High-toughness high-adhesion light-cured tin printing ink and preparation method thereof

Abstract

The invention relates to the technical field of photocuring tin printing ink, and particularly discloses high-toughness high-adhesion photocuring tin printing ink and a preparation method thereof. The invention relates to a high-toughness high-adhesion light-cured tin printing ink, which comprises 20-60 parts of a reactive liquid rubber toughening agent; 40 to 80 parts of an acrylic ester active monomer; 8 to 10 parts of a photoinitiator; the reactive liquid rubber flexibilizer comprises phosphate modified liquid rubber and acrylic acid modified liquid rubber. The high-toughness and high-adhesion light-cured tin printing ink can be used for the surface of an iron package, the phosphate modified liquid rubber provides adhesion and toughness, the acrylic acid modified liquid rubber provides compatibility and toughness, a crosslinking system is constructed by the phosphate modified liquid rubber, the acrylic acid modified liquid rubber and the acrylate active monomer, and the high-toughness and high-adhesion light-cured tin printing ink has the advantages of being high in adhesion, good in toughness and not prone to yellowing. The coating can be used for the surface of a light-color iron material packaging base material.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of light-cured printing ink, more particularly to a high-toughness and high-adhesion light-cured printing ink and a preparation method thereof. BACKGROUND

[0002] With the vigorous development of iron or metal packaging, the application of printing ink is also more and more extensive. Among them, the light-cured printing ink is widely used in the printing industry due to its advantages of fast curing speed, environmental protection, energy saving, good economic benefit, etc.

[0003] There are two schemes in the prior art: Scheme 1) The phosphite ester acrylate compound is connected with a polysiloxane chain having a low surface tension, so that the monomer is floated to the surface of the coating / ink in the formula system. This technology inhibits oxygen inhibition, increases the probability of connecting the siloxane chain segment to the crosslinked network, improves the compatibility of the silicone component with the main acrylate, improves the overall firmness of the coating, and thus significantly improves the anti-fouling and wiping resistance.

[0004] Scheme 2) A chain extender with an acyl phosphine oxide structure is used in the raw material, so that the polyurethane acrylate oligomer has a self-initiating function. The polyurethane acrylate oligomer has a methyl methacrylate phosphate structure at both ends, so that the oligomer can be UV light-cured and has good adhesion to the substrate.

[0005] However, scheme 1 above uses an organic silicone chain segment and a phosphate structure, which makes the modified phosphate substance have the risk of floating and separating, and the improvement of the adhesion to the substrate is limited. Scheme 2 introduces a polyurethane component to improve toughness, but the polyurethane itself has a yellowing risk, which limits its application in applications requiring yellowing resistance. SUMMARY

[0006] In order to make the light-cured printing ink have high toughness and high adhesion to the surface of the metal substrate, the present application provides a high-toughness and high-adhesion light-cured printing ink and a preparation method thereof.

[0007] In a first aspect, the present application provides a high-toughness and high-adhesion light-cured printing ink, which adopts the following technical scheme: A high-toughness and high-adhesion light-cured printing ink comprises the following components in parts by weight: a reactive liquid rubber toughening agent 20-60 parts; an acrylate active monomer 40-80 parts; a photoinitiator 8-10 parts; a pigment 20-40 parts; a dispersant 1-2 parts; a leveling agent 0.5-2 parts; Defoaming agent 0.1-0.5 parts; The reactive liquid rubber toughening agent includes phosphoric acid ester modified liquid rubber and acrylic acid modified liquid rubber.

[0008] By adopting the technical scheme, the two modified liquid rubbers are used as the toughening components, the liquid rubber itself has excellent flexibility and aging resistance (anti-yellowing), the self-made phosphoric acid ester modified liquid rubber is introduced, the phosphoric acid ester groups in the molecular structure can form a firm chemical bond with the metal substrate surface, thereby significantly improving the adhesion of the ink coating to the iron / metal packaging. At the same time, the component “anchors” the phosphoric acid ester structure on the flexible long chain of the liquid rubber through chemical bonding, and the acrylic acid modified liquid rubber is used as a compatibilizer to improve the compatibility of the modified liquid rubber with the acrylic ester monomer, avoiding the risk of phase separation of the modified liquid rubber component. Finally, the acrylic ester groups participate in the photocuring crosslinking network, fundamentally solving the core defects of the prior art (solution 1) that the adhesion improvement is limited and the system stability is poor due to the physical migration and floating phase separation of the phosphoric acid ester or silicone chain segment. The phosphoric acid ester groups are firmly fixed in the crosslinking network, avoiding the weakening of the interfacial adhesion due to phase separation, and ensuring the durability and stability of the performance.

[0009] The acrylic acid modified liquid rubber ensures good compatibility with the acrylic ester main resin and participates in the formation of a uniform and dense crosslinking network, thereby maintaining high transparency and low yellowing index of the system while imparting high toughness and impact resistance to the coating. This overcomes the inherent yellowing risk of relying on polyurethane acrylate (which itself has a urethane bond and is prone to yellowing due to the generation of quinone structure under ultraviolet light aging) to toughen, and is particularly suitable for white or light-colored printing iron packaging with high color stability requirements. The flexible long chain of the liquid rubber acts as a “soft segment” dispersed in the “hard segment” crosslinking network of the acrylic ester, forming a rigid-flexible interpenetrating / half-interpenetrating network structure, so that the coating has high hardness and scratch resistance while having excellent flexibility, and can withstand subsequent canning, stamping and other processing deformations without cracking or peeling.

[0010] The phosphoric acid ester modified liquid rubber (providing adhesion and toughness), the acrylic acid modified liquid rubber (providing compatibility and toughness), and the acrylic ester active monomer (adjusting viscosity and constructing network) have a significant synergistic effect.

[0011] Optionally, the weight ratio of the phosphoric acid ester modified liquid rubber and the acrylic acid modified liquid rubber is (10-30):(10-30).

[0012] By adopting the technical scheme, the total amount and the ratio of the two modified rubbers in the ink determine the comprehensive performance of the coating.

[0013] Phosphate-modified rubber: excellent adhesion of the coating, but too much phosphate structure may slightly affect the system compatibility and transparency, and has potential impact on the color of light-colored paint. The improvement of toughness mainly depends on physical toughening, and the network integration is slightly weak.

[0014] Acrylate-modified rubber: excellent compatibility of the coating with the resin, uniform curing network, and significant improvement of toughness. However, the adhesion improvement to the metal substrate mainly depends on the overall improvement of the system, which is not as direct and efficient as the targeted adsorption of phosphate.

[0015] When the ratio of the two is within the scope of the present application, the performance can be perfectly coordinated: the phosphate-modified rubber provides strong adhesion in the form of "anchoring", and the acrylate-modified rubber ensures perfect "fusion" and toughening with the main body, together building a coating that is strong and tough, firmly adhered, and excellent in appearance.

[0016] Optionally, the preparation method of the phosphate-modified liquid rubber comprises the following steps: Add liquid rubber to an organic solvent and dissolve at a temperature of 110-130℃; Cool the system to 100-120℃, and uniformly drop the mixture of dibenzoyl peroxide, vinyl phosphonic acid, and organic solvent within 1-3 hours, After the dropping is completed, continue to react at 100-120℃ for 1-3 hours, and then remove the organic solvent by reduced pressure distillation to obtain the phosphate-modified liquid rubber.

[0017] By adopting the above technical solution: instead of simply physically blending commercially available phosphate monomers and liquid rubber, two functional toughening agents with unique molecular structures are independently synthesized through specific chemical reactions: Under heating conditions, free radical initiators such as dibenzoyl peroxide (BPO) decompose to produce primary free radicals. The primary free radicals attack the active allyl hydrogen or double bond on the molecular chain of the liquid rubber to form macromolecular chain free radicals. The macromolecular radicals copolymerize with the vinyl phosphonic acid monomer, thereby grafting the vinyl phosphonic acid molecular chain to the liquid rubber skeleton through covalent bonds. The final product is a polymer in which phosphate groups are firmly connected to the long chain of flexible rubber through chemical bonds.

[0018] Optionally, in the phosphate-modified liquid rubber, the weight ratio of liquid rubber, dibenzoyl peroxide, and vinyl phosphonic acid is 100:0.5-1.8:5-18.

[0019] By adopting the above technical solution: the ratio between liquid rubber, vinyl phosphonic acid, and free radical initiator is crucial, directly determining the grafting efficiency, molecular structure, and final function.

[0020] When the amount of vinyl phosphonic acid is too low, the phosphonate groups grafted onto the rubber chains are too few, resulting in that the modified product cannot provide sufficient adhesion promotion effect in the ink, and its performance approaches that of the unmodified liquid rubber.

[0021] When the amount is too high, it may cause excessive grafting or increase in the homopolymerization side reaction. Too many strong polar phosphonate groups may destroy the compatibility of the modified product with the main body resin of the ink, causing instability of the system, increase in viscosity, and even gel particles. At the same time, the excessive polar groups may increase the hydrophilicity of the coating, affecting its water resistance.

[0022] Optionally, the liquid rubber is one of styrene butadiene copolymer liquid rubber, polyisoprene liquid rubber, and polybutadiene liquid rubber.

[0023] By adopting the above technical solution: the three kinds of liquid rubber contain two functional monomers during synthesis, and the main chain or end group after polymerization has more residual double bonds, which is more conducive to the grafting reaction of vinyl phosphonic acid.

[0024] Optionally, the preparation method of the acrylate modified liquid rubber comprises the following steps: Mixing the hydroxyl-terminated liquid rubber and the organic solvent, and heating to 110-130°C; Uniformly adding the acrylic acid at a speed of 1-3 hours, continuously reacting until no water is distilled out, which is regarded as the reaction endpoint, and then cooling to 100-120°C, and subsequently removing the organic solvent by reduced pressure distillation to obtain the acrylate modified liquid rubber.

[0025] By adopting the above technical solution: the hydroxyl group (-OH) at the end of the molecular chain of the hydroxyl-terminated liquid rubber undergoes dehydration reaction with the carboxyl group (-COOH) of the acrylic acid under high temperature conditions. The final product is a liquid rubber with an acrylate group (CH2=CH-COO-) at the end. The acrylate group has extremely high photo-curing reactivity.

[0026] Compared with the prior art, the beneficial effects are: 1. Excellent compatibility and network uniformity: the introduction of the acrylate end group through chemical modification greatly improves the compatibility of the non-polar liquid rubber with the polar acrylate main body resin. During curing, it can act as a reactive diluent and toughener, fully participates in the photo-curing crosslinking network, becomes part of the three-dimensional network, avoids the phase separation or performance degradation caused by non-reactive toughener, and thus improves the overall firmness of the coating.

[0027] 2. Intrinsic yellowing resistance: the hydroxyl-terminated liquid rubber skeleton is selected, and the molecular structure mainly consists of C-C and C=C bonds, without the urethane bond (-NH-COO-) that absorbs ultraviolet light to generate chromophores. Therefore, the yellowing problem is fundamentally eliminated.

[0028] Optionally, in the acrylate modified liquid rubber, the weight ratio of the hydroxyl-terminated liquid rubber and the acrylic acid is 100:0.5-1.5.

[0029] By adopting the above technical solution: the molar ratio of the hydroxyl-terminated liquid rubber and the acrylic acid is the core of controlling the modification degree and the final performance.

[0030] The amount of acrylic acid: the number of moles of acrylic acid needs to exceed the number of moles of hydroxyl, even if there is a small amount of unreacted components, it will participate in the double bond addition polymerization and crosslinking reaction in the subsequent photocuring process. When the amount is too low, the reaction is incomplete, the terminal hydroxyl group is not esterified by the acrylic acid, resulting in low photocuring activity of the modified product. In UV curing, it cannot effectively participate in the crosslinking network, and the toughening effect cannot be fully played. It is more like an inert plasticizer, which may cause the coating to be soft or not resistant to solvents.

[0031] Optionally, the hydroxyl-terminated liquid rubber is a hydroxyl-terminated polybutadiene liquid rubber.

[0032] By adopting the above technical solution: the hydroxyl-terminated liquid rubber itself contains hydroxyl groups, which can form ester bonds with the carboxyl groups of the acrylic acid, so that the liquid rubber has groups that can undergo photo-initiated reactions.

[0033] Optionally, the acrylate active monomer is one or more of ethoxylated trimethylolpropane triacrylate, propoxylated glyceryl triacrylate, pentaerythritol triacrylate, polyethylene glycol diacrylate, and polyethylene glycol dimethacrylate. The photo initiator is one or more of 2-isopropylthioxanthone, diphenyl-(2,4,6-trimethylbenzoyl) phosphine oxide, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholin-1-propanone, and 2,4-diethylthioxanthone. The pigment is one or more of permanent yellow, phthalocyanine blue, permanent red, high pigment carbon black, and titanium dioxide.

[0034] In a second aspect, the application provides a preparation method of a high-toughness high-adhesion photocured printing ink, which adopts the following technical solution: A preparation method of a high-toughness high-adhesion photocured printing ink, comprising the following steps: S1, first, the pigment, the dispersant and the acrylate active monomer are put into a sand mill, and sealed and ground for 30-40 min. After the fineness of the pigment reaches the required particle size of 1-6 μm, the color paste is obtained by filtration. S2, the phosphate modified liquid rubber, acrylic modified liquid rubber, photoinitiator, leveling agent, defoamer, ground color paste are put into the sealed stirring planetary mixer for dispersion and stirring, after uniform stirring, the material is filtered out, and sealed preservation is carried out, to obtain the tin printing ink.

[0035] In summary, the present application has the following beneficial effects: 1, the present application adopts phosphate modified liquid rubber with adhesion and toughness and acrylic modified liquid rubber with compatibility and toughness, and constructs an interpenetrating network structure with acrylic ester monomer; the structure makes the ink coating have high hardness, high adhesion, excellent flexibility, can withstand subsequent stamping, bending and forming processing of metal packaging without cracking and peeling, and has stable color and excellent yellowing resistance; 2, the present application is not simply physically blending commercially available phosphate ester monomer and liquid rubber, but independently synthesizing two functional toughening agents with unique molecular structure through specific chemical reaction; Phosphate modified liquid rubber is a polymer in which phosphate groups are firmly connected to the long chain of flexible rubber through chemical bonds, and the end or side chain has phosphate structure, which has good adhesion to metal; The introduction of acrylic ester end group in acrylic modified liquid rubber greatly improves the compatibility of non-polar liquid rubber and polar acrylic ester main resin, and when it is cured, it can act as a reactive diluent and toughening agent, fully participate in the photocuring crosslinking network, become part of the three-dimensional network, avoid the phase separation or performance degradation caused by non-reactive toughening agent, so as to improve the overall firmness of the ink; 3, the method of the present application, by introducing phosphate modified liquid rubber to provide adhesion and toughness, acrylic modified liquid rubber to provide compatibility and toughness, and acrylic ester active monomer to construct the crosslinking system, so that the ink has the advantages of strong adhesion, good toughness and not easy to yellow. BRIEF DESCRIPTION OF DRAWINGS

[0036] Figure 1 It is the structural formula of the present application in example 1. DETAILED DESCRIPTION

[0037] The present application is further described in detail in combination with the following examples. Example 1

[0038] A kind of high toughness high adhesion photocuring tin printing ink is prepared by the following steps: S1, first pigment rutile titanium dioxide 40 g, dispersant (Bichemical DISPERBYK-2013) 2 g and acrylate monomer propoxylated glyceryl triacrylate 80 g into the sand mill, sealed grinding 40 min, until the pigment fineness to meet the requirements of the particle size in 1-6 μm, filter to get pigment color paste; S2, the grinding good color paste, phosphate modified styrene butadiene copolymer liquid rubber 30 g, acrylate modified polybutadiene liquid rubber 30 g, photoinitiator diphenyl-(2,4,6-trimethyl benzoyl) oxygen phosphorus 10 g, leveling agent (BYK361N) 2 g, defoamer (BYK055) 0.5 g into the sealed stirring planetary mixer, stirring evenly, filter out the material, sealed preservation, get.

[0039] Among them, the preparation of phosphate modified liquid rubber: Liquid rubber styrene butadiene copolymer liquid rubber (L-SBR352 of Beichengfeng Chemical Co., Ltd.) 100 g was added to 1000 mL of toluene, heated to 130℃ and dissolved, cooled to 100℃, continue to add the mixture of dibenzoyl peroxide 0.5 g, vinyl phosphonic acid 5 g and toluene 10 mL, the addition time is controlled in 3 hours, after reaction at 110℃ continue to react for 1 hour, distill the toluene under reduced pressure to obtain phosphate modified styrene butadiene copolymer liquid rubber.

[0040] The preparation of acrylate modified liquid rubber: hydroxyl terminated polybutadiene liquid rubber (HTPB-IV type of Hongyuan New Material) 100 g was added to 600 mL of toluene, heated to 120℃ for 10 minutes, started to add 0.5 g of acrylic acid, the drop time of acrylic acid was 1 hour; the water produced in the reaction was collected using a cooling reflux device, after the completion of the drop of acrylic acid, the reaction was continued until no water was produced, which was considered as the end of this section of the reaction, cooled to 100℃, distilled the toluene under reduced pressure to obtain the acrylate modified polybutadiene liquid rubber. Example 2

[0041] A high toughness and high adhesion photocuring printing ink was prepared by the following steps: S1, first pigment permanent yellow 20 g, dispersant (DISPERBYK-111 of Bichemical) 1 g, and acrylate monomer ethoxylated trimethylolpropane triacrylate 40 g into the sand mill, sealed grinding 30 min, until the pigment fineness to meet the requirements of the particle size in 1-6 μm, filter to get pigment color paste; S2, the ground color paste, phosphate modified polyisoprene liquid rubber 10g, acrylate modified polybutadiene liquid rubber 10g, photoinitiator 2-isopropyl thioxanthone 8g, leveling agent (BYK361N) 0g, defoamer (BYK1797) 0.1g into the sealed stirring planetary mixer, stirring evenly, filtering out the material, sealed preservation, obtained.

[0042] The preparation of phosphate modified liquid rubber is as follows: Liquid rubber polyisoprene liquid rubber (ROCEOIL LIR50 of Rockstone Petroleum) 100g was added to 1000mL of toluene, heated to 130℃ and dissolved thoroughly, cooled to 120℃, and then a mixture of 1g of dibenzoyl peroxide, 10g of vinyl phosphonic acid and 10mL of toluene was added to the solution. The addition time was controlled for 1 hour. After the reaction, the toluene was distilled off under reduced pressure at 110℃ for 1 hour to obtain phosphate modified polyisoprene liquid rubber.

[0043] The preparation of acrylate modified liquid rubber is as follows: Hydroxyl-terminated polybutadiene liquid rubber (HTPB-IV type of Hongyuan New Material) 100g was added to 600mL of toluene, heated to 120℃ and kept for 10 minutes, and then 1g of acrylic acid was added dropwise. The acrylic acid dropwise addition time was 3 hours. A cooling reflux device was used to collect the moisture produced during the reaction. After the completion of the acrylic acid dropwise addition, the reaction was continued until no moisture was produced, which was considered as the end of this segment of the reaction. The temperature was lowered to 100℃, and the toluene was distilled off under reduced pressure to obtain acrylate modified polybutadiene liquid rubber. Example 3

[0044] A high-toughness high-adhesion photocuring printing ink was prepared by the following steps: S1, first put pigment phthalocyanine blue 30g, dispersant (DISPERBYK-2030 of BYK Chemical) 1.5g and acrylate monomer pentaerythritol triacrylate 60g into a sand mill, seal and grind for 35min, until the pigment fineness reaches the required particle size of 1-6μm, filter to obtain pigment color paste; S2, the ground color paste, phosphate modified polyisoprene liquid rubber 10g, acrylate modified polybutadiene liquid rubber 10g, photoinitiator 2-isopropyl thioxanthone 8g, leveling agent (BYK361N) 0g, defoamer (BYK1797) 0.1g into the sealed stirring planetary mixer, stirring evenly, filtering out the material, sealed preservation, obtained.

[0045] The preparation of phosphate modified liquid rubber is as follows: Liquid rubber polybutadiene liquid rubber (POLYVEST130 of WINGATE) 100g was added to 1000mL of toluene, heated to 120℃ to dissolve thoroughly, cooled to 110℃, and then a mixture of 1.5g of dibenzoyl peroxide, 15g of vinyl phosphonic acid and 10mL of toluene was continuously added to the solution for 2 hours. After the reaction, the toluene was distilled off under reduced pressure to obtain the phosphate-modified polybutadiene liquid rubber.

[0046] Preparation of acrylate-modified polybutadiene liquid rubber: Hydroxyl-terminated polybutadiene liquid rubber (HTPB-IV of Hongyuan New Material) 100g was added to 600mL of toluene, heated to 120℃ for 10 minutes, and then 1.5g of acrylic acid was added dropwise. The acrylic acid was added for 2 hours. A cooling reflux device was used to collect the water produced during the reaction. After the addition of acrylic acid was completed, the reaction continued until no water was produced, which was considered the end of this segment of the reaction. The temperature was lowered to 100℃, and the toluene was distilled off under reduced pressure to obtain the acrylic acid-modified polybutadiene liquid rubber. Example 4

[0047] A high-toughness high-adhesion photocuring printing ink was prepared by the following steps: S1, first, 25g of pigment Permanent Red, 1.2g of dispersant (DISPERBYK-111 of BYK), and 40g of acrylate monomer polyethylene glycol diacrylate and 10g of ethoxylated trimethylolpropane triacrylate were put into a sand mill and sealed for grinding for 36 minutes. When the fineness of the pigment reached the required particle size of 1-6μm, the pigment paste was filtered; S2, the ground paste, 15g of phosphate-modified polybutadiene liquid rubber, 25g of acrylate-modified polybutadiene liquid rubber, 8.5g of photoinitiator 2,4-diethylthioxanthone, 1.2g of leveling agent (BYK361N), and 0.2g of defoaming agent (BYK055) were put into a sealed planetary mixer and stirred uniformly. After filtration, the product was sealed and stored.

[0048] Preparation of phosphate-modified liquid rubber: Liquid rubber polybutadiene liquid rubber (POLYVEST130 of WINGATE) 100g was added to 500mL of toluene, heated to 120℃ to dissolve thoroughly, cooled to 110℃, and then a mixture of 1.8g of dibenzoyl peroxide, 18g of vinyl phosphonic acid and 10mL of toluene was continuously added to the solution for 2.5 hours. After the reaction, the toluene was distilled off under reduced pressure to obtain the phosphate-modified polybutadiene liquid rubber.

[0049] Preparation of acrylate-modified polybutadiene liquid rubber: Hydroxyl-terminated polybutadiene liquid rubber (HTPB-IV type of Hongyuan New Material) 100 g was added to 600 mL of toluene, heated to 120°C for 10 minutes, and then 0.5 g of acrylic acid was added dropwise. The acrylic acid was added for 2.5 hours. Water produced during the reaction was collected using a cooling reflux device. After the addition of acrylic acid was completed, the reaction continued until no water was produced, which was considered the end of this segment of the reaction. The temperature was lowered to 100°C, and toluene was distilled off under reduced pressure to obtain the acrylic acid-modified polybutadiene liquid rubber. Example 5

[0050] A high-toughness high-adhesion photocuring printing ink was prepared by the following steps: S1, first put pigment high pigment carbon black 20 g, dispersant (DISPERBYK-2013 of BYK Chemical) 1.9 g, acrylate monomer polyethylene glycol dimethacrylate 20 g and ethoxylated trimethylolpropane triacrylate 30 g into a sand mill, seal and grind for 40 min. When the fineness of the pigment reaches the required particle size of 1-6 μm, filter to obtain the pigment paste; S2, put the ground paste, phosphate-modified styrene butadiene copolymer liquid rubber 10 g, acrylic acid-modified polybutadiene liquid rubber 20 g, photoinitiator diphenyl-(2,4,6-trimethylbenzoyl) phosphine oxide 6 g and photoinitiator 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinyl-1-propanone 4 g, leveling agent (BYK361N) 1.9 g, defoaming agent (BYK1797) 0.4 g into a sealed stirring planetary mixer, stir uniformly, then filter the material and seal for storage.

[0051] Preparation of phosphate-modified liquid rubber: Styrene butadiene copolymer liquid rubber (L-SBR352 of Hubei Chengfeng Chemical Co., Ltd.) 100 g was added to 1000 mL of toluene, heated to 125°C and dissolved thoroughly, then cooled to 115°C. A mixture of 1.3 g of dibenzoyl peroxide, 13 g of vinyl phosphonic acid and 10 mL of toluene was added to the solution. The addition time was controlled at 1.5 hours. After the reaction, the temperature was continued to be 110°C for 1 hour. Toluene was distilled off under reduced pressure to obtain the phosphate-modified styrene butadiene copolymer liquid rubber.

[0052] Preparation of acrylic acid-modified polybutadiene liquid rubber: Hydroxyl-terminated polybutadiene liquid rubber (HTPB-IV type of Hongyuan New Material) 100 g was added to 600 mL of toluene, heated to 120°C for 10 minutes, and then 1.5 g of acrylic acid was added dropwise. The acrylic acid dropwise addition time was 2.5 hours. A cooling reflux device was used to collect the water produced during the reaction. After the acrylic acid dropwise addition was completed, the reaction continued until no water was produced, which was considered the end of this segment of the reaction. The temperature was lowered to 100°C, and toluene was distilled off under reduced pressure to obtain the acrylic acid modified polybutadiene liquid rubber. Example 6

[0053] A high-toughness high-adhesion photocuring printing ink was prepared by the following steps: S1, first put 30 g of pigment rutile titanium dioxide, 1.5 g of dispersant (DISPERBYK-2030 of BYK Chemical), and 80 g of acrylate monomer ethoxylated trimethylolpropane triacrylate into a sand mill, seal and grind for 40 min. When the fineness of the pigment reaches the required particle size of 1-6 μm, filter to obtain the pigment paste; S2, put the ground paste, 25 g of phosphate ester modified styrene butadiene copolymer liquid rubber, 30 g of acrylate modified polybutadiene liquid rubber, 9 g of photoinitiator diphenyl-(2,4,6-trimethylbenzoyl) phosphine oxide, 1.5 g of leveling agent (BYK361N), and 0.5 g of defoaming agent (BYK1797) into a sealed planetary mixer, stir uniformly, then filter the material and seal for storage.

[0054] The preparation of the phosphate ester modified liquid rubber is as follows: Styrene butadiene copolymer liquid rubber (L-SBR352 of Hubei Chengfeng Chemical Co., Ltd.) 100 g was added to 1000 mL of toluene, heated to 130°C to dissolve completely, cooled to 100°C, and then 0.5 g of dibenzoyl peroxide, 5 g of vinyl phosphonic acid, and 10 mL of toluene were added to the solution. The addition time was controlled at 3 hours. After the reaction, the toluene was distilled off under reduced pressure at 110°C for 1 hour to obtain the phosphate ester modified styrene butadiene copolymer liquid rubber.

[0055] Preparation of acrylate modified polybutadiene liquid rubber: Hydroxyl-terminated polybutadiene liquid rubber (HTPB-IV type of Hongyuan New Material) 100 g was added to 600 mL of toluene, heated to 120°C for 10 minutes, and then 1 g of acrylic acid was added dropwise. The acrylic acid dropwise addition time was 1 hour. A cooling reflux device was used to collect the water produced during the reaction. After the acrylic acid dropwise addition was completed, the reaction continued until no water was produced, which was considered the end of this segment of the reaction. The temperature was lowered to 100°C, and toluene was distilled off under reduced pressure to obtain the acrylic acid modified polybutadiene liquid rubber.

[0056] Comparative Example 1 An ink is prepared by the following steps: First, the pigment rutile titanium dioxide 40 g, dispersant 1.5 g (DISPERBYK-2013 of BYK Chemical), acrylate monomer ethoxylated trimethylolpropane triacrylate 40 g, pentaerythritol triacrylate 80 g are put into a sand mill, sealed and ground for 40 min, and the pigment fineness is required to reach a particle size of 1-6 μm, and the material is filtered out; Then, acrylate phosphite modified organosiloxane 30 g, photoinitiator 2,4-diethylthioxanthone 10 g, leveling agent (BYK361N) 1.7 g, defoaming agent (BYK1797) 0.3 g are put into a sealed stirring planetary mixer, stirred uniformly, and then filtered out, and sealed for storage.

[0057] Among them, the acrylate phosphite modified organosiloxane has the following structural formula, which can also be seen from Figure 1 Wherein the value of n is consistent with the monohydroxyl-terminated polysiloxane raw material, and n is 8-150.

[0058]

[0059] The preparation of the monomer in this comparative example 1 is referred to the patent with publication number CN109880103B, which is as follows: Take a standard reaction device with reflux, dropping, and stirring, and place it in a cold water bath at -10℃. Add a solution of phosphorus trichloride (10 g, 0.0728 mol) in 50 ml of anhydrous ether and triethylamine (0.220 mol, 23 g) to a three-necked flask under a nitrogen atmosphere. When the temperature stabilizes at -10℃, add hydroxyethyl acrylate HEA (0.15 mol, 17.4 g) dropwise under mechanical stirring, controlling the temperature at -10-0℃ during the dropping process. After the dropping is completed, continue stirring at this temperature for 30 min, and then add monohydroxyl-terminated polysiloxane (0.073 mol, Mn=1500, 146 g) dropwise, controlling the temperature at -10-0℃ during the dropping process. After the dropping is completed, slowly warm up to about 60℃, and keep the temperature for 3 h. After the reaction is completed, cool down, filter out the triethylamine hydrochloride, and evaporate the solvent and excess triethylamine under reduced pressure to obtain the product.

[0060] The monohydroxyl-terminated polysiloxane is from Hubei Longsheng Sihai New Material Co., Ltd., with model number 107 raw rubber.

[0061] Comparative example 2 An ink is prepared by the following steps: Pigment high pigment carbon black 20 g, dispersant (DISPERBYK-2030 of BYK chemical) 1.5 g, acrylate monomer polyethylene glycol dimethacrylate 119 g, photoinitiator 2-isopropylthioxanthone 9 g, leveling agent (BYK361N) 1.2 g, defoaming agent (BYK1797) 0.2 g were put into a sand mill, sealed and ground for 40 min, and the pigment fineness reached the required particle size of 1-6 μm, and the material was filtered out and sealed for storage.

[0062] Comparative Example 3 An ink was prepared by the following steps: Cyclohexane-modified polyurethane acrylate 70 g, epoxy soybean oil-modified acrylate (Zannan EBECRYL5848) 10 g, 1,6-hexanediol diacrylate (Changxing Chemical) 10 g, ethoxylated pentaerythritol tetraacrylate 10 g (Guojing Chemical), phthalocyanine blue 30 g, defoaming agent (BYK1797) 0.3 g, talc 10 g, diphenyl-(2,4,6-trimethylbenzoyl) phosphine oxide 9 g, leveling agent (BYK361N) 0.5 g, dispersant (DISPERBYK-2030 of BYK chemical) 0.7 g were put into a sand mill, sealed and ground for 40 min, and the pigment fineness reached the required particle size of 1-6 μm, and the material was filtered out and sealed for storage.

[0063] The cyclohexane-modified polyurethane acrylate in the present comparative example was prepared according to CN114736557A as follows: S1: HEMA, MA, HDCPMA, ACMO, AIBN and dioxane were weighed in a round-bottom flask to obtain a first reaction mixture; the molar ratio of HEMA to MA, HDCPMA and ACMO was 2:1:3:3, and the addition amount of AIBN was 0.5% of the total weight of the monomers, and the mass percentage of HEMA in dioxane was 10%; S2: The first reaction mixture was deoxygenated by passing nitrogen for 50 min, and the flask was placed in a 70°C oil bath for stirring for 24 h. After the reaction was completed, the precipitated product was washed with n-hexane, and the precipitated product was vacuum dried at 45°C overnight to obtain product A; S3: 35.2 g of product A, 0.05 g of catalyst p-toluenesulfonic acid, 0.005 g of hydroquinone and 70 mL of dimethylbenzene were added to a three-hole round-bottom flask to obtain a second reaction mixture; S4: The temperature of the round-bottom flask was raised to 70°C, and mercaptoethanol was continuously added to the reaction system while stirring. The reaction was monitored by FTIR measurement. When the absorption peak of the carboxyl group in the reactant disappeared, the addition of mercaptoethanol was stopped. After the reaction was completed, the precipitated product was washed with n-hexane, and the precipitated product was vacuum dried at 45°C overnight to obtain product B; S5: 30.5 g of product B, 0.05 g of catalyst 1173, and 100 mL of toluene were added into a three-hole round-bottom flask to obtain a third mixture; S6: The temperature of the round-bottom flask was raised to 50°C, and the CTFA was added dropwise into the flask under nitrogen protection, while irradiating with an LED lamp with a wavelength of 365 nm and stirring, and the reaction was monitored by FTIR measurement, and the reaction was terminated when the HS absorption peak disappeared to obtain a fourth mixture; S7: A toluene solution (for ease of distinction, referred to as a first toluene solution) containing IPDI and an appropriate amount of catalyst DBTDL was continuously added dropwise into the reaction system at 70°C, wherein the mass percentage content of IPDI in the toluene solution was 20%, and the addition amount of DBTDL was 0.1% of the weight of IPDI, and the stirring was terminated when the hydroxyl absorption peak in the reaction system disappeared on the FTIR spectrum, and the dropping was stopped, and a toluene solution (referred to as a second toluene solution) containing PETA and an appropriate amount of catalyst hydroquinone was continuously added dropwise into the reaction system at 70°C, wherein the mass percentage content of PETA in the toluene solution was 30%, and the addition amount of hydroquinone was 0.1% of the weight of PETA, and the continuous dropping was terminated when the isocyanate absorption peak in the reaction system disappeared on the FTIR spectrum, and the dropping was stopped, and the reaction was terminated, and finally, the solvent was removed by rotary evaporation to obtain the aliphatic cyclic side chain modified polyurethane acrylate.

[0064] Comparative Example 4 An ink was prepared by the following steps: The aliphatic cyclic side chain modified polyurethane acrylate 80 g, the epoxy soybean oil modified acrylate (Zannan EBECRYL 5848) 10 g, the 1,6-hexanediol diacrylate (Changxing Chemical) 10 g, the ethoxylated pentaerythritol tetraacrylate (Guojing Chemical) 10 g, the permanent red 30 g, the talc 10 g, the photoinitiator 2-isopropylthioxanthone 9 g, the leveling agent (BYK 361N) 0.5 g, the defoaming agent (BYK 1797) 0.4 g, and the dispersant (DISPERBYK-111 of BYK Chemical) 0.5 g were put into a sand mill, and sealed and ground for 40 min, and the pigment fineness was filtered out to a required particle size of 1-6 μm, and sealed and stored to obtain the ink.

[0065] The aliphatic cyclic side chain modified polyurethane acrylate was obtained in the same manner as in Comparative Example 3.

[0066] Comparative Example 5 An ink was prepared by the following steps: S1, first pigment permanent yellow 20 g, dispersant (Bik chemistry DISPERBYK-111) 1 g and acrylate monomer ethoxylated trimethylolpropane triacrylate 40 g were put into the sand mill, sealed grinding 30 min, until the pigment fineness reached the required particle size of 1-6 μm, filtration to get pigment color paste; S2, the ground color paste, styrene butadiene copolymer liquid rubber (Hubei Chengfeng Chemical Co., Ltd. L-SBR352) 10 g, hydroxyl-terminated polybutadiene liquid rubber (Yingchuang POLYVEST HT) 10 g, photoinitiator 2-isopropylthioxanthone 8 g, leveling agent (BYK361N) 0.5 g, defoamer (BYK1797) 0.1 g were put into the sealed stirring planetary mixer, stirred uniformly, filtered out, sealed preservation, obtained.

[0067] Comparative example 6 An ink was obtained by the following steps: S1, first pigment permanent yellow 20 g, dispersant (Bik chemistry DISPERBYK-111) 1 g and acrylate monomer ethoxylated trimethylolpropane triacrylate 40 g were put into the sand mill, sealed grinding 30 min, until the pigment fineness reached the required particle size of 1-6 μm, filtration to get pigment color paste; S2, the ground color paste, vinyl phosphonic acid 1 g, polyisoprene liquid rubber 9 g, acrylic acid 0.1 g, end-to-end hydroxyl-terminated polybutadiene liquid rubber (HTPB-IV type of Hongyuan New Material) 9.9 g, photoinitiator 2-isopropylthioxanthone 8 g, leveling agent (BYK361N) 0.5 g, defoamer (BYK1797) 0.1 g, were put into the sealed stirring planetary mixer, stirred uniformly, filtered out, sealed preservation, obtained.

[0068] Comparative example 7 An ink was obtained by the following steps: S1, first pigment permanent yellow 20 g, dispersant (Bik chemistry DISPERBYK-111) 1 g and acrylate monomer ethoxylated trimethylolpropane triacrylate 40 g were put into the sand mill, sealed grinding 30 min, until the pigment fineness reached the required particle size of 1-6 μm, filtration to get pigment color paste; S2, the ground color paste, acrylate modified polybutadiene liquid rubber 20 g, photoinitiator 2-isopropylthioxanthone 8 g, leveling agent (BYK361N) 0.5 g, defoamer (BYK1797) 0.1 g were put into the sealed stirring planetary mixer, stirred uniformly, filtered out, sealed preservation, obtained.

[0069] Preparation of acrylate modified liquid rubber: Hydroxyl-terminated polybutadiene liquid rubber (HTPB-IV type of Hongyuan New Material) 100 g was added to 600 mL of toluene, heated to 120°C for 10 minutes, and then 1 g of acrylic acid was added dropwise. The acrylic acid was added for 3 hours. A cooling reflux device was used to collect the water produced during the reaction. After the addition of acrylic acid was completed, the reaction continued until no water was produced, which was considered the end of the reaction. The temperature was reduced to 100°C, and the toluene was distilled off under reduced pressure to obtain the acrylic acid-modified polybutadiene liquid rubber.

[0070] Comparative Example 8 An ink was obtained by the following steps: S1, first put pigment permanent yellow 20 g, dispersant (DISPERBYK-111 of BYK Chemical) 1 g, and acrylate monomer ethoxylated trimethylolpropane triacrylate 40 g into a sand mill, seal and grind for 30 min, until the fineness of the pigment reaches the required particle size of 1-6 μm, filter to obtain pigment paste; S2, put the ground paste, phosphate-modified polyisoprene liquid rubber 20 g, photoinitiator 2-isopropylthioxanthone 8 g, leveling agent (BYK361N) 0.5 g, defoaming agent (BYK1797) 0.1 g into a sealed stirring planetary mixer, stir uniformly, then filter the material and seal for storage.

[0071] The preparation of the phosphate-modified liquid rubber is as follows: Liquid rubber polyisoprene liquid rubber (ROCEOIL LIR50 of Rockstone Oil) 100 g was added to 1000 mL of toluene, heated to 130°C for dissolution, cooled to 120°C, and then 1 g of dibenzoyl peroxide, 10 g of vinyl phosphonic acid, and 10 mL of toluene were added to the solution. The addition time was controlled at 1 hour. After the reaction, the temperature was continued to be 110°C for 1 hour, and then the toluene was distilled off under reduced pressure to obtain the phosphate-modified polyisoprene liquid rubber.

[0072] Performance testing The photocuring printing ink prepared in the examples and comparative examples was tested for the following properties, and the test results are recorded in Table 1.

[0073] Under the same conditions, the ink was printed on the same specification of tinplate (such as 1 mm thick), and the printing method used a laboratory printing ink printing proofing machine. The printed ink sample was cured on a photocuring device. The ink of different formulations needed to be appropriately adjusted in terms of ultraviolet light intensity and curing time, and finally a well-cured ink sample was obtained, which was attached to the tinplate.

[0074] 1. Yellowing resistance: the printed and cured sample was placed in a halogen ultraviolet aging box with an irradiation intensity of 150 W / m 2The YI increment of the ink prepared by the method is compared with that before the UV aging, and the ink prepared by the method has a small YI increment and excellent yellowing resistance. 2. Flexibility: fold the sample by 180°, and observe the ink layer burst; 3. Adhesion of the coating film is determined according to GB / T 9286-1998; 4. Impact resistance: a falling weight impact tester is used, and the impact resistance is determined according to GB / T 20624.2-2006; Table 1: Performance test results Referring to Table 1, the YI increment of the ink prepared by the method in Examples 1-6 is extremely low, the ink has excellent yellowing resistance, and the flexibility, impact resistance and adhesion all meet the use requirements, and the ink can be used as an LED printing ink. Although Comparative Examples 1-4 also contain phosphite and flexible siloxane long chains, the siloxane long chains have low surface tension when the length reaches a certain degree, are easy to float, form phase separation or separate from the metal surface layer, the phosphite component actually in contact with the metal is reduced, and the adhesion and impact resistance are negatively affected to a certain extent, and the ink cannot meet the use requirements.

[0075] The ink prepared by the method in Comparative Examples 5-8 has a different degree of decline compared with the method of the present application, which shows that only when the phosphite modified liquid rubber and the acrylic modified liquid rubber are simultaneously compounded in the ink, the performance of the ink meets the requirements.

[0076] The specific embodiments are only an explanation of the present application, and are not a limitation of the present application, and those skilled in the art can make modifications to the embodiments without creative contribution after reading the present specification, but as long as the modifications are within the scope of the claims of the present application, the present application is protected by the patent law.

Claims

1. A high-toughness high-adhesion photocuring printing ink, characterized by, Comprise the following components by weight: Reactive liquid rubber toughening agent 20-60 parts; Acrylate active monomer 40-80 parts; Photoinitiator 8-10 parts; Pigment 20-40 parts; Dispersant 1-2 parts; Leveling agent 0.5-2 parts; Defoaming agent 0.1-0.5 parts; The reactive liquid rubber toughening agent comprises phosphate ester modified liquid rubber, acrylic modified liquid rubber.

2. The high-toughness high-adhesion photocuring printing ink according to claim 1, characterized in that, The weight ratio of the phosphate ester modified liquid rubber and the acrylic modified liquid rubber is (10-30):(10-30).

3. The high-toughness high-adhesion photocuring printing ink according to claim 1 or 2, characterized in that, The preparation method of the phosphate ester modified liquid rubber comprises the following steps: Add liquid rubber to an organic solvent, heat to 110-130℃ to dissolve; Cool the system to 100-120℃, and add the mixture of dibenzoyl peroxide, vinyl phosphonic acid and organic solvent at a uniform speed within 1-3 hours, After the dropwise addition is completed, continue to react at 100-120℃ for 1-3 hours, and then remove the organic solvent by reduced pressure distillation to obtain the phosphate ester modified liquid rubber.

4. The high-toughness high-adhesion photocuring printing ink according to claim 3, characterized in that: In the phosphate ester modified liquid rubber, the weight ratio of liquid rubber, dibenzoyl peroxide and vinyl phosphonic acid is 100g:0.5-1.8:5-18.

5. The high-toughness high-adhesion photocuring printing ink according to claim 1, characterized in that: The liquid rubber is one of styrene butadiene copolymer liquid rubber, polyisoprene liquid rubber and polybutadiene liquid rubber.

6. The high-toughness high-adhesion photocuring printing ink according to claim 1, characterized in that: The preparation method of the acrylic modified liquid rubber comprises the following steps: Mix hydroxyl-terminated liquid rubber and organic solvent, and heat to 110-130℃; Add acrylic acid at a uniform speed within 1-3 hours, continue to react until no water is distilled out, which is considered as the reaction endpoint, cool to 100-120℃, and then remove the organic solvent by reduced pressure distillation to obtain the acrylic modified liquid rubber.

7. The high-toughness high-adhesion photocuring printing ink according to claim 1, characterized in that: In the acrylic modified liquid rubber, the weight ratio of hydroxyl-terminated liquid rubber and acrylic acid is 100:0.5-1.

5.

8. The high-toughness high-adhesion photocuring printing ink according to claim 1, characterized in that: The hydroxyl-terminated liquid rubber is hydroxyl-terminated polybutadiene liquid rubber.

9. The high-toughness high-adhesion photocuring printing ink according to claim 1, characterized in that: The acrylate active monomer is one or more of ethoxylated trimethylolpropane triacrylate, propoxylated glycerol triacrylate, pentaerythritol triacrylate, polyethylene glycol diacrylate and polyethylene glycol dimethacrylate; The photoinitiator is one or more of 2-isopropylthioxanthone, diphenyl-(2,4,6-trimethylbenzoyl) phosphine oxide, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholin-1-propanone and 2,4-diethylthioxanthone; The pigment is one or more of permanent yellow, phthalocyanine blue, permanent red, high pigment carbon black and titanium dioxide.

10. A process for the preparation of a high toughness, high adhesion photocuring printing ink according to any one of claims 1 to 9, characterized in that, Comprise the following steps: S1, first put the pigment, dispersant and acrylate active monomer into a sand mill, seal and grind for 30-40min, filter the color paste after the fineness of the pigment reaches the required particle size of 1-6μm; S2, put the phosphate ester modified liquid rubber, acrylic modified liquid rubber, photoinitiator, leveling agent, defoaming agent and ground color paste into a sealed planetary mixer for dispersion and stirring, filter the material after uniform stirring, seal and store to obtain the iron printing ink.

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