A flexographic photopolymer composition having uv ink resistance and a flexographic printing plate comprising the same

Abstract

The present application provides a kind of flexible version photosensitive elastomer composition with UV ink resistant performance and the flexible version containing it, by introducing the hydroxyl-terminated polybutadiene plasticizing oil containing epoxy structure in photosensitive elastomer, so as to realize that flexible version photosensitive elastomer has UV ink resistant performance.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of letterpress printing, and particularly relates to a flexible plate photosensitive elastomer composition with UV ink resistance and a flexible plate containing the same. BACKGROUND

[0002] In recent years, flexible resin plates are widely used in the printing of cartons, soft packaging, labels and other easily deformed or relatively soft printing materials. At present, common flexible plate technology is mature, and foreign companies such as DuPont, Asahi Kasei, Medha, and Furunte, and domestic companies such as Leike Huaguang Printing Technology Co., Ltd. produce plate materials. With the rapid development of China's economy, the demand for flexible plates used in printing and packaging will also increase.

[0003] Generally, water-based ink is used when printing with a flexible plate, which is beneficial to the environment and therefore is welcomed by society. When printing on rough carton substrates, a common flexible plate can easily meet the requirements; however, when printing on soft packaging materials such as film and labels, the printed products often have unclear printing defects. When UV ink is used to print on film and label substrates, the printed products are smooth and clear, and the quality is significantly improved by one level. Therefore, developing a flexible plate with UV ink resistance suitable for soft packaging and label substrates has become a technical hotspot. The flexible plate of Medha Company uses a double elastomer layer structure to effectively improve the UV ink resistance of the flexible plate material, and the structure is complex and the production is also relatively complex. SUMMARY

[0004] To solve the above problems, the present application provides a flexible plate photosensitive elastomer composition with UV ink resistance and a flexible plate containing the same. By introducing a hydroxyl-terminated polybutadiene plasticizing oil containing an epoxy structure into the photosensitive elastomer, the photosensitive elastomer of the flexible plate has UV ink resistance.

[0005] The purpose of the present application is achieved in the following manner: a flexible plate photosensitive elastomer composition with UV ink resistance, which contains: (A) a thermoplastic elastomer, (B) a liquid polybutadiene plasticizer with an epoxy structure, (C) a monomer containing at least one unsaturated double bond functional group, (D) a photoinitiator, and (E) a dye; wherein the liquid polybutadiene plasticizer with an epoxy structure is an epoxidized hydroxyl-terminated polybutadiene, and the structure is as follows:

[0006]

[0007] and the molecular weight of the epoxidized hydroxyl-terminated polybutadiene is in the range of 1000-3500.

[0008] The (A) thermoplastic elastomer is 40 to 75% by mass of the total photosensitive elastomer composition; the (B) liquid epoxy-structured polybutadiene plasticizer is 10 to 40% by mass of the total photosensitive elastomer composition; the (C) monomer having at least one or more unsaturated double bond functional groups is 5 to 20% by mass of the total elastomer composition; the (D) photoinitiator is 1 to 5% by mass of the total photosensitive elastomer composition; and the (E) dye is 0.05 to 1% by mass of the total photosensitive elastomer composition.

[0009] The (A) thermoplastic elastomer is a triblock polymer of a-b-a structure, in which a is a monoaryl alkylene monomer and b is a diene monomer.

[0010] The (A) thermoplastic elastomer can be a known material such as a styrene-butadiene-styrene triblock copolymer (SBS), a styrene-isoprene-styrene block copolymer (SIS), a partially hydrogenated SEBS, etc.

[0011] The (C) monomer having at least one or more unsaturated double bond functional groups is an unsaturated acrylate.

[0012] The unsaturated acrylate in component (C) can be 1,6-hexanediol diacrylate, dipropylene glycol diacrylate, trihydroxymethylpropane trimethacrylate, trihydroxymethylpropane triacrylate, 1,6-hexanediol dimethacrylate, tripropyleneglycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol di(meth)acrylate, pentaethylene glycol di(meth)acrylate, neopentyl glycol diacrylate, propoxylated neopentyl glycol diacrylate, 2-phenoxyethyl acrylate, 1,9-nonanediol di(meth)acrylate, 2-methyl-1,3-propanediol diacrylate, 2,2-bis(p-hydroxypropyl) acrylic di(meth)acrylate, 4-morpholinyl acrylate, 2-N-morpholinylmethyl acrylate, isobornyl acrylate, isobornyl methacrylate, etc.

[0013] The (D) photoinitiator is a compound of a cleavage type, preferably a benzoin derivative or a hydrogen abstraction type benzophenone and derivatives thereof; the (D) photoinitiator can be benzoin methyl ether, 1-hydroxy-iso-propyl-phenyl ketone, 1-hydroxy-cyclohexyl-benzophenone, 2-benzyl-2-dimethylamino-1-1(4-morpholinyl benzyl) butanone, α-amino ketone, α-hydroxy ketone, benzyl bis(2,4,6-trimethylbenzoyl) phosphine oxide, methyl o-benzoylbenzoate, benzophenone, Michler's ketone, benzoin, benzoin, etc.

[0014] The dye in the (E) is a sensitized cyanine dye with an absorption band in the range of 330-450 nm; the dye in the component (E) can be a red dye such as Red 335, Red Base 543, Neozapon 346, Solvent Red 52, a rhodamine blue, a sensitized cyanine dye such as Star Yellow KRL, etc.

[0015] The photopolymerizable elastomer composition in the present application can also be added with necessary auxiliaries such as antioxidants, room temperature thermal polymerization inhibitors, etc. during production; the antioxidant can be 2,6-di-tert-butyl-p-cresol (commonly known as 264), tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid]pentaerythritol ester (commonly known as 1010), tris[2,4-di-tert-butylphenyl]phosphite (commonly known as 168), etc. The room temperature thermal polymerization inhibitor is used to prevent the plate from polymerizing at room temperature, thereby improving the room temperature stability of the plate; the thermal polymerization inhibitor includes: hydroquinone, nitrogen oxide free radical piperidinol, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butyl catechol, benzoquinone, 4,4'-thiobis-(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-16-tert-butylphenol), and a primary cerium salt of N-nitrosophenylhydroxylamine, etc. The content of the antioxidant is 0.1%-1% of the total mass of the photopolymerizable elastomer composition. The content of the room temperature thermal polymerization inhibitor is 0.1%-1% of the total mass of the photopolymerizable elastomer composition.

[0016] A flexible plate with UV ink resistance comprises the photopolymerizable elastomer composition described above between the protective layer and the support layer. The flexible plate comprises, from top to bottom, a protective layer, an anti-adhesion composite film or a laser ablation black film, a photopolymerizable elastomer, an adhesive resin film, and a support. The photopolymerizable elastomer comprises the photopolymerizable elastomer composition described above.

[0017] During production of the flexible plate, the extruded photopolymerizable elastomer composition is firmly attached to the support substrate through the adhesive resin film by a double-screw extruder under high temperature. The extrusion is accompanied by the protective layer with the anti-adhesion composite film or the laser ablation black film being coated on the other side of the photopolymerizable elastomer.

[0018] Compared with the prior art, the present application has the following advantages:

[0019] The high-molecular liquid epoxidized hydroxyl-terminated polybutadiene is introduced into the photopolymerizable elastomer for flexible plate as a plasticizing oil, thereby realizing excellent UV ink resistance of the flexible plate. DETAILED DESCRIPTION

[0020] The following will describe the present application in detail with specific examples. It is necessary to point out here that the examples are only used to further illustrate the present application and cannot be understood as limiting the scope of protection of the present application. Those skilled in the art can make some non-essential improvements and adjustments according to the content of the present application.

[0021] Example 1

[0022] The present application discloses a flexible plate with UV ink resistance, which comprises a protective layer, an anti-adhesion composite film layer or a laser ablation black film layer from top to bottom, a photosensitive elastomer, an adhesive resin layer and a support layer.

[0023] (1) Photosensitive elastomer component:

[0024] Thermoplastic elastomer A is styrene-butadiene-styrene triblock copolymer 3527 (SBS), 400 parts, produced by the Dow Chemical Company.

[0025] Liquid epoxy-structured polybutadiene plasticizer B is epoxidized hydroxyl-terminated polybutadiene bd-605E, with a weight average molecular weight of 1450 and a 1,2-vinyl content of 20%, 400 parts, produced by Cray Valley Company.

[0026] Crosslinking monomer C is ① 1,6-hexanediol dimethacrylate (HDDA), 100 parts, produced by Tianjia Chemical Industry Co., Ltd.; and ② trimethylolpropane triacrylate (TMPTA), 40 parts, produced by Changxing Chemical Material Company.

[0027] Photoinitiator D is ① 1-hydroxycyclohexyl phenyl ketone (IRGACURE 184), 40 parts, produced by BASF; and ② benzophenone, 10 parts, produced by Juren New Material Co., Ltd.

[0028] Dye E is Red 335 red dye, 10 parts, produced by BASF.

[0029] (2) Plate production:

[0030] The photosensitive elastomer composition is added into a high-speed mixing extruder in proportion, and is subjected to high-temperature melting mixing. The photosensitive elastomer is hot-pressed on a 100-micron-thick PET support (produced by Lucky Group Company) coated with an adhesive resin layer at 90-110°C using a double-screw extruder, and at the same time, a PET peelable protective layer (produced by Lucky Group Company) with an anti-adhesion composite film layer is coated on the other side to produce a conventional flexible plate, or a PET peelable protective layer (produced by Lucky Group Company) with a laser ablation black film layer is coated to produce a digital flexible plate.

[0031] Example 2

[0032] A flexible plate with UV ink resistance performance disclosed in the present application comprises, from top to bottom, a protective layer, an anti-adhesion composite film layer or a laser ablation black film layer, a photosensitive elastomer, an adhesive resin layer, and a support layer.

[0033] (1) Photosensitive elastomer component:

[0034] Thermoplastic elastomer A is styrene-butadiene-styrene triblock copolymer 3527 (SBS), 750 parts, from the Dow Chemical Company.

[0035] Liquid epoxy-structured polybutadiene plasticizer B is epoxidized hydroxyl-terminated polybutadiene bd-605E, with a weight average molecular weight of 1450 and a 1,2-vinyl content of 20%, from Cray Valley Company, 100 parts.

[0036] Crosslinking monomer C is 1,6-hexanediol dimethacrylate (HDDA), from Tianjia Chemical Industry Co., Ltd., 100 parts. Trimethylolpropane triacrylate (TMPTA), from Changxing Chemical Material Co., Ltd., 39.5 parts.

[0037] Photoinitiator D is 1-hydroxycyclohexyl phenyl ketone (IRGACURE 184), from BASF, 8 parts; benzophenone, from Kishen Chemicals, 2 parts.

[0038] Dye E is Red 335 red dye, from Basf, 0.5 parts.

[0039] (2) Plate production: the photosensitive elastomer composition is added to a high-speed mixing extruder in proportion, melted and mixed at high temperature, and the photosensitive elastomer is hot-pressed on a 175-micron-thick PET support coated with an adhesive resin layer (produced by Lucky Group Co., Ltd.) using a double-screw extruder at 90-110°C, while the other side is covered with a PET peelable protective layer with an anti-adhesion composite film layer (produced by Lucky Group Co., Ltd.) to produce a conventional flexible plate, or a PET peelable protective layer with a laser ablation black film layer (produced by Lucky Group Co., Ltd.) to produce a digital flexible plate.

[0040] Example 3

[0041] A flexible plate with UV ink resistance performance disclosed in the present application comprises, from top to bottom, a protective layer, an anti-adhesion composite film layer or a laser ablation black film layer, a photosensitive elastomer, an adhesive resin layer, and a support layer.

[0042] (1) Photosensitive elastomer component:

[0043] Thermoplastic elastomer A is styrene-butadiene-styrene triblock copolymer 3527 (SBS), World Rubber Corporation, 600 parts.

[0044] Liquid epoxy-structured polybutadiene plasticizer B is epoxidized hydroxyl-terminated polybutadiene bd-605E, weight average molecular weight 1450, 1,2-vinyl content 20%, Cray Valley Company, 300 parts.

[0045] Crosslinking monomer C is 1,6-hexanediol dimethacrylate (HDDA), Tianjin Tianjia Chemical Industry Co., Ltd., 36 parts; trimethylolpropane triacrylate (TMPTA), Changxing Chemical Material Co., Ltd., 14 parts.

[0046] Photoinitiator D is 1-hydroxycyclohexyl phenyl ketone (IRGACURE 184), BASF, 36 parts; Benzophenone, Juren Chemical Co., Ltd., 9 parts.

[0047] Dye E is Red 335 red dye, BASF, 5 parts.

[0048] (2) Plate making: same as Example 1.

[0049] Example 4

[0050] The flexible plate disclosed by the application has the advantages of good UV ink resistance, good flexibility, good adhesion, good printing quality, and the like.

[0051] (1) Photosensitive elastomer component:

[0052] Thermoplastic elastomer A is styrene-butadiene-styrene triblock copolymer 3527 (SBS), World Rubber Corporation, 500 parts.

[0053] Liquid epoxy-structured polybutadiene plasticizer B is epoxidized hydroxyl-terminated polybutadiene bd-605E, weight average molecular weight 1450, 1,2-vinyl content 20%, Cray Valley Company, 300 parts.

[0054] Crosslinking monomer C is 1,6-hexanediol dimethacrylate (HDDA), Tianjin Tianjia Chemical Industry Co., Ltd., 128 parts; trimethylolpropane triacrylate (TMPTA), Changxing Chemical Material Co., Ltd., 51 parts.

[0055] Photoinitiator D is 1-Hydroxycyclohexylphenyl ketone (IRGACURE 184), BASF, 16 parts; Benzophenone, Jiuri New Materials Co., Ltd., 4 parts.

[0056] Dye E is Red 335, BASF, 1 part.

[0057] (2) Plate making: Same as Example 1.

[0058] Example 5

[0059] The present invention discloses a flexible plate with UV ink resistance, comprising, from top to bottom, a protective layer, an anti-stick composite film layer or a laser ablation black film layer, a photosensitive elastomer, an adhesive resin layer, and a support layer.

[0060] (1) Photosensitive elastomer components:

[0061] Thermoplastic elastomer A is styrene-butadiene-styrene triblock copolymer 3527 (SBS), Universal Rubber Co., Ltd., 550 parts.

[0062] Liquid epoxy-structured polybutadiene plasticizer B is epoxidized hydroxyl-terminated polybutadiene bd-605E, with a weight average molecular weight of 1450 and a 1,2-vinyl content of 20%, manufactured by Cray Valley, 350 parts.

[0063] Crosslinking monomer C is 1,6-Hexanediol dimethacrylate (HDDA), Tianjin Tianjiao Chemical Co., Ltd., 48.5 parts; Trimethylolpropane triacrylate (TMPTA), Changxing Chemical Materials Co., Ltd., 19.5 parts.

[0064] Photoinitiator D is 1-Hydroxycyclohexylphenyl ketone (IRGACURE 184), BASF, 24 parts; Benzophenone, Jiuri New Materials Co., Ltd., 6 parts.

[0065] Dye E is Red 335, BASF, 2 parts.

[0066] (2) Plate making: Same as Example 1.

[0067] Example 6

[0068] The present invention discloses a flexible plate with UV ink resistance, comprising, from top to bottom, a protective layer, an anti-stick composite film layer or a laser ablation black film layer, a photosensitive elastomer, an adhesive resin layer, and a support layer.

[0069] (1) Photosensitive elastomer components:

[0070] Thermoplastic elastomer A is styrene-butadiene-styrene triblock copolymer 3527 (SBS), Universal Rubber Co., Ltd., 617 parts.

[0071] Liquid epoxy-structured polybutadiene plasticizer B is epoxidized hydroxyl-terminated polybutadiene bd-605E, with a weight average molecular weight of 1450 and a 1,2-vinyl content of 20%, manufactured by Cray Valley, 250 parts.

[0072] Crosslinking monomer C is 1,6-Hexanediol dimethacrylate (HDDA), Tianjin Tianjiao Chemical Co., Ltd., 71.5 parts; Trimethylolpropane triacrylate (TMPTA), Changxing Chemical Materials Co., Ltd., 28.5 copies.

[0073] Photoinitiator D is 1-Hydroxycyclohexylphenyl ketone (IRGACURE 184), BASF, 24 parts; Benzophenone, Jiuri New Materials Co., Ltd., 6 parts.

[0074] Dye E is Red 335, BASF, 3 parts.

[0075] (2) Plate making: Same as Example 1.

[0076] Example 7

[0077] The present invention discloses a flexible plate with UV ink resistance, comprising, from top to bottom, a protective layer, an anti-stick composite film layer or a laser ablation black film layer, a photosensitive elastomer, an adhesive resin layer, and a support layer.

[0078] Support structure.

[0079] (1) Photosensitive elastomer components:

[0080] Thermoplastic elastomer A is styrene-isoprene-styrene triblock copolymer 5519 (SIS), Universal Rubber Co., Ltd., 400 parts.

[0081] Liquid epoxy-structured polybutadiene plasticizer B is epoxidized hydroxyl-terminated polybutadiene bd-605E, with a weight average molecular weight of 1450 and a 1,2-vinyl content of 20%, manufactured by Cray Valley, 400 parts.

[0082] Crosslinking monomer C is 1,6-Hexanediol dimethacrylate (HDDA), Tianjin Tianjiao Chemical Co., Ltd., 100 parts; Trimethylolpropane triacrylate (TMPTA), Changxing Chemical Materials Co., Ltd., 40 parts.

[0083] Photoinitiator D is 1-Hydroxycyclohexylphenyl ketone (IRGACURE 184), BASF, 40 parts; Benzophenone, Jiuri New Materials Company, 10 portions.

[0084] Dye E is Red 335, BASF, 10 parts.

[0085] (2) Plate making: Same as Example 1.

[0086] Example 8

[0087] The present invention discloses a flexible plate with UV ink resistance, comprising, from top to bottom, a protective layer, an anti-stick composite film layer or a laser ablation black film layer, a photosensitive elastomer, an adhesive resin layer, and a support layer.

[0088] (1) Photosensitive elastomer components:

[0089] Thermoplastic elastomer A is styrene-isoprene-styrene triblock copolymer 5519 (SIS), Universal Rubber Co., Ltd., 750 parts.

[0090] Liquid epoxy-structured polybutadiene plasticizer B is epoxidized hydroxyl-terminated polybutadiene bd-605E, with a weight average molecular weight of 1450 and a 1,2-vinyl content of 20%, manufactured by Cray Valley Corporation, 100 parts.

[0091] Crosslinking monomer C is 1,6-Hexanediol dimethacrylate (HDDA), Tianjin Tianjiao Chemical Co., Ltd., 100 parts; Trimethylolpropane triacrylate (TMPTA), Changxing Chemical Materials Co., Ltd., 39.5 parts.

[0092] Photoinitiator D is 1-hydroxycyclohexylphenyl ketone (IRGACURE 184), BASF, 8 parts; Benzophenone, Jiuri New Materials Company, 2 portions.

[0093] Dye E is Red 335, BASF, 0.5 parts.

[0094] (2) Plate making: Same as Example 1.

[0095] Example 9

[0096] The present invention discloses a flexible plate with UV ink resistance, comprising, from top to bottom, a protective layer, an anti-stick composite film layer or a laser ablation black film layer, a photosensitive elastomer, an adhesive resin layer, and a support layer.

[0097] (1) Photosensitive elastomer components:

[0098] Thermoplastic elastomer A is styrene-isoprene-styrene triblock copolymer 5519 (SIS), Universal Rubber Co., Ltd., 600 parts.

[0099] Liquid epoxy-structured polybutadiene plasticizer B is epoxidized hydroxyl-terminated polybutadiene bd-605E, with a weight average molecular weight of 1450 and a 1,2-vinyl content of 20%, manufactured by Cray Valley, 300 parts.

[0100] Crosslinking monomer C is 1,6-Hexanediol dimethacrylate (HDDA), Tianjin Tianjiao Chemical Co., Ltd., 36 parts; Trimethylolpropane triacrylate (TMPTA), Changxing Chemical Materials Co., Ltd., 14 parts.

[0101] Photoinitiator D is 1-Hydroxycyclohexylphenyl ketone (IRGACURE 184), BASF, 36 parts; Benzophenone, Jiuri New Materials Company, 9 portions.

[0102] Dye E is Red 335, BASF, 0.5 parts.

[0103] (2) Plate making: Same as Example 1.

[0104] Example 10

[0105] The present invention discloses a flexible plate with UV ink resistance, comprising, from top to bottom, a protective layer, an anti-stick composite film layer or a laser ablation black film layer, a photosensitive elastomer, an adhesive resin layer, and a support layer.

[0106] (1) Photosensitive elastomer components:

[0107] Thermoplastic elastomer A is styrene-isoprene-styrene triblock copolymer 5519 (SIS), Universal Rubber Co., Ltd., 500 parts.

[0108] Liquid epoxy-structured polybutadiene plasticizer B is epoxidized hydroxyl-terminated polybutadiene bd-605E, with a weight average molecular weight of 1450 and a 1,2-vinyl content of 20%, manufactured by Cray Valley, 300 parts.

[0109] Crosslinking monomer C is 1,6-Hexanediol dimethacrylate (HDDA), Tianjin Tianjiao Chemical Co., Ltd., 128 parts; Trimethylolpropane triacrylate (TMPTA), Changxing Chemical Materials Co., Ltd., 51 parts.

[0110] Photoinitiator D is 1-Hydroxycyclohexylphenyl ketone (IRGACURE 184), BASF, 16 parts; Benzophenone, Jiuri New Materials Company, 4 portions.

[0111] Dye E is Red 335, BASF, 1 part.

[0112] (2) Plate making: Same as Example 1.

[0113] Example 11

[0114] The present invention discloses a flexible plate with UV ink resistance, comprising, from top to bottom, a protective layer, an anti-stick composite film layer or a laser ablation black film layer, a photosensitive elastomer, an adhesive resin layer, and a support layer.

[0115] (1) Photosensitive elastomer components:

[0116] Thermoplastic elastomer A is styrene-isoprene-styrene triblock copolymer 5519 (SIS), Universal Rubber Co., Ltd., 550 parts.

[0117] Liquid epoxy-structured polybutadiene plasticizer B is epoxidized hydroxyl-terminated polybutadiene bd-605E, with a weight average molecular weight of 1450 and a 1,2-vinyl content of 20%, manufactured by Cray Valley, 350 parts.

[0118] Crosslinking monomer C is 1,6-Hexanediol dimethacrylate (HDDA), Tianjin Tianjiao Chemical Co., Ltd., 48.5 parts; Trimethylolpropane triacrylate (TMPTA), Changxing Chemical Materials Co., Ltd., 19.5 parts.

[0119] Photoinitiator D is 1-Hydroxycyclohexylphenyl ketone (IRGACURE 184), BASF, 24 parts; Benzophenone, Jiuri New Materials Company, 6 portions.

[0120] Dye E is Red 335, BASF, 2 parts.

[0121] (2) Plate making: Same as Example 1.

[0122] Example 12

[0123] The present invention discloses a flexible plate with UV ink resistance, comprising, from top to bottom, a protective layer, an anti-stick composite film layer or a laser ablation black film layer, a photosensitive elastomer, an adhesive resin layer, and a support layer.

[0124] (1) Photosensitive elastomer components:

[0125] Thermoplastic elastomer A is styrene-isoprene-styrene triblock copolymer 5519 (SIS), Universal Rubber Co., Ltd., 617 parts.

[0126] Liquid epoxy-structured polybutadiene plasticizer B is epoxidized hydroxyl-terminated polybutadiene bd-605E, with a weight average molecular weight of 1450 and a 1,2-vinyl content of 20%, manufactured by Cray Valley, 250 parts.

[0127] Crosslinking monomer C is 1,6-Hexanediol dimethacrylate (HDDA), Tianjin Tianjiao Chemical Co., Ltd., 71.5 parts; Trimethylolpropane triacrylate (TMPTA), Changxing Chemical Materials Co., Ltd., 28.5 parts.

[0128] Photoinitiator D is 1-Hydroxycyclohexylphenyl ketone (IRGACURE 184), BASF, 24 parts; Benzophenone, Jiuri New Materials Company, 6 portions.

[0129] Dye E is Red 335, BASF, 3 parts.

[0130] (2) Plate making: Same as Example 1.

[0131] Compare with Example 1

[0132] The present invention discloses a flexible plate with UV ink resistance, comprising, from top to bottom, a protective layer, an anti-stick composite film layer or a laser ablation black film layer, a photosensitive elastomer, an adhesive resin layer, and a support layer.

[0133] (1) Photosensitive elastomer components:

[0134] Thermoplastic elastomer A is styrene-butadiene-styrene triblock copolymer 3527 (SBS), Universal Rubber Co., Ltd., 400 parts.

[0135] The polybutadiene plasticizer is Polyvest 110, with a weight-average molecular weight of 2600 and a 1,2-vinyl content of 1%, manufactured by Evonik GmbH, Germany, in 400 parts.

[0136] Crosslinking monomer C is 1,6-Hexanediol dimethacrylate (HDDA), Tianjin Tianjiao Chemical Co., Ltd., 100 parts; Trimethylolpropane triacrylate (TMPTA), Changxing Chemical Materials Co., Ltd., 40 copies.

[0137] Photoinitiator D is 1-Hydroxycyclohexylphenyl ketone (IRGACURE 184), BASF, 40 parts; Benzophenone, Jiuri New Materials Co., Ltd., 10 parts.

[0138] Dye E is Red 335, BASF, 10 parts.

[0139] (2) Plate making:

[0140] The photosensitive elastomer composition is added to a high-speed compounding extruder in a certain proportion. After being heated and melted at high temperature, the photosensitive elastomer is hot-pressed onto a 100-micron-thick PET support (produced by Lucky Group) coated with an adhesive resin layer using a twin-screw extruder at 90-110°C. At the same time, a PET peelable protective layer (produced by Lucky Group) with an anti-stick composite film layer is applied to the other side to produce a conventional flexible plate, or a PET peelable protective layer (produced by Lucky Group) with a laser-ablated black film layer is applied to produce a digital flexible plate.

[0141] Compare with Example 2

[0142] The present invention discloses a flexible plate with UV ink resistance, comprising, from top to bottom, a protective layer, an anti-stick composite film layer or a laser ablation black film layer, a photosensitive elastomer, an adhesive resin layer, and a support layer.

[0143] (1) Photosensitive elastomer components:

[0144] Thermoplastic elastomer A is styrene-butadiene-styrene triblock copolymer 3527 (SBS), Universal Rubber Co., Ltd., 750 parts.

[0145] The polybutadiene plasticizer is Polyvest 110, with a weight-average molecular weight of 2600 and a 1,2-vinyl content of 1%, manufactured by Evonik GmbH, Germany, 100 parts.

[0146] Crosslinking monomer C is 1,6-Hexanediol dimethacrylate (HDDA), Tianjin Tianjiao Chemical Co., Ltd., 100 parts; Trimethylolpropane triacrylate (TMPTA), Changxing Chemical Materials Co., Ltd., 39.5 parts.

[0147] Photoinitiator D is 1-Hydroxycyclohexylphenyl ketone (IRGACURE 184), BASF, 8 parts; Benzophenone, Jiuri New Materials Company, 2 portions.

[0148] Dye E is Red 335, BASF, 0.5 parts.

[0149] (2) Plate making: The photosensitive elastomer composition is added to a high-speed compounding extruder in proportion, and after high-temperature heating and melting, the photosensitive elastomer is hot-pressed onto a 175-micron thick PET support (produced by Lucky Group) coated with an adhesive resin layer using a twin-screw extruder at 90-110℃. At the same time, a PET peelable protective layer (produced by Lucky Group) with an anti-stick composite film layer is applied to the other side to produce a conventional flexible plate, or a PET peelable protective layer (produced by Lucky Group) with a laser ablation black film layer is applied to produce a digital flexible plate.

[0150] Compare with Example 3

[0151] The present invention discloses a flexible plate with UV ink resistance, comprising, from top to bottom, a protective layer, an anti-stick composite film layer or a laser ablation black film layer, a photosensitive elastomer, an adhesive resin layer, and a support layer.

[0152] (1) Photosensitive elastomer components:

[0153] Thermoplastic elastomer A is styrene-butadiene-styrene triblock copolymer 3527 (SBS), Universal Rubber Co., Ltd., 600 parts.

[0154] The polybutadiene plasticizer is Polyvest 110, with a weight-average molecular weight of 2600 and a 1,2-vinyl content of 1%, manufactured by Evonik GmbH, Germany, in 300 parts.

[0155] Crosslinking monomer C is 1,6-hexanediol dimethacrylate (HDDA), Tianjin Tianjiao Chemical Co., Ltd., 36 parts; Trimethylolpropane triacrylate (TMPTA), Changxing Chemical Materials Co., Ltd., 14 copies.

[0156] Photoinitiator D is 1-Hydroxycyclohexylphenyl ketone (IRGACURE 184), BASF, 36 parts; Benzophenone, Jiuri New Materials Company, 9 portions.

[0157] Dye E is Red 335, BASF, 5 parts.

[0158] (2) Plate making: Same as Comparative Example 1.

[0159] Compare with Example 4

[0160] The present invention discloses a flexible plate with UV ink resistance, comprising, from top to bottom, a protective layer, an anti-stick composite film layer or a laser ablation black film layer, a photosensitive elastomer, an adhesive resin layer, and a support layer.

[0161] (1) Photosensitive elastomer components:

[0162] Thermoplastic elastomer A is styrene-butadiene-styrene triblock copolymer 3527 (SBS), Universal Rubber Co., Ltd., 500 parts.

[0163] The polybutadiene plasticizer is Polyvest 110, with a weight-average molecular weight of 2600 and a 1,2-vinyl content of 1%, manufactured by Evonik GmbH, Germany, in 300 parts.

[0164] Crosslinking monomer C is 1,6-Hexanediol dimethacrylate (HDDA), Tianjin Tianjiao Chemical Co., Ltd., 128 parts; Trimethylolpropane triacrylate (TMPTA), Changxing Chemical Materials Co., Ltd., 51 copies.

[0165] Photoinitiator D is 1-Hydroxycyclohexylphenyl ketone (IRGACURE 184), BASF, 16 parts; Benzophenone, Jiuri New Materials Company, 4 portions.

[0166] Dye E is Red 335, BASF, 1 part.

[0167] (2) Plate making: Same as Comparative Example 1.

[0168] Compare with Example 5

[0169] The present invention discloses a flexible plate with UV ink resistance, comprising, from top to bottom, a protective layer, an anti-stick composite film layer or a laser ablation black film layer, a photosensitive elastomer, an adhesive resin layer, and a support layer.

[0170] (1) Photosensitive elastomer components:

[0171] Thermoplastic elastomer A is styrene-butadiene-styrene triblock copolymer 3527 (SBS), Universal Rubber Co., Ltd., 550 parts.

[0172] The polybutadiene plasticizer is Polyvest 110, with a weight-average molecular weight of 2600 and a 1,2-vinyl content of 1%, manufactured by Evonik GmbH, Germany, in 350 parts.

[0173] Crosslinking monomer C is 1,6-Hexanediol dimethacrylate (HDDA), Tianjin Tianjiao Chemical Co., Ltd., 48.5 parts; Trimethylolpropane triacrylate (TMPTA), Changxing Chemical Materials Co., Ltd., 19.5 parts.

[0174] Photoinitiator D is 1-Hydroxycyclohexylphenyl ketone (IRGACURE 184), BASF, 24 parts; Benzophenone, Jiuri New Materials Company, 6 portions.

[0175] Dye E is Red 335, BASF, 2 parts.

[0176] (2) Plate making: Same as Comparative Example 1.

[0177] Compare with Example 6

[0178] The present invention discloses a flexible plate with UV ink resistance, comprising, from top to bottom, a protective layer, an anti-stick composite film layer or a laser ablation black film layer, a photosensitive elastomer, an adhesive resin layer, and a support layer.

[0179] (1) Photosensitive elastomer components:

[0180] Thermoplastic elastomer A is styrene-isoprene-styrene triblock copolymer 5519 (SIS), Universal Rubber Co., Ltd., 400 parts.

[0181] The polybutadiene plasticizer is Polyvest 110, with a weight-average molecular weight of 2600 and a 1,2-vinyl content of 1%, manufactured by Evonik GmbH, Germany, in 400 parts.

[0182] Crosslinking monomer C is 1,6-Hexanediol dimethacrylate (HDDA), Tianjin Tianjiao Chemical Co., Ltd., 100 parts; Trimethylolpropane triacrylate (TMPTA), Changxing Chemical Materials Co., Ltd., 40 copies.

[0183] Photoinitiator D is 1-Hydroxycyclohexylphenyl ketone (IRGACURE 184), BASF, 40 parts; Benzophenone, Jiuri New Materials Company, 10 portions.

[0184] Dye E is Red 335, BASF, 10 parts.

[0185] (2) Plate making: Same as Comparative Example 1.

[0186] Compare with Example 7

[0187] The present invention discloses a flexible plate with UV ink resistance, comprising, from top to bottom, a protective layer, an anti-stick composite film layer or a laser ablation black film layer, a photosensitive elastomer, an adhesive resin layer, and a support layer.

[0188] (1) Photosensitive elastomer components:

[0189] Thermoplastic elastomer A is styrene-isoprene-styrene triblock copolymer 5519 (SIS), Universal Rubber Co., Ltd., 750 parts.

[0190] The polybutadiene plasticizer is Polyvest 110, with a weight-average molecular weight of 2600 and a 1,2-vinyl content of 1%, manufactured by Evonik GmbH, Germany, 100 parts.

[0191] Crosslinking monomer C is 1,6-Hexanediol dimethacrylate (HDDA), Tianjin Tianjiao Chemical Co., Ltd., 100 parts; Trimethylolpropane triacrylate (TMPTA), Changxing Chemical Materials Co., Ltd., 39.5 parts.

[0192] Photoinitiator D is 1-Hydroxycyclohexylphenyl ketone (IRGACURE 184), BASF, 8 parts; Benzophenone, Jiuri New Materials Company, 2 portions.

[0193] Dye E is Red 335, BASF, 0.5 parts.

[0194] (2) Plate making: Same as Comparative Example 1.

[0195] Compare with Example 8

[0196] The present invention discloses a flexible plate with UV ink resistance, comprising, from top to bottom, a protective layer, an anti-stick composite film layer or a laser ablation black film layer, a photosensitive elastomer, an adhesive resin layer, and a support layer.

[0197] (1) Photosensitive elastomer components:

[0198] Thermoplastic elastomer A is styrene-isoprene-styrene triblock copolymer 5519 (SIS), Universal Rubber Co., Ltd., 600 parts.

[0199] The polybutadiene plasticizer is Polyvest 110, with a weight-average molecular weight of 2600 and a 1,2-vinyl content of 1%, manufactured by Evonik GmbH, Germany, in 300 parts.

[0200] Crosslinking monomer C is 1,6-Hexanediol dimethacrylate (HDDA), Tianjin Tianjiao Chemical Co., Ltd., 36 parts; Trimethylolpropane triacrylate (TMPTA), Changxing Chemical Materials Co., Ltd., 14 copies.

[0201] Photoinitiator D is 1-Hydroxycyclohexylphenyl ketone (IRGACURE 184), BASF, 36 parts; Benzophenone, Jiuri New Materials Company, 9 portions.

[0202] Dye E is Red 335, BASF, 0.5 parts.

[0203] (2) Plate making: Same as Comparative Example 1.

[0204] Compare with Example 9

[0205] The present invention discloses a flexible plate with UV ink resistance, comprising, from top to bottom, a protective layer, an anti-stick composite film layer or a laser ablation black film layer, a photosensitive elastomer, an adhesive resin layer, and a support layer.

[0206] (1) Photosensitive elastomer components:

[0207] Thermoplastic elastomer A is styrene-isoprene-styrene triblock copolymer 5519 (SIS), Universal Rubber Co., Ltd., 500 parts.

[0208] The polybutadiene plasticizer is Polyvest 110, with a weight-average molecular weight of 2600 and a 1,2-vinyl content of 1%, manufactured by Evonik GmbH, Germany, in 300 parts.

[0209] Crosslinking monomer C is 1,6-Hexanediol dimethacrylate (HDDA), Tianjin Tianjiao Chemical Co., Ltd., 128 parts; Trimethylolpropane triacrylate (TMPTA), Changxing Chemical Materials Co., Ltd., 51 copies.

[0210] Photoinitiator D is 1-Hydroxycyclohexylphenyl ketone (IRGACURE 184), BASF, 16 parts; Benzophenone, Jiuri New Materials Company, 4 portions.

[0211] Dye E is Red 335, BASF, 1 part.

[0212] (2) Plate making: Same as Comparative Example 1.

[0213] Compare with Example 10

[0214] The present invention discloses a flexible plate with UV ink resistance, comprising, from top to bottom, a protective layer, an anti-stick composite film layer or a laser ablation black film layer, a photosensitive elastomer, an adhesive resin layer, and a support layer.

[0215] (1) Photosensitive elastomer components:

[0216] Thermoplastic elastomer A is styrene-isoprene-styrene triblock copolymer 5519 (SIS), Universal Rubber Co., Ltd., 550 parts.

[0217] The polybutadiene plasticizer is Polyvest 110, with a weight-average molecular weight of 2600 and a 1,2-vinyl content of 1%, manufactured by Evonik GmbH, Germany, in 350 parts.

[0218] Crosslinking monomer C is 1,6-Hexanediol dimethacrylate (HDDA), Tianjin Tianjiao Chemical Co., Ltd., 48.5 parts; Trimethylolpropane triacrylate (TMPTA), Changxing Chemical Materials Co., Ltd., 19.5 parts.

[0219] Photoinitiator D is 1-Hydroxycyclohexylphenyl ketone (IRGACURE 184), BASF, 24 parts; Benzophenone, Jiuri New Materials Company, 6 portions.

[0220] Dye E is Red 335, BASF, 2 parts.

[0221] (2) Plate making: Same as Comparative Example 1.

[0222] The method for evaluating the UV resistance of flexographic printing plates according to the present invention:

[0223] Plate exposure: Use the CRON Concept 305 ECDLF flexographic plate making machine to back-expose the prepared flexographic plate for 30 seconds, remove the PET protective film, attach the negative film, and vacuum-expose for 15 minutes; Digital flexographic operation - use the CRON Concept 305 ECDLF flexographic plate making machine to back-expose for 30 seconds, remove the PET protective film, use the CRON HDI-900S laser engraving machine to directly make the plate, and then directly expose for 15 minutes.

[0224] Plate development: After exposure, the plate is rinsed with environmentally friendly developer for 5 minutes using the Gulongyan Concept305DW flexographic plate washer, dried at 60℃ for 1.5 hours, and then surface cured for 5 minutes under a 280nm, 5cm spacing ultraviolet lamp to obtain the printing plate.

[0225] Test sample: Cut the prepared printing plate into 2cm*2cm sample pieces.

[0226] The flexographic plates of each embodiment and control example were immersed in commercially available UV inks (Guangzhou Chaocai Ink Co., Ltd., Shandong Breit Ink Co., Ltd., and Hanghua Ink Co., Ltd.) for 5 hours (temperature 11-15℃). The immersed plates were then wiped clean of UV ink, weighed using an electronic analytical balance, and the swelling rate of the plates in the UV ink was calculated. A lower swelling rate indicates better UV ink resistance, while a higher swelling rate indicates poorer UV ink resistance. The evaluation of the flexographic plates' UV ink resistance is shown in Table 1.

[0227] Table 1. UV resistance test results of the examples and control examples

[0228]

[0229] As can be seen from Table 1, the flexographic plate prepared by the present invention has excellent UV ink resistance.

[0230] The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. It should be noted that for those skilled in the art and any person skilled in the art, any equivalent substitutions or changes made to the technical solution and inventive concept of the present invention without departing from the overall concept of the present invention, as well as any changes and improvements made, should also be considered within the scope of protection of the present invention.

Claims

1. A flexographic photosensitive elastomer composition with UV ink resistance, characterized in that: The photosensitive elastomer composition contains: (A) a thermoplastic elastomer, (B) a liquid epoxy-structured polybutadiene plasticizer, (C) a monomer containing at least one unsaturated double bond functional group, (D) a photoinitiator, and (E) a dye; wherein the (B) liquid epoxy-structured polybutadiene is epoxidized hydroxyl-terminated polybutadiene with the following structure: Furthermore, the molecular weight of epoxidized hydroxyl-terminated polybutadiene ranges from 1000 to 3500.

2. The flexographic photosensitive elastomer composition with UV ink resistance according to claim 1, characterized in that: The (A) thermoplastic elastomer accounts for 40-75% of the total mass of the photosensitive elastomer composition; (B) the liquid epoxy-structured polybutadiene plasticizer accounts for 10-40% of the total mass of the photosensitive elastomer composition; (C) the monomer containing at least one unsaturated double bond functional group accounts for 5-20% of the total mass of the elastomer composition; (D) the photoinitiator accounts for 1-5% of the total mass of the photosensitive elastomer composition; and (E) the dye accounts for 0.05-1% of the total mass of the photosensitive elastomer composition.

3. The flexographic photosensitive elastomer composition with UV ink resistance according to claim 1, characterized in that: The thermoplastic elastomer (A) is a triblock polymer with an aba structure, wherein a is a monoaryl olefin monomer and b is a diene monomer.

4. The flexographic photosensitive elastomer composition with UV ink resistance according to claim 1, characterized in that: The monomer (C) containing at least one unsaturated double bond functional group is an unsaturated acrylate.

5. The flexographic photosensitive elastomer composition with UV ink resistance according to claim 1, characterized in that: The photoinitiator (D) is a pyrolysis-type compound.

6. The flexographic photosensitive elastomer composition with UV ink resistance according to claim 5, characterized in that: The photoinitiator (D) is a benzoin derivative or a hydrogen-exempt benzophenone and its derivatives.

7. The flexographic photosensitive elastomer composition with UV ink resistance according to claim 1, characterized in that: The dye in (E) is a sensitizing cyanine dye with an absorption band in the range of 330-450 nm.

8. A flexographic plate with UV ink resistance, characterized in that: The photosensitive elastomer composition according to any one of claims 1 to 7 exists between the support layer and the protective layer.

9. A flexible plate with UV ink resistance, comprising, from top to bottom, a protective layer, an anti-stick composite film or a laser-ablated black film, a photosensitive elastomer, an adhesive resin film, and a support, characterized in that: The photosensitive elastomer includes the photosensitive elastomer composition according to any one of claims 1 to 7.

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