JPS5837532B2 - Kankoseijiyushuyoushijiban - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a support plate for photosensitive resin that is suitably used for producing printing plates from liquid photosensitive resin.

More specifically, the present invention relates to a multilayer photosensitive resin support plate having a specific adhesive layer provided on a base material.

Photosensitive resin plates used for letterpress printing plates have been known in the past, and such photosensitive resin plates usually consist of a base material of a metal plate or a plastic sheet and an adhesive layer (the photosensitive resin layer is attached to a support). (provided to facilitate adhesion to the surface) and a photosensitive resin layer.

Further, at this time, it is common to provide an antihalation layer between the adhesive layer and the base material.

Therefore, the adhesive layer does not contain any component that prevents the photosensitive resin layer from polymerizing when exposed to light or initiates polymerization without light, and also prevents the relief from peeling off from the support during printing. It is necessary to have a strong bond with the support.

Additionally, the adhesive layer is required to have a bonding force that is not weakened by the effects of temperature, humidity, solvents, etc. encountered during normal plate making and printing processes.

However, until now, a support plate having an adhesive layer that satisfies all of these required properties has not been known.

In the past (this is not to say that such attempts have not been made at all, for example, the one described in Japanese Patent Publication No. 36-23761 is known, but in this case, special measures must be taken) Therefore, it was difficult to say that it was necessarily suitable for industrial use.

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

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.

That is, the present invention provides a compound obtained by reacting an epoxy compound (4), a compound B) having both an unsaturated carbon-carbon double bond and an epoxy group or an amino group in the molecule, and a curing agent (0). This is a support plate for a photosensitive resin comprising a base material and a layer of a three-dimensional polymer having unsaturated carbon-carbon double bonds in side chains.

The epoxy compound (4) in the present invention refers to a compound having at least two or more epoxy groups in the molecule.

Such epoxy compounds include condensation of shrimp chlorohydrin and polyhydric phenols such as 2,2-bis(4'-oxyphenyl)furopane (sunawati, bisphenol A) or polyhydric alcohols such as glycerin. Linear polymeric products are commonly used.

For example, a linear polymer compound of bisphenol A and ebichlorohydrin (represented by the following formula, where n is a number of 0 or 1 or more) is particularly preferred.

Further, a compound represented by the following formula [produced by condensing two molecules of 4-formyl-3-methyl-cyclohexene obtained by Diels-Alder reaction of butadiene and crotonaldehyde, and then epoxidizing] , furthermore, vinylcyclohexene dioxide, dipentene dioxide, 2-glycidyl phenyl glycidyl ether, 2,6-diglycidyl phenyl glycidyl ether,
Compounds having a cyclic epoxy group such as , aliphatic epoxide compounds such as diglycidyl ether, butane diene dioxide, and the like can be mentioned.

In the present invention, the compound vAB) having both a carbon-carbon double bond and an epoxy group or an amino group in its molecule reacts with the epoxy compound prisoner in the presence of the curing agent described below to form a three-dimensional polymer. form a union.

The term "carbon-carbon double bond" used in the present invention means a carbon-carbon double bond that can be effectively polymerized by light.

Such a compound preferably has a boiling point of at least 120° C. at normal pressure C, and specifically includes the following compounds.

That is, examples of compounds having both a carbon-carbon double bond and an epoxy group include glycidyl acrylate,
Glycidyl methacrylate, glycidyl cronate, glycidyl allyl ether, allylphenol or crotylphenol, or a reaction product of shrimp chlorohydrin with allylphenol or crotylphenol or their nuclear substituted derivatives (0-allylphenylcricidyl ether, crotylphenylglycidyl ether, etc.)
, 1.1-bis(hydroxymethyl)cyclohexene-
Epoxidized acetals, vinyl glycidyl ethers, methacryl glycidyl ethers, polymers having many epoxy groups and a carbon-carbon double bond in one molecule, obtained from 3 or its nuclear substituted product and an aldehyde having a double bond. Examples include molecular compounds (epoxidized products of anionic polymers of butadiene, etc.).

In addition, as a compound having both a carbon-carbon double bond and an amine group, a reaction product of glycidyl methacrylate, glycidyl allyl ether, etc. with a polyvalent amine such as hexamethylene diamine (a part of the active hydrogen of the amine is Examples thereof include a reaction product of glycidyl methacrylate and a polyamine resin (which is particularly preferably used).

As the curing agent (C) in the present invention, a compound having Q2 or more active hydrogens in the molecule is usually used, but in addition to these, acid anhydrides, carboxylic acids, tertiary amines, etc. can also be used.

Specifically, for example, aliphatic amines such as diethyleneamine, diethylenetriamine, diethylaminoprobylamine, hydroxyamines such as monoethanolamine, diethanolamine, N-methylethanolamine, aminoethylethanolamine, metaphenylenediamine, Aromatic amines such as P,P'-diaminodiphenylmethane, amines in which a portion of the active hydrogen of each of these amines is substituted with an aliphatic group or an aromatic group, and acid anhydrides such as the following ( When such a curing agent is used, the heat resistance of the adhesive layer can be improved.

), but when using an acid anhydride, it is preferable to use it together with a small amount of amine or alcohol.

Specifically, acid anhydrides such as phthalic anhydride, maleic anhydride, hexahydrofucuric anhydride, dodecenylsuccinic anhydride, himelic anhydride, and hexagonal low-end methylenetetrahydrophthalic anhydride are mentioned.

Furthermore, polyhydric carboxylic acids such as phthalic acid, certain phenol resins, urea resins, polyester resins, polysulfide resins, melamine resins, polyamide resins, polymeric compounds having a large number of active hydrogens such as polyamines, triethylamine, Tertiary amines such as benzyldimethylamine, other organic amine complex salts such as trialkanolamine borate, (C4H9)2sn(OCOCoH2
g)2, Ca(AA(QC4Hg)4:]2
, (Metal compounds such as C4H904Ti, etc.) can be mentioned.

The support plate for photosensitive resin of the present invention comprises the compound (4) 2(
Six layers of a three-dimensional polymer having side chains of unsaturated carbon-carbon double bonds, which are reactants with a curing agent and a curing agent (0), are provided on a base material.

The three-dimensional polymers contain carbon-carbon double bonds in a proportion of from IXIO-' to IX10-'' moles, preferably from IX10-3 to 4X10-'' moles per gram of polymer.

Examples of the above-mentioned base material include the following.

For example, metal plates made of iron, stainless steel, zinc, aluminum, etc., rubber sheets made of natural rubber, synthetic rubber, etc., films, sheets, paper, cloth made of cellulose, cellulose derivatives, polyolefin, polyester, polycarbonate, polysulfone, etc. Those having a thickness of 0.1 to several plates are preferably used.

It may also be a film or sheet-like product produced by polymerizing a photopolymerizable composition.

Fillers and reinforcing agents can be present in these base materials, and especially when using a highly light-reflecting base material such as a metal plate, the light that has passed through the photosensitive resin layer provided in this way is When using such a substrate, it is necessary to absorb at least 50 degrees of the incident actinic rays, because after irradiating and reflecting the support surface at an angle other than 90', polymerization occurs even in areas where there is no image. It is preferable to incorporate a sufficient amount of a light absorbing agent into the three-dimensional polymer layer (adhesive layer) or to provide an antihalation layer on the surface of the substrate.

In the case where an antihalation layer is provided, the substrate provided with the antihalation layer may be considered as the substrate according to the present invention, and the present invention also includes such a case.

Such light absorbers or light absorbers in the antihalation layer may be colorless or colored.

Suitable light absorbers include, for example, inorganic and organic pigments that absorb in the near ultraviolet region, such as carbon black, trilead tetroxide, titanium dioxide, benzidine yellow, and rhodamine, as well as those conventionally known as effective ultraviolet absorbers. Examples include penzophenone type compounds and benzo t-IJ azur type compounds.

A method for forming a polymer layer (adhesive layer) on a substrate is to coat the surface of the substrate with a blended mixture of the above compound (4), a circle, and a curing agent (C), and then heat or age the mixture to form an ionized layer. Preferably, the method is carried out by carrying out an addition reaction.

The thickness of the adhesive layer is usually about 5 to 100 microns, which is sufficient to achieve its purpose.

Further, the above-mentioned blended mixture may further contain an ionic addition reaction catalyst, a radical polymerization inhibitor or inhibitor, etc., if necessary.

The adhesive layer of the photosensitive resin support of the present invention thus obtained is extremely strong, and will not be damaged even if it is brought into contact with it or is overlapped with it, and there is no risk of it sticking.

When manufacturing a photosensitive resin plate using the support plate of the present invention, a photosensitive resin composition that polymerizes under the action of light is coated on the support plate by a known coating method such as squeezing, spraying, or laminating. Apply a coating method to obtain a uniform thickness.

Photosensitive resin compositions suitable for producing letterpress printing plates include:
A solvent-soluble high molecular weight compound containing both a photopolymerization initiator that activates a radically addition-polymerizable compound having an unsaturated carbon-carbon double bond with light and, if necessary, further retaining the above-mentioned compound. It is a photosensitive resin composition containing a polymer, for example, a cellulose derivative such as cellulose ester or cellulose ether, a polyolefin such as polyvinyl alcohol, a polyamide, or a condensation polymer such as polyester.

To produce a letterpress printing plate from the photosensitive resin structure thus obtained, the photosensitive resin layer is irradiated with light through a negative film having a transparent image area, and then treated with a suitable solvent.

The portion of the photosensitive resin layer that is exposed to light and the adhesive layer Q that is close to the photosensitive resin layer contain radical addition polymerizable unsaturated carbon-carbon double bonds and unsaturated carbon in the photosensitive resin composition. The one-carbon double bonds polymerize substantially together, making it insoluble in solvents and at the same time strongly adhering.

Since polymerization does not occur in the areas that are not exposed to light, they are removed by a solvent, and a printing plate that can be immediately mounted on a printing press and printed is obtained.

The adhesion between the support and the remaining relief image after polymerization is extremely strong, and it is not attacked by ink or other solvents, so its printing durability is extremely excellent, and can be printed in the hundreds of thousands of copies or more. More continuous printing is possible.

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

Example 1 The surface was tin-plated with a thickness of 0. Epoxy paint containing red lead on a 3 mm copper plate (Epirite manufactured by Toa Paint)
was applied to a thickness of 25 microns (referred to as an undercoat layer), and 1
After heat treatment at 30°C for 20 minutes, a transparent epoxy paint containing 30% by weight of glycidyl methacrylate based on the total solid content was spray-coated to a thickness of 15 microns (referred to as a top coat layer), and after thoroughly air-dried, A non-adhesive photosensitive resin support plate was obtained by heat treatment at 100° C. for 20 minutes.

The topcoat layer thus obtained contains approximately 3.times.10@-" moles of CH22C derived from glycidylmethacrylate per layer 19.

The components, composition, and other details of the epoxy paint used for the undercoat layer and topcoat layer are as follows.

(Epoxy paint for undercoat layer) The epoxy paint for undercoat layer is an epoxy equivalent of 4×1 obtained by condensing bisphenol A and shrimp chlorohydrin.
0-3 equivalents/9r epoxy resin (average molecular weight approx. 5
00) 20 parts by weight, the amine equivalent of the terminal amino group is I
1 0-2 equivalent //! This paint is made by uniformly dissolving and dispersing 15 parts by weight of aliphatic polyamide resin (r) and about 20 parts by weight of red lead in a thinner whose main components are toluene, diacetone alcohol, and n-butanol.

(Epoxy paint for top coat layer) The epoxy paint for top coat layer includes 40 parts by weight of Clear A liquid containing 50 weight range of the above-mentioned epoxy resin, 50 parts by weight of Clear B liquid containing 40 weight φ of the above-mentioned polyamide resin, and glycidyl methacrylate. The composition was prepared by mixing 30 parts by weight and 20 parts by weight of the thinner described above several hours before use.

Such a support plate is made of unsaturated polyester, acrylamide,
A photosensitive resin composite consisting of tetramethylene glycol diacrylate and penzoyl isopropyl ether was applied to a thickness of 0.7 mm, exposed to active light from an ultraviolet fluorescent lamp for 5 minutes through a negative film, and then washed with dilute alkaline water. A letterpress printing version was created.

With this plate, no peeling of the resin was observed even after a printing test of 500,000 copies.

On the other hand, after applying an epoxy paint containing red lead to the copper plate and heat-treating it, a printing plate manufactured in the same manner except for using a support plate coated with only a transparent epoxy paint that does not contain glycidyl methacrylate and heat-treated is photosensitive. The adhesive force between the resin and the support plate was very weak, and the relief parts, which were small dots and thin lines, were peeled off from the support plate just by touching them.

As a result of a printing test of 10,000 copies with this printing plate, the leader lines, thin lines, relief parts of small independent dots, etc. were peeled off from the support plate, and it was completely unusable as a printing plate.

Example 2 A compound obtained by reacting 2 moles of glycidyl methacrylate with 1 mole of hexamethylene diamine was mixed into an epoxy paint containing cyanine green (Etone #2100 manufactured by Kawakami Paint Co., Ltd.) at 33 weight φ based on the total solid content. , this mixture was made to a thickness of 0. 3 on a 20 mm aluminum plate
Using the support plate obtained by applying the coating to a thickness of 0 micron and immediately heating it at 120°C for 30 minutes, a letterpress printing plate was made according to the method of Example 1. Even after a printing test of 100,000 copies, the resin remained No peeling was observed.

Epoxy paint used in the above (Eton # manufactured by Kawakami Paint Co., Ltd.)
The details of the paint containing 2100) are as follows.

20 parts by weight of an epoxy resin with a molecular weight of approximately 1100, which is obtained by condensing bisphenol A and epichlorohydrin in an alkaline solution, and a reaction product of 122 molar ratio of hexamethylene diamine and glycidyl methacrylate (using the same solvent as the paint, solid content concentration 30 parts) 15 parts by weight of a viscous liquid obtained by gradually heating a steamed rice cake and reacting in the presence of methoxyphenol as an anti-gelling agent, 2 parts by weight of ethylenediamine as a hardening agent, and cyanine as an anti-halation agent. It was prepared by mixing 7 parts by weight of green and 80 parts by weight of a certain mixed solvent from toluene, n-butanol and methyl cellosolve.

CH3 The content of one CH2-C group in the cured coating is approximately 1.5
X10"-3 mol/9 r.

Example 3 After sand-blasting a polyester film with a thickness of 0.15 mm, 3 moles of glycidyl allyl ether were preliminarily reacted with 2 moles of hexamethylene diamine in the same manner as in Example 2. was 6.7 weight φ, and an epoxy paint containing 6.7 weight weight of the epoxy resin used in Example 1 and 5 weight of red lead was spray-coated to a thickness of 7 microns, and after sufficiently drying, it was heated at 80°C for 60 minutes. Heat treated.

In the resulting coating film, one CH2-CH group is approximately 2 x 10-3
Contains mol/9 r.

This support plate was a support plate for photosensitive resins that had no tackiness and had excellent adhesive properties.

Example 4 A mixed solution of 30 parts by weight of benzidine yellow and 100 parts by weight of an epoxy paint obtained by removing red lead from the epoxy paint for the undercoat layer used in Example 1 was applied to a polycarbonate film with a thickness of 20 microns. After coating and drying, the hardening agent (amine equivalent: 3.7×
2 g of glycidyl methacrylate (epoxy equivalent: 7.OX10-3 equivalent #) was added to 10-"equivalent/&) 59, and the resulting compound was reacted at 130'C for 1 hour. The heavy-duty transparent epoxy paint described above was applied to a thickness of 5 microns and heat treated at 100'C for 30 minutes.

The support plate manufactured in this way had an excellent adhesive effect as a support plate for photosensitive resin, and was of extremely high quality.

Claims (1)

[Claims] 1 Epoxy compound A A compound having both an unsaturated carbon-carbon double bond and an epoxy group or an amine group in one molecule (D
A support plate for a photosensitive resin, comprising a base material and a layer of a three-dimensional polymer having an unsaturated carbon-carbon double bond in a side chain, which is obtained by reacting a polymer with a cured compound 1,KO.