JPS592019B2 - Hikari Kokasei Insatsuban Yojiyushisoseibutsu - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a photocurable printing plate resin composition that can be cured by a free radical polymerization mechanism.

Conventionally, as a curable resin composition for use in photosensitive resin printing plates, etc., which can be cured by the above reaction, those containing unsaturated polyester as a main component have been used.

Unsaturated polyesters typically include fumaric acid,
Polyhydric carboxylic acids (or functional derivatives thereof) whose main component is α/β unsaturated dicarboxylic acid such as maleic anhydride
A compound obtained by forming an ester bond with a polyhydric alcohol and a polyhydric alcohol is used. However, such unsaturated polyesters cannot fully absorb 30% unless they coexist with large amounts of so-called donor monomers having ethylenic double bonds with high electron density, such as acrylamide and styrene.
It is not possible to obtain a cured product with a developed dimensional molecular structure.

Moreover, if a large amount of acrylamide is present, it is difficult to produce a uniform printing plate due to poor miscibility. Furthermore, if a large amount of styrene is used, the composition has drawbacks such as a pronounced unpleasant odor and a high risk of ignition, and the cured product tends to have poor flexibility and impact resistance.

Therefore, by using methods such as using an aliphatic long-chain dicarboxylic acid such as adipic acid as the polyhydric carboxylic acid component, or using an ether bond-containing substance such as diethylene glycol as the polyhydric alcohol component, it is possible to obtain a material with good flexibility. Although it is possible to produce unsaturated polyesters, their hardness is low and they are not suitable as printing plates. On the other hand, a polyunsaturated compound (so-called urethane adduct) obtained by reacting a low molecular weight polyvalent isocyanate compound such as tolylene diisocyanate with a hydroxyl group-containing acrylic acid (or methacrylic acid) ester is photocured. It is also known to be used as a rubber composition, but since this composition is originally a low-molecular compound, it is difficult to obtain a sufficiently strong cured product.

Moreover, instead of the low molecular weight polyvalent isocyanate compound in the above-mentioned urethane adduct, a urethane between the hydroxyl group of a polyhydric alcohol having a molecular weight of 3000 or less, such as polyethylene glycol, and the NCO group of the low molecular weight polyvalent isocyanate compound. It is also known that a resinous urethane adduct obtained by using a high molecular weight polyvalent isocyanate compound obtained by bond formation can be used as a composition for photocurable printing plates, and it has excellent toughness. A cured product is obtained. However, these urethane adducts do not dissolve even in alkaline aqueous solutions, so various alkaline water-soluble polymer substances have been mixed to make photosensitive resin printing plates, but these polymers have poor polymerization and crosslinking properties. Therefore, it could not be said that the curability was sufficiently high, and the hardness of the cured product was not necessarily satisfactory. Furthermore, an acrylic resin or a polyester containing hydroxyl groups is synthesized in advance, and then combined with a hydroxyl group-containing acrylic ester etc. via a polyvalent isocyanate compound to form a photocurable resin composition. It is also known to obtain unsaturated resins suitable for use as.

, its production involves long and complicated reaction steps. The present inventors provide a curable resin composition suitable for use as paints, photosensitive resin printing plates, etc., which does not have any of the drawbacks of conventional unsaturated resins or curable resin compositions as described above. Therefore, as a result of various studies, the present invention has been arrived at. That is, the present invention provides at least 30 mol% of the (A) polycarboxylic heptacid component.
is obtained from a polymerizable ethylenically unsaturated polyhydric carboxylic acid or a functional derivative thereof, and has a number average molecular weight of 3.
00 to 3000 and 90 to 10% by weight of an unsaturated polyester having an acid value of 30 to 150, (B) General formula (1) Z-X-Z and [General formula (1) and ([[) is the part obtained by removing the NCO group from the molecular formula of the diisocyanate compound, Y is the part obtained by removing the 0H group from the molecular formula of the di- to hexavalent polyhydric alcohol and has a molecular weight of 3000 or less, and p is 1 to 1. 6 and an integer less than or equal to the valence of Y, an integer whose sum with Qll@p is equal to the valence of Y, or 0, and Z is a general formula (wherein R1 is a hydrogen atom or a methyl group, and A is 1~2(
In the formula, R2 represents a hydrogen atom, a methyl group, or a chloromethyl group, and n represents the sum of the molecular weights of A or the sum of the molecular weights of Y in general formula (1) or 40
00 or less) represents an alkeneoxy group or a polyalkenoxy group represented by A. Rl, R2 and This is a resin composition for a photocurable printing plate, which contains a resin composition as a main component.

The unsaturated polyester of the present invention has a number average molecular weight of 300
~3000, acid value 30-150, and at least 30 mol% of the polycarboxylic acid component is obtained from an ethylenically unsaturated polycarboxylic acid having a polymerizable unsaturated bond or a functional derivative thereof. If any, conventionally known ones can be used as they are.

That is, at least 30 mol% of the polyhydric carboxylic acid component in the unsaturated polyester structure is a polymerizable inorganic acid such as fumaric acid, maleic acid, itaconic acid, citraconic acid, mesaconic acid, terraconic acid, muconic acid, aconitic acid, etc. Ethylenically unsaturated polycarboxylic acids having saturated bonds or functional derivatives thereof (“functional derivatives” in this specification refer to acid anhydrides, lower alcohol esters, acid
(e.g., carboxylic acid derivatives that can easily react with alcoholic hydroxyl groups to form ester compounds), and these polymerizable ethylenic inorganic compounds must be derived from Other polyhydric carboxylic acid components used in combination with saturated carboxylic acids include, for example, phthalic acid, isophthalic acid, tetrahydrophthalic acid,
Succinic acid, adipic acid, aconitic acid, trimellitic acid, pyromellitic acid and the like or their functional derivatives are particularly suitably used.

If the proportion of the polymerizable ethylenically unsaturated polycarboxylic acid component is less than 30 mol%, the curability of the composition using the unsaturated polyester will be low, and a network molecular structure will not develop sufficiently with the acrylic urethane molecules. This is not preferred because a strong cured product cannot be obtained. The polyhydric alcohol component in the unsaturated polyester may be the same as that used in general unsaturated polyesters, and is not particularly limited. The number average molecular weight of the unsaturated polyester needs to be 300 to 3000 (preferably 400 to 1500),
When it is less than 300, the photocurability of the composition tends to be insufficient, and when it exceeds 3000, the miscibility with acrylic urethane decreases or the composition tends to have high viscosity, so operations such as coating and molding are difficult. It may be inconvenient when
In addition, the acid value of this unsaturated polyester needs to be 30 to 150, particularly preferably 50 to 120, and this can be achieved by increasing the proportion of dicarboxylic acid used to form a carboxyl group at the end of the molecular chain. leave a large amount of
Alternatively, by using a trivalent or tetravalent carboxylic acid such as aconitic acid, trimellitic acid, or pyromellitic acid, a carboxyl group can be added to the middle part of the molecular chain in the form of a side chain. By setting the acid value to 30 or higher, the composition of the present invention can be photocured as a printing plate, and the uncured portion can be easily washed out and removed with an aqueous solution of a basic substance (such as caustic alkali). This is not preferable because the physical and chemical properties of the part deteriorate. Acrylic urethane, which is the other component of the mixture in the resin composition for photocurable printing plates in the present invention, is a compound represented by the general formula (1) or (6) in the component (B) described above. , general formula (1) is CH2=C-C-
It is a reaction product of an acrylic ester or methacrylic ester represented by 0-A-H (hereinafter collectively referred to as "hydroxyacrylic esters") and a diisocyanate represented by the general formula 0CN-X-NCO,
In the general formula (6), a compound containing a free isocyanate group obtained by the reaction of the above hydroxyacrylic acid ester and a diisocyanate is combined with the general formula Y-(
It is produced by reacting polyhydric alcohols shown by 0H), +,.

In the production of acrylic urethane of general formula (IJ), the order in which the three components are reacted is that hydroxyacrylic esters are sequentially added to diisocyanate and reacted to form a so-called monoacrylic adduct; A method in which a polyhydric alcohol is reacted with an adduct, a method in which a diisocyanate is added to a polyhydric alcohol, and then a hydroxyacrylic acid ester is added in this order, and a reaction is carried out in which the three components are simultaneously present in the reaction system. Any method can be applied. Known techniques can be applied to the reaction operating conditions. Known techniques may be applied to the reaction operating conditions. In the present invention, diisocyanate (0CN-X-NCO)
For example, the following can be used. Tolylene diisocyanates, xylylene diisocyanates, phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, methylene diisocyanate, polymethylene diisocyanates (for example, hexamethylene diisocyanate, etc.), Naphthalene diisocyanates, isophorone diisocyanate, lysine methyl diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, and di- to hexavalent polyhydric alcohols (Y-
For example, the following are used as j(0H), +, ).

Ethylene glycol, diethylene glycol, polyethylene glycol (number average molecular weight 300 excluding the terminal 0H group)
0 or less), 1,2-propanediol (propylene glycol), dipropylene glycol, polypropylene glycol (number average molecular weight 3000 excluding the terminal 0H group)
(the following), 1,3-propanediol, neopentyl glycol, phthanediol, pentanediol, hexanedi4ol, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, pentahydric sugar alcohols (e.g. xylitol, etc.), Pentaerythritol, hexahydric sugar alcohols (e.g. D-
sorbitol, etc.), and a reaction product in which ethylene oxide or propylene oxide is polyadded to a trivalent to hexavalent alcohol, and the number average molecular weight excluding the 0H group moiety is 3000 or less.For example, a molecular formula or (r1 to R6 are numbers) Polyhydric alcohol whose average molecular weight can be within the above-mentioned limits. If the alcohol component is monovalent, an acrylic urethane with good curability cannot be obtained, and if a polyhydric alcohol with a valence exceeding 6 is used, the gel There is a risk that the acrylic urethane or the composition may become difficult to manufacture or store, or the remaining hydroxyl groups may reduce the water resistance of the cured product.

In addition, it is preferable that the molecular weight (or number average molecular weight) of these polyhydric alcohols is 3000 or less (preferably 400 to 1500) excluding the 0H group portion, and if a polyhydric alcohol exceeding this is used, It becomes difficult to completely mix the obtained acrylic urethane and the unsaturated polyester, and the composition tends to have a high viscosity, which may cause inconvenience during operations such as coating and molding. Examples of hydroxyacrylic acid esters include 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxyethyl acrylate,
These include 2-hydroxypropyl acrylate, 2-chloromethyl-2-hydroxyethyl methacrylate, monomethacrylic ester (or monoacrylic ester) of polyethylene glycol, and monomethacrylic ester (or monoacrylic ester) of polypropylene glycol.

When using polyalkylene glycol monoacrylic acid (or methacrylic acid) ester such as polyethylene glycol monomethacrylate, the total molecular weight of the A part in the above general formula or a di- to hexavalent polyhydric alcohol in the same acrylic urethane molecule. is used, it is further preferred that the total molecular weight of the Y moiety in the general formula does not exceed 4000 (preferably 500 to 2000);
If it exceeds 0, problems similar to those regarding the molecular weight of the polyhydric alcohol will occur. A mixture of unsaturated polyester and acrylic urethane can also be produced by using both as they are and kneading them with hot rolls, but at least one of them can be prepared in advance by adding a volatile organic solvent or a radically polymerizable ethylenically unsaturated This can be done very easily by mixing it with a monomer and making it into a liquid.

This ethylenically unsaturated monomer also has the effect of indirectly binding the two components during curing of the finished composition. Ethylenically unsaturated monomers used for this purpose include, for example, styrene, aromatic vinyl compounds such as vinyltoluene, methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, and 2-ethylhexyl acrylate. , 2-hydroxyethyl acrylate, acrylic esters such as 2-hydroxypropyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, lauryl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate Particularly preferred are methacrylic acid esters such as lattice, etc., and also vinyl esters such as vinyl acetate, unsaturated nitriles such as acrylonitrile, and ethylenically unsaturated carboxylic acids such as acrylic acid and methacrylic acid. When the unsaturated polyester has structural units of alternating copolymerizable αβ monounsaturated dicarboxylic acids such as maleic acid and fumaric acid, so-called donor monomers having ethylenically unsaturated bonds with high electron density, such as styrene, are used. , vinyltoluene, etc., is desirable because it facilitates bond formation with unsaturated polyester molecules. When using styrene etc. for this purpose, part or all of the styrene etc. may be substituted with donor monomers such as acrylamide, methacrylamide, N- Methyloacrylamide, alkyl (n-butyl etc.) etherification-N
-methylol acrylamide, etc. The mixing ratio of unsaturated polyester and acrylic urethane needs to be within the range of 10/90 to 90/10, preferably 25/75 to 75/25 by weight,
If the unsaturated polyester is used in an excess amount, it is difficult to obtain a composition that has excellent curability and is easy to obtain a cured product with excellent toughness. On the other hand, if acrylic urethane is used in an excessive amount, the liquid curable resin composition will tend to have structural viscosity, making it inconvenient to use, or the water resistance of the cured product will decrease, and it may become insoluble in dilute alkaline water. This is not desirable. When an ethylenically unsaturated monomer is used, its proportion in the composition should be as much as 50% by weight or less, preferably 30% by weight or less; if it is used in excess of 50% by weight, it will generally It is difficult to obtain a cured product with excellent toughness from the composition, the characteristics of the composition of the present invention are not fully exhibited, and the volume shrinkage is significant during curing, so it is difficult to obtain a cured product with excellent toughness. It becomes undesirable to submit the product to

In order to avoid viscosity increase and gelation during the production of the unsaturated polyester and acrylic urethane of the present invention and during storage of the resulting composition, if necessary, release into the composition within a range that does not affect curability. A radical polymerization inhibitor can be included in the composition.

Furthermore, various photosensitizers are added to make a photocurable resin composition, which is used as a photosensitive resin printing plate material, and after molding, active light is irradiated onto imagewise selected areas to initiate a photopolymerization reaction. harden by As the photosensitizer, the following can be used, for example. d-carbonyl alcohols such as benzoin, butyroin, trioin, acetoin, acroin, acyloin ethers such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, pivaloin ethyl ether, anisoin ethyl ether, α-methylbenzoin ,
α-substituted acyloins such as α-phenylbenzoin, 9.
10-anthraquinone, 2-chloroanthraquinone, 2
-Methylanthraquinone, 1,4-naphthoquinone, 2.
Polynuclear quinones such as 3-benzanthraquinone, diacetyl, dibenzoyl, diphenyltriketone, phenylglyoxal, adjacent polyketone compounds such as pentanedione-2 and 3, 2-mercaptobenzothiazole-2-mercaptobenzoxazole, 2-mercaptonaphtho Mercaptans such as oxazole and 2-mercaptobenzimidazole, disulfides such as diphenyl disulfide, dibenzyl disulfide, di-n-butyl disulfide, dibenzoyl disulfide, diacetyl disulfide, dibornyl disulfide, thio phenol, o
- Thiols such as aminothiophenol, thiuram derivatives such as tetramethylthiuram monosulfide, tetramethylthiuram disulfide, tetramethylthiuram tetrasulfide, metal complex salts such as acetylacetone nickel salt, benzophenone, ω-bromoacetophenone, etc. Phenylketones, aromatic sulfonyl halides such as 1-naphthalenesulfonyl chloride, metal mercapta and f-dos such as mercury phenyl mercaptide.

, : The proportion of these photosensitizers added is usually 0.01 to 5% by weight in the photocurable resin composition.

If it is less than 0.01% by weight, it will not be possible to impart sufficient photocurability to the composition, and if it is added in excess of 5% by weight, not only will there be no particular increase in photocurability.
There is a risk of deterioration of storage stability due to dark reaction or deterioration of the properties of the cured product due to the large amount of non-polymerizable low molecular weight components contained.

The active light irradiated for photopolymerization after molding is usually near ultraviolet light or visible light with a wavelength of 230 to 500 nm, and the light source includes, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, a fluorescent lamp, a xenon lamp, and a carbon arc lamp. Choose from , tungsten lamps, solar light, laser equipment, etc. When performing partial irradiation to obtain a photosensitive resin printing plate, transparent negative films, paper patterns, etc. are superimposed and irradiated from the outside, or the irradiation is performed by scanning with a beam of actinic light modulated according to a signal. After irradiation, the uncured portion is removed (developed). In the present invention, since an unsaturated polyester having an acid rating of 30 or more is used, washing out and development with an aqueous solution such as caustic alkali is possible. The photocurable resin composition of the present invention has excellent curability due to the formation of crosslinks in the urethane group based on the photosensitization effect caused by light absorption of the urethane group in the acrylic urethane. It provides a cured product with high elasticity, excellent flexibility and impact resistance, and a suitable degree of elasticity.Also, when cured on the surface of an object, it exhibits a high level of adhesion, making it suitable for photosensitive resin printing plates and photoresists for etching. It is suitable for applications such as

When itaconic acid is used as an ethylenically unsaturated polycarboxylic acid, it is not necessary to use a donor monomer with high volatility and strong unpleasant odor such as styrene, and in extreme cases, Since it is easy to make a composition with good curability without using the ethylenically unsaturated monomer directly, it is also very convenient in handling. To use as a photosensitive resin printing plate, it is possible to use either a liquid resin plate or a solid resin plate.For the production of a solid resin plate, for example, soluble cellulose derivatives, ethylenically unsaturated carboxylic acids (acrylic acid, etc.) can be used. ) copolymers of polyvinyl alcohols (including partially saponified polyvinyl esters and partially acetalized products) or acid anhydrides of acrylic copolymers with hydroxyl groups (phthalic anhydride, etc.)
This is possible by blending semi-esterified products such as

The cured product also has excellent chemical resistance, so when used as an etching photoresist, fine and deep etching is possible.

Unsaturated Polyester Production Example 1 Into a reactor equipped with a stirrer, a thermometer, an inert gas blowing tube, and a rectification tube, 344 parts of maleic anhydride (parts by weight, same hereinafter) and 17.5 parts of phthalic anhydride were added.
3 parts, 17.8 parts of tetrahydrophthalic anhydride, and 38.1 parts of ethylene glycol, and the flow rate was 50 m1/M.
By blowing nitrogen gas at m and heating at 180 to 210°C for 4 hours while maintaining an inert atmosphere to cause dehydration condensation, an average molecular weight (calculated value, the same applies hereinafter) of 530, an acid value (actual value, below) Same) 85 unsaturated polyester I was obtained.

When the reaction was completed and cooled to 160°C, 0.01 part of 2,5-di-tert-butylhydroquinone was added to the unsaturated polyester I, and after further cooling to 80°C, 25 parts of styrene was added. This was dissolved to obtain a solution of unsaturated polyester having a resin content of 80% by weight. Unsaturated polyester production example 2 Using the same reaction apparatus as unsaturated polyester production example 1,
12.9 parts of maleic anhydride, 36.7 parts of adipic acid, 1
・17.6 parts of 1,1-trimethylolpropane and 34.8 parts of diethylene glycol were reacted by heating at 180 to 210°C for about 4 hours, and then when cooled to 130°C, 9.7 parts of phthalic anhydride was reacted. The ethylenically unsaturated monomer mixture (2,6-diTert-
(Addition of 0.01 part of butyl-4-methylphenol) to obtain a solution of unsaturated polyester H having an acid value of 36 and an average molecular weight of 1558 (resin content 72% by weight).

Unsaturated Polyester Production Examples 3 to 6 Using the same reaction apparatus as in Unsaturated Polyester Production Example 1, ethylenically unsaturated monomer solutions of unsaturated polyesters (1) to (4) were produced by the same steps.

The raw material formulation, acid value and average molecular weight of the produced unsaturated polyester, type and amount of ethylenically unsaturated monomer used, etc. for each production example are shown in Table 1 together with the values for the previous two examples. Acrylic urethane production example 1 xylylene diisocyanate 188f7 (1.0 mol)
and polypropylene glycol monomethacrylate (number average molecular weight 415) 830y (2 mono(c) (addition of 0.102 p-benzoquinone)) and kept at 40°C for 8 hours to react, resulting in acrylic urethane. I and further 2-hydroxyethyl methacrylate 2547
Add and dissolve acrylic urethane content (solution concentration)
A solution of 80% by weight of acrylic urethane I was prepared.

Acrylic urethane production example 2 Tolylene diisocyanate 1907 (1.1 mol) was heated to 40°C.
Polypropylene glycol monomethacrylate (number average molecular weight 415) 4157 (1.0 mol) while maintaining
(Hydroquinone 0.106f7 added) was added dropwise and kept at the same temperature for 4 hours to generate an adduct.Furthermore, glycerin 31y (0.33 mol) was added and kept at the same temperature for 8 hours. The material was made into acrylic urethane ■, and then styrene 807 and 2-hydroxyethyl methacrylate 807 were added and dissolved therein.
Acrylic urethane with acrylic urethane content of 80% by weight■
A solution of was obtained.

Acrylic urethane production example 3 Polyethylene glycol (number average molecular weight 400) 400 to tolylene diisocyanate 3601 (2.06 mol)
After adding y and heating to 140℃ for 30 minutes, 40℃
2-hydroxyethyl methacrylate 2607 (2.0 mol) (p-benzoquinone 0.102
7 addition) was added, and the mixture was kept at 40'C for 8 hours to react to obtain acrylic urethane (2), which was further dissolved in 2-hydroxyethyl methacrylate 255y to obtain a solution of acrylic urethane (2) containing 80% by weight of acrylic urethane.

Acrylic urethane production examples 4 to 7 Acrylic urethane solutions were prepared at the blending ratios shown in numbers ■ to ■ in Table 2.

The treatment method in each production example is shown in acrylic urethane production example 1 to
Table 2 shows cases 3 (corresponding to numbers 1 to ■).

The reaction steps are the same as in acrylic urethane production example 3 for production examples 4, 5, and 6, and the same as in acrylic urethane production example 2 for production example 7. Comparative Examples 1 to 2 The solution of unsaturated polyester I and the solution of acrylic urethane (I) were mixed in the proportions (parts by weight) listed in Table 3, and each added benzoin ethyl ether per 100 parts by weight of the total amount. Three types of photosensitive curable resin compositions (Examples 1 to 3) were obtained by adding 1 weight product.

For comparison, benzoin ethyl ether was added in equal proportions to the above two types of solutions using these alone to prepare two types of compositions. These compositions were cast onto a copper plate with an adhesive resin layer on the surface to prevent halation, to form a layer with a thickness of 0.65 mm, and a polyester film with a thickness of 25 μm was adhered on top of the layer. Then, a negative film was placed on top of the film, and ultraviolet rays were irradiated using a high-pressure mercury lamp (2RW) installed at a distance of 55 cm above until the exposed area was completely cured.

After irradiation, a sodium hydroxide aqueous solution with a concentration of 0.2% or 0.4% was washed out at a pressure of 35 k in a washing device at 30°C.
9/Cd was sprayed onto each resin plate for about 1 minute (or 2 minutes) to wash out the composition in the non-exposed areas and develop to complete a letterpress printing plate. For each printing plate, the hardness of the cured resin part was measured using a Shore D hardness meter at 20°C, and the flexibility was determined by wrapping it around a cylinder with a diameter of 60 mm or 10 mm at O'C to determine the presence or absence of cracks. was determined.

The test results are shown in Table 3. Examples 4 to 8 Using unsaturated polyester I, ■, ■, ■, and ■ and acrylic urethane I, ■, ■, V, and ■, their respective solutions were mixed in the proportions listed in Table 4, and further The total amount 1
Four types of photocurable resin compositions were completed by adding and mixing benzoin isopropyl ether at a ratio of 1 part by weight per 00 parts by weight.

These compositions were tested in the same manner as in Examples 1 to 3 to prepare letterpress printing plates, and the resulting printing plates were subjected to curing measurements and flexibility tests. As a result, the results shown in Table 4 were obtained. It was done. Regarding washability, each composition could be easily developed in 1 minute using a 0.4% aqueous sodium hydroxide solution. In addition, compositions made from each unsaturated polyester with only the addition of the same photosensitizer failed in the flexibility test; Compared to the unsaturated polyester of the present invention mixed therein, the required exposure time is 1 to 1.5 minutes longer, the hardness is 10 or more lower, and moreover, it is easy to wash out with a 0.4% sodium hydroxide aqueous solution. It was impossible. 'Example 9 to Example 11 The solution of acrylic urethane (I) was added to the solution of unsaturated polyester (V) at a weight ratio of 7/3 (Example 9),
5/5 (Example 10) or 3/7 (Example 11), and add 1 part by weight of benzoin ethyl ether per 100 parts by weight of the total amount to prepare a photocurable resin composition, A layer with a thickness of 0.65 mm was formed and the time required for complete curing was compared by irradiating ultraviolet rays using the same light source device as in Example 1.
They were 2.5 minutes and 2.0 minutes.

In addition, in any composition, the unexposed area was 0.4
% sodium hydroxide aqueous solution (35°C) within 1 minute. In addition, a solution of unsaturated polyester V or a solution of acrylic urethane 100
The exposure times under the same conditions for a composition containing 1 part by weight of benzoin ether ether were 7 minutes and 2 minutes, respectively.
It was hot in minutes.

Claims (1)

[Scope of Claims] 1(A) At least 30 mol% of the polycarboxylic acid component is obtained from a polymerizable ethylenically unsaturated polycarboxylic acid or a functional derivative thereof, and has a number average molecular weight of 300 to 3000 and 90 to 10% by weight of unsaturated polyester with an acid value of 30 to 150, (B) General formula (I) Z-X-Z and (II) ▲ Numerical formula, chemical formula, table, etc. ▼ [General formula (
In I) and (II), X is the part obtained by removing the NCO group from the molecular formula of the diisocyanate compound, and Y is the part obtained by removing the OH group from the molecular formula of the di- to hexavalent polyhydric alcohol, and the molecular weight is 3000. The following, p
is an integer between 1 and 6 and less than or equal to the valence of Y, q is an integer whose sum with p is equal to the valence of Y, or 0, and Z is a general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ {In the formula, R_1 is a hydrogen atom or a methyl group, and A is a ▲numeric formula, chemical formula, table, etc.▼(In the formula, R_2 is a hydrogen atom,
a methyl group or a chloromethyl group, and n represents an integer that can make the sum of each of the molecular weights of A, or the sum of the molecular weight of Y, 4000 or less in general formula (I) or (II). 10 to 90% by weight of acrylic urethane represented by A, R_1, R_2 and X do not need to be of the same type in the same molecule] and A resin composition for photocurable printing plates, the main component of which is a mixture of a photosensitizer and, if necessary, a vinyl monomer.