CN107141880B - LED (light-emitting diode) curing UV (ultraviolet) offset printing ink as well as preparation method and application thereof - Google Patents

Abstract

The invention discloses an LED curing UV offset printing ink which comprises the following components: modified polyester acrylate; dipentaerythritol penta/hexaacrylate; ethoxylated trimethylolpropane trimethacrylate; 1, 6-hexanediol diacrylate, a photoinitiator; a pigment; a filler; 1-2% of an auxiliary agent. The solvent-free environment-friendly LED curing UV offset printing ink overcomes the defects of the prior art, has good drying property, strong adhesive force and good fluidity after curing, and can meet the requirements of decorative printing ink on PVC films of various common IC cards.

Description

LED (light-emitting diode) curing UV (ultraviolet) offset printing ink as well as preparation method and application thereof

Technical Field

The invention relates to an LED (light-emitting diode) curing UV offset printing ink, and also relates to a preparation method and application thereof.

Background

Offset printing ink on PVC film materials such as credit cards, IC cards and the like on the market is mainly solvent type, the components of the offset printing ink contain a large amount of organic solvents, and the organic solvents are volatilized and discharged in the air during construction, so that the offset printing ink pollutes the environment and is not beneficial to environmental protection, and particularly, benzene solvents are not beneficial to the health of operators. There are patents reporting UV offset inks, such as my application publication number: CN106046923A application no: 2016106411355A PVC material is scalded with UV offset ink. However, the UV offset printing ink is cured by the traditional UV mercury lamp, and still has the defects of high energy consumption, high temperature during curing, short service life of a lamp tube, only about 1000 hours, high irradiation distance between a printed product and the UV mercury lamp and prevention of deformation of a printed material with high temperature, and the need of an air cooling system for heat dissipation.

The UV mercury lamp emits UV light only 30%, while infrared light 40%, 10% visible light, 10% heat conduction, 10% electrode heat radiation. Only 30% uv light is useful.

Therefore, a novel curing mode which is energy-saving, low in temperature and low in heat during UV curing is required, the curing heat of the LED type UV lamp is low, the temperature rise of the temperature within the range of 5 ℃ can be guaranteed only by one water cooling system, the wavelength is 365-395 nanometers, the service life of the lamp tube is long, and the service life is 20000-30000 hours or so. Conventional inks on the market, however, require higher curing energy and do not adapt well to LED-type UV lamps. Therefore, a UV ink with low curing energy needs to be developed to meet the requirement.

Disclosure of Invention

The invention aims to solve the technical problem of providing the solvent-free environment-friendly LED curing UV offset printing ink which overcomes the defects of the prior art, has low curing energy, better adapts to an LED type UV lamp, has good drying property, strong adhesive force and good fluidity after curing and can meet the requirements of decorative printing ink.

The technical problem to be solved by the invention is realized by the following technical scheme:

an LED curing UV offset printing ink comprises the following components in percentage by weight:

15-25% of modified polyester acrylate;

15-25% of dipentaerythritol penta/hexaacrylate;

15-25% of ethoxylated trimethylolpropane trimethacrylate;

5-15% of 1, 6-hexanediol diacrylate;

10-16% of a photoinitiator;

15-20% of pigment;

3-5% of a filler;

1-2% of an auxiliary agent.

The dipentaerythritol penta/hexaacrylate is also called dipentaerythritol penta/hexaacrylate, and is abbreviated as DPHA in English.

Further, the ethoxylated trimethylolpropane trimethacrylate is EM2382 of taiwan chang chemical industry (guangdong) limited.

Further, the modified polyester acrylate is poly (phthalic acid diacrylate), and further, the difunctional acrylate is 6327-100 of Taiwan Changxing chemical industry (Guangdong) Co.

Further, the DPHA is a hexa-functional monomer, and further, the DPHA is EM265 of Changxing chemical industry (Guangdong) Co., Ltd, Taiwan.

Further, the photoinitiator consists of the following components in percentage by weight:

37.5-40% of 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide;

2-dimethylamino-2-benzyl-1- [ -4 (4-morpholinyl) phenyl ] -1-butanone 30-31.25%;

30-31.25% of 2, 4-diethyl thioxanthone, and simultaneously adopts three photoinitiators, and the synergistic effect of the three photoinitiators can ensure that the UV crosslinking process is rapid and efficient, is prevented from drying, and is suitable for high-speed printing speed of 100-120 m/min offset printing.

The pigment is any one of permanent red, permanent yellow and phthalocyanine blue, the permanent red is Switzerland organic pigment permanent red F5RK and pigment red No. 170, the permanent yellow is Switzerland organic pigment permanent yellow HR and pigment yellow No. 83, and the phthalocyanine blue is BASF K7090 BASF phthalocyanine blue and pigment blue No. 15: 3.

Further, the filler is calcium carbonate. The addition of the calcium carbonate improves the covering power of the printing ink and ensures better coloring power of the printing ink during printing.

Furthermore, the auxiliary agent comprises an organic silicon defoaming agent and an organic silicon leveling agent, and the organic silicon leveling agent and the organic silicon defoaming agent can improve the leveling property of a printed matter and prevent the defects of easy foaming and the like during high-speed printing.

The preparation method of the LED curing UV offset printing ink comprises the following steps:

s1, adding pigment and filler into ethoxylated trimethylolpropane trimethacrylate and 1, 6-hexanediol diacrylate at a stirring speed of 800-1000 rpm, increasing the rotation speed to 1600-1800 rpm, stirring for 30-50 minutes until the mixture is uniformly dispersed, cooling to normal temperature, and grinding the mixture by using a three-roll machine until the fineness is less than or equal to 10 microns to obtain a semi-finished product;

s2, adding the modified polyester acrylate, the DPHA and the auxiliary agent into the semi-finished product, uniformly mixing, wherein the stirring speed is 800-1000 revolutions per minute, and stirring for 5-15 minutes;

and S3, adding a photoinitiator, controlling the stirring speed to be 800-1000 rpm, uniformly stirring, and filtering and packaging by using a 150-mesh filter screen.

And the application of the LED curing UV offset printing ink on the PVC film of the conventional IC card.

The invention has the following beneficial effects:

the invention selects the modified polyester acrylate and the DPHA as main body resin, can endow the LED curing UV offset printing ink with better adhesive force and lower energy required by curing, and is better suitable for LED 365-395 type UV lamps. The output power of the LED 365-395 type UV lamp is 20-30W, the distance between a light source and a workpiece is 12-15 mm, and the energy reaching the surface of the workpiece is controlled to be 40 mJoule/CM²The ink can be completely cured at the normal offset printing speed of 100 m/min, so that a higher curing speed is achieved.

The invention also selects 1, 6-hexanediol diacrylate monomer with difunctional, which can improve the adhesive force of the printing ink to PVC material; the curing speed [ h1] can be improved by selecting a trifunctional monomer for ethoxylation of trimethylolpropane trimethacrylate, and simultaneously, the crosslinking density is provided, so that the printing ink has higher flexibility and scratch resistance; the 1, 6-hexanediol diacrylate and the ethoxylated trimethylolpropane trimethacrylate also have dilutability, can reduce the viscosity of the printing ink, and can completely meet the UV offset printing condition without adding organic solvents, and because the whole formula does not contain organic solvents such as ketones, benzenes, esters, alcohols and the like, the emission of the organic solvents does not exist in the construction process, thereby meeting the requirement of environmental protection; in addition, the 1, 6-hexanediol diacrylate and the ethoxylated trimethylolpropane trimethacrylate can enable the printing ink to generate a net structure in the UV illumination process, so that the printing ink can be firmly attached to the PVC material, and the adhesive force of the printing ink to the PVC material is improved.

Detailed Description

The present invention will be described in detail with reference to examples, which are only preferred embodiments of the present invention and are not intended to limit the present invention.

The following examples and comparative examples used the following raw material types:

the poly (phthalic acid) diacrylate is 6327-100 of Changxing chemical industry (Guangdong) Co., Ltd., Taiwan;

hexafunctional DPHA is EM265 from changxing chemical industry (guangdong) ltd, taiwan;

ethoxylated trimethylolpropane trimethacrylate is EM2382 from chang chemical industry (guangdong) ltd, taiwan;

other ones not specifically designated are common commercial products.

Example 1

An LED curing UV offset printing ink comprises the following components in parts by weight:

ethoxylated trimethylolpropane trimethacrylate 25 kg

25 kg of poly (diacrylate) phthalate

15 kg of hexafunctional DPHA

5 kg of 1, 6-hexanediol diacrylate

Phthalein blue 15 kg

Calcium carbonate 3 kg

Organic silicon flatting agent 1 kg

1 kg of organic silicon defoamer

4 kg of 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, 3 kg of 2-dimethylamino-2-benzyl-1- [ -4 (4-morpholinyl) phenyl ] -1-butanone, and 3 kg of 2, 4-diethylthioxanthone.

The preparation method of the LED curing UV offset printing ink comprises the following steps:

s1, adding 25 kg of ethoxylated trimethylolpropane trimethacrylate and 5 kg of 1, 6-hexanediol diacrylate, adding 15 kg of phthalocyanine blue and 3 kg of calcium carbonate at a stirring speed of 800 revolutions per minute, increasing the rotating speed to 1800 revolutions per minute, stirring for 30 minutes until the mixture is uniformly dispersed, cooling to normal temperature, and grinding the mixture by using a three-roll machine until the fineness is less than or equal to 10 microns to obtain a semi-finished product;

s2, adding 25 kg of poly (diacrylate phthalate), 15 kg of hexa-functional DPHA, 1 kg of organic silicon flatting agent and 1 kg of organic silicon defoamer into the semi-finished product, uniformly mixing at a stirring speed of 800 revolutions per minute for 15 minutes;

s3, adding 4 kg of initiator 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, 3 kg of 2-dimethylamino-2-benzyl-1- [ -4 (4-morpholinyl) phenyl ] -1-butanone and 3 kg of 2, 4-diethylthioxanthone, controlling the stirring speed to be 800 revolutions per minute, stirring for 15 minutes, filtering and packaging by using a 150-mesh filter screen after uniformly stirring.

Example 2

An LED curing UV offset printing ink comprises the following components in parts by weight:

18 kg of ethoxylated trimethylolpropane trimethacrylate

18 kg of poly (diacrylate) phthalate

15 kg of hexafunctional DPHA

15 kg of 1, 6-hexanediol diacrylate

Permanent red 17 kg

Calcium carbonate 4 kg

0.5 kg of organic silicon flatting agent

1 kg of organic silicon defoamer

4.5 kg of 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, 3.5 kg of 2-dimethylamino-2-benzyl-1- [ -4 (4-morpholinyl) phenyl ] -1-butanone, and 3.5 kg of 2, 4-diethylthioxanthone.

The preparation method of the LED curing UV offset printing ink comprises the following steps:

s1, adding 18 kg of ethoxylated trimethylolpropane trimethacrylate and 15 kg of 1, 6-hexanediol diacrylate, adding 17 kg of permanent red and 4 kg of calcium carbonate at the stirring speed of 900 revolutions per minute, increasing the rotating speed to 1700 revolutions per minute, stirring for 40 minutes until the mixture is uniformly dispersed, cooling to normal temperature, and grinding the mixture by using a three-roll machine until the fineness is less than or equal to 10 microns to obtain a semi-finished product;

s2, adding 18 kg of poly (diacrylate phthalate), 15 kg of hexa-functional DPHA, 0.5 kg of organic silicon flatting agent and 1 kg of organic silicon defoamer into the semi-finished product, uniformly mixing at the stirring speed of 900 revolutions per minute for 10 minutes;

s3, adding 4.5 kg of initiator 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, 3.5 kg of 2-dimethylamino-2-benzyl-1- [ -4 (4-morpholinyl) phenyl ] -1-butanone and 3.5 kg of 2, 4-diethylthioxanthone, controlling the stirring speed to be 900 revolutions per minute, stirring for 10 minutes, filtering and packaging by using a 150-mesh filter screen after uniform stirring.

Example 3

An LED curing UV offset printing ink comprises the following components in parts by weight:

ethoxylated trimethylolpropane trimethacrylate 15 kg

15 kg of poly (diacrylate) phthalate

20 kg of hexafunctional DPHA

12 kg of 1, 6-hexanediol diacrylate

Permanent red 20 kg

Calcium carbonate 3 kg

0.5 kg of organic silicon flatting agent

0.5 kg of organic silicon defoamer

6 kg of 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, 3 kg of 2-dimethylamino-2-benzyl-1- [ -4 (4-morpholinyl) phenyl ] -1-butanone, and 5 kg of 2, 4-diethylthioxanthone.

The preparation method of the LED curing UV offset printing ink comprises the following steps:

s1, adding 15 kg of ethoxylated trimethylolpropane trimethacrylate and 12 kg of 1, 6-hexanediol diacrylate, adding 20 kg of permanent yellow and 3 kg of calcium carbonate at the rotating speed of 1000 r/min, increasing the rotating speed to 1600 r/min, stirring for 50 min until the mixture is uniformly dispersed, cooling to normal temperature, and grinding the mixture by using a three-roll machine until the fineness is less than or equal to 10 microns to obtain a semi-finished product;

s2, adding 15 kg of poly (diacrylate phthalate), 20 kg of hexa-functional DPHA, 0.5 kg of organic silicon flatting agent and 0.5 kg of organic silicon defoamer into the semi-finished product, uniformly mixing at a stirring speed of 1000 revolutions per minute for 5 minutes;

s3, adding 6 kg of initiator 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, 3 kg of 2-dimethylamino-2-benzyl-1- [ -4 (4-morpholinyl) phenyl ] -1-butanone and 5 kg of 2, 4-diethylthioxanthone, controlling the stirring speed to be 1000 revolutions per minute, stirring for 5 minutes, filtering and packaging by using a 150-mesh filter screen after uniformly stirring.

Preparation of comparative example 1:

s1, adding 25 kg of trimethylolpropane trimethylpropionate [ EM231 of Taiwan Changxing chemical industry (Guangdong) Co., Ltd ], adding 15 kg of phthalocyanine blue and 5 kg of calcium carbonate into 5 kg of 1, 6-hexanediol diacrylate at a stirring speed of 800 revolutions per minute, increasing the rotating speed to 1800 revolutions per minute, stirring for 30 minutes until the mixture is uniformly dispersed, cooling to normal temperature, and grinding by a three-roller machine until the fineness is less than or equal to 10 microns to obtain a semi-finished product;

s2, adding 25 kg of poly (diacrylate phthalate), 10 kg of hexa-functional DPHA, 1 kg of organic silicon flatting agent and 1 kg of organic silicon defoamer into the semi-finished product, uniformly mixing at a stirring speed of 800 revolutions per minute for 15 minutes;

s3, adding 4 kg of initiator 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, 5 kg of 2-dimethylamino-2-benzyl-1- [ -4 (4-morpholinyl) phenyl ] -1-butanone and 3 kg of 2, 4-diethylthioxanthone, controlling the stirring speed to be 800 revolutions per minute, stirring for 15 minutes, filtering and packaging by using a 150-mesh filter screen after uniformly stirring.

Preparation of comparative example 2:

s1, adding 18 kg of ethoxylated trimethylolpropane trimethacrylate and 15 kg of 1, 6-hexanediol diacrylate, adding 18 kg of permanent red and 4 kg of calcium carbonate at the stirring speed of 900 revolutions per minute, increasing the rotating speed to 1700 revolutions per minute, stirring for 40 minutes until the mixture is uniformly dispersed, cooling to normal temperature, and grinding the mixture by using a three-roll machine until the fineness is less than or equal to 10 microns to obtain a semi-finished product;

s2, adding 18 kg of poly (diacrylate phthalate), 13 kg of hexa-functional DPHA, 0.5 kg of organic silicon flatting agent and 1 kg of organic silicon defoamer into the semi-finished product, uniformly mixing at the stirring speed of 900 revolutions per minute for 10 minutes;

s3, adding 4.5 kg of initiator 1-hydroxycyclohexyl phenyl ketone, 4 kg of 2-dimethylamino-2-benzyl-1- [ -4 (4-morpholinyl) phenyl ] -1-butanone and 4 kg of 2, 4-diethyl thioxanthone, controlling the stirring speed to be 900 revolutions per minute, stirring for 10 minutes, filtering and packaging by using a 150-mesh filter screen after uniformly stirring.

Preparation of comparative example 3:

s1, adding 15 kg of ethoxylated trimethylolpropane trimethacrylate and 12 kg of 1, 6-hexanediol diacrylate, adding 20 kg of permanent yellow and 3 kg of calcium carbonate at the rotating speed of 1000 r/min, increasing the rotating speed to 1600 r/min, stirring for 50 min until the mixture is uniformly dispersed, cooling to normal temperature, and grinding the mixture by using a three-roll machine until the fineness is less than or equal to 10 microns to obtain a semi-finished product;

s2, adding 15 kg of epoxy acrylate [ 621A-80 of Taiwan Changxing chemical industry (Guangdong) Co., Ltd ], 20 kg of hexa-functional DPHA, 0.5 kg of an organic silicon leveling agent and 0.5 kg of an organic silicon defoaming agent into the semi-finished product, uniformly mixing at the stirring speed of 1000 revolutions per minute for 5 minutes;

s3, adding 6 kg of initiator 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, 3 kg of 2-dimethylamino-2-benzyl-1- [ -4 (4-morpholinyl) phenyl ] -1-butanone and 5 kg of 2, 4-diethylthioxanthone, controlling the stirring speed to be 1000 revolutions per minute, stirring for 5 minutes, filtering and packaging by using a 150-mesh filter screen after uniformly stirring.

The inks prepared in examples and comparative examples were blue or red or yellow, and the prepared UV ink was applied to a PVC material, UV-cured, and the performance of the ink was examined, and the results of the performance test are shown in table 1.

The performance detection method comprises the following steps:

adhesion force: the surface of the coating film is tested by a Baige method according to the national standard GB 9286-1988.

Tinting strength: testing according to the national standard GB/T14624.2-2008;

fineness: testing according to the national standard GB/T13217.3-2008;

viscosity: testing with a rotational viscometer;

gloss: testing according to GB/T13217.2-2009;

bending: testing according to a paint film flexibility testing method in GB T1731 + 1993;

water resistance: testing according to a method A of measuring water resistance of a paint film in GB T1733 + 1993;

ethanol resistance: rubbing the mixture with 99.6% alcohol to and fro once with a force of 500 g/square centimeter, wherein the stroke is 2-3 centimeters;

wear resistance: testing by RCA175 gram force friction with a paper tape tester;

solid content: testing according to the national standard GB/T1725-2007;

TABLE 1 test results of LED curing UV offset printing inks prepared in examples and comparative examples

Detecting items

Example 1

Example 2

Example 3

Comparative example 1

Comparative example 2

Comparative example 3

Adhesion/grade

0

0

0

2

2

3

Coloring power

100%

100%

100%

100%

100%

100%

Fineness of fineness

<10um

<10um

<10um

<10um

<10um

<10um

Viscosity (CP/25 ℃ C.)

1200

1380

1500

1300

1450

1600

Gloss/60 degree

93

95

91

95

91

99

Bend (mm)

1

1

1

3

1

3

Water-resistant (hours)

≥48

≥48

≥48

≥48

<24

≥48

Ethanol resistance (times)

≥100

≥100

≥100

≥100

<50

≥100

Wear-resisting eraser (Ring)

≥100

≥100

≥100

≥100

<50

≥100

Solid content

≥98

≥98

≥98

≥98

≥98

≥98

The above-mentioned embodiments only express the embodiments of the present invention, and the description is more specific and detailed, but not understood as the limitation of the patent scope of the present invention, but all the technical solutions obtained by using the equivalent substitution or the equivalent transformation should be included in the protection scope of the claims of the present invention.

Claims (7)

1. The LED curing UV offset printing ink is characterized by comprising the following components in percentage by weight:

15-25% of modified polyester acrylate;

15-25% of dipentaerythritol penta/hexaacrylate;

15-25% of ethoxylated trimethylolpropane trimethacrylate;

5-15% of 1, 6-hexanediol diacrylate;

10-16% of a photoinitiator;

15-20% of pigment;

3-5% of a filler;

1-2% of an auxiliary agent;

wherein the modified polyester acrylate is poly phthalic acid diacrylate;

the photoinitiator consists of the following components in percentage by weight:

37.5-40% of 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide;

2-dimethylamino-2-benzyl-1- [ -4 (4-morpholinyl) phenyl ] -1-butanone 30-31.25%;

30-31.25% of 2, 4-diethyl thioxanthone.

2. The LED cured UV flexographic ink according to claim 1, wherein said dipentaerythritol penta/hexaacrylate is dipentaerythritol hexaacrylate.

3. The LED curing UV offset printing ink according to claim 1, wherein the pigment is any one of permanent red, permanent yellow and phthalocyanine blue.

4. The LED curing UV flexographic ink according to claim 1, characterized in that said filler is calcium carbonate.

5. The LED-cured UV offset printing ink according to claim 1, wherein the auxiliary agent comprises a silicone defoamer and a silicone leveling agent.

6. A method for preparing the LED curing UV offset printing ink according to any one of claims 1 to 5, which comprises the following steps:

s1, adding pigment and filler into ethoxylated trimethylolpropane trimethacrylate and 1, 6-hexanediol diacrylate at a stirring speed of 800-1000 rpm, increasing the rotation speed to 1600-1800 rpm, stirring for 30-50 minutes until the mixture is uniformly dispersed, cooling to normal temperature, and grinding the mixture by using a three-roll machine until the fineness is less than or equal to 10 microns to obtain a semi-finished product;

s2, adding the modified polyester acrylate, dipentaerythritol penta/hexaacrylate and the auxiliary agent into the semi-finished product, uniformly mixing, stirring at the speed of 800-1000 rpm, and stirring for 5-15 minutes;

and S3, adding a photoinitiator, controlling the stirring speed to be 800-1000 rpm, uniformly stirring, and filtering and packaging by using a 150-mesh filter screen.

7. Use of the LED-cured UV offset printing ink according to any of claims 1 to 5 on PVC films of conventional IC cards.