JPS5841288B2 - Photoinsolubilizable resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a novel photoinsolubilizable resin composition, particularly a photosensitive resin having a nitrogen-containing heterocyclic residue in its molecule as a photocrosslinkable residue, and an acid. The present invention relates to a photoinsolubilizable resin composition.

Photosensitive resins are used as printing plate manufacturing materials, photoresists for photoetching, photomilling, and the like, and as photosensitive vehicles for paints, printing inks, and the like.

Typical photosensitive resins that have been put into practical use include those having photocrosslinkable residues such as azide groups, cinnamoyl groups, and acryloyl groups.

However, it is practically necessary to introduce these photocrosslinkable residues into the base polymer in a fairly large amount, and the reality is that these photosensitive resins are mixed with a sensitizer.

For example, polyvinyl cinnamate into which cinnamoyl groups have been introduced, which is a typical photosensitive resin, must have a large amount of cinnamoyl groups, which are photocrosslinkable residues, in the base polymer in order to be put to practical use as a photosensitive resin. (M, Tsuda: J, Poly, S
ci, A, 2.290464).

Moreover, in practical use, it is necessary to use a sensitizer in an amount of about 10% by weight.

This means that these conventionally used photosensitive resins require a large amount of raw material for introducing photocrosslinkable residues, which is much more expensive than the resin component raw material, and that The introduction of photocrosslinkable residues changes the original properties of the base polymer, such as adhesion to substrates, developability, chemical resistance, and printability, and these properties usually decrease or worsen. Therefore, it has to be selected depending on the purpose of use, which has the disadvantage of severely limiting its use.

In order to improve these practical disadvantages, photosensitive resins with special photocrosslinkable residues have been proposed, such as polyvinyl alcohol with styryl quaternary salt residues ( (Japanese Patent Publication No. 56-5761, Japanese Unexamined Patent Publication No. 11906/1982).

However, such photosensitive resins using polyvinyl alcohol as a backbone polymer have a disadvantage in that they are extremely hydrophilic and can only use water or an aqueous organic solvent containing water as a developer.

The present inventor took advantage of the excellent photo-crosslinking properties of styryl quaternary salts, and discovered that although the photosensitivity is lowered, the non-quaternized styryl nitrogen-containing heterocycles have excellent solubility and quaternary salts in their side chains. As a result of extensive research to develop a photosensitive resin that combines the higher sensitivity characteristics that can be obtained by grading, we have developed a polymer compound with a non-quaternized styryl nitrogen-containing heterocycle in its side chain. It has been found that a composition to which an acid is added can be an excellent photosensitive resin material.

That is, the present invention uses styryl represented by the general formula -* (wherein R1 represents a hydrogen atom or an alkoxy group, and Z represents an atomic group forming an aromatic heterocycle) as a photocrosslinkable residue. At least 0.2 mol% of nitrogen-containing heterocyclic residues
Provided is a photo-insolubilizable resin composition containing a photo-insolubilizable resin in an amount of 0.5 to 10 times the molar amount of an organic or inorganic acid based on the nitrogen-containing heterocyclic residue contained in the resin. It is something to do.

Examples of the aromatic heterocycle contained in the above general formula (I) conjugated with a double bond introduced into the resin in the present invention include the following examples.

These rings may be nuclearly substituted with an alkyl group, an alkoxy group or a hydroxyl group.

The base polymer into which the styryl nitrogen-containing heterocycle is introduced is not particularly limited, but includes hydrolyzates of vinyl acetate polymers or copolymers, olefin polymers or copolymers,
Polymers or copolymers of acrylic acid or methacrylic acid are suitable.

The photoinsolubilizable resin used in the present invention has the above general formula (I).
It is necessary that at least 0.2 mol% of a photocrosslinkable residue having the structure represented by is introduced.

If it is less than 0.2 mol%, a practically usable photoinsolubilizable resin composition cannot be obtained, and if the introduction rate of the photocrosslinkable residue is too high, it will adversely affect the desired properties of the resin, and This is not preferred because the material cost increases significantly.

This photo-insolubilizable resin has a molecular weight of 2000 to 1oooooo
A value of approximately 0 is practical, while a value of less than 2,000 is not preferred because it requires a significantly long irradiation time for insolubilization.

Further, those having a molecular weight of 1,000,000 or more have a marked increase in viscosity, and therefore have difficulty in workability or applicability.

The preferred molecular weight range is about 10,000 to 300,000.

The basicity of the nitrogen-containing heterocycle contained in general formula (I) varies somewhat depending on its type, but is usually in the range of about 0.6 to 7 in terms of pKa.

Such a resin composition of the present invention is usually produced by dissolving the resin component in a solvent and adding an acid thereto, but the introduction rate of photocrosslinkable residues introduced into the resin is Even if the content is as small as, for example, 1 mol % or less, it is possible to provide a highly sensitive photon-soluble resin material that is far superior to conventionally commercially available and practically used photosensitive materials.

The composition of the present invention includes a resin containing a styryl nitrogen-containing ring residue represented by the above general formula in a proportion of at least 0.2 mol% based on the nitrogen-containing heterocycle contained in the resin. It is prepared by adding 0.5 to 10 times the molar amount of organic or inorganic acid.

If the amount added is less than 0.5 times the mole, the effect of improving sensitivity will be insufficient, and if the amount added exceeds 10 times the mole, the effect of improving the sensitivity will be rather reduced and will have an adverse effect on the properties of the resin, which is not desirable.

The preferred addition amount is 1 to 5 times the mole.

It was completely unexpected that by adding an acid, a sensitivity higher than that of the commercially available product was obtained, even though the resin itself had a considerably lower photosensitivity than the commercially available product. .

The reason for this drastic improvement in sensitivity due to the addition of acid is not clear, but it is clear that the acid-containing resin composition has a general formula (wherein R1 and Z have the same meanings as above, and It is presumed that the photosensitivity increases due to the change to the quaternized structure represented by (representing the residue).

Examples of acids used in the composition of the present invention include hydrochloric acid,
Inorganic acids such as perchloric acid, phosphoric acid, sulfuric acid, nitric acid, acetic acid,
Chloroacetic acid, lactic acid, tartaric acid, benzoic acid, nitrobenzoic acid, benzenesulfonic acid, naphthalenesulfonic acid, p-1
- Organic acids such as luenesulfonic acid and methanesulfonic acid are representative examples.

These acids may be used alone or in combination of two or more.

In addition, when the resin is water-soluble and water is used as a solvent,
Although an inorganic acid or an organic acid may be used, it is more advantageous to use an organic acid when an organic solvent is used.

Furthermore, the type and amount of the acid added depends on the basicity of the heterocycle of the photocrosslinkable residue as described above; for example, in the case of a strong base (pKa-5, 23) such as a pyridine ring, A strong acid can be advantageously used, and an equimolar amount is sufficient, whereas a weak acid is used in an amount of about 2 to 5 times the molar amount.

In the composition of the present invention, the photosensitive resin has a
The photocrosslinkable residues undergo a trimerization reaction to form a cyclobutane ring, which creates crosslinks between linear chains of the polymer, making it insolubilized in solvents.

A film containing a resin that has been crosslinked and insolubilized by irradiation with light is usually developed with a photosensitive resin solvent, and the resin that has not been exposed to light is dissolved to form a residual image.

At this time, it will be easier if a basic substance is added to the developing solvent.

Alternatively, add a basic substance to a solvent that does not dissolve the resin,
After the exposed sensitive coating film is immersed, it may be developed using a soluble solvent.

Examples of basic substances added to the solvent in such development processing include inorganic substances such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium bicarbonate, sodium carbonate, and ammonia, as well as pyridine, triethylamine, Organic basic substances such as dimethylamine and diethylamine can be mentioned.

Furthermore, examples of weak basic substances include dimethylformamide, formamide, dimethylacetamide, N-methylpyrrolidone, tetramethylurea, and dimethylsulfoxide.

Although not basic, methanol, ethanol, methoxyethanol, ethoxyethanol, acetone, tetrahydrofuran, dioxane, water, etc. are often effective and may be included in the basic substances.

Weak basic substances, water, etc. are conveniently used when the heterocycle of the photosensitive group has weak basicity.

The photon-soluble resin composition of the present invention can be used not only as a material for printing plates and a material for resists, but also as a base for printing inks and paints.

Furthermore, since the composition of the present invention is photoinsolubilized with excellent sensitivity in the long wavelength region, by utilizing this property, it is extremely useful as a photosensitive material for lasers and an enlarged copying material.

Next, the present invention will be explained in more detail with reference to Examples.

Examples 1-4 4-methylquinoline 26.73P and vanillin 31.25
After refluxing f in 62.91 acetic anhydride overnight and treating the reaction mixture with alkali, the resulting product was recrystallized from butyl cellosolve to give 4-(
2-(4-hydroxy-3-methoxyphenyl)ethynyl]quinoline 29f was obtained.

This compound 0.55f, triethylamine L75? , 4-[2-(
4-Methacroyloxy-3-methoxyphenyl)ethynyl]quinoline 4.70f (yield: 80.3%) was obtained.

This was recrystallized from ethyl acetate, and its structure was confirmed by infrared absorption spectrum and elemental analysis.

The obtained quinoline derivative was mixed with methyl methacrylate (MMA
) under the conditions shown in Table 1, and the copolymerization solution was added to methanol to precipitate and separate the resin.

All of these resins showed an absorption maximum at 335 nm.

The copolymer of 4-[2-(4-methacryloyloxy-3-methoxyphenyl)ethynyl]quinoline and MMA thus obtained was dissolved in 1.2 dichloroethane, and the copolymer was dissolved in 1.2 dichloroethane at 7/L/min with a spinner. It was applied to a plate, and the photosensitivity was measured by the grayscale method using a xenon lamp as a light source.

Table 2 shows the relative results of the sensitivity when 1,2-dichloroethane was used as the developer with respect to the value shown by commercially available TPR (manufactured by Tokyo Ohka Co., Ltd.).

In addition, in the experiment, these resins were dissolved in 1.2 dichloroethane, and 1 to 1 O was added per mole of photocrosslinkable residue.
The photosensitivity was measured in the same manner as above using the liquids to which molar equivalents of p-)luenesulfonic acid were added, and the results are also summarized in Table 2.

It has been found that the photosensitivity of the resin itself can be greatly improved by adding p-)luenesulfonic acid from the Kono group.

Furthermore, the lower the introduction rate of photocrosslinkable residues (2 mol %), the better the sensitivity.

Example 5 γ-picoline 20. 4-1:2-(4-hydroxyphenyl)ethynyl]hyrisine 21 obtained by reacting C1 with 26.2f of p-hydroxybenzaldehyde in 65.8f of acetic anhydride was dissolved in 10Cr/l dimethylacetamide. , further added 1.23 P of triethylamine, and then added 1.3 P of methacrylic acid chloride while cooling with water.
4P was added dropwise.

After the reaction was completed, water was added to precipitate crystals and separated.

This was recrystallized using a mixed solvent of ethyl acetate and hexane to give 4-[2-(4-methacryloyloxyphenyl)
Ethynyl]hyricin 2.16f (yield 80%) was obtained.

The crystal mp was 156-158°C.

The obtained pyridine derivative 398rn9 and MMA2.85
′? were added to 3 ml of benzene, 15 ml of AIBN was added, and the mixture was polymerized by heating at 60° C. in a degassed sealed tube.

After the reaction was completed, the product was poured into methanol to precipitate the resin.

Although this resin exhibits only about 1/20 the photosensitivity of the commercially available TPR, by placing the thin film in an atmosphere of hydrogen chloride gas, the sensitivity was improved to 0.8 times that of TPR.

Furthermore, the sensitivity of a resin composition prepared by adding p-toluenesulfonic acid in an equimolar amount to the photocrosslinkable residue to a 1,2-dichloroethane solution of this resin was almost the same as that of TPR.

Example 6 In the same manner as in Example 1, 2-methylbenzothiazole 9
．． 77'if, vanillin 9.97P and acetic anhydride 16.
72f, 2-[2-(3-methoxy4-hydroxy)ethynyl]benzothiazole was obtained.

This was methacryloylated in the same manner as in Example 1 to obtain 2-(2-(3-methoxy-4-methacryloyloxy)ethynyl)benzothiazole in a yield of 80%.

This chemical structure was confirmed and identified by infrared absorption spectroscopy and elemental analysis.

Obtained benzothiazole derivative 125 having polymerization ability
．． 51 ng was added to 1.5 l of benzene together with MMAl, 01', and polymerized using a 51n9 AIBN catalyst in a degassed sealed tube at a temperature of 60°C.

After polymerization, the contents were poured into methanol to precipitate and settle,
Separated and dried.

This resin showed an absorption maximum value at 3481 m in chloroform.

When the sensitivity of the obtained resin was measured in the same manner as in Examples 1 to 4, it showed twice the sensitivity of TPR.

In a chloroform solution of this resin, 2
The sensitivity of the composition to which twice the molar amount of p-toluenesulfonic acid was added was improved to about 10 times that of TPR.

Examples 7 and 8 2-methylquinoline 34.41' and vanillin 36.51
was reacted in 61.341 ml of acetic anhydride under reflux for 16 hours, and then 50 cr/1 of acetic acid was distilled off.

Add 250c of 3N hydrochloric acid to the residue! was added, heated for 1 hour, cooled, and the precipitated crystals were separated.

The crystals were suspended in aqueous ammonia and stirred for 1 hour to remove hydrogen chloride from the crystals, and the dehydrochlorinated crystals were filtered again and collected.

This was recrystallized from 2-ethoxyethanol and 2-(
2-(4-hydroxy-3-methoxyphenyl)ethynyl]quinoline was obtained in a yield of 63%.

2.771 of the obtained quinoline derivative was mixed with 5 cr of dimethylacetamide! , and then dissolve glycidyl methacrylate 1.42P and tetrabutylammonium chloride o, i
oy was added, and the mixture was heated and reacted at 90 to 100°C for 5 hours.

Water was added to the reaction mixture, and the separated oil was extracted with ethyl acetate, thoroughly washed with water, and dried.

After distilling off the solvent, 2-(2-C3-methoxy-4-(2-hydroxy-3-methacryloyloxypropyloxy)phenyl]ethynyl)quinoline was obtained by separating and purifying with silica gel chromatography in a yield of 50%. Ta.

By recrystallizing this using methyl acetate-hexane, a pure product with mpH of 9°C was obtained.

This was confirmed to be the above chemical substance by elemental analysis and infrared absorption spectrum.

The obtained high-purity quinoline derivative was copolymerized with MMA to produce a photosensitive resin having an extremely thick absorption at 359 Hm.

The production conditions for two types of resins with different amounts of quinoline derivative and MMA are shown in Table 3 below. Table 4 summarizes the relative sensitivities to the TPR sensitivities of the compositions to which p-)luenesulfonic acid was added.

In the case of a composition containing the acid, development was performed using 1,2-dichloroethane containing a small amount of dimethylformamide.

In addition, 3 ca of benzene was used as the polymerization medium.

From the above table, in the quinoline derivative-MMA copolymer,
Those with a photocrosslinkable residue introduction rate of 2 mol% are TP alone.
Although the sensitivity is weaker than that of R, the sensitivity of the composition in which p-)luenesulfonic acid is added in twice the molar amount relative to the photocrosslinkable residue increases to more than four times, and the sensitivity of the composition increases by more than four times. rate 5 mol%
It can be seen that although the photocrosslinkable residue introduction rate is far lower than that of the commercially available product, it is equivalent or more sensitive by itself, and the sensitivity is improved 10 times by addition of an acid.

In addition, in the above sample resin with a photocrosslinkable residue introduction rate of 5 mol%,
TPR was obtained by adding 10 times the molar amount of acetic acid to the photocrosslinkable residue and applying this to an aluminum plate using a spinner.
It showed 6 times the sensitivity compared to .

Example 9 2-(2-(3-methoxy-※※4-
(2-Hydroxy-3-methacryloyloxypropyloxy)phenyl]ethynyl)quinoline 77.6rI1
9 with methyl methacrylate 3901n9 and methacrylic acid n
Polymerization was carried out in 1♂ of benzene with 750 μl of -butyl using AIBN51n9 as a polymerization initiator.

Polymerization was carried out by keeping the above mixture at a temperature of 60 to 65° C. for 20 hours in a degassed sealed tube.

After polymerization, the tube was shaken and the contents were poured into methanol to precipitate and isolate the resin.

This resin showed only 1/20 the sensitivity of TPR, but when exposed to a hydrogen chloride gas atmosphere, it showed a sensitivity of about 3 that of TPR.

Examples 10 and 11 2-(2-[3-methoxy-4-(2-hydroxy-3
-methacryloyloxypropyloxy)phenyl]ethynyl)quinoline with MMA and acrylonitrile (AN)
) to produce two types of terpolymers having the compositions shown in Table 5.

In the polymerization, 1.5i benzene was used as a reaction medium, and 2-51n9 AIBN was used in both cases.

2 for the resulting resin and its photocrosslinkable residues.
The relative sensitivity to TPR of each composition to which twice the molar amount of p-)luenesulfonic acid was added was examined.

The results are also listed in Table 5. Both resins have excellent relative sensitivity (6 times) without addition of acid, but with the addition of acid, a sensitivity approximately 60 times higher than that of TPR is obtained.

Examples 12-14 2-(2-(3-methoxy-4-(2-hydroxy-3
-Methacryloyloxypropyloxy3phenyl]ethynyl)quinoline 38.8■ to methyl methacrylate 79
A terpolymer having the composition shown in Table 6 was produced by radical polymerization in benzene for 4 hours with the acrylic monomer shown in Table 6.

At this time, the amount charged was adjusted so that the photosensitive group component was 1 mol %.

Regarding the composition in which p-toluenesulfonic acid was added in twice the molar amount relative to the photocrosslinkable residue of the obtained resin, T
The relative sensitivity to PR was investigated.

The results are also listed in Table 6.

Claims (1)

[Claims] 1. As a photocrosslinkable residue, a styryl group represented by the general formula (wherein R1 represents a hydrogen atom or an alkoxy group, and Z represents an atomic group forming an aromatic heterocycle) At least 0.2 mol% of nitrogen-containing heterocyclic residues
A photo-insolubilizable resin composition comprising a photo-insolubilizable resin contained in an amount of 0.5 to 10 times the mole of an organic or inorganic acid based on the nitrogen-containing heterocyclic residue contained in the resin. 2 The organic acid is acetic acid, chloroacetic acid, benzoic acid, nitrobenzoic acid, benzenesulfonic acid, naphthalenesulfonic acid,
A composition according to claim 1, wherein the composition is selected from p-)luenesulfonic acid and methanesulfonic acid. 3. The composition according to claim 1, wherein the inorganic acid is selected from hydrochloric acid, perchloric acid, phosphoric acid, sulfuric acid and nitric acid.