CN114231081B

CN114231081B - Ultra-high aging-resistant UV (ultraviolet) ink and preparation method thereof

Info

Publication number: CN114231081B
Application number: CN202210060737.7A
Authority: CN
Inventors: 陈宏伟; 李亮; 袁旭华; 王靖
Original assignee: Shenzhen Li Li Zhuo Hong Technology Co ltd
Current assignee: Shenzhen Li Li Zhuo Hong Technology Co ltd
Priority date: 2022-01-19
Filing date: 2022-01-19
Publication date: 2023-03-24
Anticipated expiration: 2042-01-19
Also published as: CN114231081A

Abstract

The invention relates to ultra-high aging-resistant UV ink and a preparation method thereof, wherein the ultra-high aging-resistant UV ink comprises the following components in parts by weight: 50-70 parts of a multifunctional polyurethane acrylate mixture, 20-30 parts of a composite reactive diluent, 2-5 parts of a photoinitiator, 2-5 parts of an auxiliary agent, 2-10 parts of a filler and 10-15 parts of a pigment. Compared with the prior art, the UV printing ink disclosed by the invention solves the problem of poor ageing resistance of the existing UV printing ink, and is safe and environment-friendly, simple in preparation method and good in process performance.

Description

Ultra-high aging-resistant UV (ultraviolet) ink and preparation method thereof

Technical Field

The invention relates to the field of ultraviolet curing ink, in particular to ultra-high aging-resistant UV ink and a preparation method thereof.

Background

UV ink (ultraviolet curing ink) is a kind of ink which is irradiated by ultraviolet light with a certain wavelength to make a linking material in the ink generate a cross-linking reaction and quickly change from a liquid state to a solid state to finish curing.

In the curing process, the UV printing ink has a composition structure generated by high-density crosslinking reaction of polymers, has the characteristics of high toughness, pollution resistance, abrasion resistance and solvent resistance, and is excellent in visual effect of printed products, bright in color and bright. The UV ink is not only suitable for printing common printing stocks, but also suitable for printing non-absorbent materials such as metallized paper, synthetic paper, plastic films and the like. The ink is a novel ink which attracts the most attention at present due to the advantages of environmental protection, energy conservation, high efficiency and the like.

For example, chinese patent application with publication No. CN104086701A discloses an alkali-soluble epoxy acrylic acid UV resin with high temperature resistance and yellowing resistance, wherein alicyclic epoxy acrylic acid ester monomer, glycidyl methacrylate, hydroxyethyl methacrylate or hydroxypropyl methacrylate are subjected to polymerization reaction to prepare alicyclic epoxy acrylic acid copolymer, acrylic acid is used for reacting with epoxy group to introduce double bond to enable the alicyclic epoxy acrylic acid copolymer to have photosensitive activity, and acid anhydride is used for reacting with hydroxyl group to prepare alkali-soluble epoxy acrylic acid UV resin with carboxyl group and high temperature resistance and yellowing resistance, so that the ultraviolet UV resin has the advantages of strong adhesion, chemical corrosion resistance and good pigment wettability. The modification degree is adjusted by controlling the addition amount of the acid anhydride, so that the epoxy acrylic UV resin with alkali solubility, high temperature resistance and yellowing resistance is prepared. However, the epoxy acrylic UV resin prepared in the way generally has the problems of high viscosity, brittle cured film, poor flexibility and poor aging resistance. Therefore, the viscosity reduction, toughening modification and aging performance improvement of the modified polypropylene are always the hot points of research.

Disclosure of Invention

The invention aims to solve the problem that the UV ink in the prior art is poor in ageing resistance, and provides the safe, environment-friendly and ultrahigh ageing-resistant UV ink and the preparation method thereof.

The purpose of the invention can be realized by the following technical scheme:

the invention aims to provide ultra-high aging resistant UV ink which comprises the following components in parts by weight:

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preferably, the multifunctional urethane acrylate mixture has an average functionality of 3 to 5, a molecular weight of 500 to 1200g/mol, and a double bond density of 2.5 to 6val/kg.

Preferably, the multifunctional urethane acrylate mixture comprises at least one multifunctional urethane acrylate having a molecular weight of 1000g/mol or more and a double bond density of 4.5val/kg or less (exemplified by Desmolux U100 and Desmolux U400), and at least one multifunctional urethane acrylate having a molecular weight of 1000g/mol or less and a double bond density of 4.5val/kg or more (exemplified by Roskydal UA VP LS 2265).

More preferably, the multifunctional urethane acrylate mixture comprises at least two multifunctional urethane acrylates having a molecular weight of 1000g/mol or more and a double bond density of 4.5val/kg or less, and at least one multifunctional urethane acrylate having a molecular weight of 1000g/mol or less and a double bond density of 4.5val/kg or more.

More preferably, the mass ratio of the multifunctional urethane acrylate having a molecular weight of 1000g/mol or more and a double bond density of 4.5val/kg or less to the multifunctional urethane acrylate having a molecular weight of 1000g/mol or less and a double bond density of 4.5val/kg or more is 10.

Preferably, the composite active diluent is a mixture consisting of beta-hydroxyethyl methacrylate (HEMA), 1, 6-hexanediol diacrylate (HDDA) and dipentaerythritol pentaacrylate (DPEPA) according to a mass ratio of 1.5-2.5.

Further preferably, the photoinitiator is selected from at least one of 2-hydroxy-2-methyl-1-phenylpropanone (1173) and 1-hydroxycyclohexyl benzophenone (184).

Preferably, the adjuvant comprises at least one of a defoamer and an antioxidant.

Preferably, the pigment is a commercially available toner.

Preferably, the filler comprises nano silica.

The invention also aims to provide a preparation method of the UV ink with ultrahigh aging resistance, which comprises the following steps:

s1: weighing the raw materials in parts by weight for later use;

s2: adding a photoinitiator and a composite reactive diluent into the multifunctional polyurethane acrylate mixture, and stirring until the photoinitiator and the composite reactive diluent are dissolved;

s3: adding the pigment and the filler into the mixture obtained in the step S2, and stirring and dispersing uniformly;

s4: and slowly adding the auxiliary agent, and stirring to obtain the ultra-high aging-resistant UV ink.

Preferably, in step S2, the stirring speed is 1200-2000rpm and the temperature is 50-65 ℃.

Preferably, in step S3, the stirring speed is 800-1000rpm, the stirring process is naturally cooled, and the stirring time is 0.5-1h.

Preferably, in step S4, the stirring speed is 60-80rpm, the temperature is normal temperature, and the time is 2-4h.

Compared with the prior art, the invention has the following beneficial effects:

(1) The UV ink disclosed by the invention has good aging resistance, and aging phenomena such as color change, pulverization, cracking, foaming, falling and the like are not easy to occur.

(2) The UV ink disclosed by the invention has the characteristics of safety and environmental friendliness, the curing time of the selected composite reactive diluent is only slightly reduced compared with that of the selected composite reactive diluent when DPEPA is used alone, and the dilution performance, the toughness and the tensile property are obviously improved, so that the anti-aging performance of the UV ink is facilitated.

(3) The prepolymer and the composite active diluent are combined, and no additional leveling agent is added, so that the process is simpler.

Detailed Description

The disclosure may be understood more readily by reference to the following detailed description of preferred embodiments of the invention and the examples included therein. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.

As used herein, the term "consisting of 8230; preparation" is synonymous with "comprising". The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus. When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a range of values is described herein, unless otherwise specified, the range is intended to include the endpoints thereof, and all integers and fractions within the range.

The singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. "optional" or "any" means that the subsequently described event or events may or may not occur, and that the description includes instances where the event occurs and instances where it does not.

Approximating language, as used herein throughout the specification and claims, is intended to modify a quantity, such that the invention is not limited to the specific quantity, but includes portions that are literally received for modification without substantial change in the basic function to which the invention is related. Accordingly, the use of "about" to modify a numerical value means that the invention is not limited to the precise value. In some instances, the approximating language may correspond to the precision of an instrument for measuring the value. In the present description and claims, range limitations may be combined and/or interchanged, including all sub-ranges contained therein if not otherwise stated.

In addition, the indefinite articles "a" and "an" preceding an element or component of the invention are not intended to limit the number requirement (i.e., the number of occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component also includes the plural unless the stated number clearly indicates that the singular form is intended.

In order to solve the technical problems in the prior art, one of the technical schemes of the invention provides the ultra-high aging resistant UV ink which comprises the following components in parts by weight:

in some embodiments, the multifunctional urethane acrylate mixture has an average functionality of 3 to 5, a molecular weight of 500 to 1200g/mol, and a double bond density of 2.5 to 6val/kg. By selecting prepolymer urethane acrylate with proper functionality, molecular weight and double bond density, the viscosity, curing speed, tensile strength, flexibility, hardness, yellowing resistance, chemical resistance and other properties of the UV ink can be adjusted.

In some embodiments, the multifunctional urethane acrylate is selected from at least two of commercially available Roskydal UA VP LS2265 (hereinafter LS 2265), desmolux U100 (hereinafter U100), and Desmolux U400 (hereinafter U400).

In some embodiments, the multifunctional urethane acrylate mixture is obtained by mixing a multifunctional urethane acrylate with a molecular weight of 1000g/mol or more and a double bond density of 4.5val/kg or less with a multifunctional urethane acrylate with a molecular weight of 1000g/mol or less and a double bond density of 4.5val/kg or more in a mass ratio of 10.

In some embodiments, the complex reactive diluent is a mixture of beta-hydroxyethyl methacrylate (HEMA), 1, 6-hexanediol diacrylate (HDDA), and dipentaerythritol pentaacrylate (DPEPA) in a mass ratio of 1.5 to 2.5.

The composite active diluent is a mixture consisting of beta-hydroxyethyl methacrylate (HEMA), 1, 6-hexanediol diacrylate (HDDA) and dipentaerythritol pentaacrylate (DPEPA) according to the mass ratio of 1.5-2.5. Wherein:

HEMA has moderate slow reactivity, but significantly lower volatility, and thus is less toxic, less odorous, and less expensive. HDDA is a bifunctional reactive diluent with low viscosity, strong dilutability and excellent adhesion. The dissolving capacity is good. DPEPA has high viscosity, extremely low odor and skin irritation, extremely high reaction activity, high crosslinking degree of a cured film, good scratch resistance and good chemical resistance, and one hydroxyl contained in a molecule is beneficial to increasing the wettability of the cured film.

The multifunctional polyurethane acrylate with the molecular weight of more than 1000g/mol and the double bond density of less than 4.5val/kg has the characteristics of good toughness, high hardness, good wear resistance, yellowing resistance and good chemical resistance, and as the main component of the prepolymer, the multifunctional polyurethane acrylate with the molecular weight of less than 1000g/mol and the double bond density of more than 4.5val/kg has the characteristics of low viscosity, high solid content, good leveling property, high tensile strength, good yellowing resistance, chemical resistance and wear resistance, and as the auxiliary component of the prepolymer, the multifunctional polyurethane acrylate endows the UV ink with good aging resistance, and is not easy to generate aging phenomena such as discoloration, pulverization, cracking, foaming, falling off and the like.

The invention compounds the reactive diluent DPEPA with HEMA and HDDA, so as to obtain the composite reactive diluent which has slightly reduced curing time compared with the single use of the DPEPA, but has obviously improved diluting performance, toughness and tensile property, thereby avoiding the foaming, cracking and peeling of the UV ink.

The composite reactive diluent has good diluting performance, and the multifunctional polyurethane acrylate material has good leveling performance and proper viscosity, so that the UV ink does not need to be added with an additional leveling agent and an additional defoaming agent, and the technological performance of the UV ink is improved. In addition, the composite active diluent of the invention adopts substances with small irritation, is more environment-friendly and safer,

in some embodiments, the photoinitiator includes at least one of 2-hydroxy-2-methyl-1-phenylpropanone (1173) and 1-hydroxycyclohexyl benzophenone (184). The photoinitiator is preferably compounded by 2-hydroxy-2-methyl-1-phenyl acetone and 1-hydroxycyclohexyl benzophenone, and the photoinitiator has different absorption wave numbers, so that the absorption wave number range of an initiation system is widened, an ultraviolet light source is more effectively utilized, and the photoinitiation efficiency can be improved to a certain extent. Is beneficial to shortening the light curing time.

In some embodiments, the adjuvant comprises at least one of a defoamer and an antioxidant.

In some embodiments, the preferred anti-foaming agent may be a hume 6800.

In some embodiments, the antioxidant is EDAB. EDAB can eliminate peroxide free radical generated in the ultraviolet light curing process, generate new free radical and is a hydrogen donor.

Preferably, the pigment is a commercially available toner, for example a toner having a crine light fastness of grade 7-8.

Preferably, the filler comprises nanosilica. The nanosilica may be a fumed silica. Can improve the wear resistance and surface moistening property and promote the adhesive force.

The second technical scheme of the invention provides a preparation method of the ultra-high aging-resistant UV ink, which comprises the following steps:

s1: weighing the raw materials in parts by weight for later use;

s2: adding a photoinitiator and a composite reactive diluent into the multifunctional polyurethane acrylate, and stirring until the photoinitiator and the composite reactive diluent are dissolved;

s3: adding the pigment and the filler into the mixture obtained in the step S2, and uniformly stirring and dispersing;

In some embodiments, the stirring rate in step S2 is 1200-2000rpm and the temperature is 50-65 ℃. The higher temperature and rotation speed makes the dissolution process faster.

In some embodiments, in step S3, the stirring speed is 800-1000rpm, the stirring process is naturally cooled, and the stirring time is 0.5-1h. And (3) dispersing the pigment and the filler under the condition of lower viscosity by utilizing the residual temperature in the previous step, so that the pigment and the filler are dispersed in the system more uniformly.

In some embodiments, in step S4, the stirring speed is 60-80rpm, the temperature is normal temperature, and the time is 2-4h.

The present invention will be described in detail with reference to specific examples.

Example 1

The ultra-high aging-resistant UV ink comprises the following components in parts by weight: LS2265 parts, U100 parts, HEMA5 parts, HDDA 10 parts, DPEPA 10 parts, photoinitiator 1173.5 parts, photoinitiator 184.5 parts, defoaming agent 1 part, antioxidant 1 part, filler 5 parts and toner 12 parts.

Example 2

Example 3

Example 4

The ultra-high aging-resistant UV ink comprises the following components in parts by weight: LS2265 parts, U100 parts, HEMA5 parts, HDDA 10 parts, DPEPA 10 parts, photoinitiator 184.5 parts, defoaming agent 1 part, antioxidant 1 part, filler 5 parts and toner 12 parts.

Example 5

The ultra-high aging-resistant UV ink comprises the following components in parts by weight: LS2265 parts, U400 parts, HEMA5 parts, HDDA 7.5 parts, DPEPA 7.5 parts, photoinitiator 1173 parts, photoinitiator 184 parts, defoaming agent 1.5 parts, antioxidant 2 parts, filler 3 parts and toner 13 parts.

Example 6

The ultra-high aging-resistant UV ink comprises the following components in parts by weight: LS2265 parts, U400 35 parts, HEMA5 parts, HDDA 12.5 parts, DPEPA 12.5 parts, photoinitiator 1172 parts, photoinitiator 184 parts, defoaming agent 3 parts, antioxidant 2 parts, filler 10 parts and toner 10 parts.

Example 7

The ultra-high aging-resistant UV ink comprises the following components in parts by weight: 100 parts of U, 5 parts of HEMA, 10 parts of HDDA, 10 parts of DPEPA, 1173.5 parts of photoinitiator, 1.5 parts of photoinitiator 184, 1 part of defoaming agent, 1 part of antioxidant, 5 parts of filler and 12 parts of toner.

Example 8

The ultra-high aging-resistant UV ink comprises the following components in parts by weight: LS2265 parts, U100 parts, HEMA5 parts, HDDA 7.5 parts, DPEPA 12.5 parts, photoinitiator 1172 parts, photoinitiator 184 parts, defoaming agent 1.5 parts, antioxidant 1.5 parts, filler 2 parts, toner 15 parts,

example 9

Comparative example 1

The UV printing ink comprises the following components in parts by weight: LS2265 parts, U100 parts, DPEPA 10 parts, photoinitiator 1173.5 parts, photoinitiator 184.5 parts, defoaming agent 1 part, antioxidant 1 part, filler 5 parts and toner 12 parts.

Comparative example 2

The UV ink consists of the following components in parts by weight: LS2265 parts, U100 parts, HEMA5 parts, HDDA 10 parts, DPEPA 10 parts, photoinitiator 1173.5 parts, photoinitiator 184.5 parts, filler 5 parts and toner 12 parts.

Comparative example 3

The UV printing ink comprises the following components in parts by weight: LS2265 parts, U100 50 parts, HEMA5 parts, HDDA 10 parts, DPEPA 10 parts, photoinitiator 1173.5 parts, photoinitiator 184.5 parts, defoamer 1 part, antioxidant 1 part and toner 12 parts.

The method for preparing the UV inks of the above examples and comparative examples, using the following steps:

s1: weighing the raw materials in parts by weight for later use;

s2: adding a photoinitiator and a composite reactive diluent into the multifunctional polyurethane acrylate, and stirring until the photoinitiator and the composite reactive diluent are dissolved, wherein the stirring speed is 1500rpm, and the temperature is 60 ℃;

s3: adding the pigment and the filler into the mixture obtained in the step S2, stirring and dispersing uniformly at the stirring speed of 800rpm, and naturally cooling the mixture in the stirring process for 0.5h;

s4: slowly adding the auxiliary agent, and stirring to obtain a target product, wherein the stirring speed is 60rpm, the temperature is normal temperature, and the time is 3 hours.

The ultra-high aging UV inks of examples 1 to 9 and comparative examples 1 to 3 were subjected to aging performance tests with reference to GBT1766-2008 "rating method for color and clear coat aging", and the results are shown in Table 1; the UV inks of examples 1 to 9 and comparative examples 1 to 3 were applied by spraying a liquid film having a thickness of 4 to 6 μm on the surface of A4 paper and cured under a UV lamp, and the curing time was recorded, and the results are shown in Table 2.

TABLE 1 aging Performance test of examples 1-9 and comparative examples 1-3

TABLE 2 UV ink curing time for each example and comparative example

As can be seen from the above tables 1 and 2, the UV ink provided by the invention has good aging resistance, is cured quickly, and has good application prospects.

The embodiments described above are intended to facilitate the understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.

Claims

1. The ultra-high aging-resistant UV ink is characterized by comprising the following components in parts by weight:

50-70 parts of polyfunctional polyurethane acrylate mixture,

20-30 parts of a composite active diluent,

2-5 parts of a photoinitiator,

2-5 parts of an auxiliary agent,

2-10 parts of a filler,

10-15 parts of pigment;

the average functionality of the multifunctional polyurethane acrylate mixture is 3-5, the molecular weight is 500-1200g/mol, and the double bond density is 2.5-6val/kg; the multifunctional polyurethane acrylate mixture comprises at least one multifunctional polyurethane acrylate with the molecular weight of more than 1000g/mol and the double bond density of less than 4.5val/kg and at least one multifunctional polyurethane acrylate with the molecular weight of less than 1000g/mol and the double bond density of more than 4.5 val/kg; the mass ratio of the multifunctional urethane acrylate with the molecular weight of more than 1000g/mol and the double bond density of less than 4.5val/kg to the multifunctional urethane acrylate with the molecular weight of less than 1000g/mol and the double bond density of more than 4.5val/kg is 10-5; the composite active diluent is a mixture consisting of beta-hydroxyethyl methacrylate, 1, 6-hexanediol diacrylate and dipentaerythritol pentaacrylate according to the mass ratio of 1.5-2.5: 1.5-2.5.

2. The ultra-high aging UV ink as claimed in claim 1, wherein the photoinitiator is at least one selected from 2-hydroxy-2-methyl-1-phenyl acetone and 1-hydroxycyclohexyl benzophenone.

3. The ultra-high aging UV ink as claimed in claim 1, wherein: the auxiliary agent comprises at least one of a defoaming agent and an antioxidant.

4. The ultra-high aging UV ink as claimed in claim 1, wherein the filler comprises nano silica.

5. The method for preparing the ultra-high aging resistant UV ink as claimed in claim 1, characterized by comprising the steps of:

s1: weighing the raw materials in parts by weight for later use;

6. The method for preparing the ultra-high aging resistant UV ink according to claim 5, wherein:

(i) In the step S2, the stirring speed is 1200-2000rpm, and the temperature is 50-65 ℃;

(ii) In the step S3, the stirring speed is 800-1000rpm, the stirring process is naturally cooled, and the stirring time is 0.5-1h;

(iii) In step S4, the stirring speed is 60-80rpm, the temperature is normal temperature, and the time is 2-4h.