JP2001092132A - Photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition capable of forming a relief having enhanced aging stability of photosensitivity and enhanced plate wear property. SOLUTION: The photosensitive resin composition contains a polyamide containing a unit of formula I and a unit of formula II and/or a unit of formula III and having a terminal acryloyl group and/or a terminal methacryloyl group as a soluble high molecular compound. In formula I, R1 is a >=5C alkylene. In formula II, R2 is a 2-10C alkylene, an aromatic group or an alicyclic group and R3 and R4 are each a 1-5C alkylene. In formula III, R5 is a 2-10C alkylene, an aromatic group or an alicyclic group and R6 is a 2-3C alkylene.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a photosensitive resin composition, and more particularly to a photosensitive resin composition for producing a relief plate for printing.

[0002]

2. Description of the Related Art In general, a photosensitive resin composition used for a relief plate for printing contains a soluble polymer compound (hereinafter also referred to as a filling polymer), a photopolymerizable unsaturated compound and a photopolymerization initiator as essential components. If necessary, additives such as a stabilizer and a plasticizer are compounded.

[0003] Among the above-mentioned essential components, the characteristics of the filled polymer in particular greatly affect the physical properties of the photosensitive resin composition and the performance of the relief plate for printing. For this reason, the filled polymer must have (a) good solubility in an appropriate solvent, and (b) be combined with a polymer obtained by polymerizing the photopolymerizable monomer, and be insolubilized by curing. (C) It is required to have excellent transparency, abrasion resistance after insolubilization, excellent solvent resistance, and the like, and polyamides have been widely used as suitable for such requirements. In recent years, water development has been the mainstream in terms of handleability and cost, and polyamides excellent in water solubility (water dispersibility) have been used in many respects.

[0004] The photosensitive resin composition is usually formed into a sheet and stored after being made into a photosensitive resin master (raw plate).
When necessary, light irradiation and development are performed to produce a relief (plate material). However, the photosensitive resin composition using polyamide (photosensitive resin original plate) has low photosensitivity stability over time and is stored. However, there is a problem that the light sensitivity is reduced during the operation.

[0005]

SUMMARY OF THE INVENTION In view of the above circumstances, an object of the present invention is to provide a photosensitive resin composition having excellent photosensitivity over time while using polyamide as a filling polymer. Another object of the present invention is to provide a photosensitive resin composition which is excellent in stability over time of photosensitivity and can form a relief having improved printing durability as compared with the related art.

[0006]

In order to achieve the above object,
The present inventors have conducted intensive studies and as a result, when a terminal-modified polyamide having an acryloyl group and / or a methacryloyl group introduced into the terminal of the polyamide is used as the filling polymer, a decrease in the photosensitivity of the photosensitive resin composition over time is suppressed. Have been found, and based on the knowledge, the present invention has been completed.

That is, the present invention has the following features. (1) A photosensitive resin composition containing a soluble polymer compound, a photopolymerizable unsaturated compound and a photopolymerization initiator, wherein the soluble polymer compound is a unit represented by the following general formula (I) And a polyamide comprising a unit represented by the following general formula (II) and / or a unit represented by the following general formula (III), and having an acryloyl group and / or a methacryloyl group at a terminal. Photosensitive resin composition.

[0008]

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(In the formula, R ¹ is an alkylene group having 5 or more carbon atoms.)

[0010]

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Wherein R ² is an alkylene group having 2 to 10 carbon atoms, an aromatic group or an alicyclic group, and R ³ and R ⁴ are each an alkylene group having 1 to 5 carbon atoms. )

[0012]

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(Wherein, R ⁵ is an alkylene group having 2 to 10 carbon atoms, an aromatic group or an alicyclic group, and R ⁶ is an alkylene group having 2 to 3 carbon atoms). The acryloyl group and / or methacryloyl group content in the polyamide is 0.05 to 0.5 mol / k;
g. The photosensitive resin composition according to (1) above,

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The photosensitive resin composition of the present invention comprises a unit represented by the general formula (I) and a compound represented by the general formula (II)
And / or a unit having an acryloyl group and / or a methacryloyl group at a terminal, which contains a unit represented by the general formula (III) and / or a unit represented by the general formula (III). Saturated compound, photopolymerization initiator as an essential component, if necessary,
It is configured to contain additives such as a stabilizer and a plasticizer.

The polyamide represented by the general formula (I)
Is a unit having 6 or more carbon atoms (6 to 12 carbon atoms).
Is preferable), a condensed residue of an ω-amino acid or a lactam. As the ω-amino acid, aminocaproic acid, aminoheptanoic acid, aminocaprylic acid, aminolauric acid and the like are preferable, and as the lactam, ε-caprolactam,
ω-Laurolactam and the like are preferred. By using these ω-amino acids and lactams as copolymer components, these units can be introduced into polyamide.

The unit represented by the general formula (II) is a condensed residue of a dicarboxylate of an amino compound (diamine) having a piperazine ring. Wherein the number of carbon atoms represented by R ² is 2
The alkylene group of 10 to 10 is preferably a linear group such as an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, an octamethylene group, a decamethylene group, and the like. Groups are preferred, and the cycloaliphatic group is preferably a cyclohexylene group. Wherein -CO to CO- are aliphatic;
Indicates a residue of an aromatic or alicyclic dicarboxylic acid, and the aliphatic, aromatic or alicyclic dicarboxylic acid includes succinic acid, adipic acid, glutaric acid, azelaic acid, sebacic acid, decanedicarboxylic acid, and terephthalic acid , Isophthalic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and the like. In the formula, the alkylene group having 1 to 5 carbon atoms represented by R ³ and R ⁴ is preferably a methylene group, an ethylene group, a trimethylene group, a 1-ethyl-trimethylene group, or the like. In the formula, -NH to NH- represent a residue of a diamine having a piperazine ring, and examples of the diamine having a piperazine ring include N, N'-bis (aminomethyl) -piperazine and N, N'-bis (β -Aminoethyl) -piperazine, N, N'-bis ([gamma] -aminopropyl) piperazine, N, N'-bis ([gamma] -aminopentyl) piperazine and the like are preferred examples. The general formula (II)
Can be introduced into a polyamide by using a salt of the above diamine having a piperazine ring and an aliphatic, aromatic or alicyclic dicarboxylic acid as a copolymerization component.

The unit represented by the general formula (III) is a condensed residue of a dicarboxylic acid salt of an amino compound having a piperazine ring, wherein one imino group of the piperazine ring and one carboxyl group of the dicarboxylic acid are dehydrated and condensed. Is the residue As the alkylene group having 2 to 10 carbon atoms represented by R ⁵ in the formula, straight-chain groups such as ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, and decamethylene group. A chain is preferred, and a phenylene group is preferred as the aromatic group, and a cyclohexylene group is preferred as the alicyclic group. In the formula, -CO to CO- represent a residue of an aliphatic, aromatic or alicyclic dicarboxylic acid, and the aliphatic, aromatic or alicyclic dicarboxylic acid includes succinic acid, adipic acid,
Preferred examples include glutaric acid, azelaic acid, sebacic acid, decanedicarboxylic acid, terephthalic acid, isophthalic acid, 1,3-cyclohexanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid. In the formula, examples of the alkylene group having 2 to 3 carbon atoms represented by R ⁶ include an ethylene group, a trimethylene group, and a propylene group. In the formula, -N to NH- represent a residue of an amino compound having a piperazine ring. Examples of the amino compound having a piperazine ring include N- (β-aminoethyl) piperazine,
-(Β-aminopropyl) piperazine, N- (γ-aminopropyl) piperazine and the like. The unit represented by the general formula (III) is introduced into a polyamide by using a salt of the above-mentioned amino compound having a piperazine ring and an aliphatic, aromatic or alicyclic dicarboxylic acid as a copolymerization component. be able to.

The polyamide may be a condensed residue of the above ω-amino acid or lactam (unit of the general formula (I)) and a condensed residue of a dicarboxylic acid salt of an amino compound having a piperazine ring (the unit of the general formula (II) and / or General formula (II
Units other than the unit (I)) may be included, and when such units are included, dicarboxylic acid, diamine, or the like used for normal polymerization of polyamide is used as a copolymer component to convert these units into polyamide. To be introduced. Such dicarboxylic acids include, for example, succinic acid, adipic acid, glutaric acid, azelaic acid, sebacic acid, decanedicarboxylic acid, aliphatic, aromatic or alicyclic dicarboxylic acids such as terephthalic acid, isophthalic acid and cyclohexanedicarboxylic acid And these lower alkyl esters,
And acid halides. As a diamine,
For example, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, heptamethylene diamine, octamethylene diamine, nonamethylene diamine,
Examples thereof include aliphatic, aromatic or alicyclic diamines such as decamethylenediamine, metaxylylenediamine, paraxylylenediamine, and cyclohexanebismethylamine.

The polyamide used in the present invention is, as described above, a component comprising a condensed residue of ω-amino acid or lactam (unit of the general formula (I)) (hereinafter referred to as component A).
And a component consisting of a condensed residue of a dicarboxylate of an amino compound having a piperazine ring (unit of the general formula (II) and / or unit of the general formula (III)) (hereinafter, referred to as component B). Thereby, a filled polymer which gives the photosensitive resin composition extremely good physical properties can be obtained. That is,
It is excellent in transparency, the photo-curing progresses promptly by short-time light irradiation, sufficient insolubilization occurs in a short time, and the non-light-irradiated portion is easily washed and removed with water. In addition, the mechanical strength of the photo-cured portion also becomes sufficiently high.

The content of the component A is 3 per total polyamide.
It is preferably from 0 to 70% by weight, particularly preferably from 40 to 60% by weight.
% By weight. The content of the component B is preferably 30 to 70% by weight, particularly preferably 4 to 70% by weight, based on the entire polyamide.
0 to 60% by weight.

The polyamide containing the component A and the component B at the above-mentioned preferable contents is prepared so that the component A and the component B in the polymer have the desired contents, respectively, so that the ω-amino acid and / or lactam and piperazine can be used. It can be obtained by charging a predetermined amount of a dicarboxylic acid salt of an amino compound having a ring, and subjecting them to polycondensation.

The polyamide used in the present invention contains a component A which is a condensed residue of an ω-amino acid or a lactam and a component B which is a condensed residue of a dicarboxylic acid salt of an amino compound having a piperazine ring, and has a terminal. Has an acryloyl group and / or a methacryloyl group. Such acryloyl and / or methacryloyl groups are
For example, the functional group (epoxy group, isocyanate group, carbonyl chloride group) of a compound having a functional group such as an epoxy group, an isocyanate group, and a carbonyl chloride group together with a (meth) acryloyl group is added or condensed to a terminal amino group of the polyamide. Can be introduced in a manner that allows

By having an acryloyl group and / or a methacryloyl group at the terminal of the polyamide, a decrease in the photosensitivity of the photosensitive resin composition containing the polyamide over time is suppressed. Furthermore, the physical properties after photo-curing of the photosensitive resin composition are further improved, and the photo-cured portion has an effect of having sufficiently high mechanical strength while having moderate flexibility which could not be obtained conventionally. . This is because the acryloyl group and / or methacryloyl group introduced at the terminal of the polyamide is incorporated into the polymer of the photopolymerizable unsaturated compound, and the polyamide as the filling polymer is stored in the crosslinked structure, and as a result, It is thought that it is possible. Therefore, a relief plate obtained by plate making can obtain sufficient printing durability even under various printing conditions in which printing pressure, printing speed, and the like are different.

The content of the acryloyl group and / or the methacryloyl group in the polyamide is preferably 0.05 to 0.5 mol / kg, particularly preferably 0.1 to 0.2 mol / kg. The molecular weight of the polyamide is not particularly limited, but is preferably in the range of 10,000 to 100,000,000 in number average molecular weight, and particularly preferably 15,000 to 100,000.
30,000.

The photopolymerizable unsaturated compound used in the present invention is a compound containing one or more photopolymerizable unsaturated groups in the molecule, and known compounds can be used. Such compounds include, for example, acrylic acid, methacrylic acid, itaconic acid, 2-hydroxyethyl acrylate,
2-hydroxypropyl acrylate, acrylamide, methacrylamide, N-methylolacrylamide, N-acryloylmorpholine, pentaerythritol diacrylate, pentaerythritol triacrylate, glycerol dimethacrylate, ethylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether and the like Unsaturated epoxy compounds, such as polyhydric acrylates, methacrylates, and glycidyl acrylates, obtained by the addition reaction of polyhydric glycidyl ether with a compound having an active hydrogen and an ethylenically unsaturated bond such as an unsaturated carboxylic acid or unsaturated alcohol Examples include addition products of compounds having active hydrogen such as acids and amines, unsaturated polyesters and unsaturated polyurethanes. These compounds can be used alone or in combination of two or more. Further, the content of the photopolymerizable unsaturated compound in the photosensitive resin composition is preferably appropriately selected from the range of 5 to 50% by weight. If the amount is less than 5% by weight, the photocurability of the resin composition is impaired. If the amount is more than 50% by weight, the composition after photocuring shrinks greatly, which may impair the reproducibility of the image pattern.

Known photopolymerization initiators can be used, and specific examples thereof include benzophenones, benzoins, acetophenones, polynuclear quinones, benzyls, benzoin alkyl ethers, and benzyl alkyl ketals. , Anthraquinones, thioxanthones and the like can be used. Preferred examples include benzophenone, benzoin, acetophenone, 1,4-naphthoquinone, benzoin methyl ether, benzoin ethyl ether, benzyldimethyl ketal, anthraquinone,
-Chloroanthraquinone, thioxanthone, 2-chlorothioxanthone and the like. These can be used alone or in combination of two or more. The photopolymerization initiator is a component that starts or sensitizes the polymerization reaction of the photopolymerizable unsaturated compound by light irradiation. The content of the photopolymerization initiator in the composition is preferably 0.05 to 5% by weight. 0.05
If the amount is less than 5% by weight, the photopolymerization initiation and / or sensitizing ability is hindered. If the amount is more than 5% by weight, the composition is not uniformly dispersed in the composition, and conversely, the photoreactivity may be reduced.

The photosensitive resin composition of the present invention may contain additives such as stabilizers and plasticizers as required in addition to the soluble polymer compound, the photopolymerizable unsaturated compound and the photopolymerizable initiator. Can be. As the stabilizer, for example, hydroquinone, hydroquinone monomethyl ether, 2,2
6-di-t-butyl-p-cresol and the like,
These are preferably contained in the composition at about 0.001 to 5% by weight. The plasticizer is added as a seed for the purpose of improving the transparency of the photocured product, and examples thereof include low-molecular plasticizers such as esters and amides, and oligomers such as polyester, polyether, and liquid rubbers. These are preferably contained in the composition at about 5 to 10% by weight. In addition, according to the product use obtained after exposure and development, a known dye or pigment may be added to color the photosensitive resin composition.

The photosensitive resin composition of the present invention is usually prepared by dissolving a viscous composition obtained by dissolving in a solvent into a sheet on a substrate, solidifying the composition, and then subjecting the composition to heat treatment. In addition to molding into a raw plate, the raw plate is formed by any known method such as hot pressing, casting, melt extrusion, and solution casting.

The raw plate can be used by laminating it on a support with or without a known adhesive. As the support, any material such as steel, aluminum, glass, a plastic film such as a polyester film, and a metal-deposited film can be used. When the raw plate is supplied as a laminated body laminated on a support, a protective layer is further laminated in contact with the raw plate. The protective layer is made of a film-like plastic, for example, a polymer having a thickness of 1 to 3 μm which is transparent and does not adhere to a polyester film and is dispersed or dissolved in a developer.
What is applied with the thickness of is used. By bringing the protective layer having the thin polymer film into contact with the raw plate, the protective layer can be easily peeled off during the next exposure operation even when the raw plate has strong surface tackiness.

A photosensitive resin original plate consisting of a raw plate alone or a laminate of a raw plate and a support is tightly overlapped with a negative film or a positive film having a transparent image portion on the raw plate, and activated from above. When exposure is performed by irradiating a light beam, the exposed portion is hardened and insolubilized. Usually 3 for actinic rays
A light source such as a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, a xenon lamp, and a chemical lamp having a wavelength of from 00 to 450 nm is used.

The photosensitive resin composition of the present invention is preferably developed in a short time and quickly by dissolving and removing non-exposed portions using water, particularly neutral water, as a solvent. As the developing method, it is preferable to use a spray developing device, a brush developing device, or the like.

[0032]

The present invention will be described below in more detail with reference to Examples and Comparative Examples. The number of parts in the following Examples and Comparative Examples is parts by weight.

(Example 1) ε-caprolactam 525
Part, 400 parts of a nylon salt of N- (2-aminoethyl) piperazine and adipic acid, and 75 parts of a nylon salt of 1,3-bis (aminomethyl) cyclohexane and adipic acid were subjected to solution polycondensation in an autoclave to form a copolymer. Polymerized nylon was obtained. The maximum polymerization temperature is 210 ° C and the number average molecular weight is 150
00, melting point 140 ° C. When the amount of amino group end groups was measured by neutralization titration, the amount of amino group end groups was 0.1%.
Mol / kg. Next, 55 parts of the above copolymerized nylon was dissolved in 200 parts of methanol at 60 ° C., and 2 parts of glycidyl methacrylate was further dissolved and reacted for 2 hours. From the results of NMR analysis, it was confirmed that all of the terminal amino groups of the copolymerized nylon reacted with the epoxy groups of glycidyl methacrylate, and that a methacryloyl group was introduced at the terminal of the copolymerized nylon. Therefore, the methacryloyl group in the polyamide was 0.2 mol / kg, calculated from the amino group end group content of 0.1 mol / kg.

To this solution was added 4 parts of methacrylic acid, and then 35 parts of acrylate obtained by a ring-opening reaction of trimethylolpropane with triglycidyl ether acrylic acid, 5 parts of N-ethyltoluenesulfonic acid amide, hydroquinone monomethyl ether 0.1 part and benzyl methyl ketal 1.0 part were added to obtain a solution of the photosensitive resin composition. This solution was cast on a polyester film and methanol was removed by evaporation to obtain a 800 μm thick sheet of the photosensitive resin composition. This sheet is attached to a 250 μm-thick polyester film coated with an adhesive containing a brown pigment, and the top surface of the composition is covered with a 125 μm-thick polyester film. Prepared a photosensitive resin master having a thickness of about 700 μm. The cover film was peeled off from the photosensitive resin original plate, a negative film was adhered to the surface of the photosensitive resin layer, and exposed to a chemical lamp for 4 minutes. Then, the negative film was peeled off and developed with tap water for 2 minutes and 30 seconds using a brush type washer. And dried. The obtained relief had 14 steps of step guides manufactured by Dainippon Screen Co., Ltd. The fine lines faithfully reproduced a fine line having a width of 40 μm. In addition, 30
After printing all copies, no relief jumps (defects) or cracks occurred, and good printing durability was exhibited. 50 days later
When the original plate stored at 2 ° C for 2 months (aged) was subjected to plate making in the same manner as above, the resulting relief faithfully reproduced 13 steps of step guides and a fine line of 40 μm width for the fine line. The properties were similarly good. Therefore, it was confirmed that the photosensitive resin composition of this example hardly deteriorates in photosensitivity over time.

Comparative Example 1 An original photosensitive resin plate was prepared in the same manner as in Example 1 except that glycidyl methacrylate was not reacted with the terminal amino group of the copolymerized nylon synthesized in Example 1 and the copolymerized nylon was used as it was. Created. When the obtained original plate was prepressed under the same conditions as in Example 1, the number of step guide steps was 14, and the fine lines were faithfully reproduced as fine lines having a width of 40 μm. However, for 300,000 copies, 20
The relief was skipped (deleted) on the tenth sheet. Also,
When the original plate stored at 50 ° C. for 2 months (aged) was subjected to plate making, the number of step guide steps was 11, and the fine line did not reproduce a fine line having a width of 70 μm, and a decrease in the light sensitivity of the original plate over time was observed.

[0036]

As is clear from the above description, according to the photosensitive resin composition of the present invention, since the polyamide has a (meth) acryloyl group at the terminal, the polyamide resin is used as a filler polymer, It is possible to obtain a photosensitive resin composition with excellent sensitivity stability over time, and the photosensitive resin master after aging shows almost the same light sensitivity as the photosensitive resin master immediately after preparation, gradation, reproduction of fine lines. A printing relief having good properties can be obtained.

Further, the (meth) acryloyl group at the terminal of the polyamide is incorporated in the polymer with the photopolymerizable unsaturated compound, contrary to the photopolymerizable unsaturated compound, and the polyamide as the filling polymer is stored in the crosslinked structure. Therefore, the photocured portion has appropriate flexibility and sufficiently high mechanical strength, and it is possible to obtain a printing relief with improved printing durability as compared with the related art.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08G 73/00 C08G 73/00 4J043 G03F 7/00 502 G03F 7/00 502 7/028 7/028 (72 ) Inventor Satoshi Takahashi 2-1-1 Katata, Otsu-shi, Shiga Prefecture Inside Toyobo Co., Ltd. Research Institute (72) Inventor Koji Koji 2-1-1 Katata, Otsu-shi Shiga Prefecture Inside Toyobo Co., Ltd. Research Institute (72 ) Inventor Kimiko Minamimura 2-1-1 Katata, Otsu-shi, Shiga F-term in Toyobo Co., Ltd. Research Laboratory (Reference) 2H025 AA04 AA06 AA11 AA12 AB02 AC01 AD01 BC13 BC31 BC68 BC81 BC83 CA00 FA17 2H096 AA02 BA05 BA06 EA02 GA08 4J001 DA01 DB04 DC01 DC25 DD02 DD11 EA06 EA08 EA14 EB04 EB06 EB07 EB08 EB09 EB14 EB36 EB37 EC29 FA03 FB03 FC03 GE02 JA20 4J011 QA01 QA02 QA03 QA06 QA17 QA23 QA34 QA37 QA39 QB17 QB19 QC01 SA02 SA22 SA34 SA54 SA63 SA64 UA01 VA01 WA01 4J027 AB36 AD02 AE04 AG36 AJ04 AJ08 AJ09 BA04 BA06 BA08 BA13 BA14 BA19 BA24 CB10 CD10 4J04 SA05 QA03 QA04 QAQA SB01 SB02 TA12 TB01 TB02 UA042 UA122 UA381 UA762 UA772 VA012 VA042 VA052 VA082 WA06 WA16 WA22 WA29 YB08 YB19 YB29 ZB22

Claims (2)

[Claims] 1. A photosensitive resin composition comprising a soluble polymer compound, a photopolymerizable unsaturated compound and a photopolymerization initiator, wherein the soluble polymer compound is represented by the following general formula (I). And a unit having a unit represented by the following general formula (II) and / or a unit represented by the following general formula (III), and having an acryloyl group and / or a methacryloyl group at a terminal. Characteristic photosensitive resin composition. Embedded image (In the formula, R ¹ is an alkylene group having 5 or more carbon atoms.) (In the formula, R ² is an alkylene group having 2 to 10 carbon atoms, an aromatic group or an alicyclic group, and R ³ and R ⁴ are each an alkylene group having 1 to 5 carbon atoms.) 3] (In the formula, R ⁵ is an alkylene group having 2 to 10 carbon atoms, an aromatic group or an alicyclic group, and R ⁶ is an alkylene group having 2 to 3 carbon atoms.) 2. An acryloyl group in a polyamide and / or
Or the content of the methacryloyl group is 0.05 to 0.5
The photosensitive resin composition according to claim 1, wherein the amount is mol / kg.