JP2000039716A - Positive type visible light sensitive resin composition and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a positive type visible light sensitive resin compsn. capable of handling under the condition of bright safelight and excellent in sensitivity by incorporating a specified pyrrole compd. as a sensitizer. SOLUTION: The visible light sensitive resin compsn. is used in an environment irradiated with high relative luminosity safelight having the max. wavelength selected from the range of 500-620 nm and contains a positive type visible light sensitive resin and a pyrrole compd. of the formula as a sensitizer. The absorbance of an unexposed coating formed from the compsn. is <=0.5 in the range of (the max. wavelength of the safelight) ±30 nm. In the formula, R1 is H, <=20C alkyl, hydroxyalkyl, alkoxyalkyl or the like and R2-R10 are each H halogen, nitro, cyano, hydroxy, amino, aminocarbonyl or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positive visible light-sensitive resin composition containing a photosensitizer of a pyrrole compound having a peculiar structure for use with a specific safety light.

[0002]

2. Description of the Related Art In recent years, in the field of information using light reaction or image recording, instead of the conventional recording method using ultraviolet light using a film original or the like, an electronically edited original by a computer is directly used as a high output laser. A method of directly outputting and recording the data by using is being studied. This method has the advantage that the recording and image forming steps can be greatly simplified by direct writing with a laser.

At present, many high-power and stable laser light sources generally used have an output wavelength in the visible region. Specifically, the wavelength 488 nm and 51
Argon laser with stable oscillation line at 4.5 nm or YAG with emission line at 532 nm as second harmonic
Lasers and the like are widely used. Therefore, compounds having high sensitivity to these wavelengths have been desired, but conventionally used ultraviolet light-sensitive agents cannot be used due to low sensitivity in the visible region. Although the addition of a pyrylium salt or a thiopyrylium salt can improve the sensitivity in the visible region, the storage stability of the photosensitive layer is low and it has been difficult to use the photosensitive layer.

As compounds having photosensitivity in the visible region,
For example, 7-diethylamino-3-benzothiazoylcoumarin (common name: coumarin-6) or bis [3
-(7-diethylaminocoumaryl)] ketone (common name:
Ketocoumarin) is known, but since these have a maximum absorption wavelength of about 450 nm, they have a shorter wavelength than 488 nm of an argon laser and have insufficient sensitivity. Further, the 4-substituted-3-benzothiazoyl coumarin compound described in JP-A-4-18088 has high sensitivity at 488 nm of an argon laser,
At 4.5 nm or at 532 nm, which is the second harmonic of the YAG laser, there was almost no absorption, leaving room for improvement in sensitivity.

[0005] When handling the positive-type visible light-sensitive resin composition to be reacted with visible light as described above, a dark red colorant is coated on the outer tube or the dark red film is removed. An electric light such as a fluorescent light colored by being wound around a tube is used as a safety light (work light). However, under such a dark red safety light environment, it is not easy to inspect the state of the coating film after application, and it is not easy to inspect the coating device, irradiation device, transport device, etc. There is a problem that work efficiency, product quality stability and the like are inferior. When a non-colored fluorescent lamp is used as a safety light, the working environment is bright and there is no problem.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a positive type visible light photosensitive resin composition which can be handled under bright safe light conditions and has excellent sensitivity.

[0007]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have developed a specific visible light photosensitive resin composition used with a specific safety light. As a result, they have found that the conventional problems can be solved, and have completed the present invention.

That is, the present invention relates to a positive-type visible light-sensitive resin composition for use in an environment in which a safety light having a maximum wavelength selected from the range of 1,500 to 620 nm and a high relative luminous efficiency is used. The composition is a positive-type visible light-sensitive resin composition containing a positive-type visible light-sensitive resin and a photosensitizer of a pyrrole compound represented by the following general formula (1), and formed from the composition. The positive visible light-sensitive resin composition, wherein the absorbance of the unexposed film is 0.5 or less in a range of ± 30 nm of the maximum wavelength of the safe light,

[0009]

Embedded image

[0010] wherein, R ₁ represents a hydrogen atom, an alkyl group having up to 20 carbon atoms, a hydroxyalkyl group, an alkoxyalkyl group, an alkoxycarbonylalkyl group, an aryl group, an aralkyl group or an alkenyl group, R ₂ to R
₁₀ is each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxy group, an amino group, an aminocarbonyl group, a carboxyl group, a sulfonic acid group, an alkyl group having up to 20 carbon atoms, a halogenoalkyl group, an alkoxyalkyl group , Alkoxy group, alkoxyalkoxy group, acyl group, alkoxycarbonyl group, alkylaminocarbonyl group, dialkylaminocarbonyl group, alkylcarbonylamino group, aryl group, aralkyl group, arylcarbonylamino group, arylaminocarbonyl group, aryloxy group, Aryloxycarbonyl, heteroaryl, alkylthio, arylthio, alkenyloxycarbonyl, aralkyloxycarbonyl, alkoxycarbonylalkoxycarbonyl, alkylcarbonyl Alkoxycarbonyl group, a mono (hydroxyalkyl) aminocarbonyl group, di (hydroxyalkyl) aminocarbonyl group, mono (alkoxyalkyl) aminocarbonyl group, di (alkoxyalkyl)
Represents an aminocarbonyl group or an alkenyl group]

(2) The positive visible light-sensitive resin composition as described above, wherein the safety light is generated by a discharge lamp containing sodium as a main component (mainly a D line having a light wavelength of 589 nm). 3, a composition for a positive-type visible light-sensitive material comprising the above-described positive-type visible light-sensitive resin composition and a solvent; And a positive visible light-sensitive material.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is a photosensitive resin composition having excellent photosensitivity to visible light, and the safe light used in the present invention is not sensitive to the visible light photosensitive resin composition of the present invention. In addition to the safety light that does not cause a light reaction, the safety light to be used is a region with high relative luminous efficiency of human beings, so it feels very bright at the same illumination light intensity compared to the conventional one, so that safe workability, It has excellent effects on work efficiency, product quality stability, etc.

The term "composition for positive-type visible light-sensitive material" used in the present invention includes, for example, paints, inks, adhesives,
It means a printing plate material, a resist material, and a non-photosensitive film formed from these materials.

Further, the conventional safety light is a fluorescent light in which a fluorescent lamp is colored red, but the emission spectrum of the fluorescent lamp has a wavelength range (FIG. 5) covering a wide range from ultraviolet light to visible light. In addition, even the visible light-sensitive resin coating portion that does not require a light reaction is reacted, and a clear resist pattern cannot be formed by the development process. For this reason, there is a problem that the working environment is further darkened since the intensity of the illumination light is reduced. On the other hand, the safety light used in the present invention has a sharp wavelength like a sodium lamp, for example, so that the above-mentioned problem is solved.

The safety light used in the present invention is 500 to 62.
It is a visible light having a large relative luminous efficiency having a maximum wavelength within a range of 0 nm, preferably 510 to 600 nm. This safety light can be obtained, for example, by using a discharge lamp that emits light having a maximum wavelength in the above-described range by discharging in a gas such as sodium. Among these, the sodium lamp emits light having a wavelength of 58 nm.
It is mainly composed of a 9-nm yellow D line, and since it is monochromatic light, chromatic aberration is small and an object can be seen sharply, so that safety, work environment and the like are excellent. FIG. 1 shows the wavelength of the spectral distribution of the low-pressure sodium lamp. As shown in the spectral distribution diagram of the sodium lamp, other than the D-line having the maximum wavelength of the sodium lamp, the lamp has a high energy ray (low wavelength region) to such an extent that the visible light curable resin composition is not adversely affected. No problem. In addition, a filter in which a high-energy ray other than the D ray is cut by applying a filter to a sodium lamp can also be used. FIG. 2 shows the spectral distribution of the sodium lamp from which the high energy rays have been cut.

Further, a filter can be used for the safety light used in the present invention. As the filter,
For example, "Fantac FD-1081 Scarlet", "Fantac FC-1431 Sunflower"
Yellow (trade name, manufactured by Kansai Paint Co., Ltd.), Lintec Lumicool Film No. 190
5 "(trade name, manufactured by Lintec Corporation).

As the safety light used in the present invention, it is preferable to use a sharp monochromatic light having a light ray of 589 nm like a sodium lamp. Safety light having wavelengths distributed in the wavelength ranges of light and infrared light may be used. However, when using safety light having such a distribution, it is necessary that the distributed light beam region is a safe light region which does not adversely affect (photosensitize) the positive-type visible light photosensitive resin composition. It is.

Such a safe high-energy light region (low-wavelength region) is related to the energy intensity of the distributed light beam and the absorbance of the positive-type visible light-sensitive resin composition in the region, and the energy intensity of the light beam is large. In the case where the composition has a small absorbance, and in the case where the energy intensity of the light beam is small, the composition can be used in which the absorbance is relatively larger than that of the former, so that the composition is taken into consideration. Can have a high-energy ray region to such an extent that it does not adversely affect light. However, even if an ordinary fluorescent lamp having a maximum wavelength in the range of 500 to 620 nm is used as the safety light, it is still 5 mils.
Since it has a large light energy intensity of less than 00 nm, particularly 400 to 499 nm, it cannot be used as a safety light for a positive-type visible light photosensitive resin composition which is exposed to a visible light laser having an oscillation line at 488 nm or 532 nm.

The absorbance used in the present invention is -log (I
/ I ₀ ). Here, I is the intensity of transmitted light of the coating obtained by applying the photosensitive resin composition on the surface of the transparent substrate and drying (removing the solvent), and I ₀ is a blank [sample (photosensitive resin composition) is applied. Of a transparent substrate (eg, a polyethylene terephthalate sheet) for transmission.

How bright light is perceived by human eyes can be represented by relative luminous efficiency. The relative luminous efficiency is JI
As defined in SZ8113, 2005, under certain observation conditions, when it is determined that the monochromatic radiation of a certain wavelength λ has the same brightness as the radiation used as a reference for comparison, the monochromatic radiation of a wavelength λ is determined. It is defined as a value obtained by normalizing the reciprocal of the relative value of the radiance, usually, the maximum value when λ is changed to 1. FIG. 3 shows a relative luminous efficiency curve of 380 to 780 nm, which is a wavelength region of visible light. In FIG. 3, the vertical axis represents the ratio, with the maximum value of the relative luminous efficiency set to 100. From this curve, the conventional red wavelength range of 640 to
At 780 nm, the relative luminous efficiency is low, and it is perceived as dark by human eyes. For example, it can be seen that the radiation intensity must be further increased in order to feel the same brightness as the wavelength of 589 nm. The maximum value of relative luminous efficiency is about 555 nm (J
IS-Z8113 2008).

The positive visible light-sensitive resin composition of the present invention is a positive visible light-sensitive resin composition containing a positive visible light-sensitive resin and a photosensitizer of a pyrrole compound having a specific structure. Wherein the absorbance of the unexposed film formed from the composition is within a range of ± 30 nm (-30 nm to +30 nm) of the maximum wavelength of the safe light selected from the range of the maximum wavelength.
nm), preferably in the range of ± 20 nm (−20 nm to +
20 nm), and a range of ± 10 nm (−10 nm to +
(At 10 nm) is 0.5 or less, preferably 0.2 or less, and more preferably 0.1 or less.

The photosensitizer of the pyrrole compound represented by the general formula (1) can be used for light in a visible light region of 400 to 700 nm,
In particular, it is a compound that is excited by absorbing light of 400 to 600 nm and has an interaction with a resin or a photoacid generator. The term "interaction" as used herein includes energy transfer and electron transfer from the excited photosensitizer to the resin or photoacid generator. For this reason, the pyrrole compound represented by the general formula (1) used here is an extremely useful compound as a photosensitizer.

In the compound represented by the general formula (1) of the present invention, R ₁ is a hydrogen atom, an alkyl group having up to 20 carbon atoms, a hydroxyalkyl group, an alkoxyalkyl group, an alkoxycarbonylalkyl group, an aryl group, an aralkyl group. Or an alkenyl group.

Specific examples of R ₁ include a hydrogen atom; methyl, ethyl, n-propyl, isopropyl, n-
Alkyl groups such as butyl group, iso-butyl group, t-butyl group, n-pentyl group, iso-pentyl group, n-hexyl group; hydroxymethyl group, 2-hydroxyethyl group,
-Hydroxypropyl group, 3-hydroxypropyl group,
Hydroxyalkyl groups such as 2-hydroxybutyl group; alkoxyalkyl groups such as methoxymethyl group, 2-methoxyethyl group, 2-ethoxymethyl group, 2-ethoxyethyl group, 3-ethoxypropyl group; methoxycarbonylmethyl, ethoxycarbonyl Alkoxycarbonylalkyl groups such as methyl, 2-ethoxycarbonylethyl group, phenyl group, 4-methylphenyl, 3-methylphenyl,
Aryl groups such as -methylphenyl and 2,4-dimethylphenyl groups; aralkyl groups such as benzyl group and phenethyl group; alkenyl groups such as allyl group, 2-butenyl group and 2-pentenyl group.

In the general formula (1), R _{2 to} R ₁₀
Examples thereof include a hydrogen atom; a nitro group; a cyano group; a hydroxy group; an amino group; an aminocarbonyl group; a carboxyl group; a sulfonic acid group; a halogen atom such as a fluorine atom, a chlorine atom, and a bromine atom; n-propyl group, isopropyl group, n-butyl group, isobutyl group,
t-butyl group, n-pentyl group, isopentyl group, n-
Hexyl group, n-octyl group, 2-ethylhexyl group,
Alkyl group such as cyclohexyl group; halogenoalkyl group such as chloromethyl group, dichloromethyl group, fluoromethyl group, trifluoromethyl group, pentafluoroethyl group, nonafluorobutyl group; methoxyethyl group, ethoxyethyl group, isopropyloxyethyl An alkoxyalkyl group such as a group, 3-methoxypropyl group or 2-methoxybutyl group; a methoxy group, an ethoxy group, an n-propoxy group,
Isopropoxy group, n-butoxy group, n-pentyloxy group, n-hexyloxy group, n-octyloxy group,
alkoxy groups such as n-decyloxy group, cyclopentyloxy group, cyclohexyloxy group and 4-methylcyclohexyloxy group; alkoxyalkoxy groups such as methoxyethoxy group, ethoxyethoxy group, 3-methoxypropoxy group and 3- (isopropyloxy) propoxy group Group;

Acyl groups such as formyl group, acetyl group, ethylcarbonyl group, n-propylcarbonyl group, isopropylcarbonyl group, isobutylcarbonyl group, t-butylcarbonyl group, isopentylcarbonyl group and benzylcarbonyl group; methoxycarbonyl group; Ethoxycarbonyl group, n-butoxycarbonyl group, n-hexyloxycarbonyl group, n-octyloxycarbonyl group,
n-decyloxycarbonyl group, cyclopentyloxycarbonyl group, cyclohexyloxycarbonyl group, 4
Alkoxycarbonyl groups such as -methylcyclohexyloxycarbonyl group; alkylaminocarbonyl groups such as methylaminocarbonyl group, n-butylaminocarbonyl group, n-hexylaminocarbonyl group, cyclohexylaminocarbonyl group and 4-methylcyclohexylaminocarbonyl group; Dialkylamino such as dimethylaminocarbonyl group, diethylaminocarbonyl group, di-n-butylaminocarbonyl group, di-n-hexylaminocarbonyl group, di-n-octylaminocarbonyl group, N-isoamyl-N-methylaminocarbonyl group A carbonyl group; an alkylcarbonylamino group such as an acetylamino group, an ethylcarbonylamino group, and an isobutylcarbonylamino group;

Phenyl group, 3-nitrophenyl group, 4-
Cyanophenyl group, 4-hydroxyphenyl group, 2-methylphenyl group, 3,5-dimethylphenyl group, 3-trifluoromethylphenyl group, 4-chlorophenyl group,
Aryl groups such as 4-methoxyphenyl group, 4- (dimethylamino) phenyl group and naphthyl group; aralkyl groups such as benzyl group and phenethyl group; phenylcarbonylamino group, 4-ethylphenylcarbonylamino group and 3-isopropylphenylcarbonyl Arylcarbonylamino groups such as amino group and 2-methoxyphenylcarbonylamino group; aryl groups such as phenylaminocarbonyl group, 4-methylphenylaminocarbonyl group, 2-methoxyphenylaminocarbonyl group and 4-n-propylphenylaminocarbonyl group Aminocarbonyl group; aryloxy group such as phenoxy group, 2-methylphenoxy group, 4-methylphenoxy group, 4-t-butylphenoxy group, 2-methoxyphenoxy group and 4-isopropylphenoxy group; phenoxyca Boniru group, 4-methylphenoxy group, 3-methylphenoxy group,
Aryloxycarbonyl groups such as 2-methylphenoxycarbonyl group, 2,4-dimethylphenoxycarbonyl group, 2,6-dimethylphenoxycarbonyl group, 2,4,6-trimethylphenoxycarbonyl group and 4-phenylphenoxycarbonyl group;

Pyrrolyl, thienyl, furanyl, oxazoyl, isoxazoyl, oxadiazoyl, thiadiazoyl, imidazoyl, benzothiazoyl, benzoxazoyl, benzoimidazoyl, benzofuranyl, indo-3-yl A heteroaryl group such as a group; an alkylthio group such as a methylthio group, an ethylthio group, an n-propylthio group, an isopropylthio group, an n-butylthio group, an isobutylthio group, a t-butylthio group, a 3,5,5-trimethylhexylthio group; An arylthio group such as a phenylthio group, a 4-methylphenylthio group, a 2-methoxyphenylthio group, a 4-t-butylphenylthio group, a naphthylthio group; an allyloxycarbonyl group;
Alkenyloxycarbonyl groups such as 2-butenoxycarbonyl group; aralkyloxycarbonyl groups such as benzyloxycarbonyl group, 4-methylbenzyloxycarbonyl group and phenethyloxycarbonyl group; methoxycarbonylmethoxycarbonyl group, ethoxycarbonylmethoxycarbonyl group; alkoxycarbonylalkoxycarbonyl groups such as n-propoxycarbonylmethoxycarbonyl group and isopropoxycarbonylmethoxycarbonyl group; alkylcarbonylalkoxycarbonyl groups such as methylcarbonylmethoxycarbonyl group and ethylcarbonylmethoxycarbonyl group;

Hydroxyethylaminocarbonyl group, 2
Mono (hydroxyalkyl) aminocarbonyl groups such as -hydroxypropylaminocarbonyl group and 3-hydroxypropylaminocarbonyl group; di (hydroxyethyl) aminocarbonyl group, di (2-hydroxypropyl) aminocarbonyl group, di (3-hydroxy Di (hydroxyalkyl) such as propyl) aminocarbonyl group
Aminocarbonyl group; methoxymethylaminocarbonyl group, methoxyethylaminocarbonyl group, ethoxymethylaminocarbonyl group, ethoxyethylaminocarbonyl group, mono (alkoxyalkyl) aminocarbonyl group such as propoxyethylaminocarbonyl group; di (methoxymethyl) amino Di (alkoxyalkyl) aminocarbonyl groups such as carbonyl group, di (methoxyethyl) aminocarbonyl group, di (ethoxymethyl) aminocarbonyl group, di (ethoxyethyl) aminocarbonyl group, di (propoxyethyl) aminocarbonyl group; vinyl Group, propenyl group, 1-butenyl group, 1-pentenyl group, 2-pentenyl group, 3-methyl-1-butenyl group,
Alkenyl groups such as a 2,2-dicyanovinyl group and a 1,2,2-tricyanovinyl group can be exemplified.

The pyrrole compound represented by the general formula (1) of the present invention is typically represented by the general formula (2) in the presence of an acid catalyst such as hydrobromic acid or trifluoroacetic acid. Can be easily produced by reacting a compound represented by the general formula (3) and / or the compound represented by the general formula (4), oxidizing with chloranil, and finally reacting with boron trifluoride. .

[0031]

Embedded image (In the above formula, R _{1 to} R ₁₀ have the same meaning as described above.)

The photosensitizer contains at least one type of pyrrole compound represented by the general formula (1), and may be used in combination with other known photosensitizers. .

The known photosensitizer is not particularly limited as long as it is a commonly used photosensitizer, and examples thereof include ketocoumarin, coumarin-6, and coumarin compounds described in JP-A-4-18088. Is mentioned.

In this case, the content of the photosensitizer of the pyrrole compound represented by the general formula (1) in the photosensitizer is not particularly limited, but in order to obtain a desired effect in the present invention. Is
The content of the photosensitizer of the pyrrole compound represented by the general formula (1) in the photosensitizer is preferably 10% by weight or more, more preferably 20% by weight or more, and still more preferably. Photosensitizers containing 30% by weight or more and 50% by weight or more are particularly preferred.

The amount of the pyrrole compound photosensitizer used depends on the type and amount of the pyrrole compound photosensitizer represented by the general formula (1) contained in the photosensitizer and the resin to be interacted with. The amount of the photosensitizer of the pyrrole compound represented by the general formula (1) is usually from 0.1 to 10 parts by weight, preferably from 0.3 to 10 parts by weight, per 100 parts by weight of the resin component.
A range of 5 parts by weight is suitable. If the amount of the pyrrole compound photosensitizer is less than 0.1 part by weight, the photosensitivity of the film to be formed tends to decrease. Tend to be difficult to maintain in a uniform state.

The positive-type visible light-sensitive resin composition of the present invention comprises a conventionally known positive-type visible light-sensitive resin composition (for example, paint , An ink, an adhesive, a printing plate material, and a resist material for a printed wiring board) containing a photosensitizer of a pyrrole compound represented by the general formula (1) as an essential component.

Representative examples of the above-described conventionally known positive-type visible light-sensitive resin compositions will be described below.

Examples of the composition include a resin containing a photoacid generator, a resin containing components other than the photoacid generator component (eg, a photobase generator, etc.), and a resin which itself decomposes by light. No. When these resins are decomposed by light, their properties, such as polarity and molecular weight, change, whereby the resins become soluble in substances such as a developer (aqueous solution, organic solvent, etc.). The resin may have a component such as a photoacid generator incorporated therein or may be a mixture of a component such as a photoacid generator and a resin having a group that is decomposed by an acid or the like. Further, other resins or the like for adjusting the solubility of the developing solution can be further added to these as required.

The resin containing the above-mentioned photoacid generator component will be described. The resin includes a resin in which a photoacid generator is incorporated in a resin skeleton (for example, a resin in which a resin generates an acid group upon exposure to light, thereby enabling alkali development) or a mixture of a photoacid generator and a resin [ The acid generated by the photoacid generator causes the resin to be cut to have a low molecular weight, an acid group to be added to the resin, or a change into a soluble substance (for example, (poly) P-hydroxystyrene). Or exhibiting dispersibility or solubility in an organic solvent or an aqueous developer].

Examples of such a composition include a composition containing, as a main component, a resin in which quinonediazidesulfonic acid is bonded to a base resin such as an acrylic resin having an ion-forming group via a sulfonic ester bond. -20
No. 6293, JP-A-7-133449, etc.), that is, a naphthoquinonediazide photosensitive composition utilizing a reaction of photolyzing a quinonediazide group by irradiation light to form indenecarboxylic acid via ketene; A chemically amplified photosensitive material utilizing a change in solubility between an irradiated part and an unirradiated part by causing a elimination reaction in a base resin (polymer) in a chain using a photoacid generator that generates an acid group as a catalyst ( JP-A-4-226461, U.S. Pat.
491,628, JP-A-59-45439, JP-A-63-250542, Polymers in El
ectronics "Edited by Davidson T. ACS Symposium Series 24
2, American Chemical Society, Washington DC, 198
4, 11 ", N. Hayashi, T. Ueno, M. Toriumi, etc, AC
S Polym. Materials Sci. Eng., 61, 417 (1989), H.I.
to, CG Wilson, ACS Symp. Ser., 242, 11 (1984), etc.); photoacid generation that forms a crosslinked film that is insoluble in solvents and aqueous alkalis by heating, and generates acid groups by irradiation with light. Positive type photosensitive composition utilizing a mechanism in which a crosslinked structure is cut by an agent and an irradiated portion becomes soluble in a solvent or an aqueous alkaline solution (Japanese Patent Laid-Open No. 6-29506).
4, JP-A-6-308733 and JP-A-6-308733.
JP-A-313134, JP-A-6-313135,
JP-A-6-313136, JP-A-7-14655
No. 2, etc.) and the like.

In the above-mentioned compounds, the functional groups (hydroxyl group, carboxyl group, etc.) which control the solubility in a developing solution in the resin are blocked (acid-labile groups) to make them insoluble, and the blocks are blocked by a photoacid generator. It dissociates and restores the solubility of the polymer. Examples of the acid labile group (R group of —OR) in which the hydroxyl group (—OH group) is blocked include, for example, t-butoxycarbonyl group (t-BOC group), t-butoxy group, t-butoxycarbonylmethyl group, Examples include a tetrahydropyranyl group, a trimethylsilyl group, an iso-propoxycarbonyl group, and the like. The resin having a hydroxyl group is not particularly limited as long as it exhibits the above-mentioned effects, but is usually a phenolic hydroxyl group. As the acid labile group, a t-BOC group and a t-butoxy group are particularly preferable, and examples thereof include poly (t-butoxycarbonyloxystyrene) and poly (t-butoxycarbonyloxy-α-styrene). , Poly (t-butoxystyrene) and copolymers of these monomers with other polymerizable monomers (eg, C1-24 alkyl or cycloalkyl esters of methyl (meth) acrylic acid, maleimide, sulfone, etc.) And the like. The t
The composition of poly (t-butoxycarbonyloxystyrene) containing a -BOC group is described, for example, as follows.
The acid generated by the photoacid generator decomposes the t-BOC group, evaporates isobutene and carbon dioxide to form polystyrene, and changes (increases) the polarity of the resin by changing the t-BOC group to a hydroxyl group. This makes use of the property of improving the solubility in a developing solution (aqueous alkaline solution). Examples of the acid labile group (R ′ group of —COOR ′) in which a carboxyl group (—COOH group) is blocked include carboxylic acid ester derivatives having a t-butyl group.

As the components of this, a two-component system of a resin having an acid labile group and a photoacid generator, and a three-component system of a resin having an acid labile group, a photoacid generator and other resins Can be used as The other resin is
By using this, for example, the coating workability of the composition can be improved or the solubility in a developer can be changed.

The above compounds contain a resin (a) containing a carboxyl group and / or a hydroxyphenyl group, an olefinically unsaturated compound containing an ether bond (b), and a photoacid generator that generates an acid group upon irradiation with light. Or a liquid or solid resin composition.

When the resin (a) has both a carboxyl group and a hydroxyphenyl group, even if the resin has these groups in the same molecule, the resin containing one of these groups and the resin containing the other group may be used. It does not matter even if it is a mixed resin of the resin containing.

Examples of the carboxyl group-containing resin (a-1) include acrylic resins and polyester resins.

The above resin (a-1) is generally used in an amount of about 500
It preferably has a number average molecular weight of from about 100,000, especially from about 1500 to 30,000, and the carboxyl group is preferably from about 0.5 to 10 mol, especially about 0.7 to 5 mol per kg of resin. .

Hydroxyphenyl group-containing resin (a-2)
As a condensate of a monofunctional or polyfunctional phenol compound, an alkylphenol compound, or a mixture thereof with a carbonyl compound such as formaldehyde and acetone; and a hydroxyphenyl group-containing unsaturated monomer such as P-hydroxystyrene. Depending on the above, copolymers with the above-mentioned other polymerizable unsaturated monomers can be used.

The above resin (a-2) is generally used in an amount of about 500
It preferably has a number average molecular weight of about 10000 to about 100000, particularly about 1500 to 30000, and the hydroxyphenyl group is preferably about 1.0 mol or more, more preferably about 2 to 8 mol per kg of resin.

When the resin (a-1) and the resin (a-2) are used as a mixture, the mixing ratio is 90/1.
It is preferable to mix them in a weight ratio of 0 to 10/90.

Examples of the resin (a-3) having a carboxyl group and a hydroxyphenyl group include a carboxyl group-containing polymerizable unsaturated monomer (such as (meth) acrylic acid) and a hydroxyphenyl group-containing polymerizable unsaturated monomer. (Hydroxystyrene, etc.) and, if necessary, other polymerizable unsaturated monomers (methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) A) C1-C12 alkyl esters of acrylic acid such as acrylate, aromatic compounds such as styrene, (meth)
A copolymer with hydroxybenzoic acids, gallic acid, resorcinic acid, or a mixture thereof with phenol, naphthols, resorcinol, catechol, etc., with formaldehyde. And the like.

The above resin (a-3) is generally used in an amount of about 500
It preferably has a number average molecular weight of from about 100,000, especially from about 1500 to 30,000, and the carboxyl group is preferably from about 0.5 to 10 mol, especially about 0.7 to 5 mol per kg of resin. . The hydroxyphenyl group is present in an amount of about 1.0 mol or more, preferably about 2 to 8
Molar is preferred.

The olefinically unsaturated compound (b) containing an ether bond includes, for example, about 1 to 4 unsaturated ether groups such as a vinyl ether group, a 1-propenyl ether group and a 1-butenyl ether group at the molecular terminal. To do. The compound (b) has the formula -R "-
OA [where A represents a vinyl group, a 1-propenyl group or an olefinically unsaturated group of 1-butenyl, and R "represents a linear or branched C1-C6 group such as ethylene, propylene or butylene. Represents a chain alkylene group], preferably at least one unsaturated ether group
It is a low molecular weight or high molecular weight compound containing four, for example, polyphenol compounds such as bisphenol A, bisphenol F, bisphenol S, phenol resin, ethylene glycol, propylene glycol, trimethylolpropane, trimethylolethane, pentaerythritol, etc. Condensation products of polyols of the above with alkyl halide unsaturated ethers such as chloroethyl vinyl ether; polyisocyanate compounds such as tolylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate and isophorone diisocyanate and hydroxyalkyl unsaturated such as hydroxyethyl vinyl ether Reaction products with ether, etc. In particular, a condensate of the above polyphenol compound and a halogenated alkyl unsaturated ether and a reaction product of a polyisocyanate compound having an aromatic ring and a hydroxyalkyl unsaturated ether are preferable from the viewpoint of etching resistance, accuracy of a formed pattern, and the like. It is. The compound (b) is used in an amount of usually about 5 to 150 parts by weight, preferably about 10 to 100 parts by weight, based on 100 parts by weight of the resin (a).

The composition containing the components (a) and (b) is characterized in that the coating formed therefrom is crosslinked by heating and by an addition reaction between a carboxyl group and / or a hydroxyphenyl group and an unsaturated ether group to form a solvent. Or insoluble in aqueous alkali solution, then irradiate with active energy rays, and then heat after irradiation, the cross-linking structure is cut by the catalytic action of the generated acid, and the irradiated part becomes soluble again in solvent or aqueous alkali solution It is a positive photosensitive resin composition.

In the composition, an acid hydrolysis reaction is caused in an exposed portion by an acid generated when a film to be formed is exposed, but water must be present to allow the acid hydrolysis reaction to proceed smoothly. Is desirable. Therefore, in the composition of the present invention, by incorporating a hydrophilic resin such as polyethylene glycol, polypropylene glycol, methylcellulose, and ethylcellulose, the water required for the above reaction can be easily incorporated into the formed coating film. You can do so. The amount of the hydrophilic resin to be added is generally 20 parts by weight or less, preferably 0.1 to 10 parts by weight, per 100 parts by weight of the resin component.

Further, the photoacid generator described above is
It is a compound that generates an acid upon exposure and decomposes the resin using the generated acid as a catalyst. A conventionally known compound can be used. Examples thereof include sulfonium salts, ammonium salts, phosphonium salts, onium salts such as iodonium salts and selenium salts, iron-allene complexes, silanol-metal chelate complexes, triazine compounds, diazidonaphthoquinone compounds, sulfones Acid esters, sulfonic imide esters, halogen compounds, and the like can be used.
Further, in addition to the above, JP-A-7-146552,
Photoacid generators described in Japanese Patent Application No. 9-289218 can also be used. This photoacid generator component may be a mixture with the above-mentioned resin or a compound bonded to the resin. The content of the photoacid generator is preferably about 0.1 to 40 parts by weight, particularly about 0.2 to 20 parts by weight, based on 100 parts by weight of the resin.

In the composition of the present invention, in addition to the above-mentioned resin, the solubility in an organic solvent or an aqueous developer can be improved,
In addition, the above-mentioned other resins which are insoluble or dissolved (or dispersed) in water or an organic solvent, which can make the composition worse, can be added as necessary.
Specifically, for example, a phenolic resin, a polyester resin, an acrylic resin, a vinyl resin, a vinyl acetate resin, an epoxy resin, a silicone resin, a fluororesin, and a mixture or modified product of two or more of these resins Is mentioned.

Further, in order to impart appropriate flexibility and non-adhesiveness to a film formed using the composition of the present invention, a plasticizer such as a phthalate ester is added to the composition of the present invention. A polyester resin, an acrylic resin, or the like can be added.

Further, a coloring agent such as a fluidity regulator, a plasticizer, a dye and a pigment may be added to the composition of the present invention, if necessary.

The positive-type visible light-sensitive resin composition of the present invention can be prepared by using a known photosensitive material generally used, for example,
It can be used for a wide range of applications, such as paints, inks, adhesives, resist materials, printing plate materials (plate making materials for flat plates and letterpress, PS plates for offset printing, etc.), information recording materials, and relief image forming materials.

The dry film thickness (excluding the solvent) formed from the positive-type visible light-sensitive resin composition of the present invention is the maximum value in which the absorbance of the non-photosensitive film formed from the composition is selected from the above range. ± 30 nm of the maximum wavelength of safety light having a wavelength
May be set to be 0.5 or less in the range, but from the viewpoint of practicality, it is usually in the range of 0.5 to 50 μm, preferably 1 to 30 μm. The absorbance varies depending on the type and the amount of the photoacid generator, the photosensitizer and the like contained in the composition, but varies depending on the thickness of the film even with the same composition. That is, in the same composition, as the film thickness increases, the absorbance increases due to an increase in the concentration of the photoacid generator and the photosensitizer contained in the film, while on the other hand, when the film thickness decreases, the absorbance increases. The absorbance is reduced due to the lower concentration of the above components. From these facts, by adjusting the film thickness to be formed, the absorbance can be adjusted to fall within the above-mentioned range.

Next, typical resist materials (for example, a general positive photosensitive resist material and a positive resist material for electrodeposition coating) of the visible light curable resin composition of the present invention will be described.

As a general positive photosensitive resist material, for example, the positive visible light-sensitive resin composition of the present invention is dispersed or dissolved in a solvent (including water) (when a pigment is used as a coloring agent, Pigment is finely dispersed) to prepare a photosensitive solution,
This can be used as a positive resist material by a method of applying it on a support using a coating device such as a roller, a roll coater, or a spin coater, and drying.

Solvents used for dissolving or dispersing the positive-type visible light photosensitive resin composition include, for example, ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.) and esters (ethyl acetate, butyl acetate, benzoic acid) Methyl ether, methyl propionate, etc.), ethers (tetrahydrofuran, dioxane, dimethoxyethane, etc.), cellosolves (methyl cellosolve, ethyl cellosolve, diethylene glycol monomethyl ether, etc.), aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) , Halogenated hydrocarbons (chloroform, trichloroethylene, dichloromethane, etc.), alcohols (ethyl alcohol, benzyl alcohol, etc.), others (dimethylformamide, dimethylsulfoxide, etc.), water and the like. .

The support may be, for example, a sheet of a metal such as aluminum, magnesium, copper, zinc, chromium, nickel, iron or an alloy containing them, a printed circuit board whose surface is treated with these metals, or a plastic. , Glass or silicon wafer, carbon and the like.

When used as a positive resist material for electrodeposition coating, first, the positive visible light-sensitive resin composition of the present invention is made into a water-dispersed product or a water-soluble product.

The aqueous dispersion or water-solubility of the positive-type visible light photosensitive resin composition is determined by neutralizing with an alkali (neutralizing agent) when an anionic group such as a carboxyl group is introduced into the resin. Or when a cationic group such as an amino group is introduced, neutralization with an acid (neutralizing agent) is performed. Examples of the alkali neutralizer used in this case include alkanolamines such as monoethanolamine, diethanolamine, and triethanolamine; alkylamines such as triethylamine, diethylamine, monoethylamine, diisopropylamine, trimethylamine, and diisobutylamine; Alkyl alkanolamines such as dimethylaminoethanol; alicyclic amines such as cyclohexylamine; alkali metal hydroxides such as sodium hydroxide and sodium hydroxide; ammonia; Further, examples of the acid neutralizing agent include monocarboxylic acids such as formic acid, acetic acid, lactic acid, and butyric acid. These neutralizing agents can be used alone or in combination. The amount of the neutralizing agent used is the amount of the ionic group 1 contained in the photosensitive resin composition.
0.2 to 1.0 equivalent, particularly 0.3 to 1.0 equivalent per equivalent
A range of 0.8 equivalents is desirable.

In order to further improve the fluidity of the water-soluble or water-dispersed resin component, if necessary, a hydrophilic solvent such as methanol, ethanol, isopropanol, n- Butanol, t-butanol, methoxyethanol, ethoxyethanol, butoxyethanol, diethylene glycol monomethyl ether, dioxane, tetrahydrofuran and the like can be added. The amount of the hydrophilic solvent used is generally 30 per 100 parts by weight of the resin solid component.
It can be up to 0 parts by weight, preferably up to 100 parts by weight.

In order to increase the amount of coating on the object to be coated, a hydrophobic solvent such as a petroleum solvent such as toluene or xylene; methyl ethyl ketone or methyl isobutyl is added to the positive type visible light photosensitive resin composition. Ketones such as ketones; esters such as ethyl acetate and butyl acetate; alcohols such as 2-ethylhexyl alcohol and benzyl alcohol can also be added. The amount of these hydrophobic solvents is usually 2 parts per 100 parts by weight of the resin solid component.
It can be up to 00 parts by weight, preferably 100 parts by weight or less.

The preparation of the positive visible light-sensitive resin composition as an electrodeposition coating composition can be carried out by a conventionally known method. For example, it can be prepared by sufficiently mixing a resin or a resin mixture water-soluble by the above-described neutralization, a photosensitizer of a pyrrole compound, and, if necessary, a solvent and other components, and adding water.

The composition thus prepared is further diluted with water in a usual manner, for example, in a pH range of 4 to 9 and a bath concentration (solid concentration) of 3 to 25% by weight, preferably Can be an electrodeposition coating (or electrodeposition bath) in the range of 5 to 15% by weight.

The electrodeposition paint prepared as described above is
The coating can be performed on the surface of the conductor to be coated as follows. That is, first, the pH and bath concentration of the bath are adjusted to the above ranges, and the bath temperature is adjusted to 15 to 40 ° C., preferably 1
Control at 5-30 ° C. Next, in the electrodeposition coating bath controlled in this way, the conductor to be coated is immersed in a conductor to be coated as an anode when the electrodeposition coating is of an anionic type and as a cathode when the electrodeposition coating is of a cationic type. Apply DC current. An appropriate energization time is 10 seconds to 5 minutes.

The resulting film thickness is a dry film thickness, generally 0.5
５０50 μm, preferably 1-20 μm. After the electrodeposition coating, the object to be coated is pulled up from the electrodeposition bath and washed with water, and then the water and the like contained in the electrodeposition coating film are dried and removed with hot air or the like (the compositions (a) and (b) are used). In this case, the coated substrate is subjected to temperature and time conditions under which a crosslinking reaction between the carboxyl group and / or hydroxyphenyl group-containing polymer and the vinyl ether group-containing compound substantially occurs, for example, from about 60 to about Heat at a temperature of 150 ° C for about 1 minute to about 30 minutes to crosslink and cure the coating).

As the conductor, a conductive material such as metal, carbon, tin oxide or the like, or a material in which these are fixed to the surface of plastic or glass by lamination, plating or the like can be used.

The visible light resist material formed on the conductor surface as described above, and the visible light resist electrodeposition coating film obtained by electrodeposition coating are exposed to visible light according to an image and decomposed. An image can be formed by removing the exposed portion by a developing process.

As the light source for exposure, light sources such as ultra-high pressure, high pressure, medium pressure and low pressure mercury lamps, chemical lamps, carbon arc lamps, xenon lamps, metal halide lamps, fluorescent lamps, tungsten lamps, sunlight and the like can be used. Among the light sources used, there can be used light rays in the visible region in which ultraviolet rays are cut by an ultraviolet cut filter, various lasers having oscillation lines in the visible region, and the like. As a high power and stable laser light source,
An argon laser or a second harmonic (532 nm) of a YAG laser is preferable.

The developing treatment is carried out by washing with an aqueous alkali solution when the exposed portion film is anionic, or with an aqueous acid solution having a pH of 5 or less when the exposed portion film is cationic. Alkaline aqueous solutions that can be neutralized with free carboxylic acids in the coating film, such as sodium hydroxide, sodium carbonate, sodium hydroxide, aqueous ammonia, etc., to give water solubility, and acid aqueous solutions are acetic acid, formic acid, lactic acid, etc. Can be used.

In the case of a photosensitive resin having no ionic group, development processing is performed by dissolving the exposed portion using a solvent such as 1,1,1-trichloroethane, tricrene, methyl ethyl ketone, or methylene chloride. The coated film after development is washed with water and dried with hot air or the like, so that a desired image is formed on the conductor. If necessary, the printed circuit board can be manufactured by performing etching to remove the exposed conductor portion, and then removing the resist film.

When (a) and (b) are used as the composition, the cross-linked structure of the cured coating film is cut off on the substrate irradiated with visible light in the presence of the acid generated by the irradiation. Under such temperature and time conditions, for example, heating is performed at a temperature of about 60 to about 150 ° C. for about 1 to about 30 minutes to substantially cut the crosslinked structure of the coating film on the irradiated portion. At that time, preferably,
The substrate irradiated with visible light is brought into contact with water in advance. The contact with water facilitates the generation of an acid and facilitates the subsequent cleavage reaction of the crosslinked structure. The contact with water can be performed by immersing the substrate in room temperature water or hot water, or by spraying water vapor.

The positive-type visible light-sensitive resin composition of the present invention may further include, for example, a transparent resin film such as a polyester resin such as polyethylene terephthalate, an acrylic resin, polyethylene, or a polyvinyl chloride resin to be a cover film layer. On top, the composition of the present invention roll coater,
It is applied using a blade coater, a curtain flow coater or the like, and dried to form a resist film (dry film thickness of about 0.5 to 5 μm).
After forming m), the film can be used as a dry film resist in which a protective film is attached to the surface of the film.

After the protective film is peeled off from the dry film resist, the resist film can be bonded to the support by thermocompression bonding so that the resist film comes into contact with the support to form a resist film. The resist film can be exposed to visible light and developed according to the image in the same manner as the above-mentioned electrodeposition coating film to form an image.

[0081]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in detail with reference to embodiments. In the examples and comparative examples, “parts” indicates “parts by weight”.

Example 1 200 parts of tetrahydrofuran, 65 parts of P-hydroxystyrene, 28 parts of n-butyl acrylate, acrylic acid 1
1 part and 3 parts of azobisisobutyronitrile are mixed with 1 part
The reaction product obtained by reacting at 00 ° C. for 2 hours is 1500 c
The resulting mixture was poured into a toluene solvent (c) to precipitate and separate the reaction product. The precipitate was dried at 60 ° C. to obtain a photosensitive resin having a molecular weight of about 5200 and a hydroxyphenyl group content of 4.6 mol / kg. Next, 60 parts of a divinyl ether compound (condensate of 1 mol of a bisphenol compound and 2 mol of 2-chloroethyl vinyl ether) was added to 100 parts of this product, and NAI-
105 (photoacid generator, manufactured by Midori Kagaku Co., Ltd., trade name)
A photosensitive solution was obtained by dissolving a mixture of 10 parts and 1.5 parts of the following formula (A) as a photosensitizing dye in diethylene glycol dimethyl ether to adjust the solid content to 20%.

[0083]

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The photosensitive solution was applied to a glass fiber reinforced epoxy substrate plated with copper in a dark room using a bar coater to give a dry film thickness of 5 μm.
m and dried at 120 ° C. for 8 minutes to prepare a substrate having a resist film.

Next, the surface of the substrate having the resist film obtained above was irradiated with the sodium lamp of FIG. 1 for 24 hours so that the illuminance intensity became 40 lux. Then
After heating this at 80 ° C for 10 minutes in a dark room, 1%
As a result of immersion in an aqueous solution of sodium carbonate as a developing solution at 30 ° C. for 1 minute, the resist film was not dissolved in the aqueous solution of sodium carbonate and was good without being adversely affected by irradiation with a sodium lamp.

Further, the substrate having the resist film was irradiated with an argon laser of 1 mJ / m ² intensity through a positive pattern mask, heated at 120 ° C. for 10 minutes, and developed using a 1% aqueous solution of sodium carbonate. Then, the exposed part was completely dissolved by the aqueous sodium carbonate solution,
Thus, a resist pattern having excellent contrast was formed. Also, no decrease or swelling of the film in the unexposed portion was observed. Similar results were obtained by irradiation with a xenon lamp (cutting the ultraviolet wavelength region) and the second harmonic (532 nm) of a YAG laser.

The above photosensitive solution was applied to a transparent polyethylene terephthalate sheet with a bar coater so as to have a thickness of 7 μm, and dried at 60 ° C. for 10 minutes, and the absorbance of the film was measured. FIG. 4 shows the results. The vertical axis indicates absorbance and the horizontal axis indicates wavelength nm.

From the wavelength of the safety light in FIG. 1 and the absorbance curve in FIG. 4, it was confirmed that the safety light did not adversely affect the photosensitive solution and that the safety light was bright light from the relative visibility curve in FIG. it can.

Examples 2 to 18 Photosensitive liquids having the same composition as in Example 1 were obtained except that the following photosensitizers (B) to (R) were used.

The photosensitive solution was applied to a glass fiber reinforced epoxy substrate plated with copper in a dark room with a bar coater to a dry film thickness of 5 μm.
m and dried at 120 ° C. for 8 minutes to prepare a substrate having a resist film.

Next, the surface of the substrate having the resist film (dry film thickness 5 μm) obtained above was irradiated with the sodium lamp of FIG. 1 for 24 hours so that the illuminance intensity was 40 lux. Next, this was heated in a dark room at 80 ° C. for 10 minutes, and then immersed in a 1% aqueous solution of sodium carbonate at 30 ° C. for 1 minute using a 1% aqueous solution of sodium carbonate as a developer. It was good without any adverse effects.

[0092]

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[0093]

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[0094]

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[0095]

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[0096]

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Example 19 22 parts of acrylic acid, 50 parts of styrene, 28 parts of n-butyl methacrylate, azobisisobutyronitrile (AI
BN) A mixture consisting of 5 parts was dropped into 60 parts of methyl isobutyl ketone, which was heated to 80 ° C. and stirred, over 2 hours, and then kept at that temperature for another 2 hours to obtain a solid content of about 62.5%. %, 3 mol / kg of carboxyl group was obtained.

80 parts of the carboxyl group-containing polymer (solid content: 62.5%) obtained above, 20 parts of a P-hydroxystyrene polymer (molecular weight: 1,000), a divinyl ether compound (1 mol of a bisphenol compound and 2-chloroethyl 60 parts of a condensate with 2 mol of vinyl ether), 2 parts of polyethylene glycol (average molecular weight: 400), NAI-10
5 (photoacid generator, manufactured by Midori Kagaku Co., Ltd., trade name) 10
Of a photosensitizer (A) used in Example 1 was dissolved in diethylene glycol dimethyl ether to obtain a 20% by weight photosensitive solution.

The photosensitive liquid was applied to a glass-fiber reinforced epoxy substrate plated with copper in a dark room with a bar coater to a dry film thickness of 5 μm.
m and dried at 120 ° C. for 8 minutes to prepare a substrate having a resist film.

Next, the surface of the substrate having the resist film (dry film thickness 5 μm) obtained above was irradiated with the sodium lamp of FIG. 1 for 24 hours so that the illuminance intensity was 40 lux. Next, this was heated in a dark room at 80 ° C. for 10 minutes, and then immersed in a 1% aqueous solution of sodium carbonate at 30 ° C. for 1 minute using a 1% aqueous solution of sodium carbonate as a developer. It was good without any adverse effects.

Example 20 P-hydroxystyrene polymer (molecular weight: 1000) 10
0 parts, a divinyl ether compound (condensate of 1 mol of bisphenol compound and 2 mol of 2-chloroethyl vinyl ether) 60 parts, polyethylene glycol (average molecular weight 4
00) 2 parts, 10 parts of NAI-105 (photoacid generator, manufactured by Midori Kagaku Co., Ltd., trade name) and 1.5 parts of the photosensitizer (A) used in Example 1 were mixed with diethylene glycol dimethyl ether. Upon dissolution, a 20% by weight photosensitive solution was obtained.

The photosensitive solution was applied to a glass fiber reinforced epoxy substrate plated with copper in a dark room with a bar coater to a dry film thickness of 5 μm.
m and dried at 120 ° C. for 8 minutes to prepare a substrate having a resist coating.

Next, the surface of the substrate having the resist film (dry film thickness 5 μm) obtained above was irradiated with the sodium lamp of FIG. 1 for 24 hours so that the illuminance intensity became 40 lux. Next, this was heated in a dark room at 80 ° C. for 10 minutes, and then immersed in a 1% aqueous solution of sodium carbonate at 30 ° C. for 1 minute using a 1% aqueous solution of sodium carbonate as a developer. It was good without any adverse effects.

Example 21 100 parts (solid content) of the photosensitive solution obtained in Example 1 was mixed with 0.8 equivalent of triethylamine with respect to the carboxyl group, stirred and then dispersed in deionized water to obtain a water-dispersed resin solution ( (Solid content 15%).

The obtained water-dispersed resin solution was used as an electrodeposition coating bath, anion electrodeposition coating was performed so that the dried copper film was used as an anode, and the dry film thickness was 5 μm.
After heating for a minute, a substrate having a resist coating was prepared.

Next, the surface of the substrate having the resist film (dry film thickness of 5 μm) obtained above was irradiated with the sodium lamp of FIG. 1 for 24 hours so that the illuminance intensity became 40 lux. Next, this was heated in a dark room at 80 ° C. for 10 minutes, and then immersed in a 1% aqueous solution of sodium carbonate at 30 ° C. for 1 minute using a 1% aqueous solution of sodium carbonate as a developer. It was good without any adverse effects.

Example 22 200 parts of tetrahydrofuran, 65 parts of P-hydroxystyrene, 18 parts of dimethylaminoethyl methacrylate,
A reaction product obtained by reacting a mixture of 17 parts of n-butyl acrylate and 3 parts of azobisisobutyronitrile at 100 ° C. for 2 hours is poured into 1500 cc of a toluene solvent, and the reaction product is precipitated and separated. The product was dried at 60 ° C. to obtain a photosensitive resin having a molecular weight of about 5000 and a hydroxyphenyl group content of 4.6 mol / kg. Next, 60 parts of a divinyl ether compound (condensate of 1 mol of bisphenol compound and 2 mol of 2-chloroethyl vinyl ether) and 10 parts of NAI-105 (photoacid generator, manufactured by Midori Kagaku Co., Ltd.) A mixture of 1.5 parts of the photosensitizer (A) used in Example 1 was dissolved in diethylene glycol dimethyl ether and adjusted to a solid content of 60% to obtain a photosensitive solution.

100 parts of the photosensitive solution obtained above (solid content)
After mixing and stirring 0.8 equivalents of acetic acid with respect to the amino group,
Disperse in deionized water to form a water-dispersed resin solution (solid content 15
%).

The obtained water-dispersed resin solution was used as an electrodeposition coating bath, a cationic electrodeposition coating was performed so that the dry film thickness was 5 μm, using a laminated copper plate as a cathode, followed by washing with water and drying at 120 ° C. for 8 hours.
After heating for a minute, a substrate having a resist coating was prepared.

Next, the surface of the substrate having the resist film (dry film thickness 5 μm) obtained above was irradiated with the sodium lamp of FIG. 1 for 24 hours so that the illuminance intensity became 40 lux. Next, this was heated in a dark room at 80 ° C. for 10 minutes, and then immersed in a 1% aqueous solution of sodium carbonate at 30 ° C. for 1 minute using a 1% aqueous solution of sodium carbonate as a developer. It was good without any adverse effects.

Example 23 50 parts of poly (t-butoxycarbonyloxystyrene) (molecular weight: 1000) was added to 1000 parts of tetrahydrofuran,
50 parts of the following novolak phenolic resin, NAI-105
10 parts of a photoacid generator (trade name, manufactured by Midori Kagaku Co., Ltd.) and 1.5 parts of a photosensitizing dye (A) were blended to obtain a photosensitive solution having a solid content of 9%.

Production of novolak phenolic resin 1490 parts of o-cresol, 30% formalin 114
5 parts, 130 parts of deionized water and 6.5 parts of oxalic acid were placed in a flask and heated to reflux for 60 minutes. Then add 1% 15% hydrochloric acid
After adding 3.5 parts and heating and refluxing for 40 minutes, 400 parts of deionized water at about 15 ° C. were added to keep the contents at about 75 ° C. to precipitate the resin. The aqueous layer was removed after neutralization by adding 35% sodium hydroxide solution, and 400 parts of deionized water was added.
After washing the resin at 5 ° C., the aqueous layer was removed and the same washing operation was repeated twice, followed by drying at about 120 ° C. under reduced pressure to obtain a novolak phenol resin having a molecular weight of 600.

Using the photosensitive solution obtained above, coating was performed to a dry film thickness of 5 μm, followed by heating at 120 ° C. for 8 minutes to prepare a substrate having a resist film.

Next, the surface of the substrate having the resist film (dry film thickness 5 μm) obtained above was irradiated with the sodium lamp of FIG. 1 for 24 hours so that the illuminance intensity became 40 lux. Next, this was heated in a dark room at 80 ° C. for 10 minutes, and then immersed in a 1% aqueous solution of sodium carbonate at 30 ° C. for 1 minute using a 1% aqueous solution of sodium carbonate as a developer. It was good without any adverse effects.

Example 24 50 parts of poly (tetrahydropyranyl ether styrene) (molecular weight: 1000) was added to 1,000 parts of tetrahydrofuran.
50 parts of the novolak phenolic resin of Example 23, NAI
10 parts of -105 (photoacid generator, manufactured by Midori Kagaku Co., Ltd., trade name) and 1.5 parts of the photosensitizing dye (A) were blended to obtain a photosensitive solution having a solid content of 9%.

Using this photosensitive liquid, a photosensitive layer was formed in the same manner as in Example 1, and the solvent was evaporated.
m, and then washed with water and dried at 120 ° C for 8 hours.
After heating for a minute, a substrate having a resist coating was prepared.

Next, the surface of the substrate having the resist film (dry film thickness 5 μm) obtained above was irradiated with the sodium lamp of FIG. 1 for 24 hours so that the illuminance intensity became 40 lux. Next, this was heated in a dark room at 80 ° C. for 10 minutes, and then immersed in a 1% aqueous solution of sodium carbonate at 30 ° C. for 1 minute using a 1% aqueous solution of sodium carbonate as a developer. It was good without any adverse effects.

Comparative Example 1 A test was performed in the same manner as in Example 1 except that a fluorescent lamp was used instead of the sodium lamp. As a result, the resist film was poorly dissolved in the aqueous solution of sodium carbonate.

FIG. 5 shows the spectral distribution of the fluorescent lamp used in the comparative example.
Shown in

[0120]

According to the present invention, a positive visible light-sensitive resin composition containing a specific compound as a photosensitizer is a composition having extremely high practical utility. Conventionally, in a field of information recording using a photolysis reaction, a method of directly outputting and recording an original electronically edited by a computer directly using a laser has a problem with low sensitivity.

However, the positive-type visible light photosensitive resin composition of the present invention has a very good compatibility between the photosensitive resin and the photosensitizer, and is dissolved in a general-purpose coating solution to form a uniform solution on a support.
In addition, a coated surface having excellent storage stability over time can be obtained.

The photosensitizer of a pyrrole compound having a specific structure used in the present invention has a wavelength of 488 nm and a wavelength of 51 nm.
Since it has very high sensitivity to general-purpose visible lasers such as an argon laser having a stable oscillation line at 4.5 nm and a YAG laser having a bright line at 532 nm as a second harmonic, the positive visible light photosensitive of the present invention is used. The photosensitive material obtained using the conductive resin composition can be subjected to high-speed scanning exposure with such a laser. When an image is formed by high-speed scanning exposure, an extremely fine high-resolution image can be obtained.

The positive visible light-sensitive resin composition of the present invention can be applied and printed under bright environmental conditions without decomposing and dissociating under safe light irradiation environmental conditions. It exerts remarkable effects excellent in safety workability, work efficiency, product quality stability and the like.

[Brief description of the drawings]

FIG. 1 is a graph showing an example of a spectral distribution of a discharge lamp containing sodium as a main component of safety light that can be used in the present invention.

FIG. 2 is a graph showing a spectral distribution when the sodium discharge lamp shown in FIG. 1 is filtered.

FIG. 3 is a diagram showing a relative luminosity curve in a wavelength range of visible light of 380 to 780 nm.

FIG. 4 is a view showing an absorbance curve of a resist film used in Example 1.

FIG. 5 is a diagram showing a spectral distribution of a fluorescent lamp (daylight (D)).

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hideo Kogure 4-17-1, Higashi-Hachiman, Hiratsuka-shi, Kanagawa Prefecture Kansai Paint Co., Ltd. (72) Akira Ogiso 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Chemicals Inside the company (72) Inventor Denmi Misawa 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture Inside Mitsui Chemicals Co., Ltd. (72) Inventor Taizo Nishimoto 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Chemicals Inc. U Tsukahara 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture (72) Inventor Keisuke Takuma 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture F-term (reference) 2H025 AA00 AA01 AB01 AB02 AB03 AB15 AB20 AC01 AC08 AD03 BE00 BE10 BJ00 CA28 CA39 CB17 CB28 CB29 CB43 CB45 CC03 FA00 4H048 AA03 AB76 AB92 VA11 VA12 VA20 VA 22 VA30 VA32 VA40 VA42 VA75 VB20 4J011 QA34 QA35 RA02 RA03 RA10 RA12 RA15 SA82 SA86 TA07 UA01 WA01 WA02 WA05 WA06

Claims (4)

[Claims] 1. A positive-type visible light-sensitive resin composition used in an environment in which a safety light having a maximum wavelength selected from the range of 500 to 620 nm and a high relative luminous efficiency is used. A positive-type visible light-sensitive resin composition containing a visible light-sensitive resin and a photosensitizer of a pyrrole compound represented by the following general formula (1), wherein a non-photosensitive film formed from the composition is used. Absorbance is ± 3 of the maximum wavelength of the safety light
A positive visible light-sensitive resin composition having a thickness of 0.5 or less in a range of 0 nm. Embedded image [Wherein, R ₁ represents a hydrogen atom, an alkyl group having up to 20 carbon atoms, a hydroxyalkyl group, an alkoxyalkyl group, an alkoxycarbonylalkyl group, an aryl group, an aralkyl group or an alkenyl group, and R _{2 to} R ₁₀ each independently represent A hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxy group, an amino group, an aminocarbonyl group, a carboxyl group, a sulfonic acid group, an alkyl group having up to 20 carbon atoms, a halogenoalkyl group, an alkoxyalkyl group, an alkoxy group, Alkoxyalkoxy, acyl, alkoxycarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, alkylcarbonylamino, aryl, aralkyl, arylcarbonylamino, arylaminocarbonyl, aryloxy, aryloxy Rubonyl group, heteroaryl group, alkylthio group, arylthio group, alkenyloxycarbonyl group, aralkyloxycarbonyl group, alkoxycarbonylalkoxycarbonyl group, alkylcarbonylalkoxycarbonyl group, mono (hydroxyalkyl) aminocarbonyl group, di (hydroxyalkyl) amino Carbonyl group, mono (alkoxyalkyl)
Represents an aminocarbonyl group, a di (alkoxyalkyl) aminocarbonyl group or an alkenyl group] 2. A discharge lamp mainly composed of sodium as a safety light (mainly a D line having a light wavelength of 589 nm).
The positive visible light-sensitive resin composition according to claim 1, wherein 3. A composition for a positive-type visible light-sensitive material, comprising the positive-type visible light-sensitive resin composition according to claim 1 and a solvent. 4. A positive visible light-sensitive material comprising the positive visible light-sensitive resin composition according to claim 1 on a substrate.