JPS5954600A - Composite supporting substance for photosensitive resin printing plate - Google Patents

Abstract

PURPOSE:To obtain the titled composite supporting substance having an improved adhesive force and being free from the deterioration of the bond performance thereof due to temperature, humidity, a solvent, etc., by providing an adhesive layer formed of diene polymer and resin specified respectively on a flexible supporting substance. CONSTITUTION:An adhesive composition formed of diene polymer (e.g. polybutadiene glycol) of 2-50pts.wt. part which has a functional group (e.g. a hydroxyl group) at the end or not and whose molecular weight is 500-6,000 and resin (e.g. polyurethane being soluble to a solvent having a plurality of active hydrogens) of 98-50pts.wt. which is set with a three-dimensional mesh structure formed by the repetition of ionic addition reactions is applied onto a flexible supporting substance (e.g. polyester) and dried so as to form an adhesive layer, and thereby an aimed composite supporting substance for a photosensitive resin printing plate is obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a method for producing a relief image obtained using a photosensitive resin with a strong [+!
4. The present invention relates to a composite support that can be held by

Conventionally, in order to firmly hold a relief of 1 dt↑ fat on a support, a whole layer of adhesive is interposed on one support, and a photosensitive resin of 1 dt↑ is applied to the contact layer. A method is used in which the relief IJ6 is laminated on the layer 1j, and then exposed to light and cured to firmly adhere the relief IJ6 and the support.
During the printing process and handling, it is required to hold the support and the relief with a necessary and sufficient contact force. Specifically, it is a waste that the adhesive strength tends to decrease due to the influence of temperature, humidity, solvent, etc. in each process.

In order to expand the market for printing plates, various photosensitive resin compositions with different chemical and physical properties have been developed to meet the required characteristics for each printing application. Composite supports that have beta properties for these photosensitive resin compositions are becoming increasingly rare.

However, until now, no adhesive layer has been known that completely satisfies all of the conditions listed in -.

The inventors of the present invention have conducted extensive research on adhesive compositions in order to solve the drawbacks of the prior art, and as a result, the present inventors have discovered that an adhesive composition comprising a special diene polymer and a resin has the above-mentioned drawbacks. The present invention has been completed based on the discovery that it is possible to form a contact layer with no contact.

That is, the present invention provides a composite support for a photosensitive resin printing plate in which an adhesive layer is provided on a 61 flexible support, in which the adhesive layer has a functional group at the end or has a molecular weight of 500. ~
6,000 parts by weight of a diene-based polymer and a resin that hardens by forming a three-dimensional network structure through repeated ionic addition reactions. It is a composite support for plates.

The composite support for photosensitive (raw resin printing plates) of the present invention (hereinafter referred to as the ladle support) contains a diene polymer having a strong affinity with the photosensitive resin composition as an adhesive layer. The adhesive force with the resin composition is improved, the range of application is widened, and the conventional inconvenience of separating photosensitive resin and fBK medical support is eliminated.1. Weak resistance to developing chemicals used during plate making, printing ink during printing, oil, etc., deterioration of contact PJ performance over time, and poor resistance to high temperature conditions. Poor workability caused by sticky stains on the surface of the swimsuit agent layer is greatly improved.

The diene polymer used in this invention has a molecular weight of 500 to 0.0 G, with or without a terminal functional group.
0 diene or 1,000 diene copolymer. If the molecular weight is less than 500, the adhesive layer will not have sufficient physical properties, and if the molecular weight is more than 6.000, the compatibility with other components will be poor.

As the terminal functional group, similar groups such as Il, i-water 1'β group, carboxyl group, amino group, epoxy group, isocyanate 1-group, thioisocyanyl 1-group, etc. are used.

1.As dienes, there are notadiene, isoprene, piperine, nitride, etc., and as copolymers of monoenes, inbutylene, styrene/butadiene lahar, acrylonitrile butadiene lahar, and tongue are used. First of all. Particularly effective is one 'Ci,t.

1.2 At both ends of the polybutadiene chain of polybutadiene,
Polybutadiene glycol with hydroxyl groups, gummy polybutadiene dicarboxylic acid with carboxyl groups, polydiene with isocyanate groups at both ends obtained by reacting polybutadiene glycol with polyisocyanate, 5-terminal methacrylic or acrylic modified polybutadiene,
-77 rained polygetadiene and epoxidized epoxidized polybutadiene. Alternatively, those having a hydroxyl group or carboxyl group introduced into the main chain can also be used.

Its use is from 2 to 50% by weight, based on the total composition. If the amount is less than this, it will be difficult to obtain adhesive strength to the photosensitive (i[・l fat') button product. If the amount is more than this, the compatibility with other components will be poor and This is undesirable because it reduces the adhesive strength with the film and the resistance to solvents, inks, cleaning oils, etc. 3. Also, stickiness on the surface of the adhesive becomes sticky, causing blocking between the films, handling work, etc. This causes problems with the running properties of the film in plate making 11te1.

The ionic addition reaction referred to in the present invention refers to small molecules 11. A reaction in which functional groups bond to each other nucleophilically or electrophilically without defilling the compound. Such a reaction involves the reaction between a functional group that has an active hydrogen bond and a functional group that can be added ionically by this reaction. Examples of L-Z include urethanization reactions, epoxy ring-opening reactions, and the like.

Examples of the resin used in the present invention, which is cured by forming a three-dimensional network structure through repeated ionic addition reactions, include active hydrogen, such as hydroxyl groups.

It can be added ionically by a functional group having a plurality of amine groups, carboxyl groups, etc. or having active hydrogen. Functional groups such as isocyanate groups, thioincyanate, ll
t, polyurethane, polyurea, polyamide, polyester and epoxy soluble in solvents containing multiple epoxy base materials (J IIi: f, unsaturated polyester resin, acrylic resin, phenol + ff17J resin, melamine resin 1iii
, Alkyd 41Ij fat, etc. In order to improve the coating performance of the adhesive, it is preferable to use a functional group having active hydrogen or a low molecular weight compound having several functional groups that can be ionically added with active hydrogen. Examples of these compounds include trimethylolpropane, betaerythritol, hexanediol, etc., polyisocyanate compounds obtained by adding tolylene diisocyanate rice, polycarboxy compounds obtained by adding conohexic anhydride, etc. can.

The adhesive composition used in the present invention is prepared by dissolving 2 to 50 parts by weight of the diene polymer and 98 to 50 parts by weight of the resin using a solvent. The diene polymer may have a three-dimensional structure, or it may be simply immersed in Sakae (1).
2. At this time, a known photopolymerization initiator of 0.1 to 10 times or more is added to the adhesive composition for the purpose of promoting adhesion with the photosensitive (☆J resin) and for the purpose of preventing halation caused by ultraviolet rays. In addition, dyes, pigments, and ultraviolet absorbers are added to the adhesive layer, and fine powder of hydrophobic limestone is also added to improve the surface tackiness of the adhesive layer. As a method, C. A method in which the solvent is removed by drying after coating on the support using a cloth means of the '111 method, such as a Kuzibia coater, roll coater, bar coater, Giscoater, reverse coater, or spray. In addition, in order to increase the reactivity of the applied and dried adhesive composition, aging at 40 to 50°C, a so-called aging treatment, is generally performed.On the other hand, blocking due to stickiness on the adhesive surface is prevented. You can also add a mount during coating for this purpose.

Examples of flexible supports used in the present invention include those having a thickness of 50 μm to 3 m, such as polyester, polyvinyl chloride, 4F-lylene, polypropylene, polyacetyl-1-, aluminum rubber, steel. , natural paper, and synthetic paper.

As a representative example of the photosensitive resin composition used in the present invention, ethylene t (L unsaturated il polymer, photopolymerizable agent, heat) F There is a composition consisting of a compound that does not match.l ?j
l'.

As a prepolymer, vesicle ^kl +l: Reester, 4-saturated polyurethane, oligogoste/L acrylate 9Jj, un64 wholesale polyamide J vesicle sum'rimide, unsaturated polyether, unsaturated poly(meth)ac 1 route Examples of Meishin rubber compounds having the following can be given in 75. The number of these prepolymers, 2-average molecular weight i
It is a historical record to use something that is substantially more than 500.
It is 1 person.

To give more specific examples, examples of unsaturated polyesters and alkyds include unsaturated dibasic acids such as ma1/iyconvex1fumaric acid, itacon, and tt. J1 Its acid anhydride and ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, glycerin, trimethylolpropane, pentaerythritol,
Polyesters with polyhydric alcohols having terminal hydroxyl groups such as 1,4-polybutadiene, hydrogenated or non-hydrogenated 1,2-polybutadiene, getadiene-styrene copolymers, butadiene-acrylonitrile copolymers, Polyesters in which a portion of amber has been replaced with saturated polybasic acids such as adipic acid, phthalic acid, isophthalic acid, phthalic anhydride, and trimellitic acid, or semi-dry polyesters modified with oil fatty acids. Examples of unsaturated polyurethanes include poly(jf-)L and terminal inocyanate groups of compounds linked via urethane groups derived from polyisocyanate having two or more terminal water groups. Alternatively, polyols in which addition-polymerizable unsaturated groups are introduced by utilizing all the hydroxyl groups, such as polyols having terminal hydroxyl groups, such as the above-mentioned polyols, Tatatsuku 1 alkonodes, polyester polyols, and polyether polyols, 1,4-polybutadiene, hydrogenated or Non-hydrogenated 1.2
- Terminal isocyanate or hydroxyl group of polyurethane with polybutadiene, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer and tertiary isocyanate such as toluylene diisocyanate, diphenylmethane-4,4'-diisocyanate, hexamethylene diisocyanate, etc. Utilizing the reactivity of the unsaturated groups, the above-mentioned vesicles (1) (among the carboxylic acids or their esters, compounds having active hydrogen such as hydroxyl, carboxyl, and amino groups) Compounds into which an unsaturated group is introduced by reaction with incyanate, or a compound into which an unsaturated group is introduced by a reaction between a carboxyl group and a hydroxyl group, or a compound in which the above-mentioned unsaturated polyester is linked with a polyisocyanate. As oligoester acrylates, acrylic F-acrylic acid or methacrylic acid is made to coexist in the ester reaction system of polybasic acid and polyester alcohol, and 5 sets of oligomers (cell ratio) are mixed. The number of molecules is adjusted to about 200 to 5,000, and a compound such as adipic acid, phthalic acid, Infta #h0 or acid anhydride is mixed with ethylene glycol, propylene glycol, ethylene glycol, triethylene glycol, etc. Acrylic acid or methacrylic acid is condensed with a Nisder reaction system with a polyhydric alcohol such as licor, glycerin, trimethylolbrohane, or hentaerythritol, for example, a polyhydric alcohol. An ester of a compound having an epoxy group and acrylic acid or methacrylic acid that undergoes a polycondensation reaction between polyphenol, ebichlor, drino'+, and estergylene oxide. , a polymer compound having an interlocking carbon-carbon bond in the side chain, e.g., a polymer compound having a hydroxyl group such as hinyl alcohol, dirulosunoyl alcohol, and an unsaturated carboxylic acid or its acid. Compounds obtained by total reaction with anhydrides and polymers of acrylamide or methacrylic acid''!
or a copolymer containing a carboxyl group-containing polymer compound with an ester bond of unsaturated alcohol, glycidyl acrylate or methacrylate, or a copolymer containing gold maleic anhydride with allyl alcohol, hydroxyalkyl acrylate or Glycidyl acrylate or methacrylate, such as reaction products with methacrylate.
- A reaction product of a copolymer containing d as a copolymerization component with acrylic acid, d, or methacrylic acid can be mentioned.

1. Various rubber compounds include (I) 1,4-polybutadiene, l,2-polybutadiene, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer, EPDIVi, (II) hydrogenated compound of (I) above. vesicle No. 11 modified rubbers, etc., in which small ethylenic saturated groups are introduced into compounds of various rubbers shown in (I), such as compound compounds, imptile-in-prene copolymers, ethylene propylene copolymers, etc. can be exemplified.

Although the compound (I) can be used as it is, in order to introduce the unsaturated group, it is convenient to use various rubber compounds having a terminal functional group. Additionally, in the case of a rubber compound having a 1,2-polybutadiene segment, the unsaturated group can be easily introduced by adding anhydride 71 neu/acid to the compound.

E containing a double bond that photopolymerizes by a mechanism other than the addition of an ethylenic double bond with a prepolymer other than the above.
There is no problem in using compounds such as water-soluble nylon, polyvinyl alcohol, and conductors thereof.

Various known compounds can be used as the ethylenically unsaturated monomer, and examples of such compounds include unsaturated carboxylic acids such as acrylic acid and methacrylic acid, or esters thereof, such as alcohol, Cycloargyl, halogenated alkyl, alkoxyalkyl,
Hydroxyalkyl, aminoalkyl, tetrahydrofurfuryl, allyl, chrycidyl, benzyl
, phenoxy-acrylates and methacrylates, algylene glycols, polyoxyalkylene glycols (d-diacrylates and methacrylates,
Acrylamide, methacrylamide or derivatives thereof, such as trimethy-11-lunolobane triacrylate and methacrylate, pentaerythritol tetraacrylate and methacrylate, such as acrylamide and methacrylamide di-substituted with N-substituted or N,N'-substituted with alkyl, hydroxyalkyl. Allyl compounds, such as acetone, acrylamide and methacrylamide, N,N'-alkyl/nbisacrylamide and methacrylamide;
For example, allyl alcohol, allyl isocyanate, diallyl phthalate), l-allylycyanu l/-),
Maleic acid, maleic anhydride, fumaric acid''!i77'r
J. 'i, -( ): r- ster, e.g. It B furkyl, mono- or dimaleate and fumarate of alkylkoxyalkyl, seven other unsaturated compounds such as f-rene, hinyltetraene, Shihinino 1
/Kunzen, N-vinylcarbazole, N-vinylpyrrolidone, etc. can be used. A portion of these ammoniums is treated with an azide compound such as 4,4'-diazidostilbene, 4,4'-phenylene-bisazide,
Diazide benzophenone, 4,4'-diazide phenylmethane, 4,4'-diazide chalcone, 2,6-di(
4'-azidobenzal)-cyclohexanone, 4.4'
-Diazidostilbene-α~carvone fi, 4.4'-
Diazidiphenyl, 4,4'-cyasitostilbene-2,2'-disulfone can be replaced with Nl such as soda.

These single-position bodies are
The addition amount may be varied within the range of 0 to 200 parts.

7 was obtained by using various known photosensitizers as photopolymerization sensitizers. Examples of such substances include benzine, benzoin ethyl ether, benzoin-n-furobyl ether, penzoin-inflobyl ether, benzoin alkyl ether of benzoinbutyl-ethernato, 191.2,2-dimethoxy-2-phenyl Acetophenone, benzophenone, benzyl, cyanopur,
Dienyl sulfide, eosin, thienyl 9,10-
There are anthraginone, 2-ethyl-9,10-antho2quinone, Michler-Kutone, etc., and for the composition, o
, ooi to 10-hj.

Heat 511@ As inhibitors, hydroquinone, mono-tert-butylhydrodinone, benzoquinone, 2.5-diphenyl-p-benzoquinone, picric acid, di-l)-fluorophenylamine, p-methoxyphenol, 2.6-
-)Jp, 3-butyl-1)-cresol, and the like. It is desirable that these lp and polymerization inhibitors (French, thermal off-shore reactions (dark reaction) be prevented. Therefore, the addition of thermal off-shore reaction (dark reaction) is necessary for the addition of lp/polymerization inhibitors. It is desired that the total amount of crosslinking agent and crosslinking agent be within the range of 0.005 to 5.0 degrees (7 degrees).

In addition, a composition comprising polyelm, polythiol, and a photosensitizer disclosed in Japanese Patent Publication No. 46-29525 is also useful. As shown in FIG. 1, the composite support of the present invention has a structure in which an adhesive layer 2 is formed by applying the adhesive composition on the vibrating support 1. Layer 2 is support 1 (/
r, strongly adhered. In this case, the y thickness of the adhesive layer 2 is 0.5 to 400 microns, preferably 3 to 1
00 microns. In particular, the thickness of the adhesive layer 2 is
If the thickness exceeds , "wrinkles" may occur due to the difference in mutual expansion coefficients, so the thickness of the adhesive layer 2 needs to be equal to or less than the thickness of the support 1.

A photosensitive resin printing plate using the composite support of the present invention is produced by the following method. That is, as shown in Figure 2,
After providing the uncured photosensitive resin composition layer 3 on the adhesive layer 2 of the composite support of the present invention, as shown in FIG. 3, the uncured photosensitive resin composition layer 3 of FIG. Transparent image carrier (4) for photographing characters, patterns, halftone dots, etc. (A) A transparent image carrier (A) 1 transparent image (A) Active light source (A) from the side By irradiating the light beam a, the image on the transparent image a]r carrier 4 is uncured j(ε photosensitive resin composition) ψ
Applying r3vc, the r1 light (light irradiation) portion of the b1 composition layer 3 is substantially cured before curing: di: curing. Next, a photosensitive 11M printing plate was prepared by performing the following operations: removing the transparent image carrier 4, removing the uncured portion, washing, drying, and relighting. \Satake. In this 1ψ work, photosensitivity (
hj, mi, irradiation H4 of the fishing fat layer 3 and intensity of the ray a 1
;L is selected depending on the purpose of use of the printing plate to be produced and type 1+i1 of photosensitive resin composition 3 to be used. In this manufacturing process, a transparent support was used as the support 1.1. The 1st case is as shown in Figure 4.
In order to improve image formation properties, the photosensitive resin composition 3 in contact with the adhesive layer 2 is irradiated with a light beam from the active light source B from the side of the support 1, and the photosensitive resin composition 3 is, for example, 0.1 micron thick. 0,3～
A method of polymerizing and curing to some extent may be used. In addition, in order to reduce the amount of photosensitive resin used in the making of photosensitive resin printing plates, a method of using a relief with a lower 9J value has been adopted; As shown in FIG. 5, a net-like screen image carrier 5 is placed on the opposite side of the adhesive layer 2 of the transparent support 1 to prevent light from reaching the non-image areas. The present invention will be explained in detail below with reference to Examples.

In addition, in Examples and Comparative Examples, "part" means a part of the middle season. In addition, the measurement of adhesive force>i- was carried out as shown in σ) below.

[Method of measuring adhesive strength]

A photosensitive resin h/printing plate was prepared using the composite support to be evaluated and various photosensitive resin compositions by the method shown in Figure 3.4.5. Make a peel-destination zombule of the shape, and fix the relief side to the upper chuck on the Instron measuring machine as shown in Fig. 6 t and ζ.Fix the base film to be measured to the lower chuck. Pick up 1'j-s 50m
It was pulled at a speed of 5/min, and the peeling resistance value at this time was used as a force of -7i-. At this time, the measurement is performed with an auxiliary plate (iron plate) provided on the measurement sample so that the peeling angle is 180 degrees.

Example 1 and Comparative Examples A polyester film (part name: Diafoil, manufactured by Diafoil Co., Ltd.) with a thickness of 0.1 mm was coated with urethane adhesive.
60 parts of agent (part name: Olivine AD-335A, Toyo Moat/Stone), urethane curing agent (part name: CAT)
-xo, East? An adhesive composition obtained by dissolving and mixing 5 parts of 1,2 polybutadiene glycol (molecular weight: 1000) and 5 parts of pensoin inflobil ether with ethyl acetate was prepared. Coater VC
? Apply it to a thickness of about 10μ, and apply it to 80μ
C. for 4 hours to obtain a composite support.

On the other hand, a negative film was placed on a transparent glass substrate with a thickness of 7 parts M, and then a transparent polyester film with a thickness of 9 μm was placed over the negative film to cover the negative film. On the film, a photosensitive 4MJ resin composition having the composition shown below was applied to a thickness of 1 mJl using a doctor knife.

■ Propylene glycol, ethylene glycol, fumariso, and adipic acid in a molar ratio of 30/0.2.
0 / 0.25 / 0.25 ratio to condense an unsaturated polyester with an acid value of 25. To 100 parts of this unsaturated polyester, tetraethylene glycol dimethacrylate 4091+, 5 parts of acrylamide, N-3--Oquino 1 .15 parts of 1-dimethylbutylacrylamide,
A photosensitive resin composition containing 2 parts of benzoin ethyl ether.

■ Polypropylene adipate (number average molecule J■J, 0
00) I, add toluylene diisocyanate 0°348 powder to OKg, and then add (1,01%) to the total of 0.75 kg of polyzolobile/adipate and polyethylene glycol (number average molecular weight 1500) to be anti-glare. of dibutyltin dilaurate was added and reacted at 50°G for 3 minutes, then the temperature was raised to 70'C and reacted for another 30 minutes.Then, it was cooled to 60°C and 0.02% of dibutyltin dilaurate was added. Then, polyethylene glycol monoacrylate 7 (number average Molecule-390
) Add 0.39 to 2 and 0.025% hydroquinone based on the above total amount and react between 4 [+ and J].

Terminal vinyl sol polymer polymer 10 fl-shaped in this way
0 r, 2-hydroxyethyl methacrylate 10
A photosensitive resin composition containing a crosslinking agent consisting of 5', human 11xy polyethylene glycol monomethacrylate 301 and 2 EHA 10 r, and benzoin 32 (photosensitizer).

■ Terminal water I with an average of 1.7 hydroxyl groups per molecule
'lν group type hydrogenated 1,2-polybutadiene (average molecule M MIN = 2200 hydrogenation rate 9s%) 2zor
and TDI (2,4 bodies/2,6 bodies = 3/-2) 22-2
'After mixing and reacting at 60°C for 3 hours with stirring, 2-hydroxyethyl methacrylate 122. Hydroquinone 0.3y% dibutyltin dilaure) 0
．． 6 t of the mixed solution was heated and reacted at 80°C for 2 hours to prepare a prepolymer with a grain size of 7,300.Lauryl methacrylate 302. A photosensitive resin composition containing polypropylene/glycol dimethacrylate (trade name NK ester p-9G) 20v1 benzoin isoamyl ester 31% hydroquinone 0.15F.

■ 1.6-hegizandiol 615 (5,22)
1)) h neo hair f! Recall 233f (2,2
) and adipic acid 867 F (5 parts 4 mol) and P-toluene/sulfonic acid 8v as esterification catalyst.
'fr: In addition, a dehydration condensation reaction is carried out at 120 to 180°C in a nitrogen atmosphere for 2 hours under normal pressure, and then the degree of vacuum is 300 to 30
wi(j'.

Polyester diol A was completely synthesized by reacting at 220°C for 5 hours, and the next step was @A1404? (0.40 mol) 2
Tolylene diisocyanate 872 (o, so mol) was added once in an indoor atmosphere under four atmospheres on an oil bath at 50°C while stirring, and the mixture was allowed to react at 50 to 85°C for 4 hours. A viscous substance Az (estimated molecular weight 5000) was obtained.Next, the reaction system was changed to an atmosphere of 3,5-jet.
t-Butyl-4-hydroxytoluene (hereinafter referred to as DI-IT
) is 0. After adding ir and stirring for 10 minutes at 80°C, add epoxy ester D1 (base value 550 m2 on water).
KOl, I/', acid value 5.3 yrq KO) VS
', glycerin monomethacrylate/glycolic acid CM
46 y (o, zz
Moh ) and dibutyltin diurate (hereinafter abbreviated as BTL)
o, os y @- were added, and the vinyl group introduction reaction into A2 was carried out at 80°C for 2 hours. Now, raise the oil bath to 90℃ and add 22 f (0
, 22 mol) and stirred for 3 tRif'+4J reaction. The degree of progress of the half-esterification reaction using hydrothermal succinic acid V was tracked hourly using the acid value, and after 3 hours it became stable.
A colorless and transparent i94 mucilage (1) was obtained. The molecule 1i of (1) was estimated to be 5900, unsaturation equivalent 2900, and its acid value was 24 mgKOH/y.

Diethylene glycol dimethacrylate 301 and 2-
Hydroxypropyl methacrylate].302, benzoin butyl ether 3.21, and BHT O,1
A photosensitive resin composition prepared by adding 100 t of substance (1) to a mixed solution of 9 and stirring well. .

Then, the composite support was laminated onto the photosensitive resin composition so that the adhesive composition came into contact with the adhesive composition and no air bubbles were formed.

This was placed at a position 15-on below a light source consisting of 10 20W ultraviolet fluorescent lamps and exposed through the composite support for 30 seconds.Then, this was moved to a position 15-on above the light source and the glass plate and H light through negative film 1
I'm going for 0 minutes. After the exposure was completed, the uncured areas were washed off with a 0.3% caustic soda aqueous solution and a detergent (product name: 6 Libon (manufactured by Lion Corporation)), and no peeling or peeling was observed in the thin cured film (5 μm) that had hardened and precipitated on the adhesive layer side. In addition, the halftone dots were also adhered to the adhesive layer. Then 15 at 50℃
After drying for a minute, place it at a position 15cn1 from the light source.ii
? After 10 minutes of flashing, a printing plate was obtained./iCo This printing plate should be noted that the support was firmly adhered to the various photosensitive resin compositions mentioned above, and using this, 50 parts of force was applied. Even after rotary printing, no abnormalities were observed on the plate surface.

Table 1 shows the results of measuring the contact force of the relief on the printing plate.
'c7J<su,-, the composite support was heated at a high temperature (50
℃), 30℃ under high 5 degree (80% F, H) conditions
Re-evaluation after a period of time: E-/ζ curing showed that adhesive strength similar to f='1 was obtained, and no change over time was observed.

On the other hand, for comparison ◇2, AD-33
A 5A mouse was adjusted so that the ratio of 11112 water groups and incyanate groups was the same balance as in Example 1, and Example 1ty
The composite support was coated on a polyester film using the method described in Example 1 and Example J, and dried and made into a composite support. When the contact force was evaluated, it was found that when washing out after dispersion exposure, the thinly cured film peeled off (relief (+111)), and even small halftone dots were not washed away. The contact force after post-exposure also changed.
As shown in Figure 1, the value was very low.

Table-1 Adhesive strength [180 degree peeling 1 resistance value (?10n)
] Example 2 and Comparative Example 2 Example Comparative Example 2 The above components were dissolved and mixed in the same manner as in Example 1, coated on a support and dried for 5 minutes to form a composite support of 11 tons. For comparison, a composite support 2 was also prepared in which the 1,2 borobutadiene epoxy modified product of Example 2 was removed. (Comparative Example 2) To evaluate the chemical resistance of this composite support, ethyl acetate was used.

Perform a 24-hour immersion test at 20°C in ingropirovir alcohol, acetone, water, and tri-alkaline water. ,
As a result, in Example 2, no swelling or peeling of the ellipsoidal layer was observed, and the results were good. On the other hand, in Comparative Example 2, swelling was observed in response to ethyl acetate and acetone.
As a result of evaluation in combination with I fat composition /ζo;t', a good gripping force result was obtained which was almost the same as that of Example 1+111.

4, 1'ii between L71] simple, therefore, Ming 1st t:,
', + is the blemish fI) of the composite support for photosensitive resin printing plates of Kinoe Suj), U, N2 Figure 2 is on the adhesive layer of the composite support for photosensitive resin printing plates of the present invention. 3 shows the uncured photosensitive resin composition layer 4r in FIG.
"C4 property: MJ II: r Place a VC negative film on the composition layer and irradiate light from the negative film side/Cross-sectional view of the printing plate after this, Figure 4 (Good, R), Figure 2 Uncured photosensitive resin 11h' 1vJl Compound J-Place the negative film on the soil, and apply light from the negative film side and the support (111, l)
(Cross-sectional view of the printing plate after the irradiation, No. 51) shows a negative film on the uncured photosensitive 1L resin composition of the hook 52 in Fig. 1 and a screen negative film on the support ('I'll
G, Light irradiation from the negative film side and the screen negative film A/mu side.
1 is a one-to-one view showing the procedure for measuring the peeling test of a printing plate comprising the composite support of the present invention and a photosensitive resin composition. In the figure, l is a support, 2 is an adhesive layer, 3 id is an uncured photosensitive first J1\i' composition layer, 4 is a transparent image carrier, 5-
, Screen LL! 11 - carrier, G is a cured portion of uncured photosensitive resin composition 3, 7 - uncured photosensitive layer 1 - resin M1
1 liter of uncured composition 3, A and B are light intensity, a+b is light,
10 is the upper j1μ chuck, 11 is the T part nayak, 12 is the auxiliary plate (iron plate), 13 is the auxiliary oil reno, and the total number is 71.

License applicant: Asahi Kasei Engineering Co., Ltd. Figure 1 Figure 2 Figure 6 and A /HaV~・ Figure 4 To the play Small O Figure 5 ＼°〜B Figure 6

Claims (1)

[Claims] In a composite supporting composite for a photosensitive resin printing plate in which a contact layer is provided on a flexible support, the adhesive layer has a functional group at the terminal end or a Shun-based polymer having a molecular weight of 500 to 6,000. 2 to 50 parts by weight and a resin that hardens by forming a three-dimensional network structure through repeated ionic addition reactions; for use in photosensitive resin printing plates; composite support