CN108227380B - Photosensitive resin flexographic plate capable of eliminating anisotropy and flexographic printing plate made of same - Google Patents
Photosensitive resin flexographic plate capable of eliminating anisotropy and flexographic printing plate made of same Download PDFInfo
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- CN108227380B CN108227380B CN201611138684.7A CN201611138684A CN108227380B CN 108227380 B CN108227380 B CN 108227380B CN 201611138684 A CN201611138684 A CN 201611138684A CN 108227380 B CN108227380 B CN 108227380B
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41N—PRINTING PLATES OR FOILS; MATERIALS FOR SURFACES USED IN PRINTING MACHINES FOR PRINTING, INKING, DAMPING, OR THE LIKE; PREPARING SUCH SURFACES FOR USE AND CONSERVING THEM
- B41N1/00—Printing plates or foils; Materials therefor
- B41N1/16—Curved printing plates, especially cylinders
- B41N1/22—Curved printing plates, especially cylinders made of other substances
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
Abstract
The invention relates to a photosensitive resin flexographic plate for eliminating anisotropy and a flexographic printing plate manufactured by the photosensitive resin flexographic plate, wherein the photosensitive resin flexographic plate comprises a polyester support body, a bonding layer, at least one photosensitive resin layer, an anti-sticking layer and a protective film, wherein the bonding layer is sequentially arranged on the polyester support body from bottom to top, and the photosensitive resin layer is prepared from the following raw materials: at least one thermoplastic elastomer, at least one vinyl unsaturated monomer and at least one photoinitiator, wherein the thermoplastic elastomer is a triblock copolymer or- (A-B-) with an A-B-A structurenA multiblock copolymer in which n is an integer of 2 or more, A is a polymerized monoarylalkane monomer, and B is a polymerized diene monomer having rubber properties or a corresponding hydrogenated-product monomer thereof. Compared with the prior art, the photosensitive resin flexible plate disclosed by the invention has better isotropy, excellent wear resistance, drapability and printing resistance, high strength and good toughness, and is suitable for industrial production.
Description
Technical Field
The invention belongs to the technical field of flexographic printing, and relates to a photosensitive resin flexographic plate capable of eliminating anisotropy and a flexographic printing plate manufactured by the photosensitive resin flexographic plate.
Background
It is known to use a photosensitive resin flexographic plate to make a photosensitive resin flexographic printing plate, the printing surface of which is formed by exposing a photosensitive resin layer covered with a negative or negative film (film) and subsequently removing the unexposed, non-photopolymerizable and non-cured areas of the surface. At present, the prior art on photosensitive resin flexographic plates can be found in the following U.S. patents: US4323636, US4369246, US5135837, US5582954, US4323637, US5472824 and the like. A typical photopolymer flexographic plate is composed of several parts: the photosensitive resin film comprises a polyester support, an optional adhesive layer for adhering photosensitive resin to the support, at least one photosensitive resin layer, and a protective film with a release layer. The production of the photosensitive resin flexible plate is generally to put the photosensitive resin component into a screw extruder to be extruded, simultaneously to coat a support body and a protective film on the upper and lower sides, to send into a calender to be pressed into a sandwich structure.
The photosensitive resin layer comprises a polymeric binder (typically a thermoplastic elastomer), at least one photopolymerizable monomer (typically an ethylenically unsaturated monomer), and a photoimageable system. The photoimageable system contains, among other things, at least one photoinitiator and other additives such as antioxidants, plasticizers, fillers, dyes, and the like.
In general, thermoplastic elastomeric inlaysSegmented copolymers are useful as polymer binders, and related technical descriptions can be found in the above-cited U.S. patents. These thermoplastic elastomers generally have a triblock copolymeric structure A-B-A, where A is a thermoplastic block and B is an elastomeric block; or- (A-B-)nA multiblock copolymeric structure wherein a is a thermoplastic block and B is an elastomeric block. Typically, the thermoplastic block "a" is a polymer of monoarylalkanes having a high glass transition temperature Tg, such as polystyrene, poly (alpha-methylstyrene), poly (4-methylstyrene), polyethylene naphthalene, poly (4-butylstyrene), and the like. It belongs to a hard segment structure in the block copolymer. Generally, the elastomer block "B" is a polymer of a diene, having a relatively low glass transition temperature Tg, being relatively soft and rubbery, such as a polymer of isoprene, butadiene, etc., or a corresponding hydrogenated product thereof, such as a polymer of ethylene, butene, etc. For example, chinese patent application No. 201210368569.4 discloses a flexible photosensitive resin plate with low surface tackiness. The flexible photosensitive resin plate comprises the following photosensitive components: (1)34.5 to 75 weight percent of a thermoplastic elastomer; (2) 10-45% by weight of two plasticizers of different chemical structures; (3)4 to 15% by weight of a photo-crosslinkable ethylenically unsaturated monomer; (4)0.01 to 5% by weight of a photoinitiator or photoinitiating system; (5) 0.01-2% of other additives such as dye and the like. Wherein the thermoplastic elastomer at least comprises a polymer with a structure of A1-B1-A1, the polymer comprises a A1-B1 diblock compound, A1 is a polymerized monoaryl alkane monomer, and B1 is a polymerized alkadiene monomer. In the thermoplastic elastomer A1-B1-A1, A1 accounts for 18-37% of the total molecular weight, the weight average molecular weight is 4000-40000, and the weight average molecular weight of B1 is 100000-250000; wherein the weight of the A1-B1 diblock compound is 10-17% of the weight of the total thermoplastic elastomer.
With the rapid development of flexographic technology and the increasing social demands, the photosensitive resin flexographic printing plates used today must be printed millions of times under high-intensity printing conditions, such as high temperature, high-intensity friction, and a large amount of ink solvents. However, the conventional photosensitive resin flexographic plates made of block copolymers having a polystyrene content of less than 30% have technical defects such as poor abrasion resistance, for example, under normal printing conditions, the fine dots on the printing plate are easily worn out prematurely, so that when overprinting such as 8 colors is performed, the easily worn printing plate of some colors needs to be replaced. This requires frequent machine halt and plate change, and because the printing time is an important factor determining the final printing cost, the machine halt and plate change will reduce the printing efficiency, and is not beneficial to shortening the printing operation time, which undoubtedly will bring huge economic loss to the enterprise, and the opportunity cost is larger.
In view of the above-mentioned problems, the use of a polystyrene-polybutadiene-polystyrene or polystyrene-polyisoprene-polystyrene block copolymer having a high polystyrene content for the production of a photosensitive resin flexographic printing plate has been increasingly emphasized. This is because it has superior physical properties, toughness and abrasion resistance, and has higher printing durability than the conventional photosensitive resin flexographic plates made of block copolymers with lower polystyrene content. However, if the thermoplastic block A has a relatively high content, for example, a polystyrene content of more than 30%, among the thermoplastic elastomeric block copolymers, the thermoplastic elastomeric block copolymers exhibit severe anisotropy as a polymer base in the final photosensitive resin layer, regardless of whether polyisoprene or polybutadiene is used as a component of the elastomer block B (note: anisotropy means that the system exhibits different non-uniform physical properties in different directions such as a machine direction and a transverse direction). The presence of anisotropy results in a photosensitive resin flexographic printing plate having poor physical properties, such as poor drapability and poor printing results. Anisotropy can also lead to other undesirable properties, such as internal cracking in the stiffer direction, and more importantly, this inhomogeneity can lead to extremely poor printing results. The above-mentioned technical drawbacks due to anisotropy cannot meet the use requirements of modern photosensitive resin flexographic printing plates. Therefore, in the field of flexographic printing plate industry, in order to avoid anisotropy, in the actual production process, only the block copolymer with lower polystyrene content can be selected as the polymer base material to produce the photosensitive resin flexographic printing plate, which undoubtedly greatly limits the technical development of the block copolymer with high polystyrene content for producing the photosensitive resin flexographic printing plate.
Disclosure of Invention
The present invention is directed to overcome the above-mentioned drawbacks of the prior art and to provide a physically isotropic photosensitive resin flexographic plate with high strength, high wear resistance and high plate durability, which can eliminate anisotropy, and a flexographic printing plate made of the same.
The purpose of the invention can be realized by the following technical scheme:
the utility model provides a can eliminate anisotropic photosensitive resin flexographic plate, this photosensitive resin flexographic plate includes the polyester supporter, from bottom to top sets gradually tie coat, at least one deck photosensitive resin layer, antiseized layer and protection film on the polyester supporter, the photosensitive resin layer form by the raw materials preparation including following component: at least one thermoplastic elastomer, at least one photopolymerizable vinyl unsaturated monomer and at least one photoinitiator, wherein the thermoplastic elastomer is a triblock copolymer of an A-B-A structure or- (A-B-)nThe multi-block copolymer, wherein n is an integer more than or equal to 2, A is a polymerized monoaryl alkane monomer, and B is a polymerized diene monomer with rubber property or a corresponding hydrogenation product monomer.
The photosensitive resin layer is prepared from the following raw materials in parts by weight: 6.5-7.5 parts of thermoplastic elastomer, 2-2.3 parts of plasticizer, 0.3-0.6 part of vinyl unsaturated monomer, 0.1-0.15 part of photoinitiator and 0.05-0.1 part of antioxidant.
The thermoplastic elastomer is a styrene-isoprene-styrene triblock copolymer or a styrene-butadiene-styrene triblock copolymer, the mass percentage of the styrene-isoprene diblock copolymer in the styrene-isoprene-styrene triblock copolymer is 0-20%, and the mass percentage of the styrene-butadiene diblock copolymer in the styrene-butadiene-styrene triblock copolymer is 0-20%.
The mass percentage of the polystyrene in the thermoplastic elastomer is 30-37%.
The thermoplastic elastomer is in
The melt index is 8-15, the specific gravity is 0.90-0.95, and the modulus when elongated to 300% is 80-500 psi.
The vinyl unsaturated monomer comprises one or more of 1, 6-hexanediol diacrylate, 1, 6-hexanediol dimethacrylate or trimethylolpropane trimethacrylate.
The photoinitiator is benzoin dimethyl ether, and the antioxidant is 2, 6-di-tert-butyl-4-methylphenol.
The plasticizer is one or more selected from mineral oil with the viscosity of 60-100cps, aliphatic naphthenic oil with the viscosity of 80-150cps or styrene-butadiene oligomeric oil with the molecular weight of 2000-10000.
Preferably, when the plasticizer is formed by mixing mineral oil and styrene-butadiene oligomer oil, the mass ratio of the mineral oil to the styrene-butadiene oligomer oil is 2-4.5: 1.
Preferably, when the plasticizer is formed by mixing aliphatic naphthenic oil and styrene-butadiene oligomer oil, the mass ratio of the aliphatic naphthenic oil to the styrene-butadiene oligomer oil is 2-4.5: 1.
Preferably, when the plasticizer is a mixture of mineral oil, aliphatic naphthenic oil and styrene-butadiene oligomer oil, the ratio of the total mass of the mineral oil and the aliphatic naphthenic oil to the mass of the styrene-butadiene oligomer oil is 2-4.5: 1.
The preparation method of the photosensitive resin layer comprises the following steps: adding the thermoplastic elastomer, the plasticizer, the vinyl unsaturated monomer, the photoinitiator and the antioxidant into an extruder according to the parts by weight, mixing for 2-5 minutes at the temperature of 120-200 ℃, discharging from a die head, calendering by a calendering roller with the gap of 1.0-4.0mm, simultaneously respectively covering a supporting body for adhesion and an anti-adhesion protective film with the thickness of 100-150 mu m on the upper side and the lower side, and then cooling to room temperature.
The flexographic printing plate is prepared by adopting the photosensitive resin flexographic plate capable of eliminating the anisotropy.
In order to improve the printing resistance of the printing plate, the mechanical strength of the product is critical. The improved process and formula adopted by the invention are used for overcoming the technical problem of anisotropy, and can effectively improve physical properties so as to solve the problem of poor properties in the photosensitive resin flexible printing plate.
As mentioned in the background of the invention, the main component of a photopolymer flexographic printing plate is a thermoplastic elastomer, which provides integrity and strength to the entire printing plate. The composition of the thermoplastic elastomers mentioned in the background is a triblock copolymer of the A-B-A structure or- (A-B-)nMultiblock copolymers of the structure wherein "a" is a thermoplastic block with a high Tg, typically a polymerized monoarylalkane monomer such as styrene; "B" is an elastomeric block having a relatively low Tg, being relatively soft and rubbery, and is typically a polymerized diene monomer or its corresponding hydrogenated product monomer, such as butadiene or isoprene. The characteristics of high strength, high modulus, high wear resistance and the like of the photosensitive resin flexible printing plate are determined by the Tg harder component A; the characteristics of high ductility, high resilience and rubber physical properties are determined by the low Tg softer component B. To design a high-strength, high-wear-resistance, high-press-fastness photosensitive resin flexographic printing plate, it is necessary to use a thermoplastic elastomer having a higher polystyrene content.
It is noted, however, that high Tg thermoplastic modules are incompatible with soft elastomer modules, and this mismatch in solubility results in a so-called "microphase separation". Thus, the hard polystyrene molecular chains are clustered together to form "islands" and dispersed in the "sea" of amorphous elastomer. It is well known that thermoplastic elastomers have excellent physical properties because of the microphase separation that the hard polystyrene modules and soft polydiene modules form an interpenetrating network structure at ambient temperature and completely melt at temperatures above Tg. This is also the main reason why thermoplastic elastomeric block copolymers have superior physical properties compared to their non-block counterparts.
The formation of anisotropy of thermoplastic elastomers is mainly due to two main reasons:
first, the type of morphology:
three microphase separations occur in the A-B-A block copolymer system: the harder polystyrene component forms a spherical, or columnar, or flake-like morphology based on the varying proportions of styrene and diene in the copolymer. Photopolymer flexographic printing plates ideally tend to have polystyrene parts in the system that converge to form a two-dimensional spherical area. However, if the system is formed, one of the components forms a three-dimensional cylindrical or rod-shaped region and is uniformly oriented in one direction, or the two components are alternately arranged to form a lamellar morphology, there is a high possibility that poor anisotropic mechanical properties of the thermoplastic elastomer are formed. The formation of such block copolymer morphology is influenced by several factors including the type of monomer, the hierarchy of the monomers, the composition of the monomers, and even the processing of the thermoplastic elastomer. Therefore, the A-B-A block copolymer having a high polystyrene content is highly likely to form such a morphology, resulting in anisotropy.
Second, formation of the continuous phase of the hard component:
block copolymers containing high polystyrene content also tend to form a non-equilibrium continuous styrene mechanism in the soft component. This continuous styrene mechanism results in stiffness in one direction, thereby exhibiting an anisotropic phenomenon. This non-equilibrium continuous phase in the block copolymer is also a function of the type and level of polystyrene moieties, molecular weight of the copolymer, chemical composition or processing of the thermoplastic elastomer. Thus, one of the phenomena driving anisotropic behavior is to do the treatment below the "order-disorder" transition temperature.
Anisotropy Factor (AF) -a method for measuring anisotropy
The anisotropy factor is a measure of the degree of anisotropy in a photopolymer flexographic printing plate. A finished photopolymer flexographic printing plate should be isotropic, for example, its mechanical properties and also its print quality should be independent of the orientation of the printing plate on the printing press. While severe anisotropy will directly result in poor print quality.
Anisotropy is a prominent phenomenon in plates with greater hardness. In the case of the plate having a low hardness, the anisotropy is also a serious problem if the thermoplastic elastomer selected for the purpose of improving the mechanical properties of the product contains a high polystyrene component.
The definition and measurement of anisotropy is determined by the following mathematical formula (US8007984B2):
if σ isMD(125％)>σTD(125%), then AF ═ σMD(125％)/σTD(125％)；
If σ isTD(125％)>σMD(125%), then AF ═ σTD(125％)/σMD(125％)。
Wherein σMD(125%) is the tensile stress when stretched to 125% of the original length along the extrusion direction of the plate, and σTD(125%) is the tensile stress when the plate is stretched to 125% of its original length in a direction perpendicular to the direction of extrusion of the plate. While values for tensile stress are typically measured using a tensile strength tester.
In general, the anisotropy factor is ≧ 1. Theoretically, any data deviating from AF ═ 1 indicates the occurrence of anisotropy in the plate. However, in practical applications, if the anisotropy factor AF ≦ 1.2, the photosensitive flexographic printing resin plate may be considered to be substantially isotropic.
Overcoming anisotropy
By appropriately changing the cause of the above-described anisotropy causing poor performance, the anisotropy in the photosensitive resin flexographic printing plate can be effectively overcome. Therefore, the occurrence of anisotropy can be overcome by preventing the three-dimensional columnar or rod-like domains from being uniformly aligned in one direction, or by avoiding the alignment of lamellar structures. Similarly, isotropy in the final photopolymer flexographic printing plate can also be caused by disturbing the formation of the non-equilibrium polystyrene continuous phase in the softer components. These can be achieved by the following mechanisms: 1) use of a terminal-modified resin; 2) monomers/plasticizers compatible with the rubber phase (typically part of the diene polymer in the thermoplastic elastomer) are used.
End-modified resin: the use of a terminal modified resin, such as Kristalex series products from Istmann, can effectively lower the order-disorder transition temperature of the thermoplastic elastomer, thereby preventing or minimizing the uniform alignment of three-dimensional cylindrical or rod-like regions in a single direction (usually the plate extrusion direction), or preventing the ordered alignment of lamellar structures in the plate extrusion direction. By reducing the order-disorder conversion temperature, the viscosity of the melt during extrusion is greatly reduced, and meanwhile, the plate injection molding pressure can also be reduced.
Use of monomers/plasticizers compatible with the rubber phase: the use of monomers or plasticizers compatible with the rubber phase prevents the formation of a non-equilibrium polystyrene continuous phase in the softer rubber component. The selection of suitable monomers and plasticizers is critical to achieving an anisotropy factor AF < 1.2. This can be achieved using the solubility parameter method.
Solubility parameter
The solubility parameters of the components of the thermoplastic elastomer used in the photosensitive resin flexographic printing plate are shown in Table 1.
TABLE 1 solubility parameters of the components of the block copolymers
| Components | Solubility parameter (cal/cm)3)0.5 |
| Polybutadiene | 8.4 |
| Polyisoprene | 8.1 |
| Polystyrene | 9.1 |
While the solubility parameter of the block copolymer can be weighted according to the mass weight of each portion thereof. For example, the conventional thermoplastic elastomer Kraton D1161 contains 15% polystyrene and 85% polyisoprene, and has a solubility parameter of 8.25 (cal/cm) as calculated from the above table3)0.5。
Table 2 lists the solubility parameters of the different monomers and plasticizers used in the present invention.
TABLE 2 solubility parameters of different monomers and plasticizers
| Components | Solubility parameter (cal/cm)3)0.5 |
| Hydrocal500 | 7.7 |
| Drakeol 34 | 7.5 |
| Ricon 181 | 8.6 |
| 1, 6-hexanediol diacrylate | 9.7 |
| 1, 6-hexanediol dimethacrylate | 9.4 |
The use of monomers or plasticizers compatible with the rubber phase is critical to prevent the formation of a non-equilibrium polystyrene continuous phase in the softer rubber component. The choice of monomer or plasticizer is determined by the solubility parameters of the rubber phase to be matched.
Through complicated experimental researches, it is found that not only the selection of the types of monomers or plasticizers is important, but also the ratio between them is critical. The results of the experiments show that the use of mineral oil (such as Drakeol 34) is much more effective in plasticising the rubber phase than aliphatic naphthenic oil (such as Hydrocal 500). However, mineral oil alone is not as effective as it is with styrene-butadiene oligomeric oils (e.g., Ricon 181). Therefore, the ratio of the specific mineral oil and oligomeric oil is critical. Deviating too far from a certain ratio range may be detrimental for achieving AF <1.2 against anisotropy.
Likewise, the choice of monomers or more specifically the ratio of the different monomers is also important. The correct selection of the appropriate HDDA (1, 6-hexanediol diacrylate)/HDDMA (1, 6-hexanediol dimethacrylate) ratio or HDDA (1, 6-hexanediol diacrylate)/TMPTMA (trimethylolpropane trimethacrylate) ratio is critical to achieving specific curing conditions and overcoming anisotropy. HDDA is characterized by fast curing and allows the photopolymer flexographic plate to complete the partial curing of the bulk at the early stages of light exposure. Whereas TMPTMA or HDDMA cures at a slower rate for proper dot and shade line formation.
Therefore, in summary, a suitable terminal-modified resin is selected; and selecting appropriate monomers and plasticizers, and determining an appropriate ratio can achieve substantial isotropy and ensure AF < 1.2.
The photosensitive resin flexible plate prepared from the photosensitive resin components realizes high mechanical strength. The photosensitive resin flexible printing plate provided by the invention is mainly used for corrugated paper printing, but is also suitable for other printing base materials, and has no any disadvantage in anisotropy compared with the prior art. The photosensitive resin flexographic plate used for manufacturing the photosensitive resin flexographic printing plate of the present invention exhibits better isotropy, such as uniform physical properties in all directions, better drapability, stronger toughness and better durability than the conventional photosensitive resin flexographic plate.
Detailed Description
The present invention will be described in detail with reference to specific examples.
Example 1
Photosensitive resin component: 715g of thermoplastic elastomer SBS D4150KT (polystyrene weight content is 33%), plasticizer Drakeol 34177 g, plasticizer Ricon 18149.8 g, 19.7g of 1, 6-hexanediol diacrylate, 19.9g of 1, 6-hexanediol dimethacrylate, photoinitiator benzoin dimethyl ether 10.0g and antioxidant BHT 8.0g are mixed on an extruder at 150 ℃ for 3 minutes, discharged from a die head, rolled by a calender roll with a gap of 1.65mm, and simultaneously, release films with the thickness of 125 microns are respectively coated on the upper side and the lower side of the photosensitive resin component, and after cooling, the photosensitive resin layer is obtained for testing.
Curing of photosensitive resin layer and evaluation of anisotropy: placing the obtained photosensitive resin layer coated with the release film at the ultraviolet light intensity of 15mW/cm2The upper and lower sides were exposed for 15 minutes, respectively. After the release film was peeled off, the exposed photosensitive resin layer was cut into an I-shaped sample in which the width of the narrow part in the middle was 1.5cm and the length was 8cm, and the width of the wider part on both sides was 2cm and the length was 1.5cm, respectively, along the extrusion direction (MD) and the extrusion perpendicular direction (TD). The magnitude of the tensile force stretched 125% in the MD and TD directions was measured on a tensile tester, respectively, and the Anisotropy Factor (AF) was calculated from the above formula.
Example 2
Photosensitive resin component: 715g of thermoplastic elastomer SBS D4150KT (polystyrene weight content is 33%), plasticizer Hydrocal 500167 g, plasticizer Ricon 18147 g, 1, 6-hexanediol diacrylate 43.5g, 1, 6-hexanediol dimethacrylate 43.8g, photoinitiator benzoin dimethyl ether 15g and antioxidant BHT 8.0g are mixed for 3 minutes at 150 ℃ on an extruder, discharged from a die head, and rolled by a calender roll with a gap of 1.65mm, and release films with the thickness of 125 microns are coated on the upper side and the lower side of the photosensitive resin component respectively, and after cooling, the photosensitive resin layer is obtained for testing.
Curing of photosensitive resin layer and evaluation of anisotropy: the same as in example 1.
Example 3
Photosensitive resin component: 715g of thermoplastic elastomer SBS D4150KT (polystyrene weight content is 33%), plasticizer Drakeol 34177 g, plasticizer Ricon 18129.8 g, 29.7g of 1, 6-hexanediol diacrylate, 29.9g of 1, 6-hexanediol dimethacrylate, photoinitiator benzoin dimethyl ether 10.0g and antioxidant BHT 8.0g are mixed on an extruder at 150 ℃ for 3 minutes, discharged from a die head, rolled by a calender roll with a gap of 1.65mm, and simultaneously, release films with the thickness of 125 microns are respectively coated on the upper side and the lower side of the photosensitive resin component, and after cooling, the photosensitive resin layer is obtained for testing.
Curing of photosensitive resin layer and evaluation of anisotropy: same as example 1
Comparative example 1
Photosensitive resin component: 760g of thermoplastic elastomer SBS D1102K (polystyrene weight content is 28%), 60.4g of plasticizer Hydrocal 500154 g, 60.1 g of 1, 6-hexanediol diacrylate, 15.1g of photoinitiator benzoin dimethyl ether and 10.1g of antioxidant BHT are mixed on an extruder at 150 ℃ for 3 minutes, discharged from a die head, rolled by a calendering roller with a gap of 1.65mm, simultaneously coated with release films with the thickness of 125 microns on the upper side and the lower side of the photosensitive resin component respectively, and cooled to obtain the photosensitive resin layer for testing.
Curing of photosensitive resin layer and evaluation of anisotropy: the same as in example 1.
Comparative example 2
Photosensitive resin component: 760g of thermoplastic elastomer SBS D4150KT (polystyrene weight content is 33%), plasticizer Hydrocal 500154 g, 1, 6-hexanediol diacrylate 60.4g, photoinitiator benzoin dimethyl ether 15.1g and antioxidant BHT 10.1g are mixed on an extruder at 150 ℃ for 3 minutes, discharged from a die head, rolled by a calendering roller with a gap of 1.65mm, and simultaneously coated with release films with the thickness of 125 microns on the upper side and the lower side of the photosensitive resin component respectively, and after cooling, the photosensitive resin layer is obtained for testing.
Curing of photosensitive resin layer and evaluation of anisotropy: the same as in example 1.
The test performance evaluations of examples 1 to 3 and comparative examples 1 to 2 are shown in Table 3.
TABLE 3 evaluation of printing durability and anisotropy
As analyzed according to the test results of table 3, the thermoplastic elastomer used in comparative example 1 is SBS D1102K which is commonly used in the art, and although it has excellent isotropy, the product still has room for improvement since the mass content of polystyrene is 28%. Therefore, one skilled in the art would readily recognize that SBS D4150KT, which is higher in polystyrene mass content, is used as the thermoplastic elastomer, so that the toughness and print durability of the product can be easily improved. However, comparative example 2 shows that if the two are simply replaced without changing other components and compounding ratios, the resulting product has poor print durability and anisotropy, and is hardly usable. In response to this problem, the prior art has been to reduce the mass content of polystyrene to eliminate the anisotropy, but the adverse effect is that the print endurance of the product is not improved. In order to overcome the technical defect and obtain the photosensitive resin flexible plate which can eliminate anisotropy and has excellent printing resistance, the invention selects proper terminal modified resin, selects proper monomer and plasticizer and adjusts the compatibility among the components, thereby basically realizing isotropy and ensuring AF to be less than 1.2 and having excellent printing resistance.
Example 4
This embodiment can eliminate anisotropic photosensitive resin flexographic plate, including the polyester supporter, from bottom to top sets gradually tie coat, at least one deck photosensitive resin layer, antiseized layer and protection film on the polyester supporter, and the photosensitive resin layer is prepared by the raw materials including following component: 6.5 parts of thermoplastic elastomer, 2 parts of plasticizer, 0.3 part of vinyl unsaturated monomer, 0.1 part of photoinitiator and 0.05 part of antioxidant.
The thermoplastic elastomer is a styrene-isoprene-styrene triblock copolymer, the mass percentage of the styrene-isoprene diblock copolymer in the styrene-isoprene-styrene triblock copolymer is 20%, and the mass percentage of the polystyrene is 37%. The thermoplastic elastomer used in this example is
The lower melt index was 8, the specific gravity was 0.90, and the modulus at 300% elongation was 80 psi. The vinyl unsaturated monomer is 1, 6-hexanediol diacrylate, the photoinitiator is benzoin dimethyl ether, the antioxidant is 2, 6-di-tert-butyl-4-methylphenol, and the plasticizer is selected from mineral oil with viscosity of 60-100 cps.
In the actual preparation process, the preparation method of the photosensitive resin layer comprises the following steps: adding the thermoplastic elastomer, the plasticizer, the vinyl unsaturated monomer, the photoinitiator and the antioxidant into an extruder according to the weight parts, mixing for 5 minutes at 150 ℃, discharging from a die head, calendering by a calendering roller with a gap of 1.0mm, simultaneously covering a support body for adhesion and an anti-sticking protective film with the thickness of 100 mu m on the upper side and the lower side respectively, and then cooling to room temperature.
Example 5
This embodiment can eliminate anisotropic photosensitive resin flexographic plate, including the polyester supporter, from bottom to top sets gradually tie coat, at least one deck photosensitive resin layer, antiseized layer and protection film on the polyester supporter, and the photosensitive resin layer is prepared by the raw materials including following component: 7.5 parts of thermoplastic elastomer, 2.3 parts of plasticizer, 0.6 part of vinyl unsaturated monomer, 0.15 part of photoinitiator and 0.1 part of antioxidant.
The thermoplastic elastomer is a styrene-isoprene-styrene triblock copolymer, the mass percentage of the styrene-isoprene diblock copolymer in the styrene-isoprene-styrene triblock copolymer is 15%, and the mass percentage of the polystyrene is 32%. The thermoplastic elastomer used in this example is
The melt index below is 15, the specific gravity is 0.95, and the modulus when elongated to 300% is 500 psi. The vinyl unsaturated monomer is prepared by mixing 1, 6-hexanediol diacrylate, 1, 6-hexanediol dimethacrylate and trimethylolpropane trimethacrylate according to the molar ratio of 1:1:1, the photoinitiator is benzoin dimethyl ether, the antioxidant is 2, 6-di-tert-butyl-4-methylphenol, and the plasticizer is selected from aliphatic naphthenic oil with the viscosity of 80-150 cps.
In the actual preparation process, the preparation method of the photosensitive resin layer comprises the following steps: adding the thermoplastic elastomer, the plasticizer, the vinyl unsaturated monomer, the photoinitiator and the antioxidant into an extruder according to the weight parts, mixing for 2 minutes at 160 ℃, discharging from a die head, calendering by a calendering roller with the gap of 4.0mm, simultaneously covering a support body for adhesion and an anti-sticking protective film with the thickness of 150 mu m on the upper side and the lower side respectively, and then cooling to room temperature.
Example 6
This embodiment can eliminate anisotropic photosensitive resin flexographic plate, including the polyester supporter, from bottom to top sets gradually tie coat, at least one deck photosensitive resin layer, antiseized layer and protection film on the polyester supporter, and the photosensitive resin layer is prepared by the raw materials including following component: 7.2 parts of thermoplastic elastomer, 2.1 parts of plasticizer, 0.4 part of vinyl unsaturated monomer, 0.12 part of photoinitiator and 0.08 part of antioxidant.
Wherein the thermoplastic elastomer is a styrene-butadiene-styrene triblock copolymer, and the mass percentage of the styrene-butadiene diblock copolymer in the styrene-butadiene-styrene triblock copolymerThe content of the components is 20 percent, and the mass percentage of the polystyrene is 35 percent. The thermoplastic elastomer used in this example is
The lower melt index was 10, the specific gravity was 0.93, and the modulus at 300% elongation was 300 psi. The vinyl unsaturated monomer is 1, 6-hexanediol dimethacrylate, the photoinitiator is benzoin dimethyl ether, the antioxidant is 2, 6-di-tert-butyl-4-methylphenol, and the plasticizer is selected from styrene-butadiene oligomeric oil with the molecular weight of 2000-10000.
In the actual preparation process, the preparation method of the photosensitive resin layer comprises the following steps: adding the thermoplastic elastomer, the plasticizer, the vinyl unsaturated monomer, the photoinitiator and the antioxidant into an extruder according to the weight parts, mixing for 3 minutes at 155 ℃, discharging from a die head, calendering by a calendering roller with a gap of 3.0mm, simultaneously covering a support body for adhesion and an anti-sticking protective film with the thickness of 120 mu m on the upper side and the lower side respectively, and then cooling to room temperature.
Example 7
This embodiment can eliminate anisotropic photosensitive resin flexographic plate, including the polyester supporter, from bottom to top sets gradually tie coat, at least one deck photosensitive resin layer, antiseized layer and protection film on the polyester supporter, and the photosensitive resin layer is prepared by the raw materials including following component: 7.4 parts of thermoplastic elastomer, 2.1 parts of plasticizer, 0.4 part of vinyl unsaturated monomer, 0.14 part of photoinitiator and 0.06 part of antioxidant.
The thermoplastic elastomer is a styrene-butadiene-styrene triblock copolymer, the mass percentage of a styrene-butadiene diblock copolymer in the styrene-butadiene-styrene triblock copolymer is 10%, and the mass percentage of polystyrene is 30%. The thermoplastic elastomer used in this example is
The melt index below is 10, the specific gravity is 0.91, and the modulus at 300% elongation is 180 psi.
The vinyl unsaturated monomer is prepared by mixing 1, 6-hexanediol dimethacrylate and trimethylolpropane trimethacrylate according to the molar ratio of 1:1, the photoinitiator is benzoin dimethyl ether, the antioxidant is 2, 6-di-tert-butyl-4-methylphenol, and the plasticizer is prepared by mixing mineral oil with the viscosity of 60cps, aliphatic naphthenic oil with the viscosity of 80cps and styrene-butadiene oligomer oil with the molecular weight of 10000 according to the mass ratio of 2:1: 1.
In the actual preparation process, the preparation method of the photosensitive resin layer comprises the following steps: adding the thermoplastic elastomer, the plasticizer, the vinyl unsaturated monomer, the photoinitiator and the antioxidant into an extruder according to the weight parts, mixing for 2 minutes at 160 ℃, discharging from a die head, calendering by a calendering roller with the gap of 4.0mm, simultaneously covering a support body for adhesion and an anti-sticking protective film with the thickness of 130 mu m on the upper side and the lower side respectively, and then cooling to room temperature.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (7)
1. The utility model provides a can eliminate anisotropic photosensitive resin flexographic plate, this photosensitive resin flexographic plate includes the polyester supporter, from bottom to top sets gradually tie coat, at least one deck photosensitive resin layer, antiseized layer and protection film on the polyester supporter, the photosensitive resin layer form by the raw materials preparation including following component: at least one thermoplastic elastomer, at least one photopolymerisable ethylenically unsaturated monomer and at least one photoinitiator, characterized in that the thermoplastic elastomer is a triblock copolymer of A-B-A structure or- (A-B-)nA multiblock copolymer wherein n is an integer of 2 or more, A is a polymerized monoarylalkane monomer, and B is a polymerized rubbery diene monomer or its oppositeThe corresponding hydrogenation product monomer;
the photosensitive resin layer is prepared from the following raw materials in parts by weight: 6.0-7.5 parts of thermoplastic elastomer, 1.5-3.0 parts of plasticizer, 0.3-2.0 parts of vinyl unsaturated monomer, 0.1-0.3 part of photoinitiator and 0.05-0.2 part of antioxidant;
the thermoplastic elastomer is a styrene-isoprene-styrene triblock copolymer or a styrene-butadiene-styrene triblock copolymer;
the vinyl unsaturated monomer comprises one or more of 1, 6-hexanediol diacrylate, 1, 6-hexanediol dimethacrylate or trimethylolpropane trimethacrylate;
the plasticizer is selected from one or more of mineral oil with the viscosity of 60-100cps, aliphatic naphthenic oil with the viscosity of 80-150cps or styrene-butadiene oligomeric oil with the molecular weight of 2000-10000;
when the plasticizer is formed by mixing mineral oil and styrene-butadiene oligomer oil, the mass ratio of the mineral oil to the styrene-butadiene oligomer oil is 2-4.5: 1; or
When the plasticizer is formed by mixing aliphatic naphthenic oil and styrene-butadiene oligomer oil, the mass ratio of the aliphatic naphthenic oil to the styrene-butadiene oligomer oil is 2-4.5: 1; or
When the plasticizer is formed by mixing mineral oil, aliphatic naphthenic oil and styrene-butadiene oligomeric oil, the mass ratio of the total mass of the mineral oil and the aliphatic naphthenic oil to the mass of the styrene-butadiene oligomeric oil is 2-4.5: 1.
2. The flexographic printing plate of claim 1, wherein said thermoplastic elastomer is styrene-isoprene-styrene triblock copolymer or styrene-butadiene-styrene triblock copolymer, said styrene-isoprene-styrene triblock copolymer contains styrene-isoprene diblock copolymer in 0-20 wt%, and said styrene-butadiene-styrene triblock copolymer contains styrene-butadiene diblock copolymer in 0-20 wt%.
3. The photoresist flexographic plate of claim 2 wherein the polystyrene content in said thermoplastic elastomer is 30-37% by weight.
4. The photosensitive resin flexographic plate for eliminating anisotropy according to claim 3, wherein said thermoplastic elastomer has a melt index at 200 Â ℃ of 8 to 15, a specific gravity of 0.90 to 0.95, and a modulus at 300% elongation of 80 to 500 psi.
5. The photoresist flexographic plate of claim 1, wherein said ethylenically unsaturated monomer comprises one or more of 1, 6-hexanediol diacrylate, 1, 6-hexanediol dimethacrylate, and trimethylolpropane trimethacrylate, said photoinitiator is benzoin bis methyl ether, and said antioxidant is 2, 6-di-t-butyl-4-methyl phenol.
6. The photosensitive resin flexographic plate capable of eliminating anisotropy according to claim 1, wherein the photosensitive resin layer is prepared by a method comprising: adding the thermoplastic elastomer, the plasticizer, the vinyl unsaturated monomer, the photoinitiator and the antioxidant into an extruder according to the parts by weight, mixing for 2-5 minutes at the temperature of 120-200 ℃, discharging from a die head, calendering by a calendering roller with the gap of 1.0-4.0mm, simultaneously respectively covering a supporting body for adhesion and an anti-adhesion protective film with the thickness of 100-150 mu m on the upper side and the lower side, and then cooling to room temperature.
7. A flexographic printing plate produced by using the photosensitive resin flexographic plate for eliminating anisotropy according to any one of claims 1 to 6.
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| CN1178809A (en) * | 1996-09-26 | 1998-04-15 | 国际壳牌研究有限公司 | Thermoplastic high elastic composition with improved reinjection adhesion force |
| US6420475B1 (en) * | 1994-04-19 | 2002-07-16 | Applied Elastomerics, Inc. | Tear resistant elastic crystal gels gel composites and their uses |
| CN101663164A (en) * | 2007-02-08 | 2010-03-03 | 富林特集团德国有限公司 | Photopolymerizable flexographic printing elements and hard flexographic printing formes which are produced therefrom |
| CN101770174A (en) * | 2008-12-30 | 2010-07-07 | 乐凯集团第二胶片厂 | Flexible photosensitive resin plate and preparation method thereof |
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| US7661164B2 (en) * | 1997-05-27 | 2010-02-16 | Applied Elastomerics, Inc. | Collapsible gel articles |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6420475B1 (en) * | 1994-04-19 | 2002-07-16 | Applied Elastomerics, Inc. | Tear resistant elastic crystal gels gel composites and their uses |
| CN1178809A (en) * | 1996-09-26 | 1998-04-15 | 国际壳牌研究有限公司 | Thermoplastic high elastic composition with improved reinjection adhesion force |
| CN101663164A (en) * | 2007-02-08 | 2010-03-03 | 富林特集团德国有限公司 | Photopolymerizable flexographic printing elements and hard flexographic printing formes which are produced therefrom |
| CN101770174A (en) * | 2008-12-30 | 2010-07-07 | 乐凯集团第二胶片厂 | Flexible photosensitive resin plate and preparation method thereof |
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