JPH0643642A - Photopolymerizable composition - Google Patents

Abstract

PURPOSE:To provide a photopolymerizable composition having high photosensitivity particularly to visible ray, polymerizable by visible ray laser such as argon ion laser, capable of giving excellent contrast between non-irradiating part and a substrate in red light and giving excellent contrast between a irradiated part and non-irradiated part with laser and excellent in stability. CONSTITUTION:This photopolymerizable composition is made by blending 100 pts.wt. visible ray setting resin to which light of 400-700nm visible ray region is applied as main irradiation energy, 0.02-0.5 pts.wt. dye of at least one kind selected from a dye group having max. absorption wave length in 550-700nm such as victoria pure blue, anthraquinone dye, monoazo dye, merocyanine dye, phthalocyanine dye, 0.1-5 pts.wt. 4,4'-(phenylmethylene)-bis(N,N-diethylbenzen amine) and 0.1-5 pts.wt. tribromo-methyl phenyl sulfone.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photopolymerizable composition, which has a high photosensitivity to visible light, can be cured by a visible light laser such as an argon ion laser, and is not irradiated under a red light. The present invention relates to a photopolymerizable composition having excellent stability, which provides good contrast between a portion and a substrate and good contrast between a laser-irradiated portion and a non-irradiated portion.

[0002]

2. Description of the Related Art Conventionally, in a photopolymerizable composition such as a UV-curable dry film photoresist, a good contrast is provided between a non-irradiated portion and a substrate, and a UV-irradiated portion is not exposed even under a yellow light. Various dyes have been incorporated to provide good contrast between the illuminated areas. For example, JP-A-59-107344 describes a system comprising tribromomethylphenyl sulfone, leuco crystal violet and malachite green. However, these dye systems have poor visibility under a red light, which is necessary for a visible light curable resin, and it is not possible to clearly distinguish between a visible light irradiation portion and a non-irradiation portion. Furthermore, there is a drawback that the sensitivity becomes low as compared with the system in which no dye is added.

[0003]

In recent years, with the progress of laser scanning exposure technology, such as argon laser,
The development of a photopolymerizable composition having high photosensitivity to the emission wavelength of visible laser is desired, and various such photosensitive resins and initiator compounds have been proposed. The inventors of the present invention also have a titanocene-based compound represented by the following general formula (1).

[0004]

[Chemical 4] [In the formula, each R ¹ is independently an unsubstituted or C ₁ to
C ₆ alkyl or C ₁ -C ₆ alkoxy-substituted cyclopentadienyl ^-, indenyl ^-, or 4,5,6,7, tetrahydroindenyl ^- can be either, or linked to Equation (2)

[0005]

[Chemical 5] (In the formula, R ⁴ and R ⁵ are each independently hydrogen or methyl.). R ² is a 6-membered carbocyclic aromatic ring or a 5- or 6-membered heterocyclic aromatic ring, wherein at least one of the two ortho positions of the metal-carbon bond is a fluorine atom or a —CF ₂ R group. (In the formula, R is a fluorine atom or methyl.). R ³ is the same as R ² , or is a halogen atom, —OR ⁶ or —OR ⁷ (wherein R ⁶ is hydrogen, C ₁ to
C ₆ alkyl, phenyl, acetyl or trifluoroacetyl, R ⁷ is C ₁ -C ₆ alkyl or phenyl. ), Or R ² and R ³ are linked to each other to form formula (3) -Q-Y-Q -... (3) (wherein, Q is a 6-membered carbocyclic aromatic group, or 5-membered). Or a 6-membered heterocyclic aromatic group in which each of the two bonds is in the ortho position with respect to Y, and each meta position with respect to Y has one fluorine atom or one —CF ₂ R group. And Y is a direct bond, -O-, -S.
_{-, - SO 2 -, -} CO -, - CH 2 - or -C (CH
₃ ) _2- . ) May be a group represented by ]When,
It was found that the sensitivity can be improved by using a coumarin compound having a specific structure together.
No. 741 was filed.

However, when using such a photopolymerizable composition, it is desired that the presence or absence of the resist on the substrate can be confirmed under a red lamp when, for example, producing a printed wiring board, and the exposed and unexposed parts are not visible. To determine, or
In order to prevent double exposure, it has been desired to provide good contrast between the laser-irradiated portion and the non-irradiated portion.

[0007]

The object of the present invention relates to a photopolymerizable composition, in particular having a high photosensitivity to visible light, curable by a visible light laser, for example an argon ion laser, a red light. To provide a photopolymerizable composition having excellent stability, which gives good contrast between a non-irradiated portion and a substrate, and yet gives good contrast between a laser-irradiated portion and a non-irradiated portion. is there.

[0008]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have found that (a) a visible light curable resin whose main irradiation energy is light in the visible light region of 400 nm to 700 nm. 10
0 parts by weight, (b) 0.02 to 0.5 of at least one dye selected from the group consisting of Victoria Pure Blue, anthraquinone dye, monoazo dye, merocyanine dye, and phthalocyanine dye having a maximum absorption wavelength of 550 to 700 nm. Parts by weight, 0.1 to 5 parts by weight of (c) 4,4 ′-(phenylmethylene) bis [N, N-diethylbenzenamine], and 0.1 to 5 parts of (d) tribromomethylphenylsulfone.
5 parts by weight of the photopolymerizable composition has high photosensitivity to visible light and can be cured by a visible light laser such as an argon ion laser. It was found that a good contrast is provided between the laser irradiation area and the non-irradiation area of the laser, and the present invention has been completed.

The visible light curable resin contains, as a photopolymerization initiator, (e) a compound represented by the following general formula (1) (f) a compound represented by the following general formula (4) It was found that the polymerizable composition has higher photosensitivity and gives good contrast.

[0010]

[Chemical 6] [In the formula, each R ¹ is independently an unsubstituted or C ₁ to
C ₆ alkyl or C ₁ -C ₆ alkoxy-substituted cyclopentadienyl ^-, indenyl ^-, or 4,5,6,7, tetrahydroindenyl ^- can be either, or linked to Equation (2)

[0011]

[Chemical 7] (In the formula, R ⁴ and R ⁵ are each independently hydrogen or methyl.). R ² is a 6-membered carbocyclic aromatic ring or a 5- or 6-membered heterocyclic aromatic ring, and at least one of the two ortho positions of the metal-carbon bond is a fluorine atom or a —CF ₂ R group ( In the formula, R is a fluorine atom or methyl). R ³ is the same as R ² or further a halogen atom, —OR ⁶ or —OR ⁷ (wherein R ⁶ is hydrogen, C ₁ to
C ₆ alkyl, phenyl, acetyl or trifluoroacetyl, R ⁷ is C ₁ -C ₆ alkyl or phenyl. ), Or R ² and R ³ are linked to each other to form formula (3) -Q-Y-Q -... (3) (wherein, Q is a 6-membered carbocyclic aromatic group, or 5-membered Or a 6-membered heterocyclic aromatic group in which each of the two bonds is in the ortho position with respect to Y, and each meta position with respect to Y has one fluorine atom or one —CF ₂ R group. And Y is a direct bond, -O-, -S.
_{-, - SO 2 -, -} CO -, - CH 2 - or -C (CH
₃ ) _2- . ) May be a group represented by ]

[0012]

[Chemical 8] [Wherein R ⁸ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom, a chloro atom, a lower alkoxy group, a lower dialkylamino group, a lower dialkenylamino group or an alicyclic amino group, or , And represents a substituted or unsubstituted alicyclic amino group. X represents a substituted or unsubstituted heterocyclic group having 5 to 9 total carbon and hetero atoms. Z is
Represents a hydrogen atom or an amino group. ]

The present invention will be described in detail below. As the visible light curable resin, a composition comprising a photocrosslinkable polymer and a visible light sensitizer, a composition comprising a cationically polymerizable compound and a visible light sensitive photocationic polymerization initiator, an ethylenically unsaturated bond Examples thereof include a composition comprising a photosensitive resin having at least one addition-polymerizable compound having a and a visible light-sensitive photopolymerization initiator.
Among them, a composition comprising a photosensitive resin having at least one addition-polymerizable compound having an ethylenically unsaturated bond and a visible light-sensitive photopolymerization initiator is preferable from the viewpoint of curing rate.

The photosensitive resin having at least one addition-polymerizable compound having an ethylenically unsaturated bond may be composed of only an addition-polymerizable compound having an ethylenically unsaturated bond, or these compounds may be used. And a binder resin such as a polymer.

The addition-polymerizable compound having an ethylenically unsaturated bond may be a monomer, an oligomer, or a prepolymer having an ethylenically unsaturated bond that causes addition polymerization by the action of a photopolymerization initiator. However, in terms of high polymerization reactivity, an acryloyloxy group or a methacryloyloxy group (hereinafter referred to as (meth)
Those having an acryloyloxy group) are particularly preferable.

Examples of the monomer having a (meth) acryloyloxy group are polyether acrylate or polyether methacrylate type (hereinafter, "acrylate or methacrylate" is simply abbreviated as "(meth) acrylate"), polyester. (Meth) acrylate-based, polyol (meth) acrylate-based, epoxy (meth) acrylate-based, amidourethane (meth) acrylate-based, urethane (meth) acrylate-based, spiroacetal (meth) acrylate-based, polybutadiene (meth) acrylate-based, etc. The monomers and oligomers of can be mentioned.

Specific examples of such a monomer or oligomer include triethylene glycol diacrylate, hexapropylene glycol diacrylate, or 1,2,6-hexanetriol / propylene oxide / acrylic acid, trimethylolpropane / propylene. Polyether (meth) acrylate synthesized from oxide / acrylic acid, etc .; Polyester (meth) acrylate synthesized from adipic acid / 1,6-hexanediol / acrylic acid, succinic acid / trimethylolethane / acrylic acid; Neo Pentyl glycol diacrylate, 1,4-butanediol dimethacrylate, 2-
Ethylhexyl acrylate, tetrahydrofurfuryl acrylate, 2-hydroxyethyl methacrylate,
Ethyl carbitol acrylate, trimethyl roll propane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate,
2,2-bis (4-acryloyloxydiethoxyphenyl) propane, 2,2-bis (4-acryloyloxypropoxyphenyl) propane and other (meth) acrylates or polyol (meth) acrylates; diglycidyl etherified bisphenol A / Acrylic acid, diglycidyl etherified polybisphenol A / acrylic acid,
Epoxy (meth) acrylate synthesized from triglycidyl etherified glycerin / acrylic acid; γ-butyrolactone / N-methylethanolamine / bis (4-
Isocyanate cyclohexyl) methane / 2-hydroxyethyl acrylate, γ-butyrolactone / N-methylethanolamine / 2,6-tolylene diisocyanate / tetraethylene glycol / 2-hydroxyethyl acrylate, etc. amidourethane (meth)
Acrylate; urethane acrylate such as 2,6-tolylene diisocyanate diacrylate, isophorone diisocyanate diacrylate, hexamethylene diisocyanate diacrylate; spiro acetal acrylate synthesized from diallylidene pentaerythritol / 2-hydroxyethyl acrylate; epoxidized butadiene / Examples thereof include acrylated polybutadiene synthesized from 2-hydroxyethyl acrylate, and these monomers and oligomers may be used alone or in combination of two or more.

The binder resin used in combination with these monomers and oligomers is for the purpose of imparting various functions such as developability, adhesiveness with a substrate and flexibility, and depending on the purpose. It may be selected appropriately. For example, polyvinylpyrrolidone, polyvinyl alcohol,
(Meth) acrylic acid ester / (meth) acrylic acid copolymer, styrene / (meth) acrylic acid copolymer, styrene / maleic acid copolymer, (meth) acrylic acid ester / (meth) acrylamide copolymer, etc. Can be used. One kind of these polymers may be used, or two or more kinds may be mixed and used at an appropriate ratio. For example,
In the case of an alkali developing type visible light curable resin that develops and removes the unexposed area with an aqueous alkaline solution, it contains an α, β-unsaturated carboxyl group-containing monomer containing 3 to 15 carbon atoms as a copolymerization component. Acrylic resins are preferred, and acrylic acid and methacrylic acid are most preferred.

Next, the photopolymerization initiator used in the visible light curable resin of the present invention will be described. In the visible light curable resin of the present invention, for example, two components of compound (e) and compound (f) are used together as a photopolymerization initiator. The compound (e) is a compound represented by the following general formula (1).

[0020]

[Chemical 9] [In the formula, each R ¹ is independently an unsubstituted or C ₁ to
C ₆ alkyl or C ₁ -C ₆ alkoxy-substituted cyclopentadienyl ^-, indenyl ^-, or 4,5,6,7, tetrahydroindenyl ^- can be either, or linked to Equation (2)

[0021]

[Chemical 10] (In the formula, R ⁴ and R ⁵ are each independently hydrogen or methyl.). R ² is a 6-membered carbocyclic aromatic ring or a 5- or 6-membered heterocyclic aromatic ring, and at least one of the two ortho positions of the metal-carbon bond is a fluorine atom or a —CF ₂ R group ( In the formula, R is a fluorine atom or methyl). R ³ is the same as R ² or is further a halogen atom, —OR ⁶ or —OR ⁷ (wherein R ⁶ is hydrogen, C _{1 to} C
₆ alkyl, phenyl, acetyl or trifluoroacetyl and R ⁷ is C ₁ -C ₆ alkyl or phenyl. ), Or R ² and R ³ are linked to each other to form formula (3) -Q-Y-Q -... (3) (wherein, Q is a 6-membered carbocyclic aromatic group, or 5-membered Or a 6-membered heterocyclic aromatic group in which each of the two bonds is in the ortho position with respect to Y, and each meta position with respect to Y has one fluorine atom or one —CF ₂ R group. And Y is a direct bond, -O-, -S.
_{-, - SO 2 -, -} CO -, - CH 2 - or -C (CH
₃ ) _2- . ) May be a group represented by The compound (f) is a compound represented by the following general formula (4).

[0022]

[Chemical 11] [Wherein R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom,
It represents a chlorine atom, a lower alkoxy group, a lower dialkylamino group, a lower dialkenylamino group or an alicyclic amino group, or represents a substituted or unsubstituted alicyclic amino group. X represents a substituted or unsubstituted heterocyclic group having 5 to 9 total carbon and hetero atoms. Z is
Represents a hydrogen atom or an amino group. ] Particularly preferred as such a compound is

[0023]

[Chemical 12]

[0024]

[Chemical 13]

And most preferred of these are:

[0026]

[Chemical 14]

It is

The blending amount of the photopolymerization initiators (e) and (f) in the visible light curable resin of the present invention is the same as that of the photopolymerization initiator (e) in 100% by weight of the visible light curable resin (a). It is desirable that the total amount of (f) is 10 to 0.1% by weight. If the ratio of the two components used is less than the lower limit of the above range, the photosensitivity is lowered, and if it is more than the upper limit, improvement of the photosensitivity is not desired, and conversely the physical properties of the resin are lowered. In addition, the compounding ratio (weight ratio) of the compound (e) and the compound (f) is preferably set in the range of (f) / (e) = 1 to 0.01. The mixing ratio of these two components is 0.01
If it is less than the above range, the photosensitivity is lowered. On the other hand, even if it becomes larger than 1, improvement in photosensitivity cannot be expected.

Next, the dye, leuco dye and radical generator used in the present invention will be explained. The dye is added to give a contrast between the non-irradiated portion and the substrate under a red lamp, but for that purpose, it is necessary that the dye has absorption between 500 to 700 nm which is the emission wavelength of the red lamp. , It is necessary to have a maximum absorption wavelength at 550 to 700 nm. Further, in order to provide contrast between the laser-irradiated portion and the non-irradiated portion, it is desirable that the difference between the absorption wavelength of the leuco dye described below after color development is large. Further, it must be a dye having excellent stability that does not cause decolorization or gelation when mixed with a visible light curable resin. Further, in order not to reduce the sensitivity to visible light, it is necessary that there is no absorption for the oscillation wavelength of the visible light laser used for exposure.

The leuco dye is added to provide contrast between the irradiated and non-irradiated portions of the laser. For that purpose, it is desirable that a color is developed with high sensitivity by laser irradiation and the absorption wavelength has a large difference from the absorption wavelength of the dye described above. Further, it should be a dye having excellent stability, which does not cause coloration or gelation when mixed with a visible light curable resin. Moreover, it is also necessary not to reduce the photosensitivity of the polymerizable composition.

The inventors of the present invention have newly found that as such dyes, leuco dyes and radical generators, the following combinations of dyes, leuco dyes and radical generators are preferable.・ Dye: having a maximum absorption wavelength at 550 to 700 nm,
Victoria pure blue, anthraquinone dye, monoazo dye, merocyanine dye, phthalocyanine dye. Leuco dye: 4,4 ′-(phenylmethylene) bis [N, N-diethylbenzenamine] (Basic Green 1,
CI 42040 leuco body). -Radical generator: tribromomethylphenyl sulfone.

Solvent Blue 6 is an anthraquinone dye having a maximum absorption wavelength from 550 to 700 nm.
3, Disperse Blue 35, Disperse Blue 6
0, Disperse Blue 73, Disperse Blue 5
6, Solvent Blue 83, Solvent Blue 14, Solvent Blue 111, and the like. Examples of the monoazo dye include Solvent Blue 266, Disperse Blue 36, Solvent Blue 268 and the like. As a merocyanine dye, Disperse Blue 3
54 and the like. Examples of the phthalocyanine dye include Solvent Blue 117 and the like.

The function of the radical generator is generally, in a system added to a polymerizable composition curable by ultraviolet rays,
It is said that it is dissociated by ultraviolet irradiation to generate radicals, and the action of the radicals accelerates the color development of the leuco dye. However, tribromomethylphenyl sulfone added as a radical generator to the photopolymerizable composition of the present invention has no absorption at a visible emission wavelength of a visible light laser, for example, an argon ion laser, and is irradiated by itself. Inactive against. However, especially when tribromomethylphenyl sulfone is used at the same time as leuco diamond green and visible light curable resin, Victoria Pure Blue and leuco diamond green and visible light curable resin alone produce leuco diamond green in color. It is more accelerated and gives good contrast between the irradiated and non-irradiated parts of the laser,
We also found that it is also excellent in stability.

The amount of the dye compounded in the photopolymerizable composition of the present invention is 100 parts by weight of the visible light curable resin.
It is preferably 0.02 to 0.5 parts by weight. When the use ratio is higher than the upper limit, good contrast cannot be obtained between the laser-irradiated part and the non-irradiated part, and when it is lower than the lower limit of the above range, good contrast is obtained between the non-irradiated part and the substrate. I can't.

4,4'- in the photopolymerizable composition of the present invention
The compounding amount of (phenylmethylene) bis [N, N-diethylbenzenamine] is preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the visible light curable resin. Even if it exceeds the upper limit of the above range, the contrast between the laser-irradiated portion and the non-irradiated portion cannot be improved, which is not preferable from an economical point of view, and also storage stability and deterioration of physical properties after curing. May occur. If it is less than the lower limit of the above range, good contrast cannot be obtained between the laser-irradiated portion and the non-irradiated portion.

The blending amount of tribromomethylphenyl sulfone in the photopolymerizable composition of the present invention is preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the visible light curable resin. Even if it exceeds the upper limit of the above range, the contrast between the laser-irradiated portion and the non-irradiated portion cannot be improved, which is not preferable from an economical point of view, and also storage stability and deterioration of physical properties after curing. May occur. If it is less than the lower limit of the above range, good contrast cannot be obtained between the laser-irradiated portion and the non-irradiated portion.

The photopolymerizable composition of the present invention comprises the above-mentioned visible light curable resin, Victoria Pure Blue, anthraquinone dye, monoazo dye, merocyanine dye, and phthalocyanine dye having a maximum absorption wavelength of 550 to 700 nm. At least one dye selected from the dye group, 4,4 ′-(phenylmethylene) bis [N, N-diethylbenzenamine] and tribromomethylphenylsulfone are essential components, but if necessary, thermal polymerization is prohibited. Various additives such as agents, adhesion promoters, fillers and plasticizers can be included.

The photopolymerizable composition of the present invention can be used for printing plates, photoresists and the like, and particularly advantageous are plate-making materials and photosensitive image forming materials such as photoresists. In these applications, the photopolymerizable composition of the present invention is generally used by dissolving it in a solvent, coating it on a support and drying it to form a film, then exposing and curing it.

The photopolymerizable composition of the present invention exhibits photosensitivity as it is, but when high sensitivity is required, it is exposed to vacuum deaeration or nitrogen substitution in order to prevent polymerization inhibition by oxygen. A film of polyvinyl alcohol or the like may be formed on the photopolymerizable composition, or a plastic film having low oxygen permeability may be laminated on the surface and exposed.

The photopolymerizable composition of the present invention has a wavelength of about 220.
Since it exhibits a spectral sensitivity distribution that extends from nm to 550 nm, it has been used for high pressure mercury lamps, xenon lamps,
It can be cured with a light source such as a metal halide lamp. However, the greatest feature of the present invention is that it has a high photosensitivity to the emission wavelength of a visible light laser, for example, an argon ion laser, can be cured by a visible light laser, for example, an argon ion laser, and can be irradiated with a laser and not irradiated. Since a good contrast is given between the portions, a visible light laser such as an argon ion laser may be used for scanning exposure.

[0041]

EXAMPLES The present invention will be described in detail below based on examples. (I) Preparation of photosensitive layer (test plate) The photopolymerizable composition solutions of Examples 1 to 16 having the respective compositions shown in Tables 1 to 4 were prepared.

[0042]

[Table 1]

[0043]

[Table 2]

[0044]

[Table 3]

[0045]

[Table 4]

In the table, the crosslinkable monomers 1 to 4 are shown below. -Crosslinkable monomer 1 ... Polyethylene glycol diacrylate-Crosslinkable monomer 2 ... Polyethyleneglycol dimethacrylate-Crosslinkable monomer 3 ... Trimethylolpropane triethoxytriacrylate-Crosslinkable monomer Body 4: Propylene glycol diglycidyl ether diacrylate

In the table, the composition (weight ratio) of the polymerized monomers of the binder resins A and B is as shown below. Binder resin A ... Methacrylic acid / styrene / methyl acrylate / methyl methacrylate = 20/10 /
25/45 ・ Binder resin B ... Methacrylic acid / styrene / methyl acrylate / methyl methacrylate = 20/0/2
0 / 60.0

In Table 2, Compound A, which is a photopolymerization initiator, is

[Chemical 15]

Compound B is

[Chemical 16]

Compound C is

[Chemical 17] Is.

In the table, dyes 1 to 18 are as shown below.・ Dye 1 ・ ・ ・ Solvent Blue 63 ・ Dye 2 ・ ・ ・ Solvent Blue 266 ・ Dye 3 ・ ・ ・ Solvent Blue 268 ・ Dye 4 ・ ・ ・ Disperse Blue 354 ・ Dye 5 ・ ・ ・ Disperse Blue 35 ・ Dye 6・ ・ ・ Disperse Blue 36 ・ Dye 7 ・ ・ ・ Disperse Blue 60 ・ Dye 8 ・ ・ ・ Disperse Blue 73 ・ Dye 9 ・ ・ ・ Disperse Blue 56 ・ Dye 10 ・ ・ ・ Solvent Blue 83 ・ Dye 11 ・・ ・ Solvent Blue 25 ・ Dye 12 ・ ・ ・ Solvent Blue 14 ・ Dye 13 ・ ・ ・ Solvent Blue 117 ・ Dye 14 ・ ・ ・ Solvent Blue 111 ・ Dye 15 ・ ・ ・ Victoria Pure Blue ・ Dye 16 ・ ・ ・ Malachite Green ・Dye 17 ・ ・ ・ Crystal Violet ・ Dye 18 ・ ・ ・ Methyle Blue

In the table, leuco dyes 1 to 5 are as follows.・ Leuco dye 1 ・ ・ ・ 4,4 '-(phenylmethylene) bis [N, N-diethylbenzeneamine] ・ Leuco dye 2 ・ ・ ・ Leuco crystal violet ・ Leuco dye 3 ・ ・ ・ Leuco milling green ・ Leuco dye 4 ・..Leuco basic cyanine Leuco dye 5 ... Leucomara kite green

In the table, compound D, which is a radical generator, is tribromomethylphenyl sulfone, and compound E is 2,2 '.
-Bis (orthochlorophenyl) 4,5,4 ', 5'-tetraphenylbiimidazole.

The obtained composition was applied onto a 25 μm polyester film by an applicator. Then, dry in a dryer at 60 ° C for 30 minutes to obtain a thickness of 50μ.
m photopolymerizable composition layer was obtained. The photopolymerizable composition layer thus obtained was heat-laminated on a copper clad laminate with the polyester film side facing up to obtain a test plate.

[Comparative Example] In the same manner as in Examples, Tables 5 to 8
The photopolymerizable compositions of Comparative Examples 1 to 11 having the respective compositions shown in Table 1 were obtained and used as test plates.

[0056]

[Table 5]

[0057]

[Table 6]

[0058]

[Table 7]

[0059]

[Table 8]

(II) Measurement of Scanning Exposure Sensitivity 48 of NEC Argon Laser (GLG3028)
A laser beam having a beam diameter of 35 μm condensed through an optical system using an output of 8 nm as a light source was scan-exposed on a test plate to draw a 200 μm line-and-space pattern. Next, after leaving for 30 minutes after the exposure, the polyester film was peeled off, and then the uncured portion was dissolved and removed using a 1% sodium carbonate aqueous solution to obtain a scanning exposure pattern. The spray pressure was 1.4 kg / cm ² , the distance between the spray and the substrate was 10 cm, and the treatment was performed at a temperature of 30 ° C. for 40 seconds. The line width of the cured part of the scanning pattern is measured by sequentially changing the scanning exposure speed, and the irradiation energy per unit area at that time is calculated from the obtained scanning exposure speed with the same line width as the scanning line width. , Sensitivity.
The results are shown in Tables 9 and 10.

[0061]

[Table 9]

[0062]

[Table 10]

Based on the results shown in Table 9, a visible light curable resin and a dye having a maximum absorption wavelength in the range of 550 to 700 nm, selected from the dye group of Victoria Pure Blue, anthraquinone dye, monoazo dye, merocyanine dye and phthalocyanine dye. And the leuco dye 4,4 ′-(phenylmethylene) bis [N, N-diethylbenzenamine] and the radical generator tribromomethylphenylsulfone were used in combination for photopolymerization in Examples 1 to 16. The photosensitive composition has a high sensitivity to visible light, provides a good contrast between the non-irradiated portion and the substrate under a red lamp, and further provides a good contrast between the laser-irradiated portion and the non-irradiated portion. It was confirmed to give. In addition, stability is also good.

On the other hand, according to Table 10, Victoria Pure Blue, anthraquinone dye, monoazo dye, which has a maximum absorption wavelength at 550 to 700 nm as a dye,
In the compositions of Comparative Examples 1 to 4 in which a dye selected from the group of dyes of merocyanine dyes and phthalocyanine dyes is not blended, the composition of Comparative Example 1 in which no dye is blended has a resist and a copper surface under a red light. No difference was observed, and in the composition of Comparative Example 2 in which malachite green was blended as a dye, no difference was observed between the resist and the copper surface under red light, and malachite green was decolored. In addition, the composition of Comparative Example 3 containing crystal violet as the dye had very poor sensitivity, and the composition of Comparative Example 4 containing methylene blue as the dye showed no difference between the resist and the copper surface under red light. And the methylene blue has disappeared.

As a leuco dye, 4,4 '-(phenylmethylene) bis [N, N-diethylbenzenamine]
In Comparative Examples 5 to 9 in which the leuco dye is not blended, no difference is observed between the exposed portion and the unexposed portion in the red light, and the leuco crystal violet is used as the leuco dye. In the compounded composition of Comparative Example 6, no difference was observed between the exposed part and the unexposed part in the red light, and the sensitivity was very poor, and the leuco crystal violet was colored. Further, in the composition of Comparative Example 7 in which leuco milling green was blended as the leuco dye, no difference was observed between the exposed portion and the unexposed portion in the red lamp, and the composition of Comparative Example 8 in which leuco basic cyanine was blended as the leuco dye. The difference between the exposed part and the non-exposed part in the red lamp was slight, and the composition of Comparative Example 9 containing leuco malachite green as the leuco dye showed no difference in the exposed part and the non-exposed part in the red lamp. .

Comparative Example 10 in which tribromomethylphenyl sulfone was not added as a radical generator,
In the composition of Comparative Example 11 in which the radical generator was not blended, the difference between the exposed portion and the non-exposed portion in the red lamp was small, and the radical generator was 2,2 ′.
In the composition of Comparative Example 11 in which -bis (orthochlorophenyl) 4,5,4 ', 5'-tetraphenylbiimidazole was blended, the exposed part and the unexposed part could not be clearly recognized visually by a red lamp.

[0067]

As described above, the photopolymerizable composition of the present invention contains 100 parts by weight of a visible light curable resin whose main irradiation energy is light in the visible light region of 400 nm to 700 nm and a maximum of 550 to 700 nm. Have an absorption wavelength,
0.02 to 0.5 of at least one dye selected from the group consisting of Victoria Pure Blue, anthraquinone dye, monoazo dye, merocyanine dye, and phthalocyanine dye.
Parts by weight and 4,4 ′-(phenylmethylene) bis [N, N
-Diethylbenzenamine] in an amount of 0.1 to 5 parts by weight and tribromomethylphenyl sulfone in an amount of 0.1 to 5 parts by weight. Further, in this photopolymerizable composition, the visible light curable resin contains, as a photopolymerization initiator, a compound represented by the general formula (1) and a compound represented by the general formula (4). .

These photopolymerizable compositions of the present invention have high photosensitivity to visible light and can be cured by a visible light laser such as an argon ion laser. Good contrast, and good contrast between the laser-irradiated part and the non-irradiated part. Therefore, it is very useful when used as a resist for making a printed wiring board using a visible light laser and a plate-making material.

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Claims (2)

[Claims] 1. Victoria pure blue, anthraquinone dye, monoazo dye having 100 parts by weight of a visible light curable resin whose main irradiation energy is light in the visible light region of 400 nm to 700 nm, and having a maximum absorption wavelength at 550 to 700 nm. 0.02 to 0.5 parts by weight of at least one dye selected from the group of dyes of merocyanine dyes and phthalocyanine dyes and 0.1 parts of 4,4 ′-(phenylmethylene) bis [N, N-diethylbenzenamine]. ~
A photopolymerizable composition comprising 5 parts by weight and 0.1 to 5 parts by weight of tribromomethylphenyl sulfone. 2. The photopolymerizable composition according to claim 1, wherein the visible light curable resin comprises a compound represented by the following general formula (1) as a photopolymerization initiator and a general formula (4) below. A photopolymerizable composition comprising the compound represented. [Chemical 1] [In the formula, each R ¹ is independently an unsubstituted or C ₁ to
C ₆ alkyl or C ₁ -C ₆ alkoxy-substituted cyclopentadienyl ^-, indenyl ^-, or 4,5,6,7, tetrahydroindenyl ^- or where connection to Equation (2) ## STR2 ## (In the formula, R ⁴ and R ⁵ are each independently hydrogen or methyl.). R ² is a 6-membered carbocyclic aromatic ring or a 5- or 6-membered heterocyclic aromatic ring, and at least one of the two ortho positions of the metal-carbon bond is a fluorine atom or a —CF ₂ R group ( In the formula, R is a fluorine atom or methyl). R ³ is the same as R ² or further a halogen atom, —OR ⁶ or —OR ⁷ (wherein R ⁶ is hydrogen, C ₁ to
C ₆ alkyl, phenyl, acetyl or trifluoroacetyl, R ⁷ is C ₁ -C ₆ alkyl or phenyl. ), Or R ² and R ³ are linked to each other to form formula (3) -Q-Y-Q -... (3) (wherein, Q is a 6-membered carbocyclic aromatic group, or 5-membered). Or a 6-membered heterocyclic aromatic group in which each of the two bonds is in the ortho position with respect to Y, and each meta position with respect to Y has one fluorine atom or one —CF ₂ R group. And Y is a direct bond, -O-, -S.
_{-, - SO 2 -, -} CO -, - CH 2 - or -C (CH
₃ ) _2- . ) May be a group represented by ] [Chemical 3] [Wherein R ⁸ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom, a chloro atom, a lower alkoxy group, a lower dialkylamino group, a lower dialkenylamino group or an alicyclic amino group, or , And represents a substituted or unsubstituted alicyclic amino group. X represents a substituted or unsubstituted heterocyclic group having 5 to 9 total carbon and hetero atoms. Z is
Represents a hydrogen atom or an amino group. ]