JPH04303841A - Photodegradable microcapsule and photosensitive resin composition formed by using the same - Google Patents

Abstract

PURPOSE:To obtain a sufficient sensitivity by using two kinds of solns. contg. respectively specific compds. and bringing these compds. into reaction at the liquid boundary of the two solns. while dispersing or dissolving a core material in either of the solns. CONSTITUTION:This microcapsule is constituted by using the soln. contg. the compd. A which has a photodegradable functional group in the main chain and is expressed by formula I, and the soln. which is the soln. insoluble in the above-mentioned soln. and contains the compd. B having 2 pieces of the functional groups reacting with the compd. A expressed by the formula I and bringing the compd. A and the compd. B into reaction at the liquid boundary of the two solns. while dispersing or dissolving the core material to be incorporated into the capsule into either of the solns. In the formula I, Z is a part contg. the photofucntional group and is aldehydes, ketones, diketones, peroxides, esters, diazos, onium salts; n, m are positive integers; X1, X2 are an amino group, carboxyl group, hydroxyl group, -N=C=O.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to photodegradable microcapsules that are highly sensitive to ultraviolet rays and visible light, and photosensitive resin compositions using the same. By incorporating a polymerization initiator and a decomposition initiator into the core substance of these photodegradable microcapsules, a highly sensitive photosensitive resin composition can be obtained. Photosensitive resin compositions have a wide range of uses when coated onto various substrates and used as materials such as printing plates and photoresists. Alternatively, a photosensitive image material can be formed by containing pigments, dyes, inks, etc., and can be applied to proofs, etc.

0002

BACKGROUND OF THE INVENTION Conventionally, microcapsule wall films formed by interfacial polymerization include polyester wall films, nylon wall films, and polyurethane wall films. Microcapsule wall membranes are stable against sunlight and various active light rays, and are not suitable for applications where the partition walls are destroyed by light irradiation and the core material is extracted. As an invention for such uses, Japanese Patent Application Laid-Open No. 52-119480
There are publications, etc.

On the other hand, photosensitive resins used as conventional printing plates and photoresist materials use aromatic ketone compounds, benzoin derivatives, aromatic quinone compounds, etc. as photopolymerization initiators, and the sensitivity is low. The resistance to ultraviolet rays is not very high at around 100 mJ/cm2. Furthermore, it shows almost no photosensitivity to visible light.

On the other hand, as well as being effective against ultraviolet rays, with the recent advances in laser technology, lasers for use in laser plate making, printed circuit boards, optical disks, optical memories, holograms, and laser lithography - Development of recording materials is required. At present, laser light sources that provide stable output include argon, helium-neon, YAG, and semiconductor lasers. However, the oscillation wavelength is approximately 5
It is difficult to record with current photosensitive resins containing photopolymerization initiators, as there are wavelengths of 00 nm or more that extend into the infrared region. A highly sensitive photosensitive resin composition using a photopolymerization initiator (hereinafter referred to as a binary photopolymerization initiator) in which an organic dye compound having spectral absorption in the visible light to infrared light region is used as a sensitizer. has been developed (see JP-A-62-31848 and JP-A-63-278907).

[0005]

The above-mentioned microcapsules have low sensitivity to ultraviolet light and require a considerable amount of light irradiation. Furthermore, since it exhibits almost no sensitivity to visible light, it is difficult to use it as a component of the above-mentioned photosensitive resin composition that is highly sensitive to visible light.

Furthermore, although photosensitive resin compositions containing a binary photopolymerization initiator exhibit photosensitivity in the visible light region, their initiator efficiency is low, so they are mainly used for air-cooled argon lasers, etc. It is insufficient in terms of sensitivity as a recording material that uses a low output light source. Therefore, when current photosensitive resins are sensitized with visible light, the time required for sensitization is long, and a high-output laser is required to cause satisfactory photopolymerization, which is uneconomical.

[0007]

[Means to solve the problem] From the above,
As a result of research and development of a photosensitive resin that can be used as a recording material with sufficient sensitivity to low-power light sources, the present inventors found that the general formula (1) having a photodegradable functional group in the main chain :

0
008]

[C3]

A solution containing a compound A represented by (Z is a moiety containing a photofunctional group, such as aldehydes, ketones, diketones, peroxides, esters, diazos, onium salts, etc.); Using a solution that does not dissolve in that solution and contains a compound B that has two or more functional groups that can react with compound A, the core substance is dispersed or dissolved in either solution and the liquid interface between both solutions is used. We have invented photodegradable microcapsules made by reacting Compound A and Compound B.

Further, as a result of various studies on the core material, a new highly sensitive photosensitive resin composition was invented by using an inorganic acid, an organic acid, or a diluted solution thereof.

Furthermore, by dispersing or bonding an organic dye compound to a compound corresponding to Compound A or B, photodegradable microcapsules having photosensitivity in the visible light region can be obtained.

The first photosensitive resin composition comprises photodegradable microcapsules whose core substance is an inorganic acid, an organic acid, or a diluted solution thereof, a binder resin, and a polymerizable ethylenically unsaturated double bond. Compounds with the general formula (
2):

[0013]

[C4]

(In the formula, R1, R2, R3, R4, R5
and R6 are each independently hydrogen, carboxyl group, carboxyalkyl group, carboxyphenyl group, amino group, monoalkylamino group, dialkylamino group, alkoxy group, hydroxy group, or halogen). - A photosensitive resin composition comprising a combination of substituted pyridine derivatives.

The second photosensitive resin composition includes photodegradable microcapsules whose core substance is an inorganic acid, an organic acid, or a diluted solution thereof, a binder resin, and a polymer having a bond that is easily decomposed by an acid. Or a photosensitive resin composition consisting of a combination of oligomers.

[0016] After the first and second photosensitive resin compositions are irradiated with light, they may be further subjected to treatment such as irradiation with actinic light such as electron beams, X-rays, or ultraviolet rays, or heating. do not have.

The appropriate blending ratio of other components in the photosensitive resin composition of the present invention, assuming that the component weight part of the photodegradable microcapsules is 100 parts by weight, will be described below.

The appropriate blending ratio of the binder resin is 4
0 to 2500 parts by weight, preferably 70 to 1000 parts by weight. This range is selected mainly from the viewpoint of good film-forming properties and coating properties.

The appropriate blending ratio of the compound having a polymerizable ethylenically unsaturated double bond is 60 to 3,000 parts by weight, preferably 100 to 1,500 parts by weight. This range is mainly selected from the viewpoint of reactivity.

The amount of the organic dye compound is 1 to 100 parts by weight, preferably 2 to 30 parts by weight. When the amount of the organic dye compound is less than 1 part by weight, its sensitizing effect is not noticeable. On the other hand, if it is more than 100 parts by weight, too much light is absorbed in the surface layer of the organic dye compound itself, resulting in a decrease in photosensitivity.

1,4-substituted pyridine derivatives are 1 to 100
parts by weight, preferably 2 to 50 parts by weight. When the amount of the 1,4-substituted pyridine derivative is less than 1 part by weight, chemical amplification is not noticeable. On the other hand, if the amount exceeds 100 parts by weight, the sensitizing effect of the photosensitive resin composition may be impaired.

[0022] Furthermore, the appropriate blending ratio of polymers or oligomers having bonds that can be easily decomposed by acid is 40 to 40.
2500 parts by weight, preferably 70 to 1000 parts by weight. This range is selected mainly from the viewpoint of good resolution.

Specific examples of the compound A represented by the general formula (1) used in the photodegradable microcapsules of the present invention include 2-oxo-1,3-cyclohexanediacetic acid, 2-oxo-1,4 -cyclohexanediacetic acid, 2-oxo-1
, 5-cyclohexane diacetic acid, 2-oxo-1,6-cyclohexane diacetic acid, 3-oxo-1,6-cyclohexane diacetic acid, 3-oxo-1,5-cyclohexane diacetic acid, 2-oxo-2,4 -(1,4-diacetic acid)cyclohexadiene, 2-oxo-1,4-(1,4-diacetic acid)
Cyclohexadiene, 2-oxo-1,5-(1,4-
diacetic acid) cyclohexadiene, 2-oxo-1,3-cyclopentanediacetic acid, 2-oxo-1,4-cyclopentanediacetic acid, 2-oxo-1,5-cyclopentanediacetic acid, 2,6-diacetic acid -(ethylamino)cyclohexanone,
2,4-di(ethylamino)cyclohexanone, γ-acetylpentamethylenediamine, γ-benzoylhexamethylenediamine, 2,4-di(ω-hydroxypropyl)cyclohexanone, 2,4-di(ω-hydroxybutyl) ) cyclohexanone, 3-(ω-aminopropyl)-ethylamine perbenzoate, 3-(ω-aminopropyl)-ethanol perbenzoate, 3-(ω-aminopropyl)-propanol perbenzoate, 4-(ω- Examples include, but are not limited to, ethanol 4-(ω-carboxypropyl)-perbenzoate, 2,3-dicarbonylhexane glycol, and the like.

Further, the compound B which reacts with the compound A may be selected from the group of compounds listed as examples of the compound A, or may be one that does not contain any other photosensitive group. Examples of those that do not contain photosensitive groups include 1,4-diaminobutane, 1,6-diaminohexane, malonic acid, phthalic acid,
Terephthalic acid, isophthalic acid, succinic acid, glutaric acid,
Adipic acid, pimelic acid, 1,2-diaminoethane, 1
, 3-diaminopropane, 1,4-diaminobutane, 1
-aminoethanol, 1,aminopropanol, 1-aminobutanol, 1-hydroxyacetic acid, 1-hydroxyvaleric acid, ethylene glycol, diethylene glycol,
Examples include, but are not limited to, 1-aminobutyric acid.

Examples of the organic dye compounds used in the present invention include, but are not limited to, coumarin dyes, cyanine dyes, merocyanine dyes, pyrylium dyes, and thiopyrylium dyes.

Coumarin dyes include 3-(2/-benzimidazole)7-N,N-diethylaminocoumarin, 3,3/-carbonylbis(7-diethylaminocoumarin), and 3,3/-carbonylbiscoumarin. ,3,3/
-Carbonylbis(7-methoxycoumarin), 3,3/
-Carbonylbis(5,7-dimethoxycoumarin), 3
,3/-carbonylbis(6-methoxycoumarin),3
, 3/-carbonylbis(7-acetoxycoumarin),
3,3/-carbonylbis(5,7-di-i-propoxycoumarin), 3,3/-carbonylbis(5,7-di-n-propoxycoumarin), 3,3/-carbonylbis(5, 7-di-n-butoxycoumarin), but are not limited to these.

Further, as cyanine or merocyanine dyes, fluorescene, rhodamine, 2'7'-dichlorofluorescene, 3,3'-dicarboxyethyl-2
, 2'-thiocyanine bromide, anhydro-3,3'
-dicarboxymethyl-2,2'-thiocyanine betaine, 1-carboxymethyl-1'-carboxyethyl-
2,2'-quinocyanine bromide, anhydro-3,3
'-dicarboxyethyl-5,5',9-trimethyl-
2,2'-thiacarbocyanine betaine, 3,3'-dihydroxyethyl-5,5'-dimethyl-9-ethyl-
2,2'-thiacarbocyanine bromide, anhydro-
Examples include, but are not limited to, 3,3'-dicarboxymethyl-2,2'-thiacarbocyanine betaine.

Examples of pyrylium or thiopyrylium dyes include 2-amino-4,6-bis(4-butoxyphenyl)thiopyrylium perchlorate and 2-hydroxy-4,6-bis(4-dimethylaminostyryl)pyrylinium. perchlorate, 2-hydroxy-4,6-bis(4-dimethylaminostyryl)pyrylinium fluoroborate, 2-hydroxy-4,6-bis(4-dimethylaminostyryl)thiopyrylinium perchlorate,
2-Hydroxy-4,6-bis(4-dimethylaminostyryl)thiopyrylinium fluoroborate, 2-amino-4,6-bis(4-butoxyphenyl)pyrylium perchlorate, 2-amino-4, Examples include, but are not limited to, 6-bis(4-butoxyphenyl)pyrylium fluoroborate, 2-amino-4,6-bis(4-methoxy-β-ethylstyryl)thiopyrylium fluoroborate, etc. It's not something you can do.

On the other hand, general formula (2):

[0030]

[C5]

(In the formula, R1, R2, R3, R4, R5
and R6 are each independently hydrogen, carboxyl group,
Examples of 1,4-substituted pyridine compounds represented by a carboxyalkyl group, carboxyphenyl group, amino group, monoalkylamino group, dialkylamino group, alkoxy group, hydroxy group, or halogen include 3,
5-dicarboxy-2,6-dimethyl-1,4-dihydroxypyridine, 3,5-dicarboxymethyl-2,6
-dimethyl-1,4-dihydroxypyridine, 3,5-
Dicarboxyethyl-2,6-dimethyl-1,4-dihydroxypyridine, 3,5-dicarboxybutyl-2,
6-dimethyl-1,4-dihydroxypyridine, 3,5
-dicarboxy-t-butyl-2,6-dimethyl-1,
4-dihydroxypyridine, 3,5-dicarboxy-2
, 6-diethyl-1,4-dihydroxypyridine, 3,
5-dicarboxymethyl-2,6-diethyl-1,4-
Dihydroxypyridine, 3,5-dicarboxy-2,4
, 6-trimethylhydroxypyridine, 3,5-dicarboxy-4-ethyl-2,6-dimethylhydroxypyridine, 3,5-dicarboxy-2,6-dimethyl-1,
4-dimethylpyridine, 3,5-dicarboxy-2,6
Examples include, but are not limited to, -diethyl-1,4-dimethylpyridine and 3,5-dicarboxy-2,6-dimethyl-1,4-diethylpyridine.

Further, as an example of a polymer or oligomer having a bond that can be easily decomposed with an acid, poly(α,α-
dimethylbenzyl methacrylate), poly(α,α-diethylbenzyl methacrylate), poly(α-methylbenzyl methacrylate), poly(4-t-butylcarboxystyrene), polymethyl acrylate, polyethyl acrylate, polybutyl acrylate , polyacrylic acid-i
-butyl, poly-t-butyl acrylate, poly-butyl methacrylate, poly-t-butyl methacrylate, poly-t-butyl methacrylate, poly(p-methylcarboxystyrene), polyphthalaldehyde, etc. However, it is not limited to these.

In addition, the binder resin in the present invention includes a vinyl addition polymerization type resin, a condensation type resin such as a polyester type, a polyurethane type, a polyamide type, etc.
Preferably, the weight average molecular weight is about 10,000 to 500,000,
Examples of this resin include (meth)acrylic acid, (meth)
Acrylic ester, maleic acid, fumaric acid, maleic ester, fumaric ester, ethylene glycol,
Examples include copolymers of styrene, vinyl chloride, etc., but are not limited to these.

Finally, examples of compounds having a polymerizable ethylenically unsaturated double bond in the molecule include acrylic acid, methacrylic acid, (meth)acrylic acid ester, pentaerythritol tri(meth)acrylate, Trimethylolpropane tri(meth)acrylate, ethylene glycol
unsaturated acid esters such as di(meth)acrylate, and styrene, acrylamide, acrylonitrile, N-
Examples include vinylpyrrolidone, vinyl acetate, various unsaturated polyesters, unsaturated polyethers, unsaturated polyurethanes, and (meth)acrylate compounds having epoxy groups, but are not limited to these.

On the other hand, the photodegradable microcapsules of the present invention are highly sensitive to ultraviolet to visible light, and can be used as a component of a highly sensitive photosensitive resin composition. Furthermore, the photosensitive resin composition of the present invention using these photodegradable microcapsules has a binder as described above.
A compound having an ethylenically unsaturated double bond that can be polymerized with a resin, a 1,4-substituted pyridine compound, and a photodegradable microcapsule, or a binder resin and a polymer or oligomer having a bond that easily decomposes with an acid and a photodegradable compound. A highly sensitive recording material can be obtained by mixing these components of the sensitive microcapsules in appropriate proportions.

[0036]

[Operation] The photodegradable microcapsules of the present invention can be
Easily decomposed by active light such as X-rays and ultraviolet rays. Furthermore, by containing an organic dye compound, it can be decomposed even in the visible light region.

[0037] Furthermore, the core substance of the present invention may be an inorganic acid, an organic acid,
Alternatively, a photosensitive resin composition consisting of photodegradable microcapsules that are diluted solutions thereof, a binder resin, a compound having a polymerizable ethylenically unsaturated double bond, and a 1,4-substituted pyridine derivative is photodegradable. The 1,4-substituted pyridine derivative is decomposed by the acid released as the microcapsule collapses to generate radicals, thereby polymerizing a compound having an ethylenically unsaturated double bond.

Furthermore, the core material of the present invention is a photosensitive material comprising a combination of photodegradable microcapsules in which the core material is an inorganic acid, an organic acid, or a diluted solution thereof, a binder resin, and a polymer or oligomer having a bond that can be easily decomposed with an acid. In the photodegradable microcapsules, the polymer or oligomer having bonds that can be easily decomposed by acid is decomposed by the acid released when the photodegradable microcapsules disintegrate.

[0039]

[Effects] The photodegradable microcapsules of the present invention can be used in a wide variety of optical recording materials and photosensitive resin compositions by selecting various core materials. In addition, the photosensitive resin composition of the present invention becomes a useful recording material that can sufficiently cope with low-power visible light sources. Further, by coating the photosensitive resin composition of the present invention on various substrates, laser direct printing plates, printed circuit boards, optical disks, optical memories, holograms, and photoresists can be obtained.

[0040]

EXAMPLES The details of the present invention will be explained below with reference to Examples and Comparative Examples, but the present invention is not limited thereto. <Example 1> γ-acetylpentamethylenediamine 50
parts by weight are mixed with 50 parts by weight of 1N hydrochloric acid. Next, this was added dropwise to a solution of 100 parts by weight of ethyl acetate and 50 parts by weight of 2-oxo-1,3-cyclohexane diacetic acid with stirring at room temperature, and the stirring speed was adjusted so as to form smiling droplets. do. Further, when the reaction temperature was raised to 70° C. and stirred for 20 hours, photodegradable microcapsules containing 1N hydrochloric acid were obtained. The microcapsules were dispersed in neutral water, irradiated with light, and then examined with pH test paper, which clearly showed acidity.

Example 2 50 parts by weight of γ-acetylpentamethylenediamine are mixed with 50 parts by weight of 1N hydrochloric acid. Next, add 2-oxo-1 to 100 parts by weight of ethyl acetate.
, 50 parts by weight of 3-cyclohexane diacetic acid and the organic dye compound 3-(2/-benzimidazole)7-N
, N-diethylaminocoumarin and the solution is added dropwise at room temperature with stirring, and the stirring speed is adjusted to form minute droplets. Further, when the reaction temperature was raised to 70° C. and stirred for 20 hours, photodegradable microcapsules containing 1N hydrochloric acid were obtained. The microcapsules were dispersed in neutral water, irradiated with monochromatic light of 450 nm, and then examined with pH test paper, which clearly showed acidity.

Example 3 25 parts by weight of black ink and 50 parts by weight of 2-oxo-1,4-(1,4-diacetic acid)cyclohexadiene are mixed with 50 parts by weight of methyl ethyl ketone. Next, this was added dropwise to a solution of 50 parts by weight of γ-acetylhexamethylene glycol in 100 parts by weight of water while stirring at room temperature, and the reaction temperature was further raised to 50°C and stirred for 15 hours to form a black ink. Photodegradable microcapsules containing . When these microcapsules were irradiated with light on white paper, ink adhered to the white paper.

<Example 4> 50 parts by weight of the photodegradable microcapsules of Example 2, a copolymer of methyl methacrylate, 2-ethylhexyl acrylate and methacrylic acid (polymerization ratio: methyl methacrylate) (2-ethylhexyl acrylate: methacrylic acid = 60:20:20)
100 parts by weight and 140 parts by weight of pentaerythritol triacrylate are uniformly dispersed in 1100 parts by weight of methyl ethyl ketone. To this solution, 10 parts by weight of 3,5-dicarboxyethyl-2,6-dimethyl-1,4-dihydropyridine was added, and the mixture was stirred until homogeneous to obtain a photosensitive liquid. Further, this photosensitive liquid was applied onto an aluminum plate using a spin coater so that the dry film thickness was approximately 2 μm, and the photosensitive layer was prepared by drying in a dryer at 70° C. for 2 minutes. Hereinafter, this will be referred to as a test board.

A photomask with a pattern is closely attached to the test plate, 450 nm light is irradiated onto it, and after further heating at 100°C for 10 minutes, it is developed with a 0.1% sodium hydroxide aqueous solution to form a negative image. I was able to get

<Example 5> 50 parts by weight of the photodegradable microcapsules of Example 2 and 300 parts by weight of poly(4-t-butylcarboxy)-styrene are uniformly dispersed in 1000 parts by weight of ethyl acetate. Furthermore, this photosensitive liquid was spin-coated.
A photosensitive layer was prepared by coating the photosensitive layer on an aluminum plate to a dry film thickness of about 2 μm using a dryer and drying it at 70° C. for 2 minutes in a dryer. Hereinafter, this will be referred to as a test board.

A photomask with a pattern was placed in close contact with the test plate, 450 nm light was irradiated onto it, and after further heating at 100°C for 10 minutes, it was developed with a 0.1% aqueous sodium hydroxide solution to form a positive image. I was able to get

Claims (5)

[Claims] Claim 1: General formula (
1): [Chemical 1] (Z is a moiety containing a photofunctional group, and is an aldehyde,
Ketones, diketones, peroxides, esters, diazos, onium salts, n and m are positive integers, and
1,X2 is an amino group, a carboxyl group, a hydroxyl group, or -N=C=O. ) A solution containing compound A represented by formula (1), and a compound B that does not dissolve in the solution and has two or more functional groups that can react with the above general formula (1).
A photodegradable product characterized in that the core material contained in the capsule is dispersed or dissolved in either solution, and Compound A and Compound B are reacted at the liquid interface of both solutions. Microcapsule. 2. The photodegradable microcapsules according to claim 1, wherein the compound A or compound B has photosensitivity in the visible light region by dispersing or bonding an organic dye compound thereto. 3. The photodegradable microcapsule according to claim 1 or 2, wherein the core substance is an inorganic acid, an organic acid, or a diluted solution thereof. 4. The photodegradable microcapsule according to claim 3, a binder resin, a compound having a polymerizable ethylenically unsaturated double bond, and the general formula (2): [Formula 2] (wherein, R1 , R2, R3, R4, R5 and R6 are each independently hydrogen, carboxyl group, carboxyalkyl group, carboxyphenyl group, amino group, monoalkylamino group, dialkylamino group, alkoxy group, hydroxy group, or halogen) 1,4- expressed as
A photosensitive resin composition comprising a combination of substituted pyridine derivatives. 5. A photosensitive resin composition comprising a combination of the photodegradable microcapsules according to claim 3, a binder resin, and a polymer or oligomer having a bond that is easily decomposed by acid.