A UV-curable printing ink and a method for its preparation

Abstract

This invention discloses a UV-curable printing ink and its preparation method. The UV-curable printing ink comprises the following raw materials in parts by weight: 80-100 parts of binder, 40-60 parts of pigments and fillers, 1-5 parts of talc, 1-2 parts of dispersant, 1-1.5 parts of photoinitiator, and 0.1-0.2 parts of defoamer. The binder molecules contain double bonds between each other and at both ends of the molecular chain, enabling the molecules to form a network structure after UV curing, thereby increasing the molecular density of the printing ink. A large number of hydrophobic groups are distributed between the molecular chain segments, which can effectively prevent water molecules from eroding the ink film, thereby increasing the service life. The modified monomer contains organosilicon segments and benzene ring structures, which makes the prepared printing ink have good water resistance. The side chains contain a large number of sodium sulfonate groups and catechol structures, which can increase the adhesion of the printing ink and prevent the printing ink from falling off.

Description

Technical Field

[0001] This invention relates to the field of ink preparation technology, specifically to a UV-curable printing ink and its preparation method. Background Technology

[0002] UV curing refers to a process in which, under UV radiation, photosensitive materials in a system absorb energy within a certain wavelength range, are excited, and undergo photochemical reactions, subsequently decomposing to produce active free radicals or cations. This triggers the polymerization, cross-linking, and curing of prepolymers or active monomers within the system, resulting in the instantaneous cross-linking and polymerization of the liquid-phase system. UV-curable printing inks are mainly composed of photosensitive resins, photosensitizers, pigments, and additives. In application, UV-curable printing inks offer advantages such as energy and space savings, and improved work efficiency. Due to their significant advantages over ordinary solvent-based inks in terms of environmental protection, cost, and efficiency, they have gradually gained attention. However, because some photosensitive resins are water-soluble, the resulting ink films have poor water resistance, leading to ink peeling after a period of use, thus affecting the overall performance. Summary of the Invention

[0003] The purpose of this invention is to provide a UV-curable printing ink and its preparation method, which solves the problems of poor adhesion and easy peeling of UV-curable printing ink in the next stage.

[0004] The objective of this invention can be achieved through the following technical solutions:

[0005] A method for preparing a UV-curable printing ink specifically includes the following steps:

[0006] Weigh the following raw materials by weight: 80-100 parts binder, 40-60 parts pigments and fillers, 1-5 parts talc, 1-2 parts dispersant, 1-1.5 parts photoinitiator, and 0.1-0.2 parts defoamer. Mix the raw materials evenly to obtain UV-curable printing ink.

[0007] The photoinitiator is one or a mixture of two of photoinitiators 184 and 369 in any proportion; the dispersant is one or a mixture of one or a mixture of BYK-190, HR-4017 and YB-401 in any proportion; and the defoamer is one or a mixture of one or a mixture of DAPRO DF7073, DAPRO DF7072 and TEGO FOAMEX 1488 in any proportion.

[0008] Furthermore, the connecting material is prepared by the following steps:

[0009] Dopamine, propylene oxide, and DMF are mixed and reacted for 3-5 hours at a rotation speed of 120-150 r / min, a temperature of 30-40℃, and a pH of 11-12 to obtain intermediate 1. Intermediate 1, modified monomer, polytetrahydrofuran, and isophorone diisocyanate are mixed and reacted for 3-5 hours at a rotation speed of 150-200 r / min and a temperature of 90-95℃. Dimethylolpropionic acid is added and reacted for 2-3 hours. Hydroxyethyl acrylate is added and reacted for 1-1.5 hours. Deionized water is added and the temperature is lowered to 35-40℃. Triethylamine is added and reacted for 30-40 minutes to obtain the binder.

[0010] Furthermore, the molar ratio of dopamine to propylene oxide is 1:2, and the ratio of intermediate 1, modified monomer, polytetrahydrofuran, isophorone diisocyanate, dimethylolpropionic acid, hydroxyethyl acrylate, deionized water, and triethylamine is 10 mmol:10 mmol:20 mmol:55 mmol:1 mmol:9 mmol:60 mL:1.5 mmol, and the molecular weight of polytetrahydrofuran is 2000.

[0011] Furthermore, the modified monomer is prepared by the following steps:

[0012] Step B1: Mix 3,3'-dihydroxy-[1,1'-biphenyl]-4,4'-dicarboxaldehyde and ethanol evenly, stir and add aminopropyldimethylethoxysilane at 120-150 r / min and 40-50℃, and react for 4-6 h to obtain intermediate 2. Mix intermediate 2, acryloyl chloride, sodium hydroxide and DMF evenly, and react for 3-5 h at 150-200 r / min and 30-40℃ to obtain intermediate 3.

[0013] Step B2: Mix intermediate 3, diphenyldichlorosilane and deionized water, and stir for 10-15 minutes at a speed of 200-300 r / min and a temperature of 60-70℃. Then add concentrated sulfuric acid and 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane and react for 4-6 hours. Adjust the pH to neutral to obtain diamine-terminated polysiloxane.

[0014] Step B3: Mix diamine-terminated polysiloxane, epichlorohydrin, and DMF, and react for 3-5 hours at a rotation speed of 120-150 r / min, a temperature of 30-40℃, and a pH of 11-12 to obtain intermediate 4. Mix intermediate 4, sodium sulfite, and DMF, and react for 6-8 hours at a rotation speed of 150-200 r / min and a temperature of 145-150℃ to obtain the modified monomer.

[0015] Furthermore, the molar ratio of 3,3'-dihydroxy-[1,1'-biphenyl]-4,4'-dicarboxaldehyde and aminopropyl dimethylethoxysilane in step B1 is 1:2, and the molar ratio of intermediate 2, acryloyl chloride and sodium hydroxide is 1:2:2.1.

[0016] Furthermore, the ratio of intermediate 3, diphenyldichlorosilane, deionized water and 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane described in step B2 is 1 mmol:2 mmol:20 mL:1.5 mmol.

[0017] Furthermore, in step B3, the molar ratio of the diamine-terminated polysiloxane and epichlorohydrin is 1:4, and the molar ratio of intermediate 4 and sodium sulfite is 1:4.1.

[0018] The beneficial effects of this invention: The UV-curable printing ink disclosed in this invention comprises the following raw materials: binder, pigments and fillers, talc, dispersant, photoinitiator, and defoamer. The binder is prepared by reacting dopamine and propylene oxide as raw materials in an alkaline filler to form new hydroxyl groups, yielding intermediate 1. Intermediate 1, modified monomer, polytetrahydrofuran, and isophorone diisocyanate are reacted to form a polyurethane prepolymer, which is then chain-extended with dihydroxymethyl acrylate and finally capped with hydroxyethyl acrylate to obtain the binder. The binder molecules contain double bonds between each other, and the molecular chains also contain double bonds at both ends, enabling the molecules to form a network structure after UV curing, thereby increasing the molecular density of the printing ink. A large number of hydrophobic groups are distributed between the molecular chain segments, which can effectively prevent water molecules from eroding the ink film, thus increasing the service life. The modified monomer is prepared by reacting 3,3'-dihydroxy-[1,1'-biphenyl]-4,4'-dicarboxaldehyde and aminopropyl dimethylethoxysilane as raw materials, so that 3 The aldehyde group on 3'-dihydroxy-[1,1'-biphenyl]-4,4'-dicarboxaldehyde reacts with the amino group on aminopropyldimethylethoxysilane to form a Schiff base structure, yielding intermediate 2. Intermediate 2 is then reacted with acryloyl chloride, causing the phenolic hydroxyl group on intermediate 2 to react with the acryl chloride, yielding intermediate 3. Intermediate 3 and diphenyldichlorosilane are hydrolyzed and then polymerized with 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane to form a bis(3-aminopropyl)-dichlorosilane. Amine-terminated polysiloxanes are reacted with epichlorohydrin to form new hydroxyl groups, yielding intermediate 4. Intermediate 4 is then reacted with sodium sulfite, causing the chlorine atom sites on intermediate 4 to react with intermediate 4, yielding a modified monomer. The modified monomer contains organosilicon segments and benzene ring structures, which gives the prepared printing ink excellent water resistance. Furthermore, the side chains contain a large number of sodium sulfonate groups and catechol structures, which can increase the adhesion of the printing ink and thus prevent the printing ink from peeling off. Detailed Implementation

[0019] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention. Example

[0020] A method for preparing a UV-curable printing ink specifically includes the following steps:

[0021] Weigh the following raw materials by weight: 80 parts binder, 40 parts pigments and fillers, 1 part talc, 1 part dispersant, 1 part photoinitiator and 0.1 part defoamer. Mix the raw materials evenly to obtain UV-curable printing ink.

[0022] The photoinitiator is photoinitiator 184, the dispersant is BYK-190, and the defoamer is DAPRO DF7073.

[0023] The binder is made by the following steps:

[0024] Dopamine, propylene oxide, and DMF were mixed and reacted for 3 hours at a speed of 120 r / min, a temperature of 30 °C, and a pH of 11 to obtain intermediate 1. Intermediate 1, modified monomer, polytetrahydrofuran, and isophorone diisocyanate were mixed and reacted for 3 hours at a speed of 150 r / min and a temperature of 90 °C. Dimethylolpropionic acid was added and reacted for 2 hours. Hydroxyethyl acrylate was added and reacted for 1 hour. Deionized water was added and the temperature was lowered to 35 °C. Triethylamine was added and reacted for 30 minutes to obtain the binder.

[0025] The molar ratio of dopamine to propylene oxide is 1:2. The ratio of intermediate 1, modified monomer, polytetrahydrofuran, isophorone diisocyanate, dimethylolpropionic acid, hydroxyethyl acrylate, deionized water and triethylamine is 10 mmol:10 mmol:20 mmol:55 mmol:1 mmol:9 mmol:60 mL:1.5 mmol. The molecular weight of polytetrahydrofuran is 2000.

[0026] The modified monomer is prepared by the following steps:

[0027] Step B1: 3,3'-dihydroxy-[1,1'-biphenyl]-4,4'-dicarboxaldehyde and ethanol were mixed evenly, and aminopropyldimethylethoxysilane was added under the conditions of 120 r / min and 40 °C. The mixture was stirred and reacted for 4 h to obtain intermediate 2. Intermediate 2, acryloyl chloride, sodium hydroxide and DMF were mixed evenly and reacted under the conditions of 150 r / min and 30 °C for 3 h to obtain intermediate 3.

[0028] Step B2: Intermediate 3, diphenyldichlorosilane and deionized water are mixed and stirred for 10 min at 200 r / min and 60 °C. Then concentrated sulfuric acid and 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane are added and reacted for 4 h. The pH is then adjusted to neutral to obtain diamine-terminated polysiloxane.

[0029] Step B3: Mix diamine-terminated polysiloxane, epichlorohydrin and DMF, and react for 3 hours at a speed of 120 r / min, a temperature of 30 °C and a pH of 11 to obtain intermediate 4. Mix intermediate 4, sodium sulfite and DMF, and react for 6 hours at a speed of 150 r / min and a temperature of 145 °C to obtain modified monomer.

[0030] The molar ratio of 3,3'-dihydroxy-[1,1'-biphenyl]-4,4'-dicarboxaldehyde and aminopropyl dimethylethoxysilane in step B1 is 1:2, and the molar ratio of intermediate 2, acryloyl chloride and sodium hydroxide is 1:2:2.1.

[0031] The ratio of intermediate 3, diphenyldichlorosilane, deionized water and 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane described in step B2 is 1 mmol:2 mmol:20 mL:1.5 mmol.

[0032] The molar ratio of the diamine-terminated polysiloxane and epichlorohydrin in step B3 is 1:4, and the molar ratio of intermediate 4 and sodium sulfite is 1:4.1. Example

[0033] A method for preparing a UV-curable printing ink specifically includes the following steps:

[0034] Weigh the following raw materials by weight: 90 parts binder, 50 parts pigments and fillers, 3 parts talc, 1.5 parts dispersant, 1.3 parts photoinitiator and 0.1 parts defoamer. Mix the raw materials evenly to obtain UV-curable printing ink.

[0035] The photoinitiator is photoinitiator 184, the dispersant is HR-4017, and the defoamer is DAPRO DF7072.

[0036] The binder is made by the following steps:

[0037] Dopamine, propylene oxide, and DMF were mixed and reacted for 4 hours at a speed of 120 r / min, a temperature of 35 °C, and a pH of 12 to obtain intermediate 1. Intermediate 1, modified monomer, polytetrahydrofuran, and isophorone diisocyanate were mixed and reacted for 4 hours at a speed of 150 r / min and a temperature of 93 °C. Dimethylolpropionic acid was added and the reaction was carried out for 2.5 hours. Hydroxyethyl acrylate was added and the reaction was carried out for 1.3 hours. Deionized water was added and the temperature was lowered to 38 °C. Triethylamine was added and the reaction was carried out for 35 minutes to obtain the binder.

[0038] The molar ratio of dopamine to propylene oxide is 1:2. The ratio of intermediate 1, modified monomer, polytetrahydrofuran, isophorone diisocyanate, dimethylolpropionic acid, hydroxyethyl acrylate, deionized water and triethylamine is 10 mmol:10 mmol:20 mmol:55 mmol:1 mmol:9 mmol:60 mL:1.5 mmol. The molecular weight of polytetrahydrofuran is 2000.

[0039] The modified monomer is prepared by the following steps:

[0040] Step B1: 3,3'-dihydroxy-[1,1'-biphenyl]-4,4'-dicarboxaldehyde and ethanol were mixed evenly, and aminopropyldimethylethoxysilane was added under the conditions of 150 r / min and 45℃. The mixture was stirred and reacted for 5 h to obtain intermediate 2. Intermediate 2, acryloyl chloride, sodium hydroxide and DMF were mixed evenly and reacted under the conditions of 150 r / min and 35℃ for 4 h to obtain intermediate 3.

[0041] Step B2: Intermediate 3, diphenyldichlorosilane and deionized water are mixed and stirred for 15 min at a speed of 300 r / min and a temperature of 65℃. Then concentrated sulfuric acid and 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane are added and reacted for 5 h. The pH is then adjusted to neutral to obtain diamine-terminated polysiloxane.

[0042] Step B3: Mix diamine-terminated polysiloxane, epichlorohydrin and DMF, and react for 3-5 hours at a speed of 120 r / min, a temperature of 35℃ and a pH of 12 to obtain intermediate 4. Mix intermediate 4, sodium sulfite and DMF, and react for 7 hours at a speed of 200 r / min and a temperature of 148℃ to obtain modified monomer.

[0043] The molar ratio of 3,3'-dihydroxy-[1,1'-biphenyl]-4,4'-dicarboxaldehyde and aminopropyl dimethylethoxysilane in step B1 is 1:2, and the molar ratio of intermediate 2, acryloyl chloride and sodium hydroxide is 1:2:2.1.

[0044] The ratio of intermediate 3, diphenyldichlorosilane, deionized water and 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane described in step B2 is 1 mmol:2 mmol:20 mL:1.5 mmol.

[0045] The molar ratio of the diamine-terminated polysiloxane and epichlorohydrin in step B3 is 1:4, and the molar ratio of intermediate 4 and sodium sulfite is 1:4.1. Example

[0046] A method for preparing a UV-curable printing ink specifically includes the following steps:

[0047] Weigh the following raw materials by weight: 100 parts binder, 60 parts pigments and fillers, 5 parts talc, 2 parts dispersant, 1.5 parts photoinitiator and 0.2 parts defoamer. Mix the raw materials evenly to obtain UV-curable printing ink.

[0048] The photoinitiator is photoinitiator 369, the dispersant is YB-401, and the defoamer is TEGO FOAMEX 1488.

[0049] The binder is made by the following steps:

[0050] Dopamine, propylene oxide, and DMF were mixed and reacted for 5 hours at a rotation speed of 150 r / min, a temperature of 40 °C, and a pH of 12 to obtain intermediate 1. Intermediate 1, modified monomer, polytetrahydrofuran, and isophorone diisocyanate were mixed and reacted for 5 hours at a rotation speed of 200 r / min and a temperature of 95 °C. Dimethylolpropionic acid was added and reacted for 3 hours. Hydroxyethyl acrylate was added and reacted for 1.5 hours. Deionized water was added and the temperature was lowered to 40 °C. Triethylamine was added and reacted for 40 minutes to obtain the binder.

[0051] The molar ratio of dopamine to propylene oxide is 1:2. The ratio of intermediate 1, modified monomer, polytetrahydrofuran, isophorone diisocyanate, dimethylolpropionic acid, hydroxyethyl acrylate, deionized water and triethylamine is 10 mmol:10 mmol:20 mmol:55 mmol:1 mmol:9 mmol:60 mL:1.5 mmol. The molecular weight of polytetrahydrofuran is 2000.

[0052] The modified monomer is prepared by the following steps:

[0053] Step B1: 3,3'-dihydroxy-[1,1'-biphenyl]-4,4'-dicarboxaldehyde and ethanol were mixed evenly, and aminopropyldimethylethoxysilane was added under the conditions of 150 r / min and 50 °C. The mixture was stirred and reacted for 6 h to obtain intermediate 2. Intermediate 2, acryloyl chloride, sodium hydroxide and DMF were mixed evenly and reacted under the conditions of 200 r / min and 40 °C for 5 h to obtain intermediate 3.

[0054] Step B2: Intermediate 2, diphenyldichlorosilane and deionized water are mixed and stirred for 15 min at a speed of 300 r / min and a temperature of 70℃. Then concentrated sulfuric acid and 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane are added and reacted for 6 h. The pH is then adjusted to neutral to obtain diamine-terminated polysiloxane.

[0055] Step B3: Mix diamine-terminated polysiloxane, epichlorohydrin and DMF, and react for 5 h at a speed of 150 r / min, a temperature of 40 °C and a pH of 12 to obtain intermediate 4. Mix intermediate 4, sodium sulfite and DMF, and react for 8 h at a speed of 200 r / min and a temperature of 150 °C to obtain modified monomer.

[0056] The molar ratio of 3,3'-dihydroxy-[1,1'-biphenyl]-4,4'-dicarboxaldehyde and aminopropyl dimethylethoxysilane in step B1 is 1:2, and the molar ratio of intermediate 2, acryloyl chloride and sodium hydroxide is 1:2:2.1.

[0057] The ratio of intermediate 3, diphenyldichlorosilane, deionized water and 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane described in step B2 is 1 mmol:2 mmol:20 mL:1.5 mmol.

[0058] The molar ratio of the diamine-terminated polysiloxane and epichlorohydrin in step B3 is 1:4, and the molar ratio of intermediate 4 and sodium sulfite is 1:4.1.

[0059] Comparative Example 1

[0060] Compared with Example 1, this comparative example did not include intermediate 1, but the remaining steps were the same.

[0061] Comparative Example 2

[0062] This comparative example did not include any modified monomers compared to Example 1, but the remaining steps were the same.

[0063] Comparative Example 3

[0064] This comparative example does not include intermediate 3 compared to Example 1, but the remaining steps are the same.

[0065] The water-based inks prepared in Examples 1-3 and Comparative Examples 1-3 were tested for ink adhesion according to the standard GB / T13217.7-2009. Adhesion ≥98% was judged as Grade 0, adhesion ≥92% and <98% was judged as Grade 1, and adhesion <92% was judged as Grade 2. The ink samples were immersed in water at 100°C for 24h, 48h, and 72h respectively to observe the ink changes. The test results are shown in the table below.

[0066]

[0067] As shown in the table above, this application has excellent adhesion and water resistance.

[0068] The above description is merely an example and illustration of the concept of the present invention. Those skilled in the art can make various modifications or additions to the specific embodiments described or use similar methods to replace them, as long as they do not deviate from the concept of the invention or exceed the scope defined in the claims, they should all fall within the protection scope of the present invention.

Claims

1. A method for preparing a UV-curable printing ink, characterized in that: Specifically, the steps include the following: Weigh the following raw materials by weight: 80-100 parts binder, 40-60 parts pigments and fillers, 1-5 parts talc, 1-2 parts dispersant, 1-1.5 parts photoinitiator and 0.1-0.2 parts defoamer. Mix the raw materials evenly to obtain UV-curable printing ink. The binder is made by the following steps: Dopamine, propylene oxide, and DMF were mixed and reacted for 3-5 hours at a rotation speed of 120-150 r / min, a temperature of 30-40℃, and a pH of 11-12 to obtain intermediate 1. Intermediate 1, modified monomer, polytetrahydrofuran, and isophorone diisocyanate were mixed and reacted for 3-5 hours at a rotation speed of 150-200 r / min and a temperature of 90-95℃. Dimethylolpropionic acid was added and reacted for 2-3 hours. Hydroxyethyl acrylate was added and reacted for 1-1.5 hours. Deionized water was added and the temperature was lowered to 35-40℃. Triethylamine was added and reacted for 30-40 minutes to obtain the binder. The modified monomer is prepared by the following steps: Step B1: Mix 3,3'-dihydroxy-[1,1'-biphenyl]-4,4'-dicarboxaldehyde and ethanol evenly, stir and add aminopropyldimethylethoxysilane at 120-150 r / min and 40-50℃, and react for 4-6 h to obtain intermediate 2. Mix intermediate 2, acryloyl chloride, sodium hydroxide and DMF evenly, and react for 3-5 h at 150-200 r / min and 30-40℃ to obtain intermediate 3. Step B2: Mix intermediate 3, diphenyldichlorosilane and deionized water, and stir for 10-15 minutes at a speed of 200-300 r / min and a temperature of 60-70℃. Then add concentrated sulfuric acid and 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane and react for 4-6 hours. Adjust the pH to neutral to obtain diamine-terminated polysiloxane. Step B3: Mix diamine-terminated polysiloxane, epichlorohydrin, and DMF, and react for 3-5 hours at a rotation speed of 120-150 r / min, a temperature of 30-40℃, and a pH of 11-12 to obtain intermediate 4. Mix intermediate 4, sodium sulfite, and DMF, and react for 6-8 hours at a rotation speed of 150-200 r / min and a temperature of 145-150℃ to obtain the modified monomer.

2. The method for preparing a UV-curable printing ink according to claim 1, characterized in that: The molar ratio of dopamine to propylene oxide is 1:2, and the ratio of intermediate 1, modified monomer, polytetrahydrofuran, isophorone diisocyanate, dimethylolpropionic acid, hydroxyethyl acrylate, deionized water and triethylamine is 10 mmol:10 mmol:20 mmol:55 mmol:1 mmol:9 mmol:60 mL:1.5 mmol.

3. The method for preparing a UV-curable printing ink according to claim 1, characterized in that: The molar ratio of 3,3'-dihydroxy-[1,1'-biphenyl]-4,4'-dicarboxaldehyde and aminopropyl dimethylethoxysilane in step B1 is 1:2, and the molar ratio of intermediate 2, acryloyl chloride and sodium hydroxide is 1:2:2.

1.

4. The method for preparing a UV-curable printing ink according to claim 1, characterized in that: The ratio of intermediate 3, diphenyldichlorosilane, deionized water and 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane described in step B2 is 1 mmol:2 mmol:20 mL:1.5 mmol.

5. The method for preparing a UV-curable printing ink according to claim 1, characterized in that: The molar ratio of the diamine-terminated polysiloxane and epichlorohydrin in step B3 is 1:4, and the molar ratio of intermediate 4 and sodium sulfite is 1:4.

1.

6. A UV-curable printing ink, characterized in that: It is prepared according to any one of the preparation methods described in claims 1-5.

Images