the alkyleneoxy group of Ra in the formula (II), for example, those derived from propylene triol, glycerin, pentaerythritol and the like, and as the repeating structure of the aryleneoxy group, for example, pyrogallol , 1,3,5-benzenetriol and the like. Moreover, it is preferable that the carbon number of the alkylene group of Rb and Rc is respectively independently 1-5, and it is preferable that the (meth) acryloyloxy group in Rd is 1-7. Further, x is preferably 4 to 15, y is 1 to 10, and z is 1 to 10.

  Furthermore, as Ra, the following formula [wherein, k is an integer of 2 to 10. And Rb and Rc are each independently a dimethylene group, a monomethyldimethylene group or a trimethylene group, and Rd is particularly preferably represented by the following formula: .

Moreover, as the epoxy (meth) acrylates, specifically, for example, (meth) acrylic acid, or a hydroxy (meth) acrylate compound as described above, (poly) ethylene glycol polyglycidyl ether, (poly) propylene Glycol polyglycidyl ether, (poly) tetramethylene glycol polyglycidyl ether, (poly) pentamethylene glycol polyglycidyl ether, (poly) neopentyl glycol polyglycidyl ether, (poly) hexamethylene glycol polyglycidyl ether, (poly) trimethylol Aliphatic polyepoxy compounds such as propane polyglycidyl ether, (poly) glycerol polyglycidyl ether, (poly) sorbitol polyglycidyl ether, phenol novolac polyepoxy Compounds, brominated phenol novolac polyepoxy compounds, aromatic polyepoxy compounds such as (o-, m-, p-) cresol novolac polyepoxy compounds, bisphenol A polyepoxy compounds, bisphenol F polyepoxy compounds, sorbitan polyglycidyl ethers, Examples thereof include reactants with polyepoxy compounds such as heterocyclic polyepoxy compounds such as triglycidyl isocyanurate and triglycidyl tris (2-hydroxyethyl) isocyanurate.
In addition to the above, as other ethylenically unsaturated compounds, for example, (meth) acrylamides such as ethylenebis (meth) acrylamide, allyl esters such as diallyl phthalate, vinyl group-containing compounds such as divinyl phthalate, etc. Is mentioned. The above ethylenically unsaturated compounds may be used alone or in combination of two or more.

  As the ethylenically unsaturated compound of the above component (N-1), ester (meth) acrylates, (meth) acryloyloxy group-containing phosphates, or urethane (meth) acrylates are preferable in the present invention. Particularly preferred are (meth) acryloyloxy group-containing phosphates or urethane (meth) acrylates. The proportion of the (meth) acryloyloxy group-containing phosphates relative to the total ethylenically unsaturated compound (N-1) is preferably 1 to 60% by weight, and 2 to 40% by weight. It is particularly preferred that the urethane (meth) acrylates occupy a proportion of 0.5 to 50% by weight, particularly preferably 2 to 40% by weight.

  The (N-2) component sensitizer constituting the photopolymerizable photosensitive composition in the present invention efficiently absorbs light in the blue-ultraviolet region having a wavelength of 390 to 430 nm, and the photoexcitation energy will be described later ( N-3) has a sensitizing function for transmitting to the photopolymerization initiator of component, decomposing the photopolymerization initiator, and generating active radicals that induce polymerization of the ethylenically unsaturated compound of component (N-1) Light absorbing dyes are preferred.

Examples of the light-absorbing dye in the present invention include dialkylaminobenzene compounds, among which a dialkylaminobenzophenone compound and a heterocyclic group substituted on a carbon atom in the p-position with respect to the amino group on the benzene ring. A dialkylaminobenzene compound having a group is preferred.
The dialkylaminobenzophenone compound is preferably a compound represented by the following general formula (IIIa).

[In the formula (IIIa), R ² , R ³ , R ⁴ and R ⁵ each independently represents an alkyl group, and R ⁶ , R ⁷ , R ⁸ and R ⁹ each independently represent an alkyl group. Or R ² and R ³ , R ⁴ and R ⁵ , R ² and R ⁶ , R ³ and R ⁷ , R ⁴ and R ⁸ , and R ⁵ and R ⁹ are each independently A nitrogen-containing heterocycle may be formed. ]
Here, the carbon number of the alkyl group of R ² , R ³ , R ⁴ , and R ⁵ in formula (IIIa) and the carbon when R ⁶ , R ⁷ , R ⁸ , and R ⁹ are alkyl groups The number is preferably 1 to 6, and when a nitrogen-containing heterocyclic ring is formed, a 5- or 6-membered ring is preferable, and a 6-membered ring is particularly preferable.
Specific examples of the compound represented by the general formula (IIIa) include 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, and compounds having the following structure. It is done.

  In addition, the heterocyclic group in the dialkylaminobenzene compound having a heterocyclic group as a substituent at a carbon atom in the p-position with respect to the amino group on the benzene ring includes a nitrogen atom, an oxygen atom, or a sulfur atom. Alternatively, a 6-membered ring is preferable, a 5-membered ring having a condensed benzene ring is particularly preferable, and a dialkylaminobenzene compound represented by the following general formula (IIIb) is particularly preferable.

[In the formula (IIIb), R ¹⁰ and R ¹¹ each independently represents an alkyl group, R ¹² and R ¹³ each independently represent an alkyl group or a hydrogen atom, R ¹⁰ and R ¹¹ , R ¹⁰ and R ¹² , and R ¹¹ and R ¹³ may each independently form a nitrogen-containing heterocyclic ring. X represents an oxygen atom, a sulfur atom, a dialkylmethylene group, an imino group, or an alkylimino group, and the benzene ring condensed to the heterocyclic ring containing X may have a substituent. ]
Here, the carbon number of the alkyl group of R ¹⁰ and R ¹¹ in formula (IIIb), and the carbon number when R ¹² and R ¹³ are an alkyl group are preferably 1 to 6, and When forming a nitrogen heterocycle, a 5- or 6-membered ring is preferred, and a 6-membered ring is particularly preferred. In addition, when X is a dialkylmethylene group, the alkyl group preferably has 1 to 6 carbon atoms, and when it is an alkylimino group, the alkyl group preferably has 1 to 6 carbon atoms.

  Specific examples of the compound represented by the general formula (IIIb) include, for example, 2- (p-dimethylaminophenyl) benzoxazole, 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) benzimidazole, 2- (p-diethylaminophenyl) benzimidazole, 2- (p-dimethylaminophenyl) -3,3-dimethyl-3H-indole, 2- (p-diethylamino) Phenyl) -3,3-dimethyl-3H-indole, and Compounds of the serial structure.

  Examples of the dialkylaminobenzene compound other than the compound represented by the general formula (IIIb) having a heterocyclic group as a substituent at a carbon atom in the p-position with respect to the amino group on the benzene ring include: 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.

  The photopolymerization initiator (N-3) constituting the photopolymerizable photosensitive composition in the present invention is irradiated with light in the presence of the sensitizer (N-2) and the like. A radical generator that receives the photoexcitation energy of the sensitizer to generate active radicals and leads to polymerization of the ethylenically unsaturated compound of component (N-1), for example, a hexaarylbiimidazole compound , Titanocene compounds, halogenated hydrocarbon derivatives, diaryliodonium salts, organic peroxides, and the like. Among them, hexaarylbiimidazole compounds and titanocene compounds are preferable, and hexaarylbiimidazole compounds are particularly preferable from the viewpoints of sensitivity as a photosensitive composition, adhesion to a substrate, storage stability, and the like.

  Specific examples of the hexaarylbiimidazole compound include 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole and 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) biimidazole, 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-iodophenyl) biimidazole, 2,2′-bis (o-bromophenyl) -4,4 ′, 5,5′-tetra (o-chloro-p-methoxyphenyl) Biimidazole, 2,2′-bis (o-chlorophenyl) -4, ', 5,5'-tetra (p- chloronaphthyl) biimidazole. Among them, a hexaphenylbiimidazole compound is preferable, and a compound in which the o-position of the benzene ring bonded to the 2,2′-position on the imidazole ring is substituted with a halogen atom is more preferable. Particularly preferred are those in which the benzene ring bonded to the 4 ′, 5,5′-position is unsubstituted or substituted with a halogen atom or an alkoxycarbonyl group. These hexaarylbiimidazole compounds are synthesized by a method disclosed in, for example, Bull.Chem.Soc.Japan; 33,565 (1960), J.Org.Chem.; 36,2262 (1971), etc. It may be used in combination with a biimidazole compound.

  Specific examples of the titanocene compound include dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium bisphenyl, dicyclopentadienyl titanium bis (2,4-difluorophenyl), and dicyclopentadienyl titanium bisphenyl. Cyclopentadienyl titanium bis (2,6-difluorophenyl), dicyclopentadienyl titanium bis (2,4,6-trifluorophenyl), dicyclopentadienyl titanium bis (2,3,5,6- Tetrafluorophenyl), dicyclopentadienyl titanium bis (2,3,4,5,6-pentafluorophenyl), di (methylcyclopentadienyl) titanium bis (2,6-difluorophenyl), di (methyl Cyclopentadienyl) titanium bis (2,3,4,5,6) Pentafluorophenyl), dicyclopentadienyl-titanium-bis [2,6-difluoro-3- (1-pyrrolyl) phenyl], and the like. Of these, titanium compounds having a dicyclopentadienyl structure and a biphenyl structure are preferred, and those in which the o-position of the biphenyl ring is substituted with a halogen atom are particularly preferred.

  In the present invention, the (N-1) component ethylenically unsaturated compound, the (N-2) component sensitizer, and the (N-3) component photopolymerization start in the negative photosensitive composition. The content ratio of the agent is preferably 0.05 to 20 parts by weight of the sensitizer of the component (N-2) with respect to 100 parts by weight of the ethylenically unsaturated compound of the component (N-1). More preferably, it is 0.1 to 10 parts by weight. Further, the photopolymerization initiator of the component (N-3) is preferably 1 to 60 parts by weight, and more preferably 5 to 40 parts by weight.

  The negative photosensitive composition according to the present invention has, in addition to the components (N-1), (N-2), and (N-3), formability as a photosensitive resist material layer on a substrate, and For the purpose of improving developability, it is preferable to further contain a polymer binder (N-4) component. Examples of the polymer binder include (meth) acrylic acid and (meth) acrylic acid esters. , (Meth) acrylonitrile, (meth) acrylamide, maleic acid, styrene, vinyl acetate, vinylidene chloride, maleimide, and the like, as well as polyamide, polyester, polyether, polyurethane, polyvinyl butyral, polyvinyl alcohol, polyvinylpyrrolidone Acetyl cellulose and the like, among them, from the viewpoint of alkali developability, carboxyl group-containing vinyl resin It is preferred.

  Specific examples of the carboxyl group-containing vinyl resin include (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid and other unsaturated carboxylic acids, and 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) acryloylmorpholine, (meth) acrylonitrile, (meth) acrylamide, N-methylol (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylamide, acetic acid Examples thereof include copolymers with vinyl compounds such as vinyl. These carboxyl group-containing vinyl resins have an acid value of 30 to 250 KOH · mg / g and a polystyrene-equivalent weight average molecular weight of 1,000 to 300,000. Preferably there is.

  Further, as the carboxyl group-containing vinyl-based resin, those having an ethylenically unsaturated bond in the side chain are suitable. Specifically, for example, allyl glycidyl ether, glycidyl (meth) acrylate is added to the carboxyl group-containing polymer. , Α-ethyl glycidyl (meth) acrylate, glycidyl crotonate, glycidyl isocrotonate, crotonyl glycidyl ether, itaconic acid monoalkyl monoglycidyl ester, fumaric acid monoalkyl monoglycidyl ester, maleic acid monoalkyl monoglycidyl ester, etc. Group epoxy group-containing unsaturated compound, or 3,4-epoxycyclohexylmethyl (meth) acrylate, 2,3-epoxycyclopentylmethyl (meth) acrylate, 7,8-epoxy [tricyclo [5.2.1. ] Dec-2-yl] An alicyclic epoxy group-containing unsaturated compound such as oxymethyl (meth) acrylate, 5 to 90 mol%, preferably about 30 to 70 mol% of the carboxyl group of the carboxyl group-containing polymer Reaction products obtained by reacting, and allyl (meth) acrylate, 3-allyloxy-2-hydroxypropyl (meth) acrylate, cinnamyl (meth) acrylate, crotonyl (meth) acrylate, methallyl (meth) acrylate, Compounds having two or more unsaturated groups such as N, N-diallyl (meth) acrylamide, or vinyl (meth) acrylate, 1-chlorovinyl (meth) acrylate, 2-phenylvinyl (meth) acrylate, 1- Propenyl (meth) acrylate, vinyl crotonate, vinyl (meth) a The ratio of the compound having two or more kinds of unsaturated groups such as chloramide and the unsaturated carboxylic acid such as (meth) acrylic acid, or further unsaturated carboxylic acid ester to the whole compound having the unsaturated group. The reaction product etc. which were copolymerized so that it may become 10-90 mol%, preferably about 30-80 mol% are mentioned.

In the present invention, the content of the polymer binder as the component (N-4) in the negative photosensitive composition is 50 to 100 parts by weight with respect to 100 parts by weight of the ethylenically unsaturated compound as the component (N-1). The amount is preferably 500 parts by weight, and more preferably 70 to 200 parts by weight.
The negative photosensitive composition in the present invention preferably further contains a hydrogen donating compound (N-5) component for the purpose of improving the photopolymerization initiating ability and the like. Are, for example, 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 3-mercapto-1,2,4-triazole, 2-mercapto-4 (3H) -quinazoline, β-mercaptonaphthalene, Mercapto group-containing compounds such as ethylene glycol dithiopropionate, trimethylolpropane tristhiopropionate, pentaerythritol tetrakisthiopropionate, hexanedithiol, trimethylolpropane tristhioglyconate, pentaerythritol tetrakisthiopropionate Polyfunctional thiol compounds, N, N-dialkylaminobenzoic acid ester, N-phenylglycine, or salts thereof such as ammonium and sodium salts, derivatives such as the above esters, phenylalanine, or salts thereof such as ammonium and sodium salts An amino acid having an aromatic ring such as a derivative such as an ester as above, or a derivative thereof. In the present invention, mercapto group-containing compounds and N-phenylglycine, or salts thereof such as ammonium and sodium salts, and derivatives such as the above esters are preferred.

In the present invention, the content of the hydrogen donating compound (N-5) component in the negative photosensitive composition is 1 with respect to 100 parts by weight of the ethylenically unsaturated compound (N-1). The amount is preferably -50 parts by weight, more preferably 10-40 parts by weight.
In addition, the negative photosensitive composition in the present invention preferably contains an amine compound (N-6) component for the purpose of improving the storage stability and the like as the photosensitive composition. , Aliphatic, cycloaliphatic, or aromatic amines, and not limited to monoamines, polyamines such as diamines and triamines, primary amines, secondary amines, tertiary amines However, it is preferable that pKb is 7 or less.

  Specific examples of the amine compound include butylamine, dibutylamine, tributylamine, amylamine, diamylamine, triamylamine, hexylamine, dihexylamine, trihexylamine, allylamine, diallylamine, triallylamine, triethanolamine, Examples thereof include aliphatic amines such as benzylamine, dibenzylamine and tribenzylamine which may be substituted with a hydroxyl group or a phenyl group. Among them, tribenzylamine is preferable in the present invention.

In the present invention, the content of the amine compound as the component (N-6) in the negative photosensitive composition is 1 to 20 with respect to 100 parts by weight of the ethylenically unsaturated compound as the component (N-1). It is preferably part by weight, more preferably 5 to 10 parts by weight.
In addition, the negative photosensitive composition in the present invention is nonionic, anionic for the purpose of improving the coating property when forming a photosensitive resist material layer on a substrate and the developability of the photosensitive resist material layer. , Cationic, amphoteric, and fluorine-based surfactant (N-7) components are preferable. Specifically, for example, as the nonionic surfactant, polyoxyethylene alkyl ethers, Polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl esters, polyoxyethylene fatty acid esters, glycerin fatty acid esters, polyoxyethylene glycerin fatty acid esters, pentaerythritol fatty acid esters , Polyoxyethylene pentaerythritol fatty acid Stealth, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, sorbite fatty acid esters, polyoxyethylene sorbit fatty acid esters, etc., and anionic surfactants include alkyl sulfonates, alkyl benzene sulfonic acids Salts, alkyl naphthalene sulfonates, polyoxyethylene alkyl ether sulfonates, alkyl sulfates, alkyl sulfate esters, higher alcohol sulfates, aliphatic alcohol sulfates, polyoxyethylene alkyl ether sulfates, polyoxyethylene Alkylphenyl ether sulfates, alkyl phosphate esters, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkylphenyl ether phosphates In addition, the cationic surfactants include quaternary ammonium salts, imidazoline derivatives, amine salts, and the like, and the amphoteric surfactants include betaine-type compounds, imidazolium salts, imidazolines, Examples thereof include amino acids.

In the present invention, the content of the surfactant of the (N-7) component in the negative photosensitive composition is 0. 0 parts by weight relative to 100 parts by weight of the ethylenically unsaturated compound of the (N-1) component. The amount is preferably 1 to 10 parts by weight, and more preferably 1 to 5 parts by weight.
The negative photosensitive composition in the present invention may contain a silane coupling agent in order to improve adhesion to the substrate. Specifically, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, vinyltrichlorosilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-glycidyloxy Propyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 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] propylmethyldiethoxysilane, 3- (N-allyl-N-glycidylamino) propyltrimethoxysilane, 3- (N-allyl-N-glycidylamino) propyltriethoxysilane, 3- ( N, N-diglycidylamino) propyltrimethoxysilane, 3- (N, N-diglycidylamino) propyltriethoxysilane, 3- (N-phenylamino) propyltrimethoxysilane, 3- (N-phenylamino) Propyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-merca Topropyltriethoxysilane, 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-glycidyl-N, N-bis [3- (methyldimethoxysilyl) propyl] amine, N-glycidyl-N, N-bis [3- And silane compounds such as (methyldiethoxysilyl) propyl] amine.

  The negative photosensitive composition according to the present invention further includes various additives, for example, thermal polymerization inhibitors such as hydroquinone, p-methoxyphenol, 2,6-di-t-butyl-p-cresol, 2 parts by weight or less based on 100 parts by weight of the ethylenically unsaturated compound (N-1), 20 parts by weight or less of a colorant comprising an organic or inorganic dye / pigment, dioctyl phthalate, didodecyl phthalate, tricres It may contain 40 parts by weight or less of a plasticizer such as zircinate, 10 parts by weight or less of a sensitivity characteristic improver such as tertiary amine or thiol, and 30 parts by weight or less of a dye precursor. .

[B. Chemical amplification negative type]
The photosensitive resist material layer of the present invention is composed of a chemically amplified negative photosensitive composition containing the following components (C-1), (C-2) and (C-3). preferable.
(C-1) Alkali-soluble resin (C-2) Cross-linking agent that acts on alkali-soluble resin under acidic conditions (C-3) Photoacid generator

  Here, the alkali-soluble resin (C-1) is not particularly limited as long as the unexposed portion becomes alkali-soluble at the time of development and can be eluted into an alkali developer. Usually, novolak resins, polyvinylphenols, polyacrylic are used. Acid, polyvinyl alcohol, styrene-maleic anhydride resin, polymers containing acrylic acid, vinyl alcohol or vinyl phenol as monomer units, or derivatives thereof are used. Of these, those containing polymer units having a phenolic hydroxyl group are particularly preferred, and novolak resins or polyvinylphenols are preferred.

  As novolak resins, m-cresol, o-cresol, p-cresol, 2,5-xylenol, 3,5-xylenol, resorcin, pyrogallol, bisphenol, bisphenol-A, trisphenol, o-ethylphenol, m-ethyl At least one of aromatic hydrocarbons such as phenol, p-ethylphenol, propylphenol, n-butylphenol, t-butylphenol, 1-naphthol, 2-naphthol and the like is acid-catalyzed, and formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, Examples thereof include those obtained by polycondensation with aldehydes such as furfural and at least one aldehyde or ketone selected from ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone.

  Paraformaldehyde and paraaldehyde may be used in place of formaldehyde and acetaldehyde, respectively. Polystyrene-converted weight average molecular weight (hereinafter abbreviated as GPC measurement weight average molecular weight Mw) measured by gel permeation chromatography (hereinafter abbreviated as GPC) of novolak resin is 1,000 to 15,000, preferably 1,500. -10,000 are used.

  As the novolak resin, more preferably, at least one phenol selected from o-cresol, m-cresol, p-cresol, 2,5-xylenol, 3,5-xylenol, and resorcin is formaldehyde, acetaldehyde, propion. Examples thereof include novolak resins polycondensed with at least one selected from aldehydes such as aldehydes. Among them, the mixing ratio of m-cresol: p-cresol: 2,5-xylenol: 3,5-xylenol: resorcin is 70 to 100: 0 to 30: 0 to 20: 0 to 20: 0 to 20 in molar ratio. A novolak resin which is a polycondensate of phenols and aldehydes is preferred. Of the aldehydes, formaldehyde is particularly preferable.

Polyvinylphenols include o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, 2- (o-hydroxyphenyl) propylene, 2- (m-hydroxyphenyl) propylene, 2- (p-hydroxyphenyl) propylene Examples thereof include hydroxystyrenes alone or two or more polymers. Hydroxystyrenes may have a substituent such as a halogen such as chlorine, bromine, iodine, fluorine or a C ₁ -C ₄ alkyl substituent in the aromatic ring. or include better polyvinyl phenol which may have an alkyl substituent of C ₁ -C _4.

Polyvinylphenols are usually obtained by polymerizing hydroxystyrenes which may have a substituent, alone or in the presence of a radical polymerization initiator or a cationic polymerization initiator. Such polyvinylphenols may be partially hydrogenated to reduce the absorbance of the resin. Further, a resin in which a part of the OH groups of the polyvinylphenols is protected with a t-butoxycarbonyl group, a pyranyl group, a furanyl group, or the like may be used. The Mw of polyvinylphenols is 1,000 to 100,000, preferably 1,500 to 50,000. The polyvinyl phenols, and more preferably, have an alkyl substituent of C ₁ -C ₄ the aromatic ring include good polyvinylphenol, unsubstituted polyvinyl phenol are particularly preferred. If the molecular weight of the alkali-soluble resin is smaller than the above range, a sufficient coating film as a resist cannot be obtained. It tends to be impossible. Of the alkali-soluble resins described above, unsubstituted polyvinylphenol and novolac resins are particularly preferable.

  The crosslinking component (C-2) that acts on the alkali-soluble resin under acidic conditions as the second component of the chemically amplified negative photosensitive composition is particularly limited as long as it is a compound that undergoes a crosslinking reaction with the alkali-soluble resin to be used. However, examples include compounds in which formalin is allowed to act on melamine, benzoguanamine, glycoluril or urea, or alkyl-modified compounds thereof, epoxy compounds, resole compounds, and the like.

  Specifically, Mitsui Cyanamid's Cymel (registered trademark) 300, 301, 303, 350, 736, 738, 370, 771, 325, 327, 703, 701, 266, 267, 285, 232, 235, 238, Examples of 1141, 272, 254, 202, 1156, 1158, Nikalac (registered trademark) E-2151, MW-100LM, MX-750LM of Sanwa Chemical Co., Ltd., a compound obtained by allowing formalin to act on melamine, or an alkyl modified product thereof Can be mentioned.

  Moreover, Cymel (registered trademark) 1123, 1125, and 1128 can be given as examples of compounds obtained by allowing formalin to act on benzoguanamine or alkyl modified products thereof. Cymel (registered trademark) 1170, 1171, 1174, 1172, and Nicarak (registered trademark) MX-270 can be given as examples of compounds obtained by allowing formalin to act on glycoluril or alkyl-modified products thereof. Examples of a compound obtained by allowing formalin to act on urea or an alkyl-modified product thereof include UFR (registered trademark) 65 and 300 and Nicalac (registered trademark) MX-290 manufactured by Mitsui Cyamide.

  Examples of epoxy compounds include novolak epoxy resins (manufactured by Toto Kasei Co., Ltd., YDP N-638, 701, 702, 703, 704, etc.), amine epoxy resins (manufactured by Toto Kasei Co., Ltd., YH-434, etc.), and bisphenol A epoxy resins. (Japan Epoxy Resin, Epicoat 825, 826, 827, 828, 1001, 1002, 1003, 1055, 1004, 1007, 1009, 1010, etc.), sorbitol (poly) glycidyl ether, (poly) glycerol (poly) glycidyl ether , Pentaerythritol (poly) glycidyl ether, triglycidyl trishydroxyethyl isocyanurate, allyl glycidyl ether, ethylhexyl glycidyl ether, phenyl glycidyl ether, phenol glycidyl ether, Uryl alcohol glycidyl ether, adipic acid glycidyl ether, phthalic acid glycidyl ether, dibromophenyl glycidyl ether, dibromoneopentyl glycol diglycidyl ether, glycidyl phthalimide, (poly) ethylene glycol glycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl Examples include ether, glycerin polyglycidyl ether, trimethylolpropane polyglycidyl ether, and butyl glycidyl ether.

Among these, particularly preferred compounds include compounds having —N (CH ₂ OR) ₂ group (wherein R represents an alkyl group or a hydrogen atom) in the molecule. Specifically, a compound obtained by allowing formalin to act on urea or melamine or an alkyl-modified product thereof is particularly preferable.
As the photoacid generator (C-3), the same photoacid generator (P-2) as used in the positive photosensitive composition described later is used, and the photosensitive composition is irradiated with actinic rays. Preferred are, for example, halogen-containing compounds such as halogen-substituted alkanes, halomethylated s-triazine derivatives, onium salts, and sulfone compounds. In the present invention, halomethylated s-triazine derivatives are particularly preferable.

Here, specific examples of the halogen-substituted alkane among the halogen-containing compounds include dichloromethane, trichloromethane, 1,2-dichloroethane, 1,2-dibromoethane, and the like.
Among the halogen-containing compounds, specific examples of halomethylated s-triazine derivatives include 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 (trichloro Methyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3,4-epoxyphenyl) -4,6-bi (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 (trichloromethyl) -s-triazine, 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) -S-triazine, 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- (Trichloromethyl) -s-triazine, 2- (p-ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-ethoxycarbonylnaphthyl) -4,6-bis (trichloro) Methyl) -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 and the like, among which bis (trihalomethyl) -s-triazine is preferable, 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-hydroxystyryl) -4,6 Particularly preferred are -bis (trichloromethyl) -s-triazine, 2- (pi-propyloxystyryl) -4,6-bis (trichloromethyl) -s-triazine and the like.

  The onium salts include ammonium salts such as tetramethylammonium bromide and tetraethylammonium bromide, diphenyliodonium hexafluoroarsenate, diphenyliodonium tetrafluoroborate, diphenyliodonium p-toluenesulfonate, diphenyliodonium camphorsulfonate, dicyclohexyliodonium hexafluoro Arsenates, icyclohexyl iodonium tetrafluoroborate, icyclohexyl salts such as dicyclohexyliodonium p-toluenesulfonate, dicyclohexyliodonium camphorsulfonate, triphenylsulfonium hexafluoroarsenate, triphenylsulfonium tetrafluoroborate, triphenylsulfonium - toluenesulfonate, triphenylsulfonium camphorsulfonate, tri-cyclohexyl hexafluoroarsenate, tri-cyclohexyl sulfonium tetrafluoroborate, tri-cyclohexyl sulfonium p- toluenesulfonate, sulfonium salts such as tri-cyclohexyl sulfonium camphorsulfonate, and the like.

Specific examples of the sulfone compounds include bis (phenylsulfonyl) methane, bis (p-hydroxyphenylsulfonyl) methane, bis (p-methoxyphenylsulfonyl) methane, and bis (α-naphthylsulfonyl) methane. Bis (β-naphthylsulfonyl) methane, bis (cyclohexylsulfonyl) methane, bis (t-butylsulfonyl) methane, bis (sulfonyl) methane compounds such as phenylsulfonyl (cyclohexylsulfonyl) methane, phenylcarbonyl (phenylsulfonyl) methane, Naphthylcarbonyl (phenylsulfonyl) methane, phenylcarbonyl (naphthylsulfonyl) methane, cyclohexylcarbonyl (phenylsulfonyl) methane, t-butylcarbonyl (phenylsulfonyl) methane, Carbonyl (sulfonyl) methane compounds such as phenylcarbonyl (cyclohexylsulfonyl) methane, 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 Carbonyl (sulfonyl) such as phenylcarbonyl (naphthylsulfonyl) diazomethane, cyclohexylcarbonyl (phenylsulfonyl) diazomethane, t-butylcarbonyl (phenylsulfonyl) diazomethane, phenylcarbonyl (cyclohexylsulfonyl) diazomethane, phenylcarbonyl (t-butylcarbonyl) diazomethane A diazomethane compound etc. are mentioned.
The chemically amplified negative photosensitive composition preferably contains a sensitizer (C-4) for the purpose of improving sensitivity as a photosensitive resist agent layer. The light-absorbing dyes similar to those mentioned as the sensitizer of the component (N-2) of the photopolymerizable negative photosensitive composition can be exemplified. The sensitizer efficiently absorbs light in the blue-ultraviolet region with a wavelength of 390 to 430 nm, and transmits its photoexcitation energy to the photoacid generator of the component (C-4) described later to decompose the photoacid generator. A light-absorbing dye having a sensitizing function for generating an acid that induces crosslinking of the component (C-1) by the component (C-2) is preferable.

  In the above-mentioned chemically amplified negative photosensitive composition, the crosslinking agent (C-2) is usually 1 to 80 parts by weight, preferably 5 to 60 parts by weight with respect to 100 parts by weight of the alkali-soluble resin (C-1). The photoacid generator (C-3) is usually used in a proportion of 0.001 to 30 parts by weight, preferably 0.005 to 10 parts by weight. When the photoacid generator system is composed of a combination of a photoacid generator and a sensitizer, the amount of the sensitizer (C-4) added is 0.1% with respect to 100 parts by weight of the alkali-soluble resin (C-1). About 1 to 30 parts by weight, preferably 0.5 to 20 parts by weight.

  When the amount of the crosslinking agent (C-2) is less than the above range, a sufficient crosslinking effect cannot be obtained and the resist pattern tends to be defective. On the other hand, when the amount of the cross-linking agent is larger than this range, the resist coating characteristics tend to be lowered. Further, when the amount of the photoacid generator is less than this range, the sensitivity tends to be low. When the amount of the photoacid generator is larger than this range, the resist pattern becomes an inverted trapezoid due to a decrease in the transparency of the resist film due to the photoacid generator, and the resolution tends to decrease.

[C: Chemical amplification positive type]
Moreover, as a composition of the photosensitive resist material layer in the image forming material having the blue-violet laser photosensitive resist material layer of the present invention, the positive type contains the following components (P-1) and (P-2): It is preferable to consist of a photosensitive composition.
(P-1) Acid-decomposable group-containing polymer (P-2) Photoacid generator The acid-decomposable group-containing polymer of component (P-1) constituting the positive photosensitive composition in the present invention is photosensitive. When the active composition is irradiated with actinic rays, an acid-decomposable group that decomposes with an acid generated by the photoacid generator of component (P-2) described later and imparts alkali solubility to the polymer itself If it is a polymer containing this, it will not specifically limit.

  Specific examples of the acid-decomposable group include an alkoxy group having 1 to 15 carbon atoms such as a methoxy group, an ethoxy group, an i-propoxy group, and a t-butoxy group, a methoxymethoxy group, a dimethoxymethoxy group, and an ethoxy group. C2-C15 alkoxy such as methoxy group, 1-methoxyethoxy group, 1-ethoxyethoxy group, 1-propoxyethoxy group, 1-t-butoxyethoxy group, 1-cyclohexyloxyethoxy group, 1-ethoxypropoxy group 2-15 alkoxycarbonyloxy groups such as alkoxy group, methoxycarbonyloxy group, ethoxycarbonyloxy group, n-propoxycarbonyloxy group, i-propoxycarbonyloxy group, n-butoxycarbonyloxy group, t-butoxycarbonyloxy group , Ethoxycarbonyloxymethoxy group an alkoxycarbonyloxyalkoxy group having 2 to 15 carbon atoms such as an n-propoxycarbonyloxymethoxy group, i-propoxycarbonyloxymethoxy group, n-butoxycarbonyloxymethoxy group, t-butoxycarbonyloxymethoxy group, etc. Examples thereof include groups having a group.

  Examples of the polymer containing the acid-decomposable group include etherification or at least part of the phenolic hydroxyl group of a phenolic hydroxyl group-containing resin such as a phenolic resin such as a novolak resin and a resole resin, and a polyvinylphenol resin. A resin in which the acid-decomposable group is introduced by esterification is preferable. Among them, in the present invention, a resin in which the acid-decomposable group is introduced into a polyvinylphenol resin or a novolak resin is more preferable, and a resin in which the acid-decomposable group is introduced into a polyvinylphenol resin is particularly preferable.

  Here, the novolak resin is, for example, 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-naphthol, 2-naphthol, pyrocatechol, resorcinol, hydroquinone, pyrogallol, 1,2,4-benzenetriol, phloroglucinol, 4,4'-biphenyldiol, 2 , 2-bis (4′-hydroxyphenyl) propane and the like, under an acid catalyst, for example, aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, furfural (formaldehyde) Paraformaldehyde instead of acetaldehyde, paraaldehyde may be used instead of acetaldehyde), or a resin polycondensed with at least one of ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, The resol resin is a resin obtained by polycondensation in the same manner except that an alkali catalyst is used instead of the acid catalyst in the polycondensation of the novolak resin. These novolak resins and resol resins preferably have a polystyrene-equivalent weight average molecular weight of 1,000 to 15,000 as measured by gel permeation chromatography, and particularly preferably those of 1,500 to 10,000.

  Polyvinylphenol resins include, for example, o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, dihydroxystyrene, trihydroxystyrene, tetrahydroxystyrene, pentahydroxystyrene, 2- (o-hydroxyphenyl) propylene, 2 Hydroxystyrenes such as-(m-hydroxyphenyl) propylene and 2- (p-hydroxyphenyl) propylene (note that these are halogen atoms such as chlorine, bromine, iodine and fluorine on the benzene ring, or carbon atoms of 1 to 4 In which a single or two or more alkyl groups may be substituted as a substituent in the presence of a radical polymerization initiator or a cationic polymerization initiator. These polyvinylphenol resins preferably have a polystyrene-equivalent weight average molecular weight of 1,000 to 100,000, particularly preferably 1,500 to 50,000.

  Moreover, as the polymer containing the acid-decomposable group, for example, a resin in which at least a part of the carboxyl group of the carboxyl group-containing vinyl resin is esterified and the acid-decomposable group is introduced can be mentioned as a preferable one. . As the carboxyl group-containing vinyl resin, for example, (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid, and other unsaturated carboxylic acids, 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) ) Vinyl compounds such as acryloylmorpholine, (meth) acrylonitrile, (meth) acrylamide, N-methylol (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylamide, vinyl acetate These carboxyl group-containing vinyl resins preferably have a polystyrene-equivalent weight average molecular weight of 1,000 to 300,000.

  The photoacid generator of component (P-2) constituting the positive photosensitive composition in the present invention is a compound that generates an acid when the photosensitive composition is irradiated with actinic rays. For example, halogen-containing compounds such as halogen-substituted alkanes, halomethylated s-triazine derivatives, onium salts, sulfone compounds and the like are preferred. In the present invention, halomethylated s-triazine derivatives are preferred. Particularly preferred.

Here, specific examples of the halogen-substituted alkane among the halogen-containing compounds include dichloromethane, trichloromethane, 1,2-dichloroethane, 1,2-dibromoethane, and the like.
Among the halogen-containing compounds, specific examples of halomethylated s-triazine derivatives include 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 (trichloro Methyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3,4-epoxyphenyl) -4,6-bi (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 (trichloromethyl) -s-triazine, 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) -S-triazine, 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- (Trichloromethyl) -s-triazine, 2- (p-ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-ethoxycarbonylnaphthyl) -4,6-bis (trichloro) Methyl) -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 and the like, among which bis (trihalomethyl) -s-triazine is preferable, 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-hydroxystyryl) -4,6 Particularly preferred are -bis (trichloromethyl) -s-triazine, 2- (pi-propyloxystyryl) -4,6-bis (trichloromethyl) -s-triazine and the like.

  The onium salts include ammonium salts such as tetramethylammonium bromide and tetraethylammonium bromide, diphenyliodonium hexafluoroarsenate, diphenyliodonium tetrafluoroborate, diphenyliodonium p-toluenesulfonate, diphenyliodonium camphorsulfonate, dicyclohexyliodonium hexafluoro Arsenates, icyclohexyl iodonium tetrafluoroborate, icyclohexyl salts such as dicyclohexyliodonium p-toluenesulfonate, dicyclohexyliodonium camphorsulfonate, triphenylsulfonium hexafluoroarsenate, triphenylsulfonium tetrafluoroborate, triphenylsulfonium - toluenesulfonate, triphenylsulfonium camphorsulfonate, tri-cyclohexyl hexafluoroarsenate, tri-cyclohexyl sulfonium tetrafluoroborate, tri-cyclohexyl sulfonium p- toluenesulfonate, sulfonium salts such as tri-cyclohexyl sulfonium camphorsulfonate, and the like.

  Specific examples of the sulfone compounds include bis (phenylsulfonyl) methane, bis (p-hydroxyphenylsulfonyl) methane, bis (p-methoxyphenylsulfonyl) methane, and bis (α-naphthylsulfonyl) methane. Bis (β-naphthylsulfonyl) methane, bis (cyclohexylsulfonyl) methane, bis (t-butylsulfonyl) methane, bis (sulfonyl) methane compounds such as phenylsulfonyl (cyclohexylsulfonyl) methane, phenylcarbonyl (phenylsulfonyl) methane, Naphthylcarbonyl (phenylsulfonyl) methane, phenylcarbonyl (naphthylsulfonyl) methane, cyclohexylcarbonyl (phenylsulfonyl) methane, t-butylcarbonyl (phenylsulfonyl) methane, Carbonyl (sulfonyl) methane compounds such as phenylcarbonyl (cyclohexylsulfonyl) methane, 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 Carbonyl (sulfonyl) such as phenylcarbonyl (naphthylsulfonyl) diazomethane, cyclohexylcarbonyl (phenylsulfonyl) diazomethane, t-butylcarbonyl (phenylsulfonyl) diazomethane, phenylcarbonyl (cyclohexylsulfonyl) diazomethane, phenylcarbonyl (t-butylcarbonyl) diazomethane A diazomethane compound etc. are mentioned.

  In the present invention, each content ratio of the acid-decomposable group-containing polymer of the component (P-1) and the photoacid generator of the component (P-2) in the positive photosensitive composition is (P- It is preferable that the photoacid generator of component (P-2) is 0.1 to 50 parts by weight, based on 100 parts by weight of the acid-decomposable group-containing polymer 1), and 0.5 to 20 parts by weight. More preferably, it is part.

In addition, the positive photosensitive composition may contain a sensitizer (P-3) component for the purpose of improving sensitivity and the like as a photosensitive resist agent layer. Examples thereof include the same light-absorbing dye as mentioned as the sensitizer of the (N-2) component of the negative photosensitive composition.
The (P-3) component sensitizer constituting the positive photosensitive composition in the present invention efficiently absorbs light in the blue-ultraviolet region having a wavelength of 390 to 430 nm, and the photoexcitation energy thereof will be described later (P- 2) Light absorption having a sensitizing function that transmits to the component photoacid generator, decomposes the photoacid generator, and generates an acid that induces decomposition of the acid-decomposable group-containing resin of component (P-1). A dye is preferred.

The content ratio is preferably 1 to 30 parts by weight, more preferably 5 to 20 parts by weight, based on 100 parts by weight of the acid-decomposable group-containing polymer of the component (P-1).
The positive photosensitive composition is nonionic, anionic, and cationic for the purpose of improving the coating property when forming a photosensitive resist material layer on a substrate and the developability of the photosensitive resist material layer. , Amphoteric, and fluorine-based surfactant (P-4) components, and as the surfactant, surfactant (N-7) component of the negative photosensitive composition may be used. The content ratio is 0.1 to 10 parts by weight with respect to 100 parts by weight of the acid-decomposable group-containing polymer of the component (P-1). Preferably, it is 1 to 5 parts by weight.

The positive photosensitive composition according to the present invention further includes various additives, for example, a colorant comprising an organic or inorganic dye / pigment, a coatability improver, an adhesion improver, a sensitivity improver, and a sensitizer. An agent or the like may be contained in an amount of 10 parts by weight or less based on 100 parts by weight of the acid-decomposable group-containing polymer of the component (P-1).
The positive and negative resist compositions of the present invention contain various additives such as dyes, pigments, coatability improvers, development improvers, adhesion improvers and the like as long as the performance is not impaired. Is also possible,
In the present invention, the negative photosensitive composition or the positive photosensitive composition is usually applied on a substrate to be processed as a coating solution in which the above components are dissolved or dispersed in an appropriate solvent, and then heated and dried. The image forming material has a blue-violet laser-sensitive resist material layer made of the photosensitive composition on the substrate to be processed.

  Here, the substrate to be processed is etched using a pattern layer formed by exposing and developing the blue-violet laser-sensitive resist material layer made of the photosensitive composition with blue-violet laser light as a mask. Therefore, a circuit pattern is formed on the surface thereof, and may be a metal plate itself such as copper, aluminum, gold, silver, chromium, zinc, tin, lead, nickel, etc. Thermosetting resins such as polyimide resin, bismaleimide resin, unsaturated polyester resin, phenol resin, melamine resin, saturated polyester resin, polycarbonate resin, polysulfone resin, acrylic resin, polyamide resin, polystyrene resin, polyvinyl chloride resin, polyolefin Resin, thermoplastic resin such as fluorine resin, paper, glass And inorganic materials such as alumina, silica, barium sulfate, calcium carbonate, or composite materials such as glass cloth base epoxy resin, glass nonwoven base epoxy resin, paper base epoxy resin, paper base phenol resin, etc. In addition, the metal or a metal foil such as indium oxide, tin oxide, indium oxide doped tin oxide or the like is heated on the surface of the insulating support having a thickness of about 0.02 to 10 mm, and is laminated by pressure bonding. A metal-clad laminate in which a conductive layer having a thickness of about 1 to 100 μm is formed by a method such as sputtering, vapor deposition, or plating of metal is preferably used.

  The solvent used in the coating solution is not particularly limited as long as it has sufficient solubility for the components used and gives good coating properties. For example, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate Cellosolve solvents such as 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, propylene glycol monobutyl ether acetate, dipropylene glycol dimethyl ether, etc. Propylene glycol solvents, butyl acetate, amyl acetate, ethyl butyrate, butyl butyrate, diethyl oxalate, ethyl pyruvate Ester solvents such as ethyl-2-hydroxybutyrate, ethyl acetoacetate, methyl lactate, ethyl lactate, methyl 3-methoxypropionate, alcohol solvents such as heptanol, hexanol, diacetone alcohol, furfuryl alcohol, cyclohexanone, Examples thereof include ketone solvents such as methyl amyl ketone, highly polar solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone, mixed solvents thereof, and those obtained by adding aromatic hydrocarbons thereto. The ratio of the solvent used is usually in the range of about 1 to 20 times by weight with respect to the total amount of the photosensitive composition.

  As the coating method, conventionally known methods such as spin coating, wire bar coating, spray coating, dip coating, air knife coating, roll coating, blade coating, screen coating, and curtain coating can be used. . The coating amount in that case is 10 micrometers or more as a dry film thickness, Preferably it is 15 micrometers or more, and an upper limit is 200 micrometers or less normally, Preferably it is 100 micrometers or less. The drying temperature at that time is, for example, about 30 to 150 ° C., preferably about 40 to 110 ° C., and the drying time is, for example, about 5 seconds to 60 minutes, preferably about 10 seconds to 30 minutes. It is done.

  The photosensitive composition of the present invention is coated on a temporary support film as a coating solution in which each of the above components is dissolved or dispersed in an appropriate solvent and dried, and if necessary, the surface of the photosensitive composition layer formed. Is covered with a coating film to form the photosensitive image forming material of the present invention as a so-called dry film resist material, and the photosensitive composition layer side of the image forming material is covered with a coating film. The coating film is peeled off and laminated on the substrate to be processed, or directly applied onto the substrate to be processed and dried as a coating solution in which the above components are dissolved or dispersed in an appropriate solvent. Thus, the photosensitive image forming material of the present invention in which the layer of the photosensitive composition of the present invention is formed on a substrate to be processed, and the photosensitive composition layer of the image forming material is converted into a laser beam having a wavelength of 390 to 430 nm. By And 査露 light, suitable for use in the use form as an image forming method for revealing a negative image by development.

As a temporary support film in the case of being used as an image forming material as the dry film resist material, a conventionally known film such as a polyethylene terephthalate film, a polyimide film, a polyamideimide film, a polypropylene film, or a polystyrene film is used. At that time, when those films have the solvent resistance and heat resistance necessary for the production of the image forming material, the photosensitive composition coating solution is directly applied onto the temporary support film. Then, the image forming material of the present invention can be produced by drying, and even if those films have low solvent resistance or heat resistance, for example, polytetrafluoroethylene film, release film, etc. First, a photosensitive composition layer is formed on a film having releasability, and a temporary support film having low solvent resistance and heat resistance is laminated on the layer, and then a film having releasability is formed. By peeling, the image forming material of the present invention can be produced.
The solvent and coating method used for coating are the same as described above.

  When used as an image forming material as a dry film resist material or the like, it is preferable to cover the formed photosensitive composition layer surface with a coating film until the image forming material is laminated on a substrate to be processed. As the covering film, a conventionally known film such as a polyethylene film, a polypropylene film, a polytetrafluoroethylene film or the like is used.

  In addition, when the photosensitive composition layer side of the image forming material is covered with a coating film, the coating film is peeled off and laminated by heating, pressurizing, or the like. The substrate to be processed in producing the image forming material of the present invention by directly applying and drying the composition coating liquid is scanned and exposed to a photosensitive composition layer formed thereon by laser light and developed. Thus, a pattern such as a circuit or an electrode is formed on the surface by etching or plating using the negative image that appears as a resist.

  In the present invention, in the photopolymerizable negative image forming material, on the blue-violet laser photosensitive resist material layer comprising the photosensitive composition formed on the substrate to be processed as described above. A protective layer such as an oxygen blocking layer for preventing polymerization-inhibiting action due to oxygen of the photopolymerizable composition or a light transmittance adjusting layer for adjusting the wavelength region of the aforementioned maximum peak of spectral sensitivity is formed. It may be.

  The oxygen barrier layer is composed of water or a water-soluble polymer soluble in 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, its partial acetalized product, its cation-modified product with quaternary ammonium salt, etc., its anion-modified product with sodium sulfonate, etc., polypinylpyrrolidone, polyethylene oxide , Methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose and the like.

  Among them, polyvinyl alcohol and derivatives thereof are preferable from the viewpoint of oxygen barrier properties, etc., and polyvinyl pyrrolidone, vinylpyrrolidone-vinyl acetate copolymer, etc. from the viewpoint of adhesion to the photosensitive resist material layer, etc. A vinyl pyrrolidone polymer is preferable, and the oxygen barrier layer in the present invention is preferably 1 to 20 parts by weight, more preferably 3 to 15 parts by weight of polyvinyl pyrrolidone polymer with respect to 100 parts by weight of polyvinyl alcohol or a derivative thereof. It is preferable to use it as a mixture in which parts by weight are mixed.

  The oxygen barrier layer preferably contains an organic acid such as oxalic acid or an organic acid salt such as ethylenediaminetetraacetic acid from the standpoint of imparting storage stability, and nonionics such as polyoxyethylene alkylphenyl ether. , Surfactants such as anionic properties such as sodium dodecylbenzenesulfonate, cationic properties such as alkyltrimethylammonium chloride, antifoaming agents, dyes, plasticizers, pH adjusters, etc., and their total The content ratio is preferably 10% by weight or less, and more preferably 5% by weight or less.

The oxygen barrier layer is formed as a solution of water or a mixed solvent of water and a water-miscible organic solvent by a coating method similar to that of the photosensitive resist material layer described above. It is preferably in the range of 10 to 10 g / m ² , and more preferably in the range of 1.5 to 7 g / m ² .
In addition, as a constituent of the light transmission adjusting layer, for example, a polymer binding material containing a light-absorbing dye in the visible region such as a coumarin-based dye can be mentioned. Can be used as a protective layer having an oxygen blocking ability and a light transmittance adjusting ability.

The image forming material having the blue-violet laser-sensitive resist material layer of the present invention forms a resist image by scanning and exposing the photosensitive resist material layer with laser light and then developing the image.
Here, examples of the laser exposure light source include a HeNe laser, an argon ion laser, a YAG laser, a HeCd laser, a semiconductor laser, and a ruby laser. In particular, laser light in a blue-violet region having a wavelength range of 390 to 430 nm is used. Although the light source to generate | occur | produce is preferable and it does not specifically limit, Specifically, the indium gallium nitride semiconductor laser which oscillates 410 nm etc. is mentioned.

  Further, the scanning exposure method is not particularly limited, and examples thereof include a plane scanning exposure method, an outer drum scanning exposure method, an inner drum scanning exposure method, and the like. Preferably 100 nW to 100 mW, more preferably 1 μW to 70 mW, oscillation wavelength, preferably 390 to 430 nm, more preferably 400 to 420 nm, beam spot diameter, preferably 0.5 to 30 μm, more preferably 1 to 20 μm, Scanning exposure is performed at a scanning speed of preferably 50 to 500 m / second, more preferably 100 to 400 m / second, and a scanning density of preferably 2,000 dpi or more, more preferably 4,000 dpi or more.

  The development after the laser scanning exposure is preferably performed using an aqueous developer containing an alkali component and a surfactant. Examples of the alkali component include sodium silicate, potassium silicate, lithium silicate, ammonium silicate, sodium metasilicate, potassium metasilicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, Inorganic alkali salts such as dibasic sodium phosphate, tribasic sodium phosphate, dibasic ammonium phosphate, tribasic ammonium phosphate, sodium borate, potassium borate, ammonium borate, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, mono Isopropylamine, diisopropylamine, monobutylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine Organic amine compounds and the like, and used at a concentration of about 0.1 to 5 wt%.

  Examples of the surfactant include the same surfactants as those mentioned in the photopolymerizable negative photosensitive composition. Among them, nonionic, anionic or amphoteric surfactants are preferable, and amphoteric surfactants are particularly preferable. Surfactants, especially betaine type compounds are preferred. The surfactant is used in a concentration of preferably 0.0001 to 20% by weight, more preferably 0.0005 to 10% by weight, and particularly preferably 0.001 to 5% by weight.

  Furthermore, the developing solution can contain an organic solvent such as isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol, if necessary. Further, the pH of the developer is preferably 9 to 14, and more preferably 11 to 14.

  The development is usually about 10 to 50 ° C., more preferably 15 to 15 ° C. by a known development method such as immersing the image forming material in the developer or spraying the developer on the image forming material. It is performed at a temperature of about 45 ° C. for a time of about 5 seconds to 10 minutes. At this time, the protective layer may be removed with water or the like in advance, or may be removed during development.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist. An evaluation method as an image forming material in the following Examples and Comparative Examples is shown below.
<Absorbance>
With respect to the photosensitive resist material layer having a dry film thickness of 10 μm formed on the glass substrate, the absorbance at a wavelength of 405 nm was measured using a spectrophotometer (“UV-3100PC” manufactured by Shimadzu Corporation), and the measured value was expressed as the film thickness. The absorbance per 1 μm was calculated.

<Maximum peak of spectral sensitivity>
A sample obtained by cutting an image forming material into a size of 50 × 60 mm is 320 using a diffraction spectroscopic irradiation device (“RM-23” manufactured by Narumi) and a xenon lamp (“UI-501C” manufactured by USHIO INC.) As a light source. The light dispersed in the wavelength region of ˜650 nm was exposed by irradiating for 10 seconds with the exposure wavelength set linearly in the horizontal axis direction and the exposure intensity logarithmically changed in the vertical axis direction. By developing under the development conditions described in the examples, an image corresponding to the sensitivity of each exposure wavelength is obtained, and the exposure energy capable of forming an image is calculated from the image height, and the horizontal axis indicates the wavelength and the vertical axis indicates the energy. The maximum peak in the spectral sensitivity curve obtained by plotting the reciprocal of the exposure energy was read.

<[S ₄₁₀ / S _450], [S _450-650 / S _450]>
In the same manner as described in the above <maximum peak of spectral sensitivity>, the minimum exposure amount capable of forming an image at a wavelength of 410 nm [S ₄₁₀ (mJ / Cm ² )] and the minimum exposure amount capable of forming an image at a wavelength of 450 nm [S ₄₅₀ (mJ / cm ² )] and the minimum exposure amount capable of forming an image at each wavelength of 450 nm to 650 nm or less [S _450-650 (MJ / cm ² )] were determined, and the ratios [S ₄₁₀ / S ₄₅₀ ] and [S 4 _50-650 / S ₄₅₀ ] were calculated and evaluated according to the following criteria.

<Evaluation criteria of _S410 / _S450 >
A: _S410 / _S450 is 0.03 or less.
B: S ₄₁₀ / S ₄₅₀ is more than 0.03 and 0.05 or less.
C: S ₄₁₀ / S ₄₅₀ is more than 0.05 and 0.1 or less.
D: S ₄₁₀ / S ₄₅₀ exceeds 0.1.
<Evaluation Criteria of S _450-650 / S _450>
A: S _450-650 / S ₄₅₀ is more than 10.
B: S _450-650 / S ₄₅₀ is more than 5 and 10 or less.
C: S _450-650 / S ₄₅₀ is more than 1 and 5 or less.
D: S _450-650 / S ₄₅₀ is 1 or less.

<Exposure sensitivity>
Using a laser light source (“NLHV500C” manufactured by Nichia Corporation) with a center wavelength of 405 nm and a laser output of 5 mW, the photosensitive resist material layer of the image forming material is irradiated with an image surface illuminance of 2 μW and a beam spot diameter of 2.5 μm. The scanning exposure is performed while changing the scanning interval and the scanning speed, and then the development processing is performed under the development conditions described in each embodiment to display an image, and the line width of 10 μm is reproduced for the obtained image. The minimum exposure required was determined and used as sensitivity.
The sensitivity (S1) when the film thickness was 10 μm and the sensitivity (S2) when the film thickness was 20 μm were measured, and the ratio (S2 / S1) was calculated.

<D / L>
By changing the resist film thickness (D), laser scanning exposure is performed in the same manner as in the above <Exposure Sensitivity> measurement method to display an image, and the minimum line width (L) resolved at each resist film thickness is obtained. The ratio D / L was calculated. In addition, the sensitivity when giving the maximum value of D / L obtained in this way was defined as S3.

<Safelight characteristics under yellow light>
The image forming material was allowed to stand for 1 minute, 2 minutes, 5 minutes, 10 minutes, 20 minutes, 30 minutes under yellow light illumination (conditions in which light having a wavelength of about 470 nm or less was blocked). Scanning exposure and development processing were performed, and the standing time until the image changed compared to the above was obtained, and evaluated according to the following criteria.
A: 20 minutes or more B: 10 minutes or more and less than 20 minutes C: 1 minute or more and less than 10 minutes D: Less than 1 minute

<Registration image>
For the obtained resist image, the reproducible line width and pattern shape at the film thicknesses shown in the table were observed, and as a measure of resolution, “film thickness (μm) / reproducible line width (μm)”. ”Was calculated.
<Storage stability of photosensitive composition coating solution>
After the photosensitive composition coating solution was stored at 25 ° C. for 7 days in the dark, a resist image was formed, and the resist image was observed with a scanning electron microscope for the presence or absence of a crystalline precipitate. evaluated.
A: No precipitate was observed at all, and the sensitivity and image before and after storage were unchanged.
B: No precipitate is observed, but the sensitivity after storage is slightly lowered.
C: A very small amount of precipitate was observed, and the sensitivity after storage decreased.

Example 1-1
As a photopolymerizable negative photosensitive composition (N1), a coating solution prepared by adding the following components to a mixed solvent of 740 parts by weight of methyl ethyl ketone and 400 parts by weight of methyl cellosolve and stirring at room temperature to prepare a glass solution is used. A dry coat film is applied to the substrate in an amount of 10 μm or 20 μm using a bar coater, and dried at 170 ° C. for 2 minutes to form a photosensitive resist material layer. Further, polyvinyl alcohol and polyvinylpyrrolidone A mixed aqueous solution (polyvinyl alcohol: polyvinylpyrrolidone = 95% by weight: 5% by weight) was applied using a bar coater in an amount to give a dry film thickness of 3 μm, and dried at 50 ° C. for 3 minutes to provide a protective layer (oxygen barrier layer) Was formed to produce a photosensitive image forming material.

<(N1-1); ethylenically unsaturated compound>
(N1-1a); 10 parts by weight of the following compound (N1-1b); 5 parts by weight of the following compound (N1-1c); 8 parts by weight of the following compound (N1-1d); 22 parts by weight of dipentaerythritol hexaacrylate

<(N1-2) Sensitizer>
(N1-2a); 4,4′-bis (diethylamino) benzophenone (molar extinction coefficient 14,540 at a wavelength of 404 nm) 9 parts by weight <(N1-3) photopolymerization initiator>
(N1-3a); 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole (melting point 196 ° C., X-ray diffraction spectrum at a wavelength of 1.54Å, Bragg angle ( 2θ ± 0.2 °) having a maximum diffraction peak at 9.925 °) 15 parts by weight <(N1-4) polymer binder>
(N1-4a); reaction product (acrylic acid component) obtained by reacting styrene / α-methylstyrene / acrylic acid copolymer (molar ratio 55/15/30) with 3,4-epoxycyclohexylmethyl acrylate 45 mol% of (reacts with epoxy group) 45 parts by weight <(N1-5); hydrogen donating 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); 10 parts by weight of tribenzylamine <(N1-7) surfactant>
(N1-7a); nonionic surfactant (“Emulgen 104P” manufactured by Kao Corporation)
2 parts by weight (N1-7b); fluorine-based surfactant (“S-381” manufactured by Asahi Glass Co., Ltd.) 0.3 parts by weight <Others>
Copper phthalocyanine pigment (visible paint) 4 parts by weight Dispersant ("Disperbyk 161" manufactured by Big Chemie) 2 parts by weight

The photosensitive resist material layer of the obtained photosensitive image forming material was subjected to scanning exposure under the conditions described in the above-mentioned exposure sensitivity evaluation method, and then the oxygen blocking layer was washed with water, peeled off, and then 0.1% by weight of sodium carbonate. And an anionic surfactant (“Perex NBL” manufactured by Kao Corporation) in an aqueous solution containing 0.1% by weight at 26 ° C. for 60 seconds, and then rubbed with a sponge 5 times for development processing to obtain a resist image on the surface. A substrate to be processed on which was formed was obtained. In this case, the absorbance of the photosensitive resist material layer, the maximum peak of spectral sensitivity, the exposure sensitivity, [S410 / S450] and [S450-650 / S450], the safe light property under a yellow light, and the obtained resist image Evaluation was performed by the method described above, and the results are shown in Table 1. S ₄₁₀ was 0.1 mJ / cm ² .

Reference Example 1-2
As a chemically amplified negative photosensitive composition (N2), a coating solution prepared by adding the following components to 300 parts by weight of propylene glycol monomethyl ether acetate and stirring at room temperature to prepare a dry film thickness on a glass substrate A photosensitive image forming material was prepared by spin-coating in an amount of 10 μm or 20 μm and 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) cross-linking agent>
(N2-2a); methoxymethylated melamine (“Nicalak E-2151” manufactured by Sanwa Chemical Co., Ltd.) 50 parts by weight <(N2-3) photoacid generator (N2-3a); 2- (p-carboxyacetyloxy 1 part by weight of ethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine

The photosensitive resist material layer of the obtained photosensitive image forming material was subjected to scanning exposure under the conditions described in the method for evaluating exposure sensitivity, followed by post-heating treatment in an oven at 100 ° C. for 10 minutes, and then hydroxylated. A substrate to be processed having a resist image formed on the surface was obtained by dipping in a 1% by weight aqueous solution of potassium at 90 ° C. for 90 seconds for development. Hereinafter, evaluation was performed in the same manner. S ₄₁₀ was 4 mJ / cm ^2.
When the resist film thickness (D) was 20 μm, the resolved minimum line width (L) was 10 μm, and the maximum value of D / L was 2.0. The sensitivity S3 at this time was 7 mJ / cm ² .

Reference Example 1-3
(N2-3) A photosensitive image-forming material was prepared in the same manner as in Reference Example 1-2 except that the photoacid generator was changed to the following, and a processed substrate having a resist image formed on the surface was obtained. It was. Hereinafter, evaluation was performed in the same manner. S ₄₁₀ was 4 mJ / cm ^2.
When the resist film thickness (D) was 20 μm, the resolved minimum line width (L) was 10 μm, and the maximum value of D / L was 2.0. The sensitivity S3 at this time was 11 mJ / cm ² .
(N2-3b); 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine

Reference Example 1-4
A photosensitive image forming material was prepared in the same manner as in Reference Example 1-2 except that a processed substrate in which a 1 μm thick copper plating was applied on a silicon substrate instead of a glass substrate was prepared, and a resist was formed on the surface. A processed substrate on which an image was formed was obtained. Hereinafter, evaluation was performed in the same manner.

Reference Example 1-5
A photosensitive image forming material was prepared in the same manner as in Reference Example 1-3 except that a processed substrate in which a 1 μm thick copper plating was applied on a silicon substrate instead of a glass substrate was prepared, and a resist was formed on the surface. A processed substrate on which an image was formed was obtained. Hereinafter, evaluation was performed in the same manner.

Reference Example 1-6
As a chemically amplified positive photosensitive composition (P1), the following components were 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 the mixture was stirred at room temperature to prepare a coating solution. Was coated on a glass substrate in an amount such that the dry film thickness was 10 μm or 20 μm, and dried at 90 ° C. for 10 minutes to form a photosensitive resist material layer, thereby producing a photosensitive image forming material.

<(P1-1) Acid-decomposable group-containing resin>
(P1-1a); an acid-decomposable group-containing resin obtained by etherifying about 45 mol% of a hydroxyl group of poly (p-hydroxystyrene) and introducing a 1-ethoxyethoxy group as an acid-decomposable group <100 parts by weight < (P1-2) Photoacid generator (P1-2a); 2- (p-methoxy-m-hydroxystyryl) -4,6-bis (trichloromethyl) -s-triazine 2 parts by weight

The photosensitive resist material layer of the obtained photosensitive image forming material was subjected to scanning exposure under the conditions described in the method for evaluating exposure sensitivity, followed by post-heating treatment in an oven at 90 ° C. for 2 minutes, and then hydroxylated. A substrate to be processed having a resist image formed on the surface was obtained by dipping in a 2% by weight aqueous solution of potassium at 90 ° C. for 90 seconds for development. Hereinafter, evaluation was performed in the same manner. Incidentally, S ₄₁₀ was 15 mJ / cm ^2.
When the resist film thickness (D) was 20 μm, the resolved minimum line width (L) was 10 μm, and the maximum value of D / L was 2.0. The sensitivity S3 at this time was 20 mJ / cm ² .

Reference Example 1-7
A photosensitive image forming material was prepared in the same manner as in Reference Example 1-6 except that a processed substrate in which a 1 μm-thick copper plating was applied on a silicon substrate instead of a glass substrate was prepared, and a resist was formed on the surface. A processed substrate on which an image was formed was obtained. Hereinafter, evaluation was performed in the same manner.
The results are summarized in Table 1.

Example 2
In Example 1-1, a negative image was formed in the same manner as in Example 1-1 except that the glass substrate was changed to a 100 μm thick polyimide resin copper-clad laminate (manufactured by Sanhayato) with a 18 μm thick copper foil laminated on one side. The material was manufactured.
The obtained negative image forming material was output using a blue-violet laser exposure machine (“Cobalt8” manufactured by Escher-Grad) oscillating at a wavelength of 410 nm, an output of 0.5 mW, a laser beam spot diameter of 12 μm, a scanning density of 5080 dpi, and a scanning speed. at 167m / sec was repeated scanning exposure (exposure energy of the plate surface in this case is 100 .mu.J / cm ² when the thickness of 10 [mu] m, was 400μJ / cm ² when the thickness of 20 [mu] m.) after the oxygen barrier The layer was washed with water, peeled off, dipped in an aqueous solution containing 0.1% by weight of sodium carbonate and 0.1% by weight of an anionic surfactant (“Perex NBL” manufactured by Kao Corporation) at 26 ° C. for 60 seconds, and then with a sponge. Development processing was performed by rubbing 5 times. As a result, a substrate to be processed having a high-quality resist image formed on each surface was obtained.

The obtained substrate to be processed (when the resist material layer thickness is 20 μm) was subjected to electrolytic plating for 60 minutes at a current density of 20 mA / cm ² using an aqueous solution of copper sulfate as an electrolyte, and a copper plating layer having a plating thickness of 15 μm was obtained. Formed in the space part. Incidentally, S2 / S1 is 5, the absorbance per thickness 1 [mu] m 0.218, maximum peak of spectral sensitivity 410, S ₄₁₀ is _{^{0.1mJ / cm 2, S 410 /}} S 450 is A, S _450-650 / _S450 was A and safelight property was A.

Comparative Example 1
As a photopolymerizable negative photosensitive composition (N1), a coating solution prepared by adding the following components to 100 parts by weight of a mixed solvent of methyl ethyl ketone / isopropanol (weight ratio 8/2) and stirring the mixture at room temperature is prepared. A photosensitive composition formed on a polyethylene terephthalate film (thickness: 19 μm) as a temporary support film by applying with an applicator in an amount of 10 μm or 20 μm, and drying in an oven at 90 ° C. for 5 minutes. A dry film resist material was produced by laminating a polyethylene film (thickness: 25 μm) as a coating film on the physical layer and allowing it to stand for 1 day.

<(N1-1) ethylenically unsaturated compound (N1-1e); 15 parts by weight of the following compound (N1-1f); 30 parts by weight of the following compound

<(N1-2) Sensitizer>
(N1-2j) Compound having a molar extinction coefficient of 82,700 at a wavelength of 405 nm; 1 part by weight

<(N1-3) Photopolymerization initiator>
(N1-3b); 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole (melting point 172 ° C., X-ray diffraction spectrum having a wavelength of 1.54Å, Bragg angle ( 2θ ± 0.2 °) having a maximum 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 KOH · mg / g) 55 weight Part

<(N1-5) Hydrogen Donating Compound>
(N1-5c); Dipolar ion compound of N-phenylglycine 0.2 part 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 polyimide resin copper-clad laminate (thickness 1.5 mm, size 250 mm × 200 mm) bonded with a 35 μm-thick copper foil is buffed with “Scotch Bright SF” manufactured by Sumitomo 3M Limited. Then, after washing with water, drying with an air stream and leveling, and then preheating this to 60 ° C. in an oven, on the copper foil of the copper clad laminate, the dry film resist material obtained above is While peeling the polyethylene film, using a hand-type roll laminator on the peeling surface, laminating at a roll temperature of 100 ° C., a roll pressure of 0.3 MPa, and a laminating speed of 1.5 m / min on the copper-clad laminate. A photosensitive image forming material on which a photosensitive resist material layer was formed was produced.

The photosensitive resist material layer of the obtained photosensitive image forming material was subjected to scanning exposure under the conditions described in the above-described exposure sensitivity evaluation method, and then the polyethylene terephthalate film was peeled off, and then a 1% by weight aqueous solution of sodium carbonate at 30 ° C. Was sprayed as a developing solution to a pressure of 0.15 MPa, and spray development was performed to obtain a substrate to be processed on which a resist image was formed. Absorbance of photosensitive resist material layer at this time, maximum peak, the exposure sensitivity of the spectral sensitivity, [S ₄₁₀ / S ₄₅₀₎ and (S _450-650 / S _450], safelight of under yellow light, obtained as well The resist images were evaluated by the method described above, and the results are shown in Table 1.
When the image forming material having a photosensitive resist material layer having a thickness of 20 μm was subjected to development by scanning exposure, all the exposed portions were dissolved in the developer, and no image was formed.

Reference Comparative Example 2
As a chemically amplified negative photosensitive composition (N2), the following components were added to 290 parts by weight of propylene glycol monomethyl ether acetate and mixed at room temperature to prepare a coating solution having a dry film thickness on a glass substrate. A photosensitive image forming material was prepared by spin-coating in an amount of 10 μm or 20 μm and 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) cross-linking agent>
(N2-2a); methoxymethylated melamine (“Nicalak E-2151” manufactured by Sanwa Chemical Co., Ltd.) 50 parts by weight <(N2-3) photoacid generator (N2-3c); 5 parts by weight of the following compound

<(N2-4) sensitizer>
(N1-2j): 1 part by weight of the above compound (molar extinction coefficient 82,700 at a wavelength of 405 nm) The conditions described in the evaluation method for the exposure sensitivity of the photosensitive resist material layer of the obtained photosensitive image forming material After performing a scanning exposure at 100 ° C., a post-heat treatment is performed in an oven at 100 ° C. for 10 minutes, and then a development treatment is performed by immersing in a 0.5 wt% aqueous solution of potassium hydroxide at 20 ° C. for 60 seconds. A processed substrate on which an image was formed was obtained. Absorbance of photosensitive resist material layer at this time, maximum peak, the exposure sensitivity of the spectral sensitivity, [S ₄₁₀ / S ₄₅₀₎ and (S _450-650 / S _450], safelight of under yellow light, obtained as well The resist images were evaluated by the method described above, and the results are shown in Table 1.
When the image forming material having a photosensitive resist material layer having a thickness of 20 μm was subjected to development by scanning exposure, all the exposed portions were dissolved in the developer, and no image was formed.

Claims (12)

An image forming material having a blue-violet laser photosensitive resist material layer on a substrate to be processed,
(A) The film thickness of the resist material layer is 10 μm or more, and the absorbance at the exposure wavelength of the photosensitive resist material layer is 0.3 or less per 1 μm of film thickness,
(B) When the sensitivity when the photosensitive resist material layer has a film thickness of 10 μm at the exposure wavelength is S1, and the sensitivity when the film thickness is 20 μm is S2, S2 / S1 is 5 or less,
(C) The thickness of the photosensitive resist material layer is 200 μm or less,
(D) the photosensitive resist material has a maximum peak in spectral sensitivity at a wavelength of 390 to 430 nm,
(E) The photosensitive resist material layer is composed of a photopolymerizable negative photosensitive composition containing the following components (N-1), (N-2), and (N-3).
(N-1) Ethylenically unsaturated compound (N-2) Sensitizer (N-3) Photopolymerization initiator An image forming material. The ratio of the minimum exposure amount [S ₄₁₀ (μJ / cm ² )] at which the photosensitive resist material layer can form an image at a wavelength of 410 nm to the minimum exposure amount [S ₄₅₀ (μJ / cm ² )] at which a wavelength can be formed. The image forming material according to claim 1, wherein [S ₄₁₀ / S ₄₅₀ ] is 0.1 or less. Photosensitive resist material layer, the minimum exposure dose capable of forming an image in each of the following wavelengths wavelength 450nm exceeds 650nm [S _450-650 (μJ / cm ^2)] minimum exposure amount capable of forming an image at the wavelength 450nm of [S ₄₅₀ ( 3. The image forming material according to claim 1, wherein the ratio [S _450-650 / S ₄₅₀ ] to (μJ / cm ² )] exceeds 1.   The image forming material according to any one of claims 1 to 3, comprising a hexaarylbiimidazole compound or a titanocene compound as a photopolymerization initiator of the (N-3) component.   The image forming material according to claim 1, wherein the substrate to be processed is a laminate having a conductive layer formed on the surface of an insulating support. A photosensitive composition for creating an electronic circuit,
(1) The photosensitive resist material layer composed of the composition (D), and the photosensitive resist material layer having the thickness (D) are scanned and exposed with a laser beam having a wavelength of 390 to 430 nm and then developed. The maximum value of the ratio (D / L) to the minimum line width (L) that can be resolved by 1.0 is 1.0 or more, and (2) the minimum exposure capable of image formation at a wavelength of 410 nm of the photosensitive resist material layer The amount [S ₄₁₀ (μJ / cm ² )] is 10,000 μJ / cm ² or less,
(3) The photosensitive resist material layer is a photopolymerizable negative photosensitive composition containing the following components (N-1), (N-2), and (N-3).
(N-1) Ethylenically unsaturated compound (N-2) Sensitizer (N-3) Photopolymerization initiator A photosensitive composition for creating an electronic circuit,
(1) The photosensitive resist material layer composed of the composition (D), and the photosensitive resist material layer having the film thickness (D) are scanned and exposed with a laser beam having a wavelength of 390 to 430 nm and then developed. The maximum value of the ratio (D / L) to the minimum line width (L) that can be resolved by 1.0 is 1.0 or more,
(2) The exposure amount for achieving the D / L is 20 mJ / cm ² or less,
(3) The photosensitive resist material layer is a photopolymerizable negative photosensitive composition containing the following components (N-1), (N-2), and (N-3).
(N-1) Ethylenically unsaturated compound (N-2) Sensitizer (N-3) Photopolymerization initiator The photosensitive composition for producing an electronic circuit according to claim 6 or 7, wherein an exposure amount for achieving the D / L is 10 mJ / cm ² or less.   The photosensitive composition for producing an electronic circuit according to any one of claims 6 to 8, wherein the maximum value of D / L is 1.3 or more.   The image forming material which has the photosensitive resist material layer which consists of a photosensitive composition for electronic circuit creation in any one of Claims 6-9 on a to-be-processed substrate.   The photosensitive resist material layer of the image forming material having a blue-violet laser photosensitive resist material layer according to any one of claims 1 to 5 and 10 is scanned and exposed with a laser beam having a wavelength of 390 to 430 nm, and then developed. A resist image forming method comprising: processing.   The image forming method according to claim 11, wherein the exposure is performed with a blue-violet laser having an intensity of 100 nW to 100 mW.