CN101144980B - Photosensitive resin plate support and preparation method thereof - Google Patents

Abstract

The invention discloses a photosensitive resin plate support body and a preparation method thereof, which comprises a base material, a bottom layer and an adhesive layer in sequence from bottom to top. The preparation method is as follows: the bottom layer and the adhesive layer are pre-prepared into a solution, and the bottom layer is first coated on the polyester film or metal sheet that constitutes the substrate, and after drying, the adhesive layer is coated on the bottom layer, and it is wound up after drying. . The invention significantly strengthens the adhesive force between the support body and the photosensitive layer after exposure and plate making, and the relief image can be preserved for a long time. The above-mentioned photosensitive resin plate is cross-linked with the adhesive layer of the support when it is exposed to form relief images during plate making, and the adhesive layer and the relief layer are integrated. Since the adhesive layer and the bottom layer are also integrated, the adhesion between the relief layer and the support The relay is excellent, and the result is that the resin plate will not peel off or fall off after long-term storage.

Description

Photosensitive resin plate support and preparation method thereof

technical field

The invention relates to a photosensitive layer resin plate support with an adhesive layer designed on the surface of a base material, in particular to a photosensitive resin plate support and a preparation method thereof.

Background technique

At present, flexible photosensitive resin plates are widely used in the printing of cartons, flexible packaging, labels and other easily deformed or soft substrates. This technology has matured abroad, and there is no plate manufacturer with better quality in China. The development of flexographic plates that restricts domestic flexographic printing has always been the urgent hope of printing manufacturers. With the rapid increase of my country's export trade and stricter environmental protection requirements, flexographic printing will develop rapidly in China, and the demand for flexographic printing plates will also increase.

Usually, a film with a pattern or text is placed on an unexposed flexographic plate containing photoelastomer, exposed to ultraviolet light, and the transparent part of the film passes through ultraviolet light, and the initiator in the photoelastomer decomposes into free radicals, which can initiate crosslinking. Curing by monomer reaction. The areas that do not pass through the ultraviolet rays cannot be cross-linked, and the difference in solubility in the developer is used to develop a relief image containing text patterns. The plate material after development is dried, debonded, and post-exposed to ensure that the photosensitive layer is completely polymerized. The prepared plate is fixed on the cylinder of the flexo printing machine and is ready for printing.

In the past, the photosensitive resin plates used in flexographic printing plates etc. were coated with an adhesive layer on the surface of plastic films such as polyester resin films, and a photosensitive resin layer was formed on it. The unexposed part is not cross-linked and hardened to remove it with a developer to form a relief image.

When the above-mentioned photosensitive resin plate is printed, the relief is easy to peel off and fall off due to strong shear force and peeling force between the relief and the support. In order to prevent the relief from peeling and falling off, there must be a strong adhesive layer between the relief and the substrate.

Especially in the case of flexographic printing, it is generally used repeatedly, and most of them are used once and stored for a long time. It is required to have a strong adhesion between the relief layer and the substrate after long-term preservation. However, conventional photosensitive resin plates had a problem of relief peeling due to moisture absorption of the adhesive layer during long-term storage.

Japanese Patent Laid-Open No. 1-283557 describes the use of three layers to solve the adhesive force between the relief and the support body, which is troublesome to operate. U.S. Patent No. 4,917,990 discloses coatings on substrates such as ethylene terephthalate (PET) containing an adhesive layer containing chlorosulfonated polyethylene to improve the adhesion between the support and the photosensitive layer, but this method is When exposing the adhesive layer and the photosensitive layer, the adhesive force tends to decrease with the increase of exposure. JP-A-2000-155410 introduces a bonding method which is a moisture curing type, which is difficult to industrialize. European patent EP1209524A1 discloses a preparation method for a flexographic plate support. It coats a solution containing polyol and diisocyanate on a substrate such as PET, dries at 80°C for 2 minutes, and then dries at 40°C for 3 days to obtain a support with an adhesive layer. In general, industrial implementation is difficult.

Contents of the invention

The object of the present invention is to provide a photosensitive resin plate support and a preparation method thereof which can preserve relief images for a long time without peeling off.

The object of the present invention can be achieved through the following measures:

The invention includes base material, bottom layer and adhesive layer in order from bottom to top.

In the present invention, a protective film is also attached to the adhesive layer, but of course, the protective film may not be attached. The bottom layer contains a polymer of chlorine element, or, the bottom layer contains a polymer or a mixture mainly composed of vinylidene chloride structural units. The amount of the vinylidene chloride structural unit accounts for more than 30% of the total molar weight of the polymer. The weight ratio of the polymer material containing vinylidene chloride structural unit to the total solid content of the bottom layer is more than 50%. The adhesive layer contains acrylate urethane resin. The adhesive layer contains a photo-crosslinkable acrylate urethane resin. The softening point of acrylate polyurethane resin is between 80-150°C. The weight ratio of the photo-crosslinkable acrylate polyurethane resin in the adhesive layer to the total solids of the adhesive layer material is 30%-98%. The adhesive layer also contains a photosensitizer, a photocrosslinkable resin, and one or more ethylenically unsaturated monomers.

The preparation method of the photosensitive resin plate support of the present invention is as follows: the bottom layer and the adhesive layer are prepared into a solution in advance, and the bottom layer is first coated on the polyester film or metal sheet that constitutes the substrate, and after drying, the bottom layer is coated on the bottom layer The adhesive layer is rolled after drying.

Among the present invention, polyester film comprises: any one in polyethylene terephthalate, polybutylene terephthalate, polyvinyl chloride, polyethylene naphthalene-2.6-dicarbonate; The metal sheet includes any one of aluminum plate, stainless steel sheet and copper sheet. Of course, other suitable polyester films or metal sheets can also be used. In the preparation method, the dried adhesive layer is covered with a protective film and then rolled. In the preparation method, after the adhesive layer is dried, it is directly covered on the photosensitive resin plate, and the photosensitive resin plate is directly made by hot pressing at a temperature of 20-130° C. and a pressure of 0.15-14 MPa.

Because the present invention adopts the above structure and preparation method, the adhesive force between the support body and the photosensitive layer is significantly strengthened after exposure and plate making, and the relief image can be preserved for a long time. The above-mentioned photosensitive resin plate is cross-linked with the adhesive layer of the support when it is exposed to form relief images during plate making, and the adhesive layer and the relief layer are integrated. Since the adhesive layer and the bottom layer are also integrated, the adhesion between the relief layer and the support The relay is excellent, and the result is that the resin plate will not peel off or fall off for a long time. Use the BLD-200S electronic peeling tester produced by Jinan Languang Electromechanical Technology Co., Ltd. to measure the peeling force, and the peeling force can reach more than 1kg/cm.

Description of drawings

Accompanying drawing is the cross-sectional structure schematic diagram of photosensitive resin plate support body of the present invention;

Detailed ways

The present invention is described in detail below in conjunction with accompanying drawing and embodiment:

The first part of the embodiment

In the present invention, the structural features of the photosensitive resin plate support are shown in the accompanying drawings. In the drawings: (1) is the substrate; (2) is the bottom layer of acrylate copolymer containing vinylidene chloride structural unit (referred to as the bottom layer); (3) is the cross-linked resin bonding layer containing structural unit of polyurethane acrylate layer (referred to as the adhesive layer); (4) is a protective film.

In use of the present invention, the base material can be plastic films such as polyester, polypropylene, and triacetate. The polyester resin film is preferably extruded by twin-screw, and the thickness of these substrates is not particularly limited, and is generally 0.05-0.3 mm thick.

A bottom layer (2) of acrylate copolymer resin containing vinylidene chloride structural units is coated on the surface of the substrate, and the copolymer resin is water-soluble or organic solvent-based. The used copolymer resin of the present invention is the base resin NPR-4 of Lucky Group, and this resin uses alcohol or aqueous solvent, and the present invention also can use other solvents such as ketone solvent, amide solvent, ether solvent, hydrocarbon solvent, like this The solvent can be methanol, ethanol, propanol, butanol, ethylene glycol, acetone, butanone, cyclohexanone, pyrrolidone, N-methylpyrrolidone, N, N-dimethylformamide, N, N-di Methylacetamide, dichloromethane, chloroform, benzene, toluene, etc. Coat the film former solution on 80-150μm polyethylene terephthalate (PET), polypropylene, triacetate by well-known coating methods such as dip coating, scrape coating, extrusion coating, etc. On other substrates, the coating amount is generally 1-50g/m ² , and the film thickness is generally 0.1-5μm.

Coating adhesive layer (3) on above-mentioned bottom layer again, adhesive layer contains photocrosslinkable resin, and its resin can be polyurethane acrylate copolymer, polyurethane vinyl acetate copolymer, polyvinyl acetate/acrylate copolymer Or their mixture, preferably acrylate polyurethane resin, its softening point is preferably at 60-170°C, most preferably at 80-150°C.

The adhesive layer contains a photoinitiator as needed. Such as benzophenone, michione, 4-acetoxy-4'-diethylamine benzophenone, benzoin ethyl ether, α-hydroxyisopropyl benzophenone, α-hydroxycyclohexyl benzophenone, 2-phenyl-2,2-dimethoxyacetophenone, 2-tert-butyl anthraquinone, isopropyl thiaxanthraquinone, (morpholinobenzoyl) 1-hexayl 1,1 (di Methylamino) propane, benzil, benzoin, etc., the commercial brands include 184, 369, 651, 819, 907, 1173, BP, ITX, TPO, etc., and the added amount accounts for more than 0.2% of the total solids.

The adhesive layer also contains acryloyloxyester or methacryloyloxyester double-bond polymerizable monomers, which can be monofunctional, difunctional or multifunctional. The above-mentioned monomers preferably have a boiling point above 100°C and have good mutual solubility. Such monomers are 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, butyl acrylate, octyl acrylate, ethoxyethyl acrylate, 2-phenoxy Ethyl acrylate, 1,3-propanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,5-pentanediol di(meth)acrylate, 1, 6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, pentaethylene glycol di(meth)acrylate ester, dipropylene glycol diacrylate, tripropylene glycol di(meth)acrylate, tetrapropylene glycol di(meth)acrylate, neopentyl glycol diacrylate, diethylene glycol phthalate, Ethoxylated Bisphenol A Diacrylate, Ethoxylated Trimethylolpropane Triacrylate, Propoxylated Glycerin Triacrylate, 2,2-Di(p-hydroxyphenyl)-propane di(meth)acrylate ester, dimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate base) acrylate, etc.

The solvent used for the adhesive layer in the present invention can be alcohol solvents, ketone solvents, hydrocarbon solvents, amide solvents, ether solvents, etc., such as methanol, ethanol, propanol, butanol, ethylene glycol, acetone, butanol Ketone, cyclohexanone, pyrrolidone, N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, methylene chloride, chloroform, benzene, toluene, etc. ,

If necessary, heat inhibitors, antiozonants, and other additives such as dyes, pigments, and ultraviolet absorbers can also be added to the adhesive layer.

The above-mentioned acrylate polyurethane resin, photosensitizer, polymerizable ethylenically unsaturated monomer, etc. are dissolved in a suitable solvent, and the solid content accounts for more than 1% of the solvent, and are coated on the bottom layer, and after drying, the thickness is 0.1-5 μm.

The total thickness of the above bottom layer and the adhesive layer is 0.2-10 μm.

A protective film (4) is covered on the dried adhesive layer (3).

The photosensitive resin plate support prepared by the present invention and the photosensitive resin layer of the flexible plate produced by DuPont Company with a thickness of 3.94mm or the plate produced by Lucky Group with a thickness of 3.94mm are used at 20-150°C. Composite photosensitive resin plate under 0.15-14MPa.

The above-mentioned photosensitive resin plate is cross-linked with the adhesive layer of the support when it is exposed to form relief images during plate making, and the adhesive layer and the relief layer are integrated. Since the adhesive layer and the bottom layer are also integrated, the adhesion between the relief layer and the support The relay is excellent, and the result is that the resin plate will not peel off or fall off for a long time. Use the BLD-200S electronic peeling tester produced by Jinan Languang Electromechanical Technology Co., Ltd. to measure the peeling force, and the peeling force can reach more than 1kg/cm.

The following examples are specific descriptions of the present invention, but the content of the present invention is not limited thereto. In the examples, all components are by weight.

Example 1

Bottom layer: 230g of pure water, 20g of NPR-4# (manufactured by Lucky Company), 1.4g of 10% potassium hydroxide, 0.1g of surfactant Fc-4430# (manufactured by 3M Company), stirred at room temperature for 30 minutes to obtain an aqueous solution . This aqueous solution was coated on a polyester film (manufactured by Lucky) having a thickness of 100 μm at a speed of 30 m/min. Dry at 100° C. for 5 minutes to obtain a bottom layer with a thickness of less than 1 μm.

Adhesive layer: 100g of acetone, 50g of toluene, 20g of polyurethane vinyl acetate R-317 (manufactured by Lucky Company), dissolved at room temperature. Then add 1,3-propanediol diacrylate 2g, initiator (184) 0.5g, 2,6-di-tert-butyl-p-cresol 0.2g, Fc-4430# (produced by 3M company) 0.1g, in the yellow safety light , stirred in an airtight container for 1 hour to obtain a second layer of coating liquid. This aqueous solution was coated on the above-mentioned base film at a speed of 30 m/min. Drying was carried out at 50° C. for 5 minutes to obtain an adhesive layer with a thickness of 1 μm.

Example 2

Bottom layer: same as embodiment 1

Adhesive layer: 100g of acetone, 50g of toluene, 15g of urethane acrylate (manufactured by Lucky Company), dissolved at room temperature. Then, 7 g of 1,3-propanediol diacrylate, 0.5 g of an initiator (184), 0.2 g of 2,6-di-tert-butyl-p-cresol, and 0.1 g of Fc-4430# (manufactured by 3M Co.) were added. The operation method is the same as the adhesive layer coating method in Example 1 to obtain an adhesive layer with a thickness of 1 μm.

Example 3

Bottom layer: same as embodiment 1

Adhesive layer: 100g of acetone, 50g of toluene, 10g of urethane acrylate (manufactured by Lucky Company), dissolved at room temperature. Then, 12 g of 1,3-propanediol diacrylate, 0.5 g of an initiator (184), 0.2 g of 2,6-di-tert-butyl-p-cresol, and 0.1 g of Fc-4430# (manufactured by 3M Co.) were added. The operation method is the same as the adhesive layer coating method in Example 1 to obtain an adhesive layer with a thickness of 1 μm.

Comparative example 1

The adhesive layer in Example 2 was directly coated on the polyester film without coating the primer layer, and the operation method was the same as the adhesive layer coating method in Example 1 to obtain an adhesive layer with a thickness of 1 μm.

Comparative example 2

Bottom layer: same as embodiment 1

Adhesive layer: 100g of acetone, 50g of toluene, 25g of urethane acrylate (manufactured by Lucky Company), dissolved at room temperature. Then, 0.5 g of an initiator (184), 0.2 g of 2,6-di-tert-butyl-p-cresol, and 0.1 g of Fc-4430# (manufactured by 3M Co.) were added. The operation method is the same as the adhesive layer coating method in Example 1 to obtain an adhesive layer with a thickness of 1 μm.

Comparative example 3

Bottom layer: same as embodiment 1

Adhesive layer: 100g of acetone, 50g of toluene, 2g of urethane acrylate (manufactured by Lucky Company), dissolved at room temperature. Then, 20 g of 1,3-propanediol diacrylate, 0.5 g of an initiator (184), 0.2 g of 2,6-di-tert-butyl-p-cresol, and 0.1 g of Fc-4430# (manufactured by 3M Corporation) were added. The operation method is the same as the adhesive layer coating method in Example 1 to obtain an adhesive layer with a thickness of 1 μm.

Align the coating surface of the support body of the above examples 1-3 and comparative examples 1-3 with the photosensitive resin layer, and keep it for 20 seconds at 20-150°C under a pressure of 0.15-14MPa, and use a ZR650C flexographic plate-making machine (Jiangsu Tai Instrument Group Co., Ltd.) was exposed for 30 seconds from the support substrate (1) toward the photosensitive layer to prepare a sample. These samples were tested with BLD-200S electronic peeling tester (manufactured by Jinan Languang Electromechanical Technology Development Center), and the results are shown in Table 1.

Table 1 embodiment and comparative example peel force situation

Peeling conditions, 180°peeling at a constant speed of 150mm/min.

The standard peeling force is required to be not less than 1000g/cm. It can be seen from Table 1 that the peeling force of Examples 1, 2 and 3 of the present invention all reach more than 1500g/cm, while the peeling force of the comparative example is far lower than the standard.

The second part of the embodiment

The invention comprises base material (1), bottom layer (2) and adhesive layer (3) from bottom to top. A protective film (4) is also attached to the adhesive layer (3). The bottom layer (2) contains a polymer of chlorine element, or, the bottom layer (2) contains a polymer or a mixture mainly composed of vinylidene chloride structural units. The amount of vinylidene chloride structural units accounts for more than 30% of the total molar weight of the polymer, specifically 30%, 40%, 50%, 60%, 70%, 80%, 90% or the like, or 30% as required % above any point value. The weight ratio of the polymer material containing vinylidene chloride structural units to the total solids of the bottom layer is more than 50%, specifically it can be 50%, 60%, 70%, 80%, 90% or the like, and it can also be as required Any individual point value above 50%. The adhesive layer (3) contains acrylate polyurethane resin. Specifically, the adhesive layer (3) contains a photocrosslinkable acrylate polyurethane resin. The softening point of acrylate polyurethane resin is between 80-150°C, which can be 80, 90, 100, 110, 120, 130, 140, 150°C, etc., or other values between 80-150°C. The amount of photo-crosslinkable acrylate polyurethane resin in the adhesive layer (3) accounts for 30% to 98% by weight of the total solids of the adhesive layer material, which can be 30%, 40%, 50%, 60%, 70%, 80%, 98%, etc., can also be other point values within the range of 30% to 98%. The adhesive layer (3) also contains a photosensitizer, a photocrosslinkable resin, and one or more ethylenically unsaturated monomers.

The preparation method of the photosensitive resin plate support of the present invention is as follows: the bottom layer (2) and the adhesive layer (3) are prepared into a solution in advance, and the bottom layer (2) is first coated on the polyester film or metal sheet forming the substrate, and after drying , and then coat the adhesive layer (3) on the bottom layer (2), and roll it up after drying.

In the preparation method, the polyester film includes: any one of polyethylene terephthalate, polybutylene terephthalate, polyvinyl chloride, and polyethylene naphthalene-2.6-dicarbonate; the metal Thin sheets include any one of aluminum plates, stainless steel sheets, and copper sheets. In the preparation method, the dried adhesive layer (3) is covered with a protective film (4) and then rolled. In the preparation method, after the adhesive layer (3) is dried, it is directly covered on the photosensitive resin plate, and the photosensitive resin plate is directly made by hot pressing at a temperature of 20-130° C. and a pressure of 0.15-14 MPa. Wherein, the temperature can be 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130°C, etc., or other points within the range of 20-130°C. The pressure can be 0.15, 0.5, 1, 3, 5, 7, 9, 11, 12, 14MPa, etc., or other values within the range of 0.15-14MPa.

The present invention is to coat the acrylate copolymer resin containing water-soluble or organic solvent-type vinylidene chloride structural units on the plastic film substrates such as polyester, polypropylene and triacetate as the bottom layer, and then coat the bottom layer with An adhesive layer of a cross-linked urethane acrylate resin with a photopolymerization initiator, and then a protective film is applied on the adhesive layer and rolled up. Before compounding with the photosensitive resin layer, peel off the protective film, and compound with the photosensitive resin layer at 20-150°C and a pressure of 0.15-14MPa. After exposure and plate making, the adhesion between the support and the photosensitive layer is significantly strengthened, and the relief image can be preserved for a long time.

Claims (7)

1. a photosensitive resin plate support body, is characterized in that: it comprises base material (1), bottom layer (2) and adhesive layer (3) and protective film (4) successively from bottom to top, described bottom layer (2) ) contains a polymer mainly composed of vinylidene chloride structural units, and the adhesive layer (3) contains an acrylate polyurethane resin; the amount of the vinylidene chloride structural units accounts for 30% of the total molar weight of the polymer The above; the weight ratio of the polymer material containing vinylidene chloride structural unit to the total solids of the bottom layer is more than 50%; the amount of photocrosslinkable acrylate polyurethane resin in the adhesive layer (3) The weight ratio of the total solid content of the adhesive layer material is 30%-98%. 2. The photosensitive resin plate support according to claim 1, characterized in that: the adhesive layer (3) contains photo-crosslinkable acrylate polyurethane resin. 3. The photosensitive resin plate support according to claim 1, characterized in that: the softening point of the acrylate polyurethane resin is between 80-150°C. 4. The photosensitive resin plate support according to claim 1, characterized in that: the adhesive layer (3) also contains a photosensitizer, a photocrosslinkable resin, and a non-polymer with one or more vinyl groups. saturated monomer. 5. A method for preparing a photosensitive resin plate support as claimed in claim 1, characterized in that: on the polyester film or metal sheet forming the base material (1), the acrylic acid containing vinylidene chloride structural unit is coated The ester copolymer resin is used as the bottom layer (2), and the cross-linked polyurethane acrylate resin containing a photopolymerization initiator is coated on the bottom layer (2) as an adhesive layer (3), and on the dried adhesive layer (3) It is formed after being covered with a protective film (4). 6. the preparation method of photosensitive resin plate support according to claim 5 is characterized in that: polyester film comprises: polyethylene terephthalate, polybutylene terephthalate in the described preparation method Any one of ester, polyvinyl chloride, polyethylene naphthalene-2.6-dicarbonate; the metal sheet includes any one of aluminum plate, stainless steel sheet, and copper sheet. 7. according to the preparation method of the described photosensitive resin plate support body of claim 5 or 6, it is characterized in that: after adhesive layer (3) is dried in the described preparation method, directly cover on the photosensitive resin plate, at temperature 20～ At 130°C, under a pressure of 0.15-14MPa, hot pressing is directly made into a photosensitive resin plate.