JPS5828572B2 - Shinki Kankouseiji Yushijiban - Google Patents

Description

[Detailed description of the invention] The present invention relates to a support plate for liquid photosensitive resin.

More specifically, the present invention relates to a support plate for liquid photosensitive resin, which is formed by providing a specific adhesive layer on the surface of a flexible substrate.

Conventionally, a layer of solid or liquid photosensitive resin is placed on a steel plate, aluminum plate, or resin film plate via an adhesive layer, an antihalation layer, etc., and active light such as ultraviolet rays is irradiated through the image film to form the image area. A well-known method is to easily produce a letterpress printing plate having excellent performance by solidifying the polyester into a relief shape and dissolving the uncured portion with a developer.

In this case, if the photosensitive resin layer that can be photopolymerized is a solid that has no fluidity at room temperature, the manufacturer has adhered the substrate and the photosensitive resin layer sufficiently firmly in a manufacturing process that takes a sufficient amount of time. The adhesive layer is not as serious a problem as it is sold in Japan.

However, when the photopolymerizable photosensitive resin layer is made of a liquid resin composition that exhibits fluidity at room temperature, the resin solution is cast onto a previously prepared substrate immediately before plate making, and then exposed to light immediately. There are many problems with adhesive layers that need to be solved because reliefs of all shapes that are exposed to form image areas must be made firmly adhered to the substrate.

This is particularly difficult when using a polyethylene terephthalate film with low adhesion as a substrate, as there must be sufficient adhesion not only between the photosensitive resin layer and the adhesive layer, but also between the adhesive layer and the substrate. It develops into a serious problem.

At the same time as the photosensitive resin liquid in contact with the adhesive layer hardens, the cured resin and the adhesive layer must adhere firmly, and the adhesive must be strong enough to withstand the severe mechanical stress that occurs when handling the printing plate. In particular, properties are required such as flexibility, sufficient resistance to chemicals such as developer and ink cleaning solutions, and no unnecessary tackiness on the surface.

This does not mean that such attempts have not been made in the past.

For example, Japanese Patent Publication No. 36-23761, Japanese Patent Publication No. 40-
A method such as that described in Japanese Patent No. 12104 is known, but this method requires careful control of conditions to coat the barrier layer assembly and partially harden the barrier layer, and is not necessarily suitable for industrial use. It is hard to say that it is suitable for this purpose.

Furthermore, unsightly scratches are observed on the film-like substrate due to the polymerization reaction during the formation of the barrier layer, which often causes significant disadvantages in subsequent operations.

In addition, there are various resins that have been known to adhere relatively well to the surface of substrates that are difficult to adhere to, such as polyethylene terephthalate, such as copolyester resins (e.g. copolyester of terephthalic acid, isophthalic acid, etc. and ethylene glycol), There have been attempts to use resorcinol-formalin resins, vinyl copolymers (for example, θ vinylidene chloride copolymers known in U.S. Patent No. 2,762,720, Belgian Patent No. 655,644, etc.), but none of them It has both advantages and disadvantages and is not something to be satisfied with.

That is, it has drawbacks such as requiring high temperature and long time for thermosetting, lack of solvent resistance, poor affinity swelling with liquid photosensitive resin, and lack of flexibility. , it is completely impractical.

The present inventors have overcome the various drawbacks of these conventional techniques to provide a support plate for liquid photosensitive resin that is inexpensive, has excellent performance, and is easy to handle. be.

That is, the present invention provides a flexible base material, a layer of a composition comprising a linear polyurethane compound, a polyfunctional incyanate compound, and a polyfunctional hydroxy compound provided on the flexible base material, and (1) A compound having at least two or more 1,2-epoxy groups in the molecule (2) A photopolymerizable carbon-carbon double bond and a 1,2-epoxy group or active hydrogen in the molecule 110
(3) an organic curing agent containing at least two active hydrogen atoms and containing no light-polymerizable carbon-carbon double bonds, or which can be converted into this in situ; This is a support plate for a photosensitive resin obtained by heating a structure composed of a layer of a composition made of a compound.

An object of the present invention is to provide a support plate suitable for manufacturing a photosensitive resin printing plate with excellent resolution.

Another object of the present invention is to provide an adhesive layer that does not melt even when heated and is not easily attacked by water, acids, alkalis, organic solvents, or printing inks, and that allows the relief to be firmly supported by the adhesive layer. The object of the present invention is to provide a support plate useful for producing printing plates that are adhered to a printing plate.

Another object of the present invention is to provide a support plate that is useful for manufacturing printing plates that are free from damage due to repeated external forces applied to the printing plates and have extremely high printing durability.

As the flexible base material used in the present invention, a base material made of a thin transparent substance is preferably used.

For example, polyester films such as polyethylene terephthalate, polycarbonate, and polyethylene 2,3-naphthalate, cellulose films such as acetate, polyolefin films such as polyethylene and polypropylene, polyamide films, polyvinyl chloride films, etc. are used. Ru.

A polyethylene terephthalate film is particularly preferably used because it has dimensional stability despite being bulky and is strong against mechanical destructive forces such as tearing.

For the purpose of further improving the adhesion between the base material and the coating layer, various pretreatments may be applied to the surface of these base materials in advance.

For example, a method of making the surface grainy (matt), a method of activating it with a strong oxidizing acid, a method of activating it by corona discharge, irradiation with ionizing radiation, etc., a method of coating the surface with a thin layer of titanate esters, A method of chemically roughening the surface using a solvent or the like can be carried out.

Corona discharge treatment is effective for various films, but is particularly useful for polyolefin films.

As the base material, a transparent resin film is preferably used as described above, but opaque base materials are also useful.

For example, zinc 5. Thin metal sheets such as aluminum, copper, and steel, rubber sheets, paper, and nonwoven fabrics can also be used.

Among the layers forming the support plate of the present invention, a layer of a composition consisting of a linear polyurethane compound, a polyfunctional incyanate, and a polyfunctional hydroxy compound (hereinafter abbreviated as an undercoat layer) is on the surface of the base material. By the reaction of a polyfunctional hydroxyl compound and a polyfunctional polyisocyanate compound, linear polyurethane molecules are entangled to form a moderately network-like structure, and it is applied as a layer that firmly adheres to the base material.

If such a layer does not contain a linear polyurethane compound, the network structure of the polymer becomes too dense and the formed thin film becomes brittle and cannot be used as a support plate for photosensitive resin.

Furthermore, the combination of a linear polyurethane compound and a polyfunctional isocyanate compound has the disadvantage that the network structure becomes too coarse, resulting in poor chemical resistance.

A layer of such an undercoat layer composition can form a strong film with good chemical resistance and high elasticity, and has become extremely useful as a support plate for photosensitive resins.

Examples of the linear polyurethane compound include linear polyester polyurethane and polyether polyurethane compounds.

The linear polyester polyurethane compound is obtained by reacting a polyester resin having substantially hydroxyl groups at both ends with a bifunctional isocyanate I compound.

As a polyester resin, for example, a bifunctional organic carboxylic acid such as adipic acid, phthalic acid, maleic acid, or dimer acid is used as a dicarboxylic acid component, and a glycol such as ethylene glycol, propylene glycol, tetramethylene glycol, or diethylene glycol is used as a glycol component. Examples include polyester or polycaprolactone.

Such polyesters may partially contain amide groups, ether groups, etc. that are inert to isocyanate groups in the chain.

Such polyester has an average molecular weight of 500-600.
In particular, those having a relatively molecular weight of 800 to 3,000 are preferably used.

The polyester portions as described above incorporated into the linear polyester polyurethane chains form the soft segments.

As the bifunctional incyaneto compound, for example, 2.
4-tolylene diisocyanate and 2,6-tolylene diisocyanate (hereinafter abbreviated as TDI), diphenylmethane diisocyanate (hereinafter abbreviated as MDI),
Paraphenylene diisocyanate, 2-chloro 4-
Phenyl diisocyanate, 1,5-naphthalene diisocyanate, 3,37-dimethyl-4,4'-diphenyl diisocyanate, 3,3'-dimethyl-4,4/diphenylmethane diisocyanate, hexamethylene diisocyanate 1-, xylene diisocyanate etc. can be given.

The linear polyether polyurethane compound is obtained by reacting a polyether compound having substantially hydroxyl groups at both ends with a bifunctional incyaneto compound.

Examples of such polyethers include polytetramethylene glycol, polyethylene glycol, polypropylene glycol, and polyethylene propylene glycol.

As the difunctional incyanate, the same compound as the difunctional isocyanate mentioned for the polyester polyurethane compound can be used.

Thus, a linear polyester polyurethane compound obtained by reacting a polyester as described above with a difunctional incyane-1. and a linear polyether obtained by reacting a polyether as described above with a difunctional isocyanate. The polyurethane compound usually has an average molecular weight of about 5,000 to 100,000, particularly about 10,000 to 50,000.

The terminal groups of such linear polyester polyurethane compounds and linear polyether polyurethane compounds may be hydroxyl groups, incyanate groups, or other organic groups inert to incyanate groups.

However, in the case of isocyanate groups, when used as a coating liquid, the stability thereof is somewhat poor and is therefore not preferable.

As the linear polyurethane compound, a polyester polyurethane compound is preferred.

Furthermore, as the polyester polyurethane compound that can be most preferably used, a polyester containing adipic acid as the main dicarboxylic acid component and 1,4-butanediol or ethylene glycol as the main glycol component is TD.
It has an average molecular weight of 20,000 to 50,000 obtained by chain elongation with I or a mixture of MDI and TDI.

Next, examples of suitable polyfunctional incyane-1 compounds include adducts of trimethylolpropane and TDI (for example, Desmodur L, a product of Bayer), trimethylolpropane and xylylene diisocyanate, etc. adducts, condensates of diisocyanates (e.g. Desmodur IL, Desmodur CT, TD
trimer of I, desmodule N, etc.).

The difunctional incyanates mentioned above may also be used.

Examples of polyfunctional hydroxy compounds include aliphatic polyfunctional hydroxy compounds such as pentaerythritol, trimethylolpropane, glycerin, hexanetrioltrimethylolethane, and sorbitol, polyether compounds having hydroxyl groups at both terminals, and poly(oxypropylene).
trifunctional polyols such as triol, poly(oxypropylene) poly(oxyethylene) triol, aromatic polyfunctional hydroxy compounds such as bisphenol A and novolak resins, low molecular weight polyesters having many hydroxyl groups in the molecule (e.g. Bayer Co., Ltd. Desmorchen 2200.
Desmorchen 800, etc.).

**Also, glycicyl etherification of a part of polyfunctional hydroxy compounds having trifunctionality or more, such as glycerol monoglycidyl ether, pentaerythritol diglycidyl ether, diglycerol diglycidyl ether, flubitol tetraglycidyl ether, etc. Examples include diyl ether, sorbitol diglycidyl ether, and the like.

Further examples include linear polymer compounds (n≧2 represented by the following formula) made from epichlorohydrin and 2,2-bis(4'-oxyphenyl)furopane (ie, bisphenol A).

Preferred among these polyfunctional hydroxy compounds are those having a molecular weight of 130 to 2000, and more preferred are compounds containing both a hydroxyl group and an epoxy group.

The hydroxyl groups of such compounds react with the incyanate groups of the undercoat to form the proper network structure of the undercoat, and at the same time the epoxy groups react with the curing agent in the layer coated on top of the undercoat, improving the chemistry of both layers. strengthen physical bonds.

Among such compounds, aliphatic compounds (eg, pentaerythritol diglycidyl ether, sorbitol tetraglycidyl ether, etc.) are the most preferred examples.

The amount of each component used in the undercoat layer is 40 to 85% by weight, preferably 50 to 80% by weight of the linear polyurethane compound.
On the other hand, the total amount of the polyfunctional hydroxy compound and the polyfunctional incyanate compound is 15 to 60% by weight, preferably 20 to 60% by weight.
It is 50% by weight.

The amount of the polyfunctional hydroxy compound used is in the range of 0.3 to 3.0 in terms of hydroxyl group/isocyanate group ratio (mole ratio),
Naturally, it is most preferable for this ratio to be close to 1 in the range of 0.6 to 1.5.

If one of the combinations of a polyfunctional hydroxy compound and a polyfunctional isocyanate compound is difunctional, the other must be trifunctional or higher in order to make the undercoat layer three-dimensional.

In the present invention, such linear polyester polyurethane compounds and polyether polyurethane compounds,
Polyfunctional hydroxyl compounds and polyfunctional inorganic compounds are uniformly dissolved in a solvent inert to isocyanate groups, such as acetic acid esters, toluene, benzene, xylene, ethane dichloride, methyl ethyl ketone, dimethyl formamide, and tetrahydrofuran. The best method is to use a mixture of cyanate compounds.

In addition, a catalyst that promotes the crosslinking reaction, a stabilizer, a plasticizer such as benzyl butyl phthalate, etc. can be used in combination.

At this time, it is necessary to refrain from adding so much as to reduce the pot life extremely.

Furthermore, by adding dyes or pigments that absorb actinic rays, antihalation effects can be imparted.

Examples of the light absorbing agent include inorganic and organic pigments that absorb in the near ultraviolet region, such as carbon boot, trilead tetroxide, titanium dioxide, and benzidine yellow rhodamine, or conventionally known effective ultraviolet absorbers. Examples include benzophenone-based or benzotriazole-based compounds.

Among the layers forming the support plate of the present invention, (1) a compound having at least two or more 1,2-epoxy groups in the molecule;
(2) A photopolymerizable carbon-carbon double bond in the molecule and 1.
A compound having a 2-epoxy group or an amino group having active hydrogen and a boiling point of 110°C or higher at normal pressure, (3
) A layer (hereinafter abbreviated as adhesive layer) composed of an organic curing agent having at least two active hydrogen atoms and containing no carbon-carbon double bonds that can be polymerized by light or a compound that can be converted into this in a reaction field. ) is applied as a layer that chemically firmly bonds the undercoat layer and the photocured portion of the photosensitive resin applied on the adhesive layer**.

Examples of the compound having at least two 1,2-epoxy groups of the present invention include condensation products of the epichlorohydrin and polyhydric phenols such as bisphenol A or polyhydric alcohols such as polyethylene glycol, which are linear High molecular compound (for example, a linear high molecular compound from the above epichlorohydrin and bisphenol A, in the above formula, n is O or a number of 1 or more) 2-glycylphenyl, glycysylphenyl, glycysylphenyl, 2,6-siglycidyl phenyl, Examples include aromatic epoxy compounds such as glycidyl ether, aliphatic epoxy compounds such as diglycidyl ether, butadiene dioxide, and the like.

Furthermore, examples of trifunctional or more functional epoxy compounds include epoxy novolac resins and compounds of the following formulas.

Preferably, shrimp chlorhydrinthrin and bisphenol A
Or, a condensed linear polymer compound with polyethylene glycol or polypropylene glycol with an average molecular weight of 300.
6,000, more preferably a condensed linear polymer compound of epichlorohydrin and bisphenol A with an average molecular weight of 350 to 3,000.

The compound of the present invention having both a photopolymerizable carbon-carbon double bond and a 1,2-epoxy group or an amino group having active hydrogen in the molecule is the curing agent (component (3)) described below.
) to form a three-dimensional polymer by reacting with the epoxy compound (component (1)).

Such a compound must have a boiling point of 110°C or less at normal pressure.

If the boiling point of such a compound is lower than 110°C, the compound will evaporate together with the solvent during coating and curing of the adhesive layer, making it impossible to fix the initial target amount of the compound in the adhesive layer, resulting in photosensitivity. Adhesion with resin decreases.

Examples of compounds having a photopolymerizable carbon-carbon double bond and an epoxy group include glycysyl acrylate, glycysyl methacrylate, glycysyl allyl ether, italyl glycidyl ether, C-allylphenyl glycysyl ether, and the above epoxy compounds. An epoxy acrylate resin in which a part of the epoxy group of (component (1)) is condensed with acrylic acid or methacrylic acid or acrylic acid chloride is added, and butadiene is anionically polymerized with metallic sodium to produce liquid polybutadiene with a low degree of polymerization. Examples include those oxidized with peracetic acid.

Preferred examples include glycysyl methacrylate, glycysyl allyl ether, and epoxy acrylate-I.
Resin can be given.

Compounds with a boiling point of 110° C. or higher at normal pressure that have both a carbon-carbon double bond that can be polymerized by light and an amino group that has active hydrogen include diallylamine, an amine curing agent that has multiple active hydrogens, and polyamide as described below. Examples include a reaction product of a part of the active hydrogen of the resin and a compound having both the photopolymerizable carbon-carbon double bond and an epoxy group.

Preferred examples of such compounds include reaction products obtained by reacting glycysyl methacrylate, glycysyl allyl ether with a polyamine such as hexamethylene diamine, and a portion of the active hydrogen of a polyamide resin;
Particularly preferred is a reaction product of glycysyl methacrylate and polyamide resin.

The “photopolymerizable carbon-carbon double bond” mentioned here is
It is represented by the structure of an α-substituted vinyl group, that is, CH2=C<(R is hydrogen or an alkyl group).

Examples of the organic curing agent containing at least two active hydrogens and not containing carbon-carbon double bonds that polymerize with light include aliphatic amines such as diethylmine diethylenetriamine, diethylaminopropylamine, and the like; Hydroxyaminos such as ethanolamine, propatoolamine, monohydroxyethyldiethylenetriamine, N(2-hydroxypropyl)ethylenediamine, bishydroxyethyldiethylenetriamine, aminoethylethanolamine, metaphenylenediamine, m-aminobenzylamine, P.y Examples include aromatic amines such as -diaminodiphenylmethane and diaminodiphenylsulfone, and amines in which a portion of the active hydrogen of each of these amines is substituted with an aliphatic group or an aromatic group.

Furthermore, polyhydric carboxylic acids such as phthalic acid, certain 7-enol resins, urea resins, polyester resins, polysulfide resins, melamine resins, polyamide resins (for example, terminal amines synthesized from a dimer of lylunic acid and ethylenediamine or diethylenetriamine) Examples include polymeric compounds having a large number of active hydrogens, such as polyamide (polyamide).

Examples of compounds that can be converted into curing agents that contain two or more active hydrogen atoms in the reaction site and do not contain double bonds that can be polymerized by light include acid anhydrides, that is, phthalic anhydride, used together with a small amount of water. , pimelic anhydride, etc.

Anhydrides having a carboxyl group, such as tricarbalic anhydride and trimellitic anhydride, can be used together with a small amount of alcohol.

Preferred examples of such curing agents include amines and polyamide resins, particularly preferred examples include polyamide resins.

The amount of each component used in the adhesive layer is 20 to 90% by weight for component (1), 5 to 70% by weight for component (2), and 3 to 3% for component (3).
A range of 70% by weight is preferred, with each component totaling 100% by weight.

Particularly preferable ranges include 25 to 85% by weight for component (1), 10 to 60% by weight for component (2), and 7 to 85% by weight for component (2).
It is 50% by weight.

If one of the combinations of component (1) and Kai/A3) is difunctional, the other must be trifunctional or higher for exactly the same reason as the undercoat layer.

Dissolve these ingredients in a solvent suitable for coating,
It is suitable to mix it in a liquid state and use it for coating.

In addition, before coating, in this liquid state,
It can also be aged for several days.

Examples of solvents include aromatic hydrocarbons such as benzene, toluene, and xylene; ketones such as acetone, methyl ethyl ketone, and methyl isopropyl ketone; esters such as ethyl acetate and butyl acetate; methyl cellosolve, n-butanol, and diacetone alcohol. Alcohols such as

Among these solvents, compounds having active hydrogen capable of reacting with incyanate groups, such as primary alcohols, are not desirable solvents.

However, if a small amount of alcohol is used, if it is quickly dried, the reaction with isocyanate groups will not substantially occur and it can be used.

Furthermore, since secondary and tertiary alcohols react much more slowly with incyanate groups than primary alcohols, they can be used in considerable amounts.

That is, since tertiary alcohol such as diacetone alcohol has low reactivity with incyanate groups, there is no substantial problem even if it is used in a somewhat large amount.

Similar to the undercoat layer, the adhesive layer may also contain an ionic addition reaction catalyst, a radical polymerization inhibitor or inhibitor, the above-mentioned light absorbent, etc., if necessary.

A solution of the undercoat layer and adhesive layer composition thus obtained is coated in the following manner to produce a photosensitive resin support plate for clothing.

Spray a solution of the above undercoat layer composition onto a base material such as polyethylene terephthalate film.
Coating is performed uniformly using a bar coater, reverse coater, etc., and then the solvent is usually removed using a hot air dryer.

The thickness of the layer is preferably 5 μm or more, and particularly preferably about 10 to 50 μm.

Hot air drying is performed at a temperature of 60 to 150°C immediately after application.
This is carried out for about 0 minutes, but of course this will vary depending on the type of solvent used.

In any case, it should be understood that this heating step is merely for scattering the solvent or for partially reacting the hydroxyl groups and incyanate groups.

That is, the isocyanate groups of the polyfunctional isocyanate compound in the undercoat layer remain unreacted.

The measurement of unreacted isocyane-1. groups is as follows.

An undercoat layer was applied on a 125μ polyethylene terephthalate film, dried, and the absorption of the infrared spectrum was measured using an IRA-1 type infrared spectrophotometer manufactured by JASCO Corporation ■, and the isocyanate groups were quantified using the following simple method. Ta.

That is, let A be the maximum point of absorption of 2380c*-1, and 2
The minimum point of absorption of 040CrrL' was set as B, and a straight line was drawn between A and B, and this line segment AB was used as the baseline.

Next, let C be the absorption maximum point of the absorption position of the isocyanate group of 2270crIL', and pass through this point C to 1.0
A straight line perpendicular to the 0% absorption line was drawn, and the intersection with the baseline and the intersection with the 100% absorption line were set as E, and calculations were performed using the method shown below.

The amount of unreacted isocyanate groups in this undercoat layer is (1)
The formula preferably ranges from 0.008/μ to 0.157μ,
A range of 0.010/μ to 0.080/μ is most desirable.

The effect is that a portion of such unreacted incyanate groups reacts with the curing agent in the adhesive layer when the adhesive layer coated on the undercoat layer is cured, and chemically strongly bonds the undercoat layer and the adhesive layer. have.

On the other hand, if the amount of incyanate groups is less than 0.0057μ, this bond becomes weaker and the adhesion between both layers decreases.

In such cases, among the polyfunctional hydroxyl compound of the undercoat layer and the epoxy compound of component (1) in the adhesive layer,
The polyfunctional hydroxy compound is preferably a compound having a hydroxyl group and an epoxy group in one molecule, and the epoxy compound as component (1) of the adhesive layer preferably has an average molecular weight of 1400 or more.

A solution of the adhesive layer composition described above is uniformly coated on the undercoat layer by a conventional method, and then three-dimensionally cured while removing the solvent using a hot air dryer.

The thickness of the layer is desirably 1 μm or more, and particularly preferably about 4 to 30 μm.

Heat curing using a hot air dryer is carried out at a temperature of 50 to 180°C, preferably 80 to 150°C.

The heat curing time is almost completed within 1 to 30 minutes, forming a non-tacky adhesive layer.

If the heat curing is insufficient, curing may be performed at room temperature to 70°C for several days to more than ten days.

This heat curing makes the adhesive layer three-dimensional, and a part of the unreacted isocyanate groups in the undercoat layer reacts with the curing agent containing active hydrogen in the adhesive layer, resulting in strong adhesion between the two layers, and furthermore, the adhesive layer is cured three-dimensionally, and at the same time, unreacted incyanate groups and hydroxyl groups in the undercoat layer completely react, resulting in three-dimensional curing.

For example, amines or polyamide resins in the adhesive layer promote the three-dimensionalization reaction of the undercoat layer.

The three-dimensional adhesive layer thus obtained contains carbon-carbon double bonds that can be polymerized by light in an amount of 1Xl per 11 polymers.
0' to 1 x l0-2 mol, preferably 3 x 10 to
It is contained in a proportion of 4 x 10-3 moles.

The amount of carbon-carbon double bonds is determined by the Hanus method (H
anus).

On this adhesive layer, sensitizers and inhibitors that are easily soluble in the photosensitive resin, unless they substantially prevent the adhesion with the photosensitive resin,
A layer containing dyes, pigments, etc., or a layer that stabilizes the relief shoulder of a photosensitive resin (for example, Japanese Patent Application No. 1989-1
6314% (Method of 1983-9375) may be provided.

The support plate for a photosensitive resin of the present invention, manufactured and constructed as described above, is useful as a support plate for a liquid photosensitive resin that is fluid at room temperature.

The photosensitive resin is first a mixture of a polymerization initiator that can be easily activated by actinic rays and a composition whose main component is a compound having an ethylenic carbon-carbon double bond that can be polymerized or crosslinked. I can give you more.

Such resin is generally applied in a uniform thickness of 0.2 to 3.0 mm and in direct contact onto the adhesive layer.

Suitable examples of the liquid photosensitive resin include vinyl chloride copolymer,
Acrylic acid ester copolymers, polyvinyl alcohol derivatives, cellulose derivatives such as cellulose ether,
Polymers such as polyurethane, polyester, especially unsaturated polyester that has unsaturated bonds in the molecular chain, and acrylic acid,
Examples include liquid photopolymerizable monomers such as methacrylic acid, derivatives thereof such as esters and amides, vinyl esters, etc., or a mixture thereof.

In particular, liquid photosensitive resins are mixtures of unsaturated polyester resins having carbon-carbon double bonds in their molecular chains that are active against actinic rays, and various liquid or solid addition-polymerizable monomers. On the other hand, the support plate of the present invention is particularly suitably used.

Such liquid photosensitive resins usually contain a photopolymerization initiator such as diacetyl, benzyl, benzoyl, benzoin alkyl ether, anthraquinone, eosin, theonine, thiol, and the like.

Furthermore, such liquid photosensitive resins may be applied to a support plate by using a solvent to impart fluidity, but the solvent itself cannot be solidified by irradiation with actinic rays or become a component constituting the image area. Of course, it cannot be used in large quantities.

Plate making is carried out by imagewise exposure to actinic light.

The light-polymerizable carbon-carbon double bond contained in the light-exposed portion of the photosensitive resin and the adhesive layer below it and the unsaturated bond of the photosensitive resin composition are substantially integrated. The photosensitive resin polymerizes, making it insoluble in solvents and at the same time firmly adhering.

Since polymerization does not occur in the portion of the liquid photosensitive resin that is not exposed to light, it is removed by a solvent.

In this case, the adhesive layer is completely stable in developing solutions such as alkaline aqueous solutions under normal conditions, and it is difficult to observe a phenomenon in which the adhesive strength of the image area is reduced due to this.

Depending on the properties of the photosensitive resin, light sources that emit active rays include tungsten bulbs, fluorescent lamps, carbon arc lamps, mercury lamps,
A light source such as a xenon lamp may be used, but typically a light source that emits actinic radiation rich in ultraviolet light is used.

During exposure, it is desirable to keep the photosensitive resin composition heated to about 20°C to 70°C.

That is, low temperatures below room temperature may cause a reduction in the effective adhesive activity of various active substances.

The photosensitive resin plate thus obtained may be re-exposed as necessary to compensate for insufficient curing of the cured relief portion.

As is clear from the above detailed explanation, the photosensitive resin plate obtained using the support plate of the present invention can be produced efficiently at extremely low cost, and the resulting printing plate can be produced using a flexible substrate. It also has a stretchable undercoat layer and an adhesive layer that has good adhesion to the photosensitive resin, so it has sufficient resistance to mechanical external forces during printing or during handling after printing, and also has sufficient resistance to ink and other It can withstand long-term use without being affected by solvents, etc.

The present invention will be explained in detail below using Examples.

In addition, all % in the examples represent weight %, and parts represent parts by weight.

Example 1 Comparative Example 1 An undercoat layer having the following composition was coated on an aluminum plate having a thickness of 0 and 15 mm that had been degreased with trichlene.

That is, a polyester polyurethane resin having a molecular weight of approximately 40,000, obtained by chain-extending polyethylene adipate having an average molecular weight of 1300 and having hydroxyl groups at both ends with MDI, was synthesized by dissolving it in a mixed solvent of ethyl acetate and methyl ethyl ketone.

A terminator was added to the terminal end of this polyester polyurethane resin, and the hydroxyl value was 2 or less.

A 75% ethyl acetate solution (manufactured by Nippon Polyurethane Co., Ltd.) of trimethylolpropane and TDI adduct was added to 100 parts of this 35% solution, and the incyanate group content was 13
, 4%) and 3 parts of trimethylolpropane were added.

Next, an oil-soluble yellow dye of Color Index No. 11390 was added to the resin at a concentration of 2%, and a solvent was further added to give a mixture with a solid content of 15%.

This solution was thoroughly stirred in a ball mill, and when the viscosity of the solution reached 28 poise, it was uniformly coated onto a substrate using a bar coater.

Immediately, it was placed in a hot air dryer at 130°C and dried for about 2 minutes to remove the solvent.

The average coating thickness was about 20 microns.

Next, the following adhesive layer composition was prepared.

Shell Chemical Co., Ltd.'s product name: Pico) 1001 (molecular weight approximately 9
An epoxy resin synthesized from slepichlorohydrin and bisphenol A (with epoxy groups at both ends of the molecular chain) was dissolved in a mixed solvent of 40% toluene, 30% butyl acetate, and 30% diacetone alcohol to form a 20% solution. did.

After adding 1/2 equivalent of methacrylic acid to the existing epoxy groups and adding 0.2% of N-nitrosodiphenylamine to the solid content as a polymerization inhibitor, LiC1 was added as a reaction catalyst to the solid content. About 1% was added.

This thread was reacted at 60-80°C for about 6 hours.

When samples were taken from the reaction system over time and the acid value was measured to track the reaction, the reaction was almost complete.

Using the thus obtained epoxy acrylate containing both a vinyl group and an epoxy group, the following adhesive layer composition was prepared.

1. Epoxy novolac resin (having a viscosity of 18,400 centipoise at 25°C and having a molecular weight of approximately 432.1 molecules and an average of 2.3 epoxy groups) 2. The above epoxy acrylate resin temperature... , -go
=p liquid 3, m-xylene diamine・・・・・・・°・・・・
6 parts 4, the above mixed solvent (toluene, 09090.2 parts ethyl acetate, diacetone alcohol) Using a spray gun, apply this adhesive layer composition to the above dry solution. It was applied onto the undercoat layer and immediately dried and cured at 100° C. for 15 minutes.

The coating thickness was approximately 3X1O to 4M for 7 groups.

For comparison, an undercoat layer composition containing 20 parts of Coronate L manufactured by Nippon Polyurethane Co., Ltd. and 10 parts of trimethylolpropane was coated on a substrate under exactly the same conditions as in this example and dried.

Furthermore, the adhesive layer was also coated and dried in the same manner.

35 parts of methyl cellulose and 6 parts of triethylene glycol diacrylate were placed on the two types of support plates thus obtained.
5 parts, anthraquinone 3 parts, and hydroquinone 0.0
A translucent liquid photosensitive resin composition consisting of three parts was uniformly applied to a thickness of 0.7 mm each.

Immediately, the film surface was irradiated with 11 20W ultraviolet fluorescent lamps for 15 minutes while the negative film was in close contact with a 9μ polyester film.

The temperature of the support plate surface at this time was 55°C.

After exposure, the resin liquid that did not polymerize was forcibly washed away with water to create a printing original plate.

Further, the relief portion was completely solidified by exposure for 10 minutes with eight 20W ultraviolet fluorescent lamps.

The shape of the solidified portion is a square with a height of 0.7 mm and 10 horizontal dimensions, and a rectangular shape with a vertical dimension of 10 mm and a horizontal dimension of 20 cTL.

The test piece thus obtained has a radius of curvature of 45.20.12
．． 9.6.5.5 It was wrapped around a cylinder at 20°C and the peeling state of the relief part was observed.

The minimum radius at which peeling occurs is shown in Table 1.

All comparison rows show peeling between the undercoat layer and the base material. This caused the product to become unusable.

That is, it shows that the network structure of the undercoat layer of the comparative example was too dense and could not cope with the deformation of the base material.

Example 2, Comparative Example 2 MDI of polybutylene adipate with an average molecular weight of 1500
A polyester polyurethane resin with a molecular weight of about 30,000 that has been chain-stretched using TDI is mixed with a mixed solvent of toluene and ethyl acetate.
It was dissolved to become a 5% solution.

For 100 parts of this 45% solution, 12 parts of sorbitol tetraglycinol ether, Tetrachlor 04F 1F 19
5 parts of fufu, 60 parts of toluene, and 63 parts of ethyl acetate were added, and the mixture was milled for one day and night using a ball mill.

Subsequently, 25 parts of Coronet) L from Example (2) was added to obtain an undercoat layer composition.

This composition was uniformly applied onto a biaxially stretched polyethylene glycol terephthalate film having a thickness of 200 μm using a bar coater.

Immediately, it was placed in a hot air dryer at 120°C and dried for about 5 minutes.

The average coating thickness was 34μ.

Next, the following adhesive layer composition was prepared.

1. Epicote 834 (manufactured by Shell Chemical Co., Ltd., molecular weight approximately 500, epoxy resin having epoxy groups at both ends of the molecular chain -9, -20 = rt) 2. Glycysyl methacrylate...
・25 parts 3, polyamide resin (amine equivalent of terminal amino group is 1 x 1 O-2 equivalent / 20 parts 1
aliphatic polyamide resin) 4. Mixed solvent of Example 1...
・・・・・・・・・70 parts of the above set of precepts at 30℃ for about 2
After aging for 4 hours, it was applied uniformly onto the undercoat layer immediately after drying using a bar coater.

Immediately dry at 120'C for 2 minutes, then dry at 40'C for 4 minutes.
I did a curing session for a day.

The average coating thickness was 8 microns.

In addition, the inside of this adhesive layer.

For comparison, the following composition was prepared that did not contain glycysyl methacrylate, which is the so-called adhesive layer Seishu 2).

■, Epicote 834・・・・・・・・・
・50 parts 2, polyamide resin of Example 1...
......2.0 parts 3, mixed solvent of Example 1.
・・・・・・・・・・・・・・・・・・・・・70
The above undercoat layer was coated, dried, and coated in the same manner as in this example.
Heat treatment was performed.

The following unsaturated polyester liquid photosensitive resin was prepared in the following manner.

70 parts of unsaturated polyester (acid value 146) produced using 2 moles of maleic anhydride, 1 mole of trimellitic anhydride, 1.5 moles of ethylene glycol, and 1.5 moles of diethylene glycol, 7 parts of acrylamide, and polyethylene glycol diacrylate. (Polymerization degree of polyethylene glycol unit 4) 23 parts, benzoin methyl ether 1 part,
A photosensitive resin liquid containing 0.01 part of hydroquinone was obtained.

Apply this photosensitive resin liquid to a thickness of 0.7% on two types of support plates.
A biaxially stretched 25μ polypropylene film and a negative film were placed on the surface of the resin layer, and the film surface was irradiated for 5 minutes with a 450W high-pressure mercury lamp on a baking frame kept at 70°C.

After exposure, the uncured portions were washed and removed with a 0.5% aqueous sodium carbonate solution, and the relief was further post-exposed for 5 minutes to completely cure the relief.

When the same peel test as in Example 1 was conducted, the results shown in Table 2 were obtained.

In all of the comparative examples, peeling occurred very easily, and all of the peeling locations were from between the resin and the adhesive layer.

In other words, it was found that there was no adhesive property between the resin and the adhesive layer.

Example 3, Comparative Example 3 The photosensitive resin of Example 2 was evenly coated to a thickness of 0.6 mm on the support plates of Example 2 and Comparative Example 2, and a 9 μm layer was applied onto this resin.
Polyethylene terephthalate film and independent points of straight lines 300μ, 330μ, 400μ, 660μ, widths 50μ, 100μ, 150μ, 200μ, 300μ, 5
A negative film with 00μ ruled lines was stacked, and the negative film was irradiated with ultraviolet light for 15 minutes using 12 20W ultraviolet fluorescent lamps.

The resin layer that did not polymerize after exposure was forcibly washed for 3 minutes at 30°C with a 1% soluble sodium aqueous solution.In the case of the comparative example, independent points with diameters of 300μ, 330μ, 360μ, and 400μ, and widths of 50μ, 100μ, and 150μ were formed. The relief part of the ruled line peeled off from the support plate, making it unusable.

On the other hand, in the case of the example, an independent point with a diameter of 300μ or more, a width of 50
Both ruled lines larger than μ could be reproduced as complete relief images.

This letterpress printing plate for photosensitive resin can withstand printing at 20° C. after post-exposure.

Example 4 1 mole of hexamethylene diamine was reacted with 3 moles of glycysyl methacrylate at 25° C. for one day.

The following adhesive layer composition was prepared using this reactant.

1. Epicoat 1007 (an epoxy resin manufactured by Shell Chemical Co., Ltd. with a molecular chain of about 2900 and having an epoxy group at both ends of 010101.6 parts) 2. Reaction of the above hexamethylene diamine and glycysyl methacrylate... ...7
Part 3, polyamide resin of Example 2...
23 parts 4. Mixed solvent of 1-luene and methyl ethyl ketone (50% toluene, 23 parts methane 50% ethyl ketone) This composition was applied onto the undercoat layer of Example 2 immediately after drying. The film was dried at 100°C for 12 minutes, and then heat-treated at 60°C for 2 days.

The average coating thickness was 15μ.

When the same test as in Example 3 was conducted using this support plate, it showed excellent performance and printing durability as a letterpress print.

Example 5 A 75% ethyl acetate solution of an adduct of tolmethylolpropane and hexamethylene diisocyanate (Coronate HL manufactured by Nippon Polyurethane Co., Ltd., Incyanate content: 12 .8%) and 5 parts of Epikote 1004 (an epoxy resin manufactured by Shell Chemical Co., Ltd. with a molecular weight of about 1400 molecules and having epoxy groups at both ends and further containing a large number of hydroxyl groups) in ethyl acetate to make a 38% solution. did.

This composition was coated onto a 100μ polycarbonate film and dried at 80°C for 30 minutes to obtain a coating thickness of approximately 14μ.

Immediately after drying, apply an adhesive layer with the following composition on the undercoat layer for 25 minutes.
It was aged for 7 days at °C before coating.

1. Epicor) 1007・・・・・・・・・・・・
・・・・・・・・・16 Part 2 Glycysyl allyl ether ・・・・・・・・・2.3 Part 3, Example 2
polyamide・・・・・・・・・・・・・・・・・・
・・2 Part 4, Diazo Yellow・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・3 Part 5, mixed solvent of Example 1・・・・・・・・・・・・・・・・・・・・・
...18 parts were dried and heat cured at 100° C. for 20 minutes to obtain an adhesive layer with a coating thickness of 10 μm.

The CH2=CH- group in this adhesive layer is I x 10''
Mol/? There was a time.

When the same test as in Example 3 was conducted using this support plate, it was found that it could be used satisfactorily as a letterpress printing material.

Example 6 A polyether polyurethane with a molecular weight of about 12,000, which was obtained by chain-extending poly(oxytetramethylene) glycol with a molecular weight of about 1,500 using MDI, was synthesized by dissolving it in a mixed solvent of dimethyl formaldehyde and tetrahydrofuran. % solution.

To 300 parts of this solution, 416 parts of Epicor 1-100, Coronate HL 20 J Chromophthal Yellow A2R5
After thoroughly milling with a ball mill, the mixture was coated on a 125 μm thick polyethylene terephthalate film using a bar coater.

Immediately after drying at 120°C for 2 minutes, the adhesive layer composition of Example 5 was applied and first dried at 50°C for 10 minutes.
Heat curing was performed for 15 minutes.

The coating thickness of the undercoat layer and adhesive layer** is 20μ and i, respectively.
It was oμ.

When a photosensitive resin relief plate was made using this support plate and printed, a printed matter with clear lines was obtained.

Example 7 Example 1.2.5.6 Each undercoat composition was coated and dried under exactly the same conditions as in each example, and the isocyanate groups were measured using an infrared spectrophotometer. The results are shown in Table 3. became.

From Table 3, it can be inferred that heating and drying the undercoat layer either simply removes the solvent or causes some isocyanate groups and hydroxyl groups to react.

Furthermore, while the adhesive layer is being cured by heating, the reaction of the undercoat layer is almost completed at the same time.

Next, a solution prepared by dissolving 100 parts of the polyester polyurethane resin solution of Example 1 and 20 parts of trimethylolpropane in 100 parts of ethyl acetate was applied onto a 125 μm polyethylene terephthalate film and dried at 120° C. for 3 minutes.

When the incyanate group of this coating film was measured, it was found to be 0.0
0017μ, and this method for measuring incyanate was effective as a simple method.

Examples 8 and 9 Undercoat layer and adhesive layer compositions having compositions as shown in Table 4 were prepared.

Each of the undercoat layer compositions of Example 8 and Example 9 was coated to a thickness of 125 mm.
It was coated on a .mu. polyethylene terephthalate film in a conventional manner and immediately heated at 100.degree. C. for 40 hours.

The average thickness of each coating was 20μ and 17μ.

When the incyanate group at this time was quantified, the former was 0.
．． 00047μ, the latter was o,ooo2/μ.

Subsequently, each adhesive layer composition is applied onto this undercoat layer,
It was dried and cured at 120° C. for 15 minutes.

The coating thickness in Example 8 was 8μ on average and 101O− in Example 9.
3 and 2.3XIO-3 mol/1.

The test of Example 1 was conducted using the support plates of Examples 8 and 9.

The results are shown in Table 5. When observing the peeled surface in Example 9, the yellow surface of the undercoat layer was exposed on the substrate side.
The color of the lead circle of the adhesive layer was observed on the relief side.

That is, in the support plate of Example 9, the adhesive strength between the undercoat layer and the adhesive layer was slightly decreased.

On the other hand, in the case of Example 8, peeling clearly occurred between the base material and the undercoat layer.

That is, the epoxy group in the undercoat layer and the curing agent in the adhesive layer reacted, and the two became integrated, making it possible to sufficiently withstand changes in the photosensitive resin plate.

Claims (1)

[Claims] 1 A flexible base material, a layer of a composition comprising a linear polyurethane compound, a polyfunctional incyanate compound, and a polyfunctional hydroxy compound provided on the flexible base material; (1) There are few (both 2 or more 1) in the molecule.
・Compounds having a 2-epoxy group, (2) having both a photopolymerizable carbon-carbon double bond and a 1,2-epoxy group or an amino group having an active hydrogen in the molecule, and having 11
A compound with a boiling point of 0"C or higher, (3) at least 2
heating a construction consisting of a layer of a composition comprising an organic curing agent or a compound convertible therein in a reaction field containing active hydrogen and not containing photopolymerizable carbon-carbon double bonds; A support plate for photosensitive resin obtained by