LED offset printing interval type ink for BOPS candy film and preparation method and application of LED offset printing interval type ink

Abstract

The invention discloses a solvent-free environment-friendly LED (Light Emitting Diode) curing BOPS (Biaxially Oriented Polystyrene) film offset printing interval type ink and a preparation method thereof, and a tetrahydrofurfuryl acrylate monomer is selected, so that the adhesive force of the ink to a BOPS film material can be improved; by selecting pentaerythritol triacrylate, the curing speed can be increased, meanwhile, the crosslinking density is also provided, and the ink is endowed with relatively high flexibility and scratch resistance; the acryloyl morpholine has dilutability and can reduce the viscosity of the ink, the chlorinated polyolefin adhesion promoter is used for a corona-free substrate and can increase the adhesion without adding an organic solvent, the whole formula does not contain organic solvents such as ketones, benzenes, esters, alcohols and the like, and meanwhile, the acryloyl morpholine and tetrahydrofurfuryl acrylate are not subjected to light emitting diode (LED) illumination, so that the viscosity of the ink can be reduced. The methyl phthalate and the modified chlorinated polyolefin can enable the ink to generate a net structure, so that the ink can be firmly attached to the BOPS thin film material, and the adhesive force of the ink to the BOPS thin film material is improved.

Description

Technical Field

[0001] The invention relates to the technical field of inks, and in particular to an LED offset printing interval ink for BOPS candy film, and a preparation method and application thereof. Background Art

[0002] The inner packaging, outer packaging, and tissue packaging of candies printed on the market are generally stretched plastic films, which are printed by interval ink. The ink used is mainly solvent gravure type, which contains a large amount of organic solvents. During printing, a large amount of organic solvents will be volatilized and discharged into the air, causing pollution to the environment, which is not conducive to environmental protection. In particular, benzene solvents are not conducive to the health of operators. At present, there are also reports on BOPS (biaxially stretched polystyrene sheet) candy film LED offset interval printing ink. However, this solvent gravure ink is a traditional thermal curing type, which still has the disadvantages of high energy consumption, high temperature during curing, and the need for hot air system heat dissipation to prevent the high temperature from deforming the printing material.

[0003] Therefore, it is necessary to seek a new curing method that is energy-saving, has low temperature and less heat during curing. LED lamps have low heat during curing. The cold light source system can ensure a temperature rise of 5 degrees, a wavelength of 365-395 nanometers, and a long lamp life of about 30,000-40,000 hours. If LED lamps are used as curing energy, the BOPS film will not deform because the LED lamp is a cold light source with low energy consumption. However, conventional inks on the market require higher curing energy and cannot adapt well to LED lamps. Therefore, it is urgent to develop a BOPS candy film LED offset printing interval ink with low curing energy to meet this demand. Summary of the invention

[0004] The object of the present invention is to provide a solvent-free, environmentally friendly LED-cured BOPS film offset printing ink. The BOPS film offset printing ink of the present invention requires low curing energy, can be well adapted to LED lamps, has good drying properties, strong adhesion, and good leveling after curing, and can meet the ink stretching requirements.

[0005] In order to solve the above technical problems, the present invention adopts the following technical solutions:

[0006] An LED offset printing ink for BOPS candy film comprises the following components by weight:

[0007] Pentaerythritol triacrylate 15-20 parts

[0008] Modified chlorinated polyester acrylate 15-25 parts

[0009] 10-15 parts of tetrahydrofurfuryl acrylate

[0010] Acryloyl morpholine 4-8 parts

[0011] 8-12 parts of methyl phthalate

[0012] Modified chlorinated polyolefin 2-5 parts

[0013] 0.1-0.3 parts of p-hydroxyanisole

[0014] Photoinitiator 10-16 parts

[0015] Pigment 15-20 parts

[0016] 3-5 parts of filler

[0017] Dispersant 1-2 parts

[0018] Additives 0.3-0.6 parts.

[0019] Preferably, the photoinitiator is:

[0020] 2,4,6-trimethylbenzoyl-diphenylphosphine oxide photoinitiator, with an absorption wavelength of 280-395nm, is used to enhance the deep curing and drying of ink;

[0021] Bis-2,6-difluoro-3-pyrrolephenyl titanocene photoinitiator, absorption wavelength is 410-480nm, it is cationic and is used for curing and drying with LED lamp equipment;

[0022] 10-(4-biphenyl)-2-isopropylthioxanthone hexafluorophosphate photoinitiator, absorption wavelength

[0023] 280-395nm, cationic, used for curing and drying with LED lamp equipment;

[0024] The three photoinitiators are used simultaneously and the synergistic effect of the three photoinitiators can ensure that the LED offset printing interval ink of the present invention is fast and efficient in the crosslinking process to prevent it from not drying up, and is suitable for the high-speed printing speed of flexographic printing of 50 to 100 meters per minute.

[0025] More preferably, the photoinitiator comprises by weight:

[0026] 2-3 parts of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide

[0027] 3-4 parts of bis(2,6-difluoro-3-pyrrophenyl)titanocene

[0028] A mixture of 7-9 parts of 10-(4-biphenyl)-2-isopropylthioxanthone hexafluorophosphate.

[0029] Preferably, the pigment is any one of permanent red, permanent yellow, phthalocyanine blue and carbon black.

[0030] Preferably, the filler is calcium carbonate.

[0031] Preferably, the auxiliary agent includes a defoamer and a leveling agent to increase the leveling and defoaming of the ink.

[0032] The present invention also provides a method for preparing the above-mentioned LED offset printing ink for BOPS candy film, comprising the following steps:

[0033] (1) Preparation of semi-finished product 1: Pentaerythritol triacrylate, tetrahydrofurfuryl acrylate, methyl phthalate, and part of p-hydroxyanisole are stirred at a speed of 1000-1500 rpm, the temperature is controlled at 75-85° C., and after stirring for a period of time, no particles are detected;

[0034] (2) Preparation of semi-finished product 2: adding modified chlorinated polyester acrylate, acryloyl morpholine, p-hydroxyanisole, modified chlorinated polyolefin, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis-2,6-difluoro-3-pyrrolophenyl titanocene, 10-(4-biphenyl)-2-isopropylthioxanthone hexafluorophosphate, heating to 55-65° C., stirring at a speed of 800 rpm, and stirring for a period of time;

[0035] (3) Add semi-finished product 1 to the prepared semi-finished product 2, and then add dispersant, defoamer and leveling agent. Stir for a period of time at a stirring speed of 500 rpm, then add filler and pigment, increase the speed to 1500 rpm and stir for a period of minutes, grind on a three-roll mill 3-5 times to a fineness of 6 um, and package after passing the inspection.

[0036] Preferably, in step (1), the temperature is controlled at 75° C. and the stirring is performed for 80-120 minutes.

[0037] Preferably, in step (2), the mixture is heated to 60° C. and stirred for 30 minutes.

[0038] The present invention uses methyl phthalate DAP-A resin from Japan Daisou Co., Ltd. to improve the ink's anti-flying properties; uses modified chlorinated polyester acrylate, pentaerythritol triacrylate PET3A, tetrahydrofurfuryl acrylate and modified chlorinated polyolefin as main resins, which can give LED curing flexographic ink better adhesion and lower curing energy, and can better adapt to LED365-395 type light sources. The LED365-395 type lamp has an output power of 2000W, a distance between the light source and the workpiece of 1205 mm, and controls the energy reaching the workpiece surface to be 40 mJ / CM. The ink curing travel speed of the present invention is at a normal flexographic printing machine speed of 100 m / min, and can be completely cured, achieving a relatively high curing speed.

[0039] The invention uses tetrahydrofurfuryl acrylate to improve the adhesion of ink to BOPS film material; uses pentaerythritol triacrylate to improve the curing speed and provide crosslinking density, thereby giving the ink higher flexibility and scratch resistance; acryloyl morpholine has diluting property and can reduce the viscosity of the ink; the chlorinated polyolefin adhesion promoter is used for the corona-free substrate and can increase the adhesion; at the same time, the pigment is ground to a fine particle size so that it can fully meet the LED flexographic printing conditions without adding organic solvents; since there are no organic solvents such as ketones, benzenes, esters, alcohols, etc. in the entire formula, there is no discharge of organic solvents during the construction process, thereby meeting the environmental protection requirements; in addition, acryloyl morpholine and tetrahydrofurfuryl acrylate, methyl phthalate and modified chlorinated polyolefin can make the ink produce a network structure during the process of being illuminated by LED light, so that the ink can be firmly attached to the BOPS film material, thereby improving the adhesion of the ink to the BOPS film material. DETAILED DESCRIPTION

[0040] The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with specific embodiments.

[0041] The raw material models used in the following examples are as follows:

[0042] The modified chlorinated polyester acrylate is EB436 from Cytec Corporation of the United States;

[0043] Pentaerythritol triacrylate PET3A is EM235 from Taiwan Changxing Chemical Industry (Guangdong) Co., Ltd.;

[0044] Tetrahydrofurfuryl acrylate is EM214 from Taiwan Changxing Chemical Industry (Guangdong) Co., Ltd.;

[0045] The dispersant is Lubrizol Chemical 24000 dispersant from the United States;

[0046] Methyl phthalate was DAP-A from Daisou Co., Ltd.

[0047] The modified chlorinated polyolefin is Eastman's 343-3 adhesion promoter;

[0048] Phthalocyanine blue is BASF K7090 BASF Phthalocyanine Blue, Pigment Blue No. 15:3;

[0049] Permanent Red is Swiss Clariant organic pigment Permanent Red L501, Pigment Red 57:1;

[0050] Carbon black was Columbia 1060 carbon black;

[0051] Permanent Yellow is Swiss Clariant's organic pigment Permanent Yellow HR;

[0052] The defoaming agent is Deqian 6800 defoaming agent;

[0053] The leveling agent is Digao 2300 leveling agent.

[0054] Example 1

[0055] An LED offset printing ink for BOPS candy film, LED offset printing ink, is composed of the following weight components:

[0056] Pentaerythritol triacrylate 18 kg

[0057] Modified chlorinated polyester acrylate 20 kg

[0058] Tetrahydrofurfuryl acrylate 10 kg

[0059] Acryloyl morpholine 4.4 kg

[0060] Methyl phthalate 10 kg

[0061] Permanent Yellow 15 kg

[0062] Calcium carbonate 3 kg

[0063] Modified chlorinated polyolefin 3 kg

[0064] 0.2 kg of p-Hydroxyanisole

[0065] 24000 dispersant 1 kg

[0066] Defoamer 0.2 kg, leveling agent 0.2 kg

[0067] 5 kg of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 5 kg of bis(2,6-difluoro-3-pyrrolphenyl)titanocene, and 5 kg of 10-(4-biphenyl)-2-isopropylthioxanthone hexafluorophosphate.

[0068] The preparation method is as follows:

[0069] Semi-finished product 1: add 18 kg of pentaerythritol triacrylate, 10 kg of tetrahydrofurfuryl acrylate and 10 kg of methyl phthalate, and 0.1 kg of p-hydroxyanisole, control the temperature at 75 degrees at a stirring speed of 1000-1500 rpm, stir for 80-120 minutes, and detect whether there are no particles;

[0070] Semi-finished product 2: add 20 kg of modified chlorinated polyester acrylate, 4.4 kg of acryloylmorpholine, 0.1 kg of p-hydroxyanisole, 3 kg of modified chlorinated polyolefin, 5 kg of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 5 kg of bis-2,6-difluoro-3-pyrrolophenyl titanocene, and 5 kg of 10-(4-biphenyl)-2-isopropylthioxanthone hexafluorophosphate, mix well, heat to 60°C, stir at 800 rpm, and stir for 30 minutes;

[0071] Add semi-finished product 1, 1 kg of 2400 dispersant, 15 kg of permanent yellow, and 3 kg of calcium carbonate into semi-finished product 2, and then add 0.2 kg of defoamer and 0.2 kg of leveling agent. Stir for 15 minutes at a stirring speed of 500 rpm, and then grind with a three-roll mill 3-4 times to a fineness of 6um, and package the finished product.

[0072] Example 2

[0073] An LED offset spacer ink for BOPS candy film, comprising the following components by weight:

[0074] Pentaerythritol triacrylate 17.2 kg

[0075] Modified chlorinated polyester acrylate 20 kg

[0076] Tetrahydrofurfuryl acrylate 10 kg

[0077] 24000 dispersant 1 kg

[0078] Acryloyl morpholine 4.4 kg

[0079] Permanent Red L5B01, 18 kg

[0080] Calcium carbonate 3 kg

[0081] 0.2 kg leveling agent, 0.2 kg defoaming agent

[0082] Methyl phthalate 9 kg

[0083] Modified chlorinated polyolefin 2 kg

[0084] 0.2 kg of p-Hydroxyanisole

[0085] 5 kg of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 5 kg of bis(2,6-difluoro-3-pyrrolphenyl)titanocene, and 5 kg of 10-(4-biphenyl)-2-isopropylthioxanthone hexafluorophosphate.

[0086] The preparation method is:

[0087] Semi-finished product 1: add 17.2 kg of pentaerythritol triacrylate, 10 kg of tetrahydrofurfuryl acrylate, 9 kg of methyl phthalate, and 0.1 kg of p-hydroxyanisole, control the temperature at 75 degrees at a stirring speed of 1000-1500 rpm, stir for 80-120 minutes, and detect whether there are no particles;

[0088] Semi-finished product 2: add 20 kg of modified chlorinated polyester acrylate, 4.4 kg of acryloylmorpholine, 0.1 kg of p-hydroxyanisole, 2 kg of modified chlorinated polyolefin, 5 kg of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 5 kg of bis-2,6-difluoro-3-pyrrolophenyl titanocene, and 5 kg of 10-(4-biphenyl)-2-isopropylthioxanthone hexafluorophosphate, heat to 60°C, stir at 800 rpm, and stir for 30 minutes;

[0089] Add semi-finished product 1 and 1 kg of 2400 dispersant to semi-finished product 2, add 18 kg of Permanent Red L5B01 and 3 kg of calcium carbonate at a speed of 800 rpm, increase the speed to 1500 rpm and stir for 10 minutes, grind on a three-roll mill 3-5 times to a fineness of 6um, and package the finished product after passing the inspection.

[0090] Example 3

[0091] An LED offset spacer ink for BOPS candy film, comprising the following components by weight:

[0092] Pentaerythritol triacrylate 20 kg

[0093] Modified chlorinated polyester acrylic 18 kg

[0094] Tetrahydrofurfuryl acrylate 9 kg

[0095] Acryloyl morpholine 4 kg

[0096] 24000 dispersant 1.4 kg

[0097] Phthalocyanine Blue 18 kg

[0098] Calcium carbonate 3 kg

[0099] Methyl phthalate 9 kg

[0100] 0.2 kg of organic silicon leveling agent, 0.2 kg of organic silicon defoaming agent

[0101] 0.2 kg of p-Hydroxyanisole

[0102] 6 kg of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 4 kg of bis(2,6-difluoro-3-pyrrolophenyl)titanocene, 5 kg of 10-(4-biphenyl)-2-isopropylthioxanthone hexafluorophosphate

[0103] Modified chlorinated polyolefin 2 kg.

[0104] The preparation method is:

[0105] Semi-finished product 1: add 20 kg of pentaerythritol triacrylate, 9 kg of tetrahydrofurfuryl acrylate, 9 kg of methyl phthalate, and 0.1 kg of p-hydroxyanisole, and stir at a speed of 1000-1500 rpm, control the temperature to 75 degrees, stir for 80-120 minutes, and detect if there are no particles;

[0106] Semi-finished product 2: add 18 kg of modified chlorinated polyester acrylate, 4 kg of acryloylmorpholine, 0.1 kg of p-hydroxyanisole, 2 kg of modified chlorinated polyolefin, 6 kg of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 4 kg of bis-2,6-difluoro-3-pyrrolophenyl titanocene, and 5 kg of 10-(4-biphenyl)-2-isopropylthioxanthone hexafluorophosphate, heat to 60°C, stir at 800 rpm, and stir for 30 minutes;

[0107] Add semi-finished product 1 into semi-finished product 2, then add 1.4 kg of 2400 dispersant, 0.2 kg of defoamer and 0.2 kg of leveling agent, stir for 15 minutes at a stirring speed of 500 rpm, add 18 kg of phthalocyanine blue and 3 kg of calcium carbonate, increase the speed to 1500 rpm and stir for 10 minutes, grind on a three-roll mill 3-5 times to a fineness of 6um, and package after passing the inspection.

[0108] Example 4

[0109] An LED offset spacer ink for BOPS candy film, comprising the following components by weight:

[0110] Pentaerythritol triacrylate 20 kg

[0111] Modified chlorinated polyester acrylic 18 kg

[0112] Tetrahydrofurfuryl acrylate 8 kg

[0113] Acryloyl morpholine 3.7 kg

[0114] 24000 dispersant 2.5 kg

[0115] 0.2 kg of p-Hydroxyanisole

[0116] Methyl phthalate 9 kg

[0117] 1060 Carbon Black 15 kg

[0118] 0.3 kg of organic silicon leveling agent, 0.3 kg of organic silicon defoaming agent

[0119] Modified chlorinated polyolefin 2 kg

[0120] Calcium carbonate 3 kg

[0121] 7 kg of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 6 kg of bis(2,6-difluoro-3-pyrrolphenyl)titanocene, and 5 kg of 10-(4-biphenyl)-2-isopropylthioxanthone hexafluorophosphate.

[0122] The preparation method is:

[0123] Semi-finished product 1: 20 kg of pentaerythritol triacrylate, 8 kg of tetrahydrofurfuryl acrylate, 9 kg of methyl phthalate, and 0.1 kg of p-hydroxyanisole. Stir at a speed of 1000-1500 rpm, control the temperature at 80°C, stir for 80-120 minutes, and detect that there are no particles.

[0124] Semi-finished product 2: add 18 kg of modified chlorinated polyester acrylate, 3.7 kg of acryloylmorpholine, 0.1 kg of p-hydroxyanisole, 2 kg of modified chlorinated polyolefin, 7 kg of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 6 kg of bis-2,6-difluoro-3-pyrrolophenyl titanocene, and 5 kg of 10-(4-biphenyl)-2-isopropylthioxanthone hexafluorophosphate, heat to 60°C, stir at 800 rpm, and stir for 30 minutes;

[0125] Add semi-finished product 1 to semi-finished product 2, then add 2.5 kg of 2400 dispersant, 0.3 of defoamer and 0.3 of leveling agent, stir for 15 minutes at a stirring speed of 500 rpm, add 15 kg of 1060 carbon black and 3 kg of calcium carbonate, increase the speed to 1500 rpm and stir for 10 minutes, grind on a three-roll mill 3-5 times to a fineness of 6um, and package the finished product after passing the inspection.

[0126] The inks prepared in Examples 1-4 are yellow, red, blue and black. The prepared UV-curable inks are coated on BOPS film candy materials and UV-cured to examine the performance of the inks. The performance test results are shown in Tables 1-4.

[0127] Table 1: BOPS candy film LED offset printing ink prepared in Example 1

[0128]

[0129]

[0130]

[0131] Table 2 BOPS candy film LED offset printing ink prepared in Example 2

[0132]

[0133]

[0134] Table 3 BOPS candy film LED offset printing ink prepared in Example 3

[0135]

[0136]

[0137] Table 4 BOPS candy film LED offset printing ink prepared in Example 4

[0138]

[0139]

[0140] The above is a preferred embodiment of the present invention. It should be pointed out that a person skilled in the art can make several improvements and modifications without departing from the principle of the present invention. These improvements and modifications are also considered to be within the scope of protection of the present invention.

Claims

1. A LED offset printing ink for BOPS candy film, characterized in that: The following components are included by weight: Pentaerythritol triacrylate 15-20 parts Modified chlorinated polyester acrylate 15-25 parts 10-15 parts of tetrahydrofurfuryl acrylate Acryloyl morpholine 4-8 parts 8-12 parts of methyl phthalate Modified chlorinated polyolefin 2-5 parts 0.1-0.3 parts of p-hydroxyanisole Photoinitiator 10-16 parts Pigment 15-20 parts 3-5 parts of filler Dispersant 1-2 parts Additives 0.3-0.6 parts.

2. The LED offset printing ink for BOPS candy film according to claim 1, characterized in that: The photoinitiator is a mixture of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis-2,6-difluoro-3-pyrrolephenyl titanocene, and 10-(4-biphenyl)-2-isopropylthioxanthone hexafluorophosphate.

3. The LED offset printing ink for BOPS candy film according to claim 2, characterized in that: The photoinitiator comprises by weight: 2-3 parts of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide 3-4 parts of bis(2,6-difluoro-3-pyrrophenyl)titanocene A mixture of 7-9 parts of 10-(4-biphenyl)-2-isopropylthioxanthone hexafluorophosphate.

4. The LED offset printing ink for BOPS candy film according to claim 1, characterized in that: The pigment is any one of permanent red, permanent yellow, phthalocyanine blue and carbon black.

5. The LED offset printing ink for BOPS candy film according to claim 1, characterized in that: The filler is calcium carbonate.

6. The LED offset printing ink for BOPS candy film according to claim 1, characterized in that: The auxiliary agents include defoamers and leveling agents.

7. A method for preparing the LED offset printing ink for BOPS candy film as claimed in any one of claims 1 to 6, characterized in that: The following steps are involved: (1) Preparation of semi-finished product 1: Pentaerythritol triacrylate, tetrahydrofurfuryl acrylate, methyl phthalate, and part of p-hydroxyanisole are stirred at a speed of 1000-1500 rpm, the temperature is controlled at 75-85° C., and after stirring for a period of time, no particles are detected; (2) Preparation of semi-finished product 2: adding modified chlorinated polyester acrylate, acryloyl morpholine, p-hydroxyanisole, modified chlorinated polyolefin, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis-2,6-difluoro-3-pyrrolophenyl titanocene, 10-(4-biphenyl)-2-isopropylthioxanthone hexafluorophosphate, heating to 55-65° C., stirring at a speed of 800 rpm, and stirring for a period of time; (3) Add semi-finished product 1 to the prepared semi-finished product 2, and then add dispersant, defoamer and leveling agent. Stir for a period of time at a stirring speed of 500 rpm, then add filler and pigment, increase the speed to 1500 rpm and stir for a period of minutes, grind on a three-roll mill 3-5 times to a fineness of 6 um, and package after passing the inspection.

8. The preparation method according to claim 7, characterized in that: In step (1), the temperature is controlled at 75° C. and the mixture is stirred for 80-120 minutes.

9. The preparation method according to claim 7, characterized in that: In step (2), heat to 60°C and stir for 30 minutes.

10. Use of the LED offset printing ink for BOPS candy film as claimed in any one of claims 1 to 6 and the LED offset printing ink prepared by the method as claimed in any one of claims 7 to 9 in printing BOPS candy film.

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