JP4507026B2 - Anti-halation composition and photosensitive resin laminate using the same - Google Patents

Description

[0001]
[Technical field to which the invention belongs]
The present invention relates to a composition having an antihalation function and a photosensitive resin laminate containing the composition in an adhesive layer, and not only the antihalation function, but also has little coloration and excellent stability over time, It has sufficient slit depth and halftone dot depth.
[0002]
[Prior art]
Usually, when creating a relief for printing using a photosensitive resin laminate (hereinafter also referred to as a photosensitive resin plate), a negative film is overlaid on the photosensitive resin layer, and actinic rays are irradiated from above the film. The relief for printing is obtained by photocuring the resin in the exposed area and washing away the unexposed area with a solvent.
[0003]
The relief thus obtained should in principle be formed so as to stand vertically from the top surface of the resin layer to the surface of the support. In many cases, a cross section is formed, which is generally referred to as “the shoulder angle becomes wider”. Such a flared portion increases the fixing strength of the relief to the support, and is considered necessary from the viewpoint of the relief strength. However, if the shoulder angle becomes too large, there is a problem that when a large printing pressure is applied in the printing stage, the image portion or the dot portion is thickened, or the slit portion or the non-image portion is stained.
[0004]
As described above, the photo-curing resin of the portion that should be the unexposed portion is photo-cured, and the shoulder angle of the relief is increased or the depth of the relief is reduced. Another problem is halation due to the fact that scattered light is incident on the unexposed part adjacent to the exposed part from an oblique direction to cause a curing reaction. That is, parallel actinic rays incident from above the photocurable resin cause halation at the interface with the support, and if the support is transparent, the actinic rays pass through it to pass through the exposure machine surface (support However, it is inevitable that the reflected / scattered light associated with these halations re-enters from the bottom to the top of the photo-curable resin layer. The part to be exposed is exposed to cause a partial curing reaction, which leads to the above-described situation.
[0005]
For these reasons, it is an indispensable element to provide the photosensitive resin plate with an antihalation function. For example, an antihalation function is provided in the adhesive layer provided between the photosensitive resin layer and the support. A method, a method in which an antihalation agent layer and an adhesive layer are alternately formed between a photosensitive resin layer and a support have been put into practical use. However, when a photosensitive resin plate having an adhesive layer added with a general UV absorber that absorbs up to around 360 nm is used to make a plate with an exposure lamp such as a chemical lamp, the slit depth and the halftone depth are still shallow. There was a problem that the effect of preventing halation was small.
[0006]
In addition, it was confirmed that a compound having absorption even after 450 nm has an antihalation effect. However, when such a compound is used as an antihalation agent, the degree of coloring increases, and it is difficult to see during plate-making inspection. There are problems that the plate inspection becomes worse, such as being tired easily.
[0007]
Furthermore, there is a problem in that the antihalation agent diffuses and migrates into the photocurable resin layer during the storage period of the raw plate (unexposed plate) and changes the raw plate over time, and the fine lines (thin line relief) are kinked. In addition, there is a problem of causing a lack of independent points (small point relief).
[0008]
Therefore, as an ideal UV absorber having an antihalation effect, λmax is 360 nm, the UV absorption edge is close to 400 nm, and the isocyanate in the adhesive layer is prevented from being extracted into the photosensitive resin layer over time. It is only necessary to add a compound having a functional group (-NH ₂ , —OH, etc.) that reacts with the compound as an antihalation agent, but there are few such compounds, and these are the reasons for manufacturing cost, safety, etc. It was something that could not be used.
[0009]
[Problems to be solved by the invention]
It is an object of the present invention to obtain a photosensitive resin laminate that provides a relief plate with little coloring, an antihalation effect, excellent stability over time, and sufficient slit depth and halftone depth. It is.
[0010]
[Means for Solving the Problems]
As a result of intensive studies, studies and studies to solve the above problems, the present inventors have completed the present invention by using a composition composed of the following compound group. That is, the present invention comprises a compound represented by the following general formula (1) and general formula (2) , and a support provided with an adhesive layer has an absorbance at 360 nm of 0.60 or more, and 380 to 400 nm. An antihalation composition characterized by satisfying an absorbance of 0.25 or more and an absorbance at 450 nm or more of 0.10 or less .
[Chemical 1 ]
[Chemical 2 ]
[0015]
A photosensitive resin laminate comprising at least a support, an adhesive layer, and a photosensitive resin layer, wherein the adhesive layer contains the antihalation composition according to claim 1. Laminated body.
[0019]
Solvents for dissolving them include benzene organic solvents such as benzene and toluene, ketone organic solvents such as methyl ethyl ketone and acetone, ester solvents such as ethyl acetate, ethylene glycol solvents, dimethylaminoformaldehyde, dimethylaminoacetamide. Examples of the organic solvent include, but are not limited to.
[0020]
Next, the photosensitive resin laminate of the present invention has at least a support, an adhesive layer and a photosensitive resin layer, and the adhesive layer contains the compounds represented by the general formulas (1) and (2). The amount of the compound added is the content in the adhesive layer composition, preferably 0.1 wt% or more and 20 wt% or less, more preferably 0.2 wt% or more and 5 wt%. % Should be added. If it is less than 0.1%, the antihalation effect is small, and if it exceeds 20% by weight, the problem of coloring and the curing reaction of the coating solution are inhibited, so that the adhesive strength and solvent resistance are deteriorated.
[0021]
Although it does not specifically limit as a photosensitive resin layer which comprises the photosensitive resin laminated body in this invention, As a component which comprises the photosensitive resin layer, a base polymer, a photocrosslinking agent, a photosensitizer, polymerization prohibition Depending on the type of base polymer that is the main component, it is called, for example, polyamide, polyurethane, polyvinyl alcohol, polyester, or polyvinyl acetate. The present invention may be applied to any known photosensitive layer and is not particularly limited.
In the present invention, other elements such as the thickness of each layer and the presence or absence of a protective layer are not limited at all.
[0022]
As the support in the present invention, any material such as steel, aluminum, plastic film and glass can be used. In the present invention, a plastic film, particularly a polyester film is preferred.
[0023]
The component constituting the adhesive layer in the present invention is not particularly limited, and the support (in the case of a polyester film), the adhesive layer and the absorbance at 360 nm is 0.6 or more, preferably 0.80 or more, particularly 0.85 or more is desirable. Further, the absorbance at 380 to 400 nm is 0.3 or more, preferably 0.40 or more, particularly 0.45 or more. Further, the absorbance at 450 nm or more is 0.1 or less, preferably 0.08 or less, particularly 0.05 or less.
In addition, when the absorbance at 360 nm is less than 0.6 or the absorbance at 380 to 400 nm is less than 0.3, there is a problem that the white spot depth becomes shallow and the antihalation effect is not exhibited. Further, when the absorbance at 450 nm or more exceeds 0.1, the degree of coloring increases, and it is not preferable because there are problems such as difficulty in viewing during platemaking inspection, easy eye fatigue, and poor plate inspection.
[0024]
As a component of the adhesive layer that satisfies the above conditions, for example, a binder polymer, an antihalation agent (or UV absorber), an isocyanate compound, a polymerization inhibitor, and other additives, as a binder polymer as a main component, A polymer having a functional group capable of reacting with an isocyanate group is preferable, and specific examples thereof include a hydroxyl group, a carboxyl group, an amino group, a mercapto group, and the like. Specific examples of oligomers or polymers in the chain include acid components such as terephthalic acid, isophthalic acid, adipic acid, and sebacic acid, ethylene glycol, diethylene glycol, neopentyl glycol, and 4,4′-di (2-hydroxyethoxyphenyl) From glycol components such as 2,2'-propane Is a polyester obtained from caprolactone, a reaction product of dimerized drying oil fatty acid (such as dimer acid) and diamine or polyamine, methoxymethyl-6,6-nylon, methoxymethyl-6-nylon, nylon 6 / nylon 6,6 / nylon Polyamides such as 6,10, saponified products of polyvinyl acetate, acrylic-modified polyols (hydroxyalkyl (meth) acrylates, etc.), vinyl polymers such as saponified products of ethylene-vinyl acetate copolymer, bisphenol type, o-cresol novolak Type, epoxy resin such as tris (epoxypropyl) isocyanurate type or polyol modified with amine, polyester polyol composed of adipic acid and triol and / or butylene glycol and 4,4′-diphenylmethanediiso Oligomers or polymers having urethane bonds composed of various isocyanates such as cyanate, tolylene diisocyanate or triisocyanate, urea resins such as dimethylolurea condensates obtained from urea and formalin, formal resins such as polyvinyl formal and polyvinyl butyral , Hydroxyethylcellulose, hydroxypropylcellulose, methylcellulose, ethylcellulose, cellulose acetate, carboxymethylcellulose, propylcellulose, cellulose derivatives such as nitrocellulose, resole resin or novolak resin consisting of phenol and formaldehyde, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc. Polyether 1,6-hexanedi Polycarbonate diols obtained from rubber and ethylene carbonate, conjugated diolefin polymers such as liquid polybutadiene having a hydroxyl group or amino group at the end, phosphate-based, phosphonate-based, or phosphoramidate-based phosphorus-containing polyols In the present invention, it is preferable that the antihalation layer also serves as the adhesive layer. Therefore, it is preferable that the binder polymer has adhesive performance.
[0025]
The isocyanate compound in the adhesive layer is a compound having two or more isocyanate groups, such as 2,4- or 2,6-tolylene diisocyanate, 2,4- or 2,6-cyclohexane diisocyanate-1-methyl. , Naphthylene-1,5-diisocyanate, 1,4-tetramethylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, isopropylidenebis (cyclohexyl isocyanate), m- or p-xylylene diisocyanate 1,3- or 1,4-cyclohexanedimethyl isocyanate, isophorone diisocyanate, lysine diisocyanate, bis (2-isocyanatoethyl) fumarate, 2,2,4-trimethylhexamethyl Diisocyanate, 3,3'-dimethoxy-4,4'-diphenyl diisocyanate, 2,4-tolylene dimer, tris (4-phenylisocyanate) thiophosphate, diphenyl ether 2,4,4'-triisocyanate, 2,4'- Tolylene diisocyanate trimer, oligoisocyanate obtained from a reaction product of tolylene diisocyanate and polyfunctional alcohol (for example, trimethylolpropane-1-methyl-2-isocyano-4-carbamate), triphenylmethane p, p ′, p ″ triisocyanate , Hexamethylene diisocyanate dimer, trimer (for example, DESMODUR-N [trademark of BAYER], polymethylene polyphenyl isocyanate, 3-hydroxymethylpentane-2,4-diol and hexamethyle A reaction product of a diisocyanate, or an oxime of the isocyanates, and the like blocked isocyanates such as phenol.
[0026]
【Example】
Hereinafter, the present invention will be specifically described with reference to the following examples, but the present invention is not limited thereto.
The evaluation of the present invention was measured by the following method.
1) Absorbance at 360 nm, 380 to 400 nm, and 450 nm: The substrate was measured with a U-3210 self-recording spectrophotometer manufactured by Hitachi, Ltd.
2) Plate performance: Unexposed photosensitive resin laminate (raw plate stored at 50 ° C. for 1 week after production, raw plate stored for 3 months) was exposed for 4 minutes with an exposure machine with a chemical lamp using an inspection negative. Developed and made relief to evaluate.
3) White spot depth (slit depth): This is an evaluation of how many μm deep thin lines (600 μm width, 300 μm width) appear in a relief. The depth between reliefs such as white letters is evaluated, and the deeper the print, the sharper.
[0027]
Example 1
Dissolve 0.8 parts by weight of dehydrothio-p-toluidine of general formula (1) and 0.6 parts by weight of bisdehydrothio-p-toluidine of general formula (2) where n = 1 in 2.2 parts by weight of dimethylaminoacetamide. 100 parts by weight of “Byron 30SS” (product of Toyobo Co., Ltd., solid content concentration 30%, molecular weight 20000 to 25000) as a polyester resin solution, 0.2 parts by weight of “U-CAT SA102” as an amine salt catalyst It dissolved and prepared in 0.7 weight part of dioxane. Next, 10.2 parts by weight of “Coronate L” (product of Nippon Polyurethane Industry Co., Ltd.) as a polyfunctional isocyanate was dissolved in 1.4 parts by weight of ethyl acetate to prepare an adhesive composition solution 1. This solution was uniformly applied to a 125 μm-thick transparent polyester film (support) and dried for 1 minute with a 120 ° C. hot air dryer to obtain a support 1 having a transparent adhesive layer with a coating thickness of about 20 μm.
[0028]
Comparative Example 1
0.5 parts by weight of dehydrothio-p-toluidine of the general formula (1) is dissolved in 3.6 parts by weight of dimethylaminoacetamide, and a “ byron 30SS” (Toyobo Co., Ltd. product, solid content concentration 30 as a polyester resin solution) %, Molecular weight 20000 to 25000) 100 parts by weight, and 0.2 parts by weight of “U-CAT SA102” as an amine salt catalyst was dissolved in 0.7 parts by weight of dioxane. Next, 10.2 parts by weight of “Coronate L” (product of Nippon Polyurethane Industry Co., Ltd.) as a polyfunctional isocyanate was dissolved in 1.4 parts by weight of ethyl acetate to prepare an adhesive composition solution 2. This solution was uniformly applied to a 125 μm-thick transparent polyester film (support) and dried for 1 minute with a 120 ° C. hot air dryer to obtain a support 2 having a transparent adhesive layer having a coating film thickness of about 20 μm.
[0029]
Photoresist resin plates “printite” EF type and KF type (trademark, Toyobo Co., Ltd.) capable of water development on the supports 1 and 2 having the adhesive layers obtained in Example 1 and Comparative Example 1, respectively. A photosensitive resin composition (raw plate) 1 and 2 was obtained by laminating a 125 μm polyester film after coating each photosensitive resin composition corresponding to the product manufactured to a thickness of about 300 μm. .
Using a raw plate stored at 50 ° C. for 1 week after manufacturing and a raw plate stored for 3 months, each was exposed and developed for 4 minutes with an exposure machine equipped with a chemical lamp to make a relief and evaluated. The results are shown in Table 1 below.
[0030]
[Table 1]
[0031]
【The invention's effect】
As is clear from Table 1, the photosensitive resin laminate of the present invention has an excellent antihalation effect and resolution, and is excellent in stability over time, and therefore greatly contributes to the industry.

Claims (2)

The support containing the compound represented by the following general formula (1) and general formula (2) and provided with an adhesive layer has an absorbance at 360 nm of 0.60 or more, and an absorbance at 380 to 400 nm of 0.27 or more. Furthermore, an antihalation composition characterized by satisfying an absorbance at 450 nm or more of 0.10 or less.
A photosensitive resin laminate comprising at least a support, an adhesive layer, and a photosensitive resin layer, wherein the adhesive layer contains the antihalation composition according to claim 1. Laminated body.