KR20160062960A - Antibacterial ultra-violet curing paint composition - Google Patents

Abstract

The present invention relates to an ultraviolet-curable antibacterial paint composition. According to the present invention, the composition does not contain a solvent, and is eco-friendly. In addition, the composition is highly adhesive to paper and printing ink layer while maintaining continuous antibacterial functions. Thus, the composition can be applied to studying materials and textbooks for students, thereby preventing the students from infected by bacteria or other germs.

Description

ANTIBACTERIAL ULTRA-VIOLET CURING PAINT COMPOSITION [0002]

The present invention relates to an ultraviolet curable antimicrobial coating composition, and more particularly, to a non-solvent type solvent-free antimicrobial coating composition which is environmentally friendly and has antimicrobial properties, has excellent adhesion to a paper on which a printing ink is printed using an acrylic acrylate oligomer , And an ultraviolet curing type antibacterial agent including an ultraviolet curing type reactor. The present invention relates to an ultraviolet curing type antibacterial coating composition which can be applied not only to ordinary paper but also to textbooks widely used by children.

Rather than being used as printed (a single poster), the printed paper is usually processed again to process the printed material for use in books and other applications.

It is coated with a paint to decorate the surface of the printed paper or to add or enhance the function.

Coating on printed paper is used to increase surface protection, prevent discoloration of the ink, prevent moisture, chemical resistance, decoration, anti-counterfeiting, printing effect, paper toughness and thickness.

Generally, ultraviolet ray curable paints coated on paper have been developed with paints containing epoxy acrylate as a main component, and generally have poor adhesion to the printing ink layer.

In addition, conventional ultraviolet ray curable paints for paper coating have no antibacterial function and can be infected by E. coli or other fungi when children are touched.

The prior art regarding the antibacterial coating composition is as follows.

Korean Patent No. 1335026 discloses a composition comprising (A) 10 to 40 wt% of a urethane acrylate oligomer, (B) 10 to 40 wt% of a polyfunctional acrylate monomer, (C) 1 to 10 wt% (E) containing 0.02 to 10% by weight of an inorganic antibacterial agent and (G) 30 to 50% by weight of a solvent, wherein the inorganic antibacterial agent (E) 9, and an average particle diameter of 2 to 30 mu m.

In Korean Patent No. 748845, pigments used for paint color are dispersed in 30 to 55 parts by weight of a polyester resin paint such as a polymer polyester resin and 20 to 55 parts by weight of a solvent, 3 to 18 parts by weight of a methylated melamine curing resin as a melamine curing resin and 0.1 to 1.0 part by weight of an acid catalyst are added to the mixture to prepare a paint. 0.3 to 2 parts by weight of a polyacrylate resin as an acrylic additive, 0.5 to 3 parts by weight and an additive of 1 part by weight or less and 100 parts by weight in total is coated on a steel sheet and then the antimicrobial function of the dried coating film is exhibited.

However, the prior art does not disclose a technique capable of exhibiting excellent physical properties such as adhesion to paper and continuous antibacterial activity so as to be suitable for paper coating.

Therefore, development of an ultraviolet curable antimicrobial coating material having good adhesion to paper and good adhesion to printing ink and having continuous antibacterial performance is required.

In order to solve the problems of the prior art described above, the inventors of the present invention have found that a UV-curable antimicrobial agent for paper coating that can be applied to textbooks used by students with good adhesion to paper, good adhesion to printing ink layer, The present inventors have repeatedly conducted research to develop a coating composition, and as a result, the present invention has been completed.

Accordingly, an object of the present invention is to provide an ultraviolet curable antimicrobial coating composition for paper coating which has good adhesion to paper, good adhesion to a printing ink layer, and long-lasting antibacterial performance.

In order to accomplish the above object, the present invention provides a curable composition comprising 3 to 10 wt% of bifunctional acrylate monomer, 20 to 40 wt% of trifunctional acrylate monomer, 20 to 50 wt% of acrylic acrylate oligomer, 10 to 25 wt% of curing accelerator, 3 to 10% by weight of a photoinitiator, 0.3 to 2% by weight of an additive, and 0.5 to 2% by weight of an antimicrobial agent.

In one embodiment of the present invention, as the curing accelerator, aminoacrylate, tertiary aliphatic amine or aromatic amine may be used.

In one embodiment of the present invention, the antimicrobial agent may be an antimicrobial agent having a methacrylate group, an acrylate group or a vinyl group.

In one embodiment of the present invention, the additive may be one or a mixture of two or more selected from the group consisting of an extinction agent, an adhesion promoter, a leveling agent, a dispersant, and an antifoaming agent.

The UV-curable antimicrobial coating composition according to the present invention can maintain a constant antibacterial function and thus can prevent contamination of students from bacteria or other microorganisms by being applied to textbooks used by children and students. In addition, the UV-curing antimicrobial coating composition according to the present invention can be applied to printing paper and state textbooks which can be safely touched by children through the EN 71 PART3: 2013 test, which is a toy safety test.

Hereinafter, preferred embodiments of the present invention will be described in detail. The terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary meanings and should be construed in accordance with the technical meanings and concepts of the present invention.

The embodiments described herein are preferred embodiments of the present invention and are not intended to represent all of the technical ideas of the present invention, so that various equivalents and modifications may be substituted for them at the time of application of the present invention.

The ultraviolet curable antimicrobial coating composition according to the present invention includes bifunctional acrylate monomers, trifunctional acrylate monomers, acrylic acrylate oligomers, curing accelerators, photoinitiators, additives, and antibacterial agents.

In the present invention, the bifunctional acrylate monomer is preferably contained in an amount of 3 to 10% by weight.

The bifunctional acrylate monomer in the antimicrobial coating composition of the present invention is used to lower the viscosity in accordance with the coating viscosity.

When the content of the bifunctional acrylate monomer is less than 3% by weight in the antimicrobial coating composition of the present invention, there is a problem that the working viscosity of the coating material is difficult to meet. When the content of the bifunctional coating material composition is more than 10% by weight, This is because it may cause odor or skin irritation due to burning.

In the present invention, the trifunctional acrylate monomer is preferably contained in an amount of 20 to 40% by weight.

The trifunctional acrylate monomer is used in the antimicrobial coating composition of the present invention to adjust curability and hardness.

When the antifungal coating composition of the present invention contains less than 20% by weight of trifunctional acrylate monomer, the curability and scratch resistance of the surface tends to be lowered. When the antifungal coating composition contains more than 40% by weight of the trifunctional acrylate monomer, When coated on paper, the coating film may easily break or crack, and if too much of the coating composition occupies a large proportion, the content of the resin component may be reduced and adhesion may deteriorate.

The antimicrobial coating composition of the present invention preferably contains 20 to 50% by weight of an acrylic acrylate oligomer.

The antimicrobial coating composition of the present invention can include an acrylic acrylate oligomer to improve adhesion with printing ink-printed paper (see Example 3 and Comparative Examples 5 and 6 below).

When the acrylic acrylate oligomer is contained in an amount of less than 20% by weight in the antimicrobial coating composition of the present invention, the adhesion to printing ink tends to decrease. When the acrylic acrylate oligomer is contained in an amount exceeding 50% by weight, Curing may occur.

The curing accelerator is preferably contained in an amount of 10 to 25% by weight in the antimicrobial coating composition of the present invention.

Examples of the curing accelerator include aminoacrylates (e.g., EBECRYL 7100, EBECRYL P 104, EBECRYL P 115), curing accelerators including amine groups such as tertiary aliphatic amines (e.g., triethanolamine) (Dimethylamino) benzoate, ethyl-4- (dimethylamino) benzoate and 2-ethylhexyl-4- (Dimethylamino) benzoate may be used, but the present invention is not limited thereto.

If the curing accelerator is contained in an amount of less than 10% by weight, the curing rate may be lowered, resulting in a problem of uncured curing due to the working characteristics of the paper coating. When the curing accelerator is contained in an amount exceeding 25% by weight, Lt; / RTI >

The antimicrobial coating composition of the present invention preferably contains 3 to 10% by weight of a photoinitiator.

When the antimicrobial coating composition of the present invention contains less than 3% by weight of the photoinitiator, the curability tends to deteriorate due to a rapid curing rate after coating. If the antimicrobial coating composition contains more than 10% by weight of the photoinitiator, There is a problem with this.

As the additives included in the antimicrobial coating composition of the present invention, one or more selected from the group consisting of a quencher, an adhesion promoter, a leveling agent, a dispersing agent and an antifoaming agent may be used for imparting a matting effect, but the present invention is not limited thereto.

As the adhesion promoter, an isocyanate curing agent, an aminosilane, an epoxy silane, or the like may be used as an adhesion promoter in order to improve adhesion on the laminating film.

The antimicrobial coating composition of the present invention preferably contains 0.5 to 2% by weight of the antimicrobial agent.

The antimicrobial agent used in the present invention is an ultraviolet curing reactor, that is, an antimicrobial agent having a double bond of a methacrylate group, an acrylate group or a vinyl group, for example, MSK-271 The antibacterial performance can be maintained for a long time.

When the antimicrobial coating composition of the present invention contains less than 0.5% by weight of antimicrobial agent, the antimicrobial activity may be insignificant. When the antimicrobial agent content exceeds 2% by weight, the antimicrobial activity may be similar but the cost of the coating material may increase.

The antimicrobial coating composition according to the present invention can be applied to textbooks or students' textbooks which are mainly used by children and have good antibacterial performance with good adhesion to a paper or printing ink layer.

Example

The present invention will be described with reference to the following examples, which do not limit the scope of the present invention.

Example  1: UV-curable antimicrobial coating composition

A photoinitiator was added to a container for preparing an ultraviolet-curable antimicrobial coating composition according to the composition shown in Table 1 below. The bifunctional acrylate monomer and the trifunctional acrylate monomer were added thereto, and the photoinitiator was completely dissolved using a stirrer and a stirrer Lt; / RTI > The leveling agent was added as an additive in which the photoinitiator component was completely dissolved, and then the mixture was stirred for 10 minutes. Then, the acrylic acrylate oligomer and amino acrylate oligomer were added thereto and stirred for 30 minutes or more. After sufficiently stirring, an antimicrobial agent was added and stirred.

Comparative Example  2

An ultraviolet curing antimicrobial coating composition was prepared in the same manner as in Example 1 except that novolak epoxy acrylate was used instead of acrylic acrylate oligomer according to the composition shown in Table 1 below.

Comparative Example  3

Except that bisphenol A type epoxy acrylate was used instead of acrylic acrylate oligomer according to the composition shown in the following Table 1, to prepare an ultraviolet curable antimicrobial coating composition.

Example  2

The UV-curable antimicrobial coating composition was prepared in the same manner as in Example 1, according to the compositions shown in Table 2 below.

Comparative Example  3 and 4

UV-curable antimicrobial coating compositions were prepared in the same manner as in Example 1 except that the content of the photoinitiator was varied according to the composition shown in Table 2 below.

Example  3

UV-curable antimicrobial coating compositions were prepared in the same manner as in Example 1 according to the compositions shown in Table 3 below.

Comparative Example  5 and 6

UV-curable antimicrobial coating compositions were prepared in the same manner as in Example 1 except that the content of acrylic acrylate oligomer was varied according to the composition shown in Table 3 below.

Example  4

UV-curable antimicrobial coating compositions were prepared in the same manner as in Example 1 according to the compositions shown in Table 4 below.

Comparative Example  7 and 8

UV-curing antimicrobial coating compositions were prepared in the same manner as in Example 1 except that the aminoacrylate content was varied according to the composition shown in Table 4 below.

Test Example  : Property evaluation test

The properties of the ultraviolet-curable antimicrobial coating composition prepared in Examples 1 to 4 and Comparative Examples 1 to 8 and the coating film formed by ultraviolet curing using the same were evaluated according to the following test methods. Are shown in Tables 5 to 8 below.

≪ Physical property test environmental condition >

- Temperature: 15 ± 2 ℃

- Humidity: 60 ± 5%

- Temperature of coating composition: 25 - 30 ° C

(1) Viscosity measurement of coating composition

The viscosity of the UV-curable antimicrobial coating compositions prepared in Examples 1 to 4 and Comparative Examples 1 to 8 was measured using FORD CUP # 4 at a temperature of 25 ± 0.5 ° C.

(2) Curability

The coating films formed from the ultraviolet curable antimicrobial coating compositions prepared in Examples 1 to 4 and Comparative Examples 1 to 8 were evaluated for hardenability of the coating film by nail scratching. At this time, the curability of the coating film was evaluated according to scratch formation as follows.

- No scratch formation: Good

- scratch formed: bad

(3) Adhesiveness

The surface of the coating film formed from the UV-curable antimicrobial coating compositions prepared in Examples 1 to 4 and Comparative Examples 1 to 8 was cut into a size of 1 mm x 1 mm to form 100 scales, and 3M After attaching the tape, the number of scales to be dropped when separating the 3M tape from the test specimen was measured to evaluate the adhesion of the coating film. At this time, the adhesion of the coating film is expressed by (100-N) / 100, where N is the number of the dummy graduations falling.

(4) sulfur modification

The ΔE of the coating film formed from the UV-curable antimicrobial coating compositions prepared in Examples 1 to 4 and Comparative Examples 1 to 8 was measured using a UV irradiator (mercury lamp, light quantity 500 mJ / cm 2, number of times of passage 10 times).

(5)

The coating films formed from the UV curable antimicrobial coating compositions prepared in Examples 1 to 4 and Comparative Examples 1 to 8 were measured using a UV irradiator (mercury lamp, light quantity 500 mJ / cm 2, number of times of passage) once.

(6) Antimicrobial activity

The antimicrobial properties of the coatings formed from the UV-curable antimicrobial coating compositions prepared in Example 1 and Comparative Examples 1 and 2 were evaluated by preparing a specimen requested by SGS,

Test Report Number Psalm 1: F690101 / LF-CTSAYAA14-44500

Test report number Psalm 2: F690101 / LF-CTSAYAA14-44501

Test report number Psalm 3: F690101 / LF-CTSAYAA14-44502

<EN 71 PART3: 2013, Testing for European Toys>

The antimicrobial activity of the coatings formed from the UV-curable antimicrobial coating composition prepared in Example 1 and Comparative Examples 1 and 2 was tested by the Korea Institute of Construction and Environment Testing and the test results were obtained.

Testimonial Number Psalm 1: CT14-097616

Testimonial Number Psalm 2: CT14-097617

Testimonial Number Psalm 3: CT14-097618

Referring to Table 5, it can be seen that the coating formed from the coating composition prepared in Comparative Example 1 and Comparative Example 2 using epoxy acrylate instead of acrylic acrylate oligomer had a lower adhesion.

Referring to Table 6, the coating films formed from the coating compositions prepared in Comparative Example 3 and Comparative Example 4, which were outside the photoinitiator content range defined in the present invention, .

Referring to Table 7, the coating film formed from the coating composition prepared in Comparative Example 5 and Comparative Example 6, which is different from the acrylic acrylate oligomer content range defined in the present invention, is poor in hardenability, adhesiveness, And there is a problem that a residual is generated.

Referring to Table 8, the coating film formed from the coating composition prepared in Comparative Example 7 and Comparative Example 8, which is different from the aminoacrylate content range defined in the present invention, is inferior in curability, adhesiveness and sulfur modification It can be seen that there is a problem that the balance remains.

Claims (4)

3 to 10 wt% of bifunctional acrylate monomer, 20 to 40 wt% of trifunctional acrylate monomer, 20 to 50 wt% of acrylic acrylate oligomer, 10 to 25 wt% of curing accelerator, 3 to 10 wt% of photoinitiator, 2% by weight of an antimicrobial agent and 0.5 to 2% by weight of an antimicrobial agent.
The method according to claim 1,
Wherein the curing accelerator is aminoacrylate, a tertiary aliphatic amine or an aromatic amine.
The method according to claim 1,
Wherein the additive is selected from the group consisting of a quencher, an adhesion promoter, a leveling agent, a dispersant, and an antifoaming agent.
The method according to claim 1,
Wherein the antimicrobial agent is an antimicrobial agent having a methacrylate group, an acrylate group or a vinyl group double bond.