KR20230018729A - High hard uv coat composition, high hard uv coating paper using the same, and article using the uv coating paper - Google Patents

Abstract

The present invention relates to: a high-hardness UV coating composition which has high hardness characteristics by containing a surface-modified alumina dispersion, silicon acrylate, or both as a main component, which has scratch resistance, stain resistance, and solvent resistance, and in which glossiness thereof can be adjusted arbitrarily; high-hardness UV-coated paper using the UV coating composition; and an article to which the UV-coated paper is applied. The high-hardness UV coating composition according to the present invention includes a predetermined amount of an antifoaming agent and a photoinitiator, and is formed by including a surface-modified alumina dispersion, silicon acrylate, or both.

Description

High-hardness UV coating composition, high-hardness UV-coated paper using the same, article to which this UV-coated paper is applied

The present invention relates to a high-hardness UV coating composition and a high-hardness UV-coated paper using the same,

More specifically, the surface-modified alumina dispersion or silicon acrylate, or both, has high hardness as a main component, and further scratch resistance, stain resistance, solvent resistance, as well as glossiness can be adjusted arbitrarily. It relates to a high-hardness UV coating composition, a high-hardness UV-coated paper using the same, and an article to which the UV-coated paper is applied.

Regarding the hard coating composition, there is Patent Registration No. 10-2107662 (April 28, 2020) [double-sided hard coating film for display],

This registered patent relates to a double-sided hard coating film for display with improved anti-blocking and scratch resistance by applying a hard coating solution containing an appropriate amount of inorganic particles having an average particle diameter within an appropriate range on both sides of a base film,

Specifically, the hard coating solution may include various additives, and in particular, fluorine acrylate and silicon acrylate may be added as a leveling agent. A double-sided hard coating film for a display in which scratch resistance is secured by using a mixture of the fluorine acrylate and silicon acrylate is proposed.

In addition, there is Patent Registration No. 10-1725026 (April 3, 2017) [Composition for producing high-strength hard coating film and high-strength hard coating liquid crystal protective film produced using the same],

This registered patent is coated on a liquid crystal protective film to protect a touch screen such as a smartphone or PDA.

A composition for producing a high-strength hard coating film having more excellent physical properties such as hardness, surface smoothness and scratch resistance, and the same

It relates to a high-strength hard coating liquid crystal protective film manufactured using

Specifically, the composition for preparing a high-strength hard coating film includes a polyurethane acrylate oligomer, a monofunctional and multifunctional acrylic monomer, a photocuring agent, an organic solvent, an inorganic oxide, and additives.

However, prior literature including these two patents has nothing to do with the technology of providing sheets, especially paper, with high hardness, scratch resistance, stain resistance, and solvent resistance, as well as arbitrarily adjusting glossiness.

Accordingly, the present invention has a surface-modified alumina dispersion or silicon acrylate, or both, as a main component and has high hardness characteristics, and further scratch resistance, stain resistance, solvent resistance, as well as glossiness can be arbitrarily adjusted. It is an object of the present invention to provide a high hardness UV coating composition and a high hardness UV coated paper using the same.

In order to achieve the above object, the high-hardness UV coating composition according to the present invention

A predetermined amount of an antifoaming agent and a photoinitiator,

surface modified alumina dispersion or silicon acrylate, or both.

In addition, in the high-hardness UV coating composition according to the present invention

Based on 1 part by weight of the antifoaming agent, 2 to 10 parts by weight of a photoinitiator, 20 to 50 parts by weight of a surface-modified alumina dispersion (when added), and 10 to 70 parts by weight of silicon acrylate (when added),

Further comprising a multifunctional urethane acrylate oligomer,

The multifunctional urethane acrylate oligomer is added in an amount of 20 to 100 parts by weight,

The multifunctional urethane acrylate oligomer is composed of an aliphatic urethane acrylate oligomer and an epoxy urethane acrylate oligomer,

Further comprising a crosslinking density improver,

It is characterized in that it further comprises a diluent.

The high-hardness UV coated paper according to the present invention is coated using the coating composition,

Furthermore, it relates to various articles (processed wood, building materials, furniture, various ornaments, interior and exterior materials for automobiles, etc.) to which this UV coated paper is applied.

The high-hardness UV coating composition according to the present invention and the high-hardness UV-coated paper using the same have surface-modified alumina dispersion or silicon acrylate, or both of them as main components, and have high hardness characteristics, and further scratch resistance, stain resistance, content In addition to having various properties, the degree of gloss can be arbitrarily adjusted.

1 is a photograph of a high-hardness UV coating composition according to the present invention for a matte high-hardness coated paper.
Figure 2 is a SEM analysis picture of the surface of the matte high hardness coated paper for the coated paper of FIG.
Figure 3 is a picture substitute photo of the high-hardness UV coating composition according to the present invention for glossy high-hardness coated paper.
4 is a conceptual diagram of matte coating UV curing.

Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.

Since the present invention can have various changes and various forms, the implementation examples (or embodiments) will be described in detail in the text. However, this is not intended to limit the present invention to a specific form disclosed, and should be understood to include all modifications, equivalents, or substitutes included in the spirit and scope of the present invention.

Terms used in this specification are only used to describe a specific embodiment (aspect, aspect) (or embodiment), and are not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly dictates otherwise. In this application, terms such as ~comprising~ or ~consisting of are intended to designate that there is a feature, number, step, operation, component, part, or combination thereof described in the specification, but one or more other features It should be understood that it does not preclude the possibility of the presence or addition of numbers, steps, operations, components, parts, or combinations thereof.

Unless defined otherwise, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention belongs. Terms such as those defined in commonly used dictionaries should be interpreted as having a meaning consistent with the meaning in the context of the related art, and unless explicitly defined in the present application, they should not be interpreted in an ideal or excessively formal meaning. don't

The high-hardness UV coating composition according to the present invention and the high-hardness UV-coated paper using the same are the base composition.

It includes a predetermined amount of an antifoaming agent and a photoinitiator, and also includes a surface-modified alumina dispersion or silicon acrylate or both as main components.

Specifically, based on 1 part by weight of the antifoaming agent, 2 to 10 parts by weight of a photoinitiator, 20 to 50 parts by weight of a surface-modified alumina dispersion, and 10 to 70 parts by weight of silicon acrylate are included.

In addition, it is preferable to further include a polyfunctional urethane acrylate oligomer,

The multifunctional urethane acrylate oligomer may be added in an amount of 20 to 100 parts by weight,

The multifunctional urethane acrylate oligomer may be composed of an aliphatic urethane acrylate oligomer and an epoxy urethane acrylate oligomer,

Specifically, for improving the surface hardness of the coating layer, some or all of 6-functional aliphatic urethane acrylate oligomer, 10-functional aliphatic urethane acrylate oligomer, and 2-functional epoxy urethane acrylate oligomer may be included.

Furthermore, in the high hardness UV coating composition according to the present invention and the high hardness UV coated paper using the same, the basic high hardness coating composition may further include a crosslinking density improver,

Specifically, it is preferably trimethylolpropane triacrylate.

In addition, in the high hardness UV coating composition according to the present invention and the high hardness UV coated paper using the same, it is preferable that the basic high hardness coating composition further include a diluent,

This diluent can be part or all of Isobonyl Acrylate, Phenol (EO) Acrylate.

In addition, in the high-hardness UV coating composition according to the present invention and the high-hardness UV-coated paper using the same, the antifoaming agent added to the basic high-hardness coating composition is preferably commercially available under the trade name Airex 920, and can be replaced with various other known antifoaming agents. .

In addition, the photoinitiator is 1-hydroxycyclohexyl phenyl ketone,

It may be part or all of diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide.

Functions and characteristics of representative components constituting the high-hardness UV coating composition according to the present invention are as follows.

○ Nanoparticle dispersion: Improvement of surface hardness of coating solution

○ Silicon acrylate: causes a synergistic effect to improve the surface hardness of the coating layer

○ Isobonyl Acrylate: Dispersion medium and dilution of coating solution

○ Phenol (EO) Acrylate: Dilution of coating solution

○ Trimethylolpropane Triacrylate: Improves crosslinking density

○ Hexafunctional aliphatic urethane acrylate oligomer: Improves surface hardness of coating layer

○ 10-functional aliphatic urethane acrylate oligomer: improving the surface hardness of the coating layer

○ Bifunctional epoxy urethane acrylate oligomer: Improves the surface hardness of the coating layer

○ Airex 920: Defoamer

○ 1-hydroxycyclohexyl phenyl ketone: Photoinitiator

○ Diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide (Diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide): Photoinitiator

More preferably, the various additives may be the following components.

crosslinking density improver

Trimethylolpropane Triacrylate,

Pentaerythritol tri(meth)acrylate,

Dipentaerythritol penta(meth)acrylate,

Dipentaerythritol hexa(meth)acrylate,

Trimethylolpropane (EO) _{15 triacrylate} ,

Pentaerythritol (EO _{) n tetraacrylate} ,

Or it may be selected from the group consisting of combinations thereof.

photoinitiator

1-hydroxycyclohexyl phenyl ketone,

Hydroxydimethyl acetophenone,

Diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide,

Methyl benzoylformate, n-butylamine, triethylamine, 2-hydroxyl-1-(4-(2-hydroxyethoxy)phenyl)-2-methylpropanone,

2,2'-dimethoxy-1,2-diphenylethanone;

phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide;

2-benzyl-2-(dimethylamino)-4'-morpholinobutyrophenone;

2-methyl-4'-(methylthio)-2-morpholinopropiophenone;

Or it may be selected from the group consisting of combinations thereof.

Hereinafter, the present invention can be better understood through specific preparation examples, examples and comparative examples.

Preparation Example 1. Preparation of Surface Modified Alumina and Modified Alumina Dispersion

Alumina surface modification was performed by dispersing alumina nanoparticles (20 to 30 nm) at room temperature, adding a surface modifier, stirring for 1 hour, and filtering to prepare surface-modified alumina particles.

The surface modifier is 5 to 20 parts by weight, preferably 8 to 15 parts by weight, based on 100 parts by weight of alumina.

To prepare the surface-modified alumina dispersion, a nanomill was used for 5 hours by adding 10 parts by weight of a BYK dispersant to 100 parts by weight of the surface-modified alumina.

The surface modifier is preferably selected from the following materials.

Methyl silanetriol, dimethyl silanediol, phenyl silanetriol, diphenyl silanediol, vinyl silanetriol, divinyl silane diol ( Divinyl silanediol), Dodecyl silanetriol, Didodecyl(diphenyl) silane, Siloxane oligomer, Bis(triethoxysilylpropyl) tetrasulfide (Bis(triethoxysilylpropyl) tetrasulfide), propyl silanetriol, 3-aminopropyl silanetriol, and mercaptopropyl silanetriol, or a combination thereof.

Next, the composition ratios of Examples and Comparative Examples are shown in Table 1 below.

Composition ratio of coating solution Examples and Comparative Examples

coating composition Example 1 or 2 Example 3 or 4 Example 5 or 6 Example 7 or 8 Example 9 or 10 Example 11 or 12 Example 13 or 14 Comparative Example 1 or 2 Comparative Example 3 or 4 Dispersed Nano-alumina in IBOA 40.0 30.0 30.0 0.0 0.0 0.0 0.0 29.0 0.0 Isobornyl acrylate (IBOA) 0.0 0.0 0.0 29.0 29.0 29.0 29.0 20.0 29.0 PHEA (Phenol (EO) Acrylate) 20.0 40.0 40.0 40.0 40.0 40.0 40.0 20.0 40.0 Trimethylolpropane Triacrylate (TMPTA) 10.0 0.0 10.0 0.0 10.0 10.0 10.0 10.0 0.0 6F Aliphatic Urethane Acrylate Oligomer 50.0 20.0 10.0 20.0 10.0 10.0 20.0 10.0 20.0 10F Aliphatic Urethane Acrylate Oligomer 40.0 20.0 20.0 20.0 20.0 50.0 50.0 60.0 60.0 2F Epoxy Urethane Acrylate (Bisphenol A type) Oligomer 35.0 33.0 33.0 34.0 34.0 34.0 34.0 46.0 44.0 Silicone Acrylate 0.0 50.0 50.0 50.0 50.0 20.0 10.0 0.0 0.0 Airex 920 (Defoamer) 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 CP-4 (Photoinitiator) 2.0 3.0 3.0 3.0 3.0 3.0 3.0 2.0 3.0 TPO (Photoinitiator) 2.0 3.0 3.0 3.0 3.0 3.0 3.0 2.0 3.0

In the table above, Example 1 or 2, Example 3 or 4, Example 5 or 6, Example 7 or 8, Example 9 or 10, Example 11 or 12, Example 13 or 14 are respectively matte ( Odd-numbered examples) and glossy (even-numbered examples) are classified according to composition.

Hereinafter, it will be described in detail with respect to Table 1 (in the following description, half of the content of Table 1 was used for convenience in preparing the laboratory stage for the content of each component, and it was described as a numerical value).

Example 1.

20.0 parts by weight of the surface-modified alumina (Al2O3) dispersion in the coating solution, 10.0 parts by weight of phenol (EO) Acrylate in the coating solution, 5.0 parts by weight of trimethylolpropane triacrylate in the coating solution, 25.0 parts by weight of 6-functional group aliphatic urethane acrylate oligomer in the coating solution, 20.0 parts by weight of 10-functional group aliphatic urethane acrylate oligomer in the coating solution, and 2 functional group epoxy urethane acrylate oligomer in the coating solution 17.5 parts by weight, 0.5 parts by weight of Airex 920 in the coating solution, 1-hydroxycyclohexyl phenyl ketone, a photoinitiator for initiating photocuring by UV irradiation, 1.0 parts by weight in the coating solution, diphenyl ( 2,4,6-trimethylbenzoyl) phosphine oxide (Diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide) was added to 1.0 parts by weight of the coating solution and stirred for 1 hour to prepare a UV coating solution.

The substrate used for the coating was printed paper (thickness 120 ㎛), and after applying the UV curing coating solution prepared as described above, prevention of deterioration of curing degree by ozone generated during UV curing and matt and soft feel of the surface For the purpose of imparting texture functions such as feel, the surface of the wet film was covered with a PET film with irregularities, and high-hardness coated paper was manufactured using a UV curing machine.

Example 2.

The substrate used for coating was printing paper (thickness 120 μm), and after applying the UV curing coating solution prepared as in Example 1, prevention of curing degree deterioration due to ozone generated during UV curing and imparting a glossy function to the surface For this purpose, high-hardness coated paper was prepared by covering the wet film surface with an uneven PET film and using a UV curing machine.

Example 3.

15.0 parts by weight of the surface-modified alumina (Al2O3) dispersion, 20.0 parts by weight of Phenol (EO) Acrylate, and 10.0 parts by weight of hexafunctional aliphatic urethane acrylate oligomer in the coating solution Part by weight, 10.0 parts by weight of 10 functional group aliphatic urethane acrylate oligomer in coating solution, 16.5 parts by weight of difunctional epoxy urethane acrylate oligomer in coating solution, 25.0 parts by weight of silicone acrylate in coating solution , 0.5 parts by weight of Airex 920 in the coating solution, 1-hydroxycyclohexyl phenyl ketone, a photoinitiator for initiating photocuring according to UV irradiation, 1.5 parts by weight in the coating solution, diphenyl (2,4 1.5 parts by weight of ,6-trimethylbenzoyl)phosphine oxide (Diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide) was added to the coating solution, followed by stirring for 1 hour to prepare a UV coating solution.

The substrate used for the coating was printed paper (thickness 120 ㎛), and after applying the UV curing coating solution prepared as described above, prevention of deterioration of curing degree by ozone generated during UV curing and matt and soft feel of the surface For the purpose of imparting texture functions such as feel, the surface of the wet film was covered with a PET film with irregularities, and high-hardness coated paper was manufactured using a UV curing machine.

Example 4.

The substrate used for coating was printing paper (thickness 120 μm), and after applying the UV curing coating solution prepared as in Example 3, prevention of curing degree deterioration due to ozone generated during UV curing and imparting a glossy function to the surface For this purpose, high-hardness coated paper was prepared by covering the wet film surface with an uneven PET film and using a UV curing machine.

Example 5.

Dispersion is 15.0 parts by weight of the coating solution, Phenol (EO) Acrylate is 20.0 parts by weight of the coating solution, Trimethylolpropane Triacrylate is 5.0 parts by weight of the coating solution, Hexafunctional group aliphatic urethane acrylate oligomer (Aliphatic Urethane Acrylate Oligomer) is 5.0 parts by weight in the coating solution, 10 functional group aliphatic urethane acrylate oligomer is 10.0 parts by weight in the coating solution, 2 functional group epoxy urethane acrylate oligomer is 16.5 parts by weight in the coating solution, silicone acrylate (Silicone Acrylate) is 25.0 parts by weight in the coating solution, Airex 920 is 0.5 parts by weight in the coating solution, 1-hydroxycyclohexyl phenyl ketone, a photoinitiator for initiating photocuring according to UV irradiation, is in the coating solution 1.5 parts by weight of diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide (Diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide) was added to the coating solution by adding 1.5 parts by weight and stirred for 1 hour to prepare a UV coating solution. did

The substrate used for the coating was printed paper (thickness 120 ㎛), and after applying the UV curing coating solution prepared as described above, prevention of deterioration of curing degree by ozone generated during UV curing and matt and soft feel of the surface For the purpose of imparting a texture function such as feel, the surface of the wet film was covered with an uneven PET film, and high-hardness coated paper was manufactured using a UV curing machine.

Example 6.

The substrate used for coating was printing paper (thickness 120 μm), and after applying the UV curing coating solution prepared as in Example 5, prevention of deterioration in curing degree by ozone generated during UV curing and imparting a glossy function to the surface For this purpose, high-hardness coated paper was prepared by covering the wet film surface with an uneven PET film and using a UV curing machine.

Example 7.

14.5 parts by weight of Isobonyl Acrylate in the coating solution, 20.0 parts by weight of Phenol (EO) Acrylate in the coating solution, and 10.0 parts by weight of the hexafunctional aliphatic urethane acrylate oligomer in the coating solution Part by weight, 10.0 parts by weight of 10 functional group aliphatic urethane acrylate oligomer in the coating solution, 17.0 parts by weight of 2 functional group epoxy urethane acrylate oligomer in the coating solution, and 25.0 parts by weight of silicone acrylate in the coating solution , 0.5 parts by weight of Airex 920 in the coating solution, 1-hydroxycyclohexyl phenyl ketone, a photoinitiator for initiating photocuring according to UV irradiation, 1.5 parts by weight in the coating solution, diphenyl (2,4 1.5 parts by weight of ,6-trimethylbenzoyl)phosphine oxide (Diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide) was added to the coating solution, followed by stirring for 1 hour to prepare a UV coating solution.

The substrate used for coating was printing paper (thickness 120 ㎛), and after applying the UV curing coating solution prepared as described above, prevention and prevention of curing degree deterioration by ozone generated during UV curing and matt and soft feel of the surface For the purpose of imparting texture functions such as soft feel, the surface of the wet film was covered with a PET film with irregularities, and high-hardness coated paper was manufactured using a UV curing machine.

Example 8.

The substrate used for the coating was printing paper (thickness 120 μm), and after applying the UV curing coating solution prepared as in Example 7, prevention of curing degree deterioration due to ozone generated during UV curing and imparting a glossy function to the surface For this purpose, high-hardness coated paper was prepared by covering the wet film surface with an uneven PET film and using a UV curing machine.

Example 9.

14.5 parts by weight of Isobonyl Acrylate in the coating solution, 20.0 parts by weight of Phenol (EO) Acrylate in the coating solution, 5.0 parts by weight of Trimethylolpropane Triacrylate in the coating solution, 5.0 parts by weight of 6-functional group aliphatic urethane acrylate oligomer in the coating solution, 10.0 parts by weight of 10-functional group aliphatic urethane acrylate oligomer in the coating solution, and 2 functional group epoxy urethane acrylate oligomer in the coating solution 17.0 parts by weight, 25.0 parts by weight of silicone acrylate in the coating solution, 0.5 parts by weight of Airex 920 in the coating solution, 1-hydroxycyclohexyl phenyl ketone (1-hydroxycyclohexyl phenyl ketone, a photoinitiator for initiating photocuring according to UV irradiation) 1.5 parts by weight of hydroxycyclohexyl phenyl ketone in the coating solution and 1.5 parts by weight of diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide in the coating solution were added for 1 hour. After stirring while, a UV coating solution was prepared.

The substrate used for the coating was printed paper (thickness 120 ㎛), and after applying the UV curing coating solution prepared as described above, prevention of deterioration of curing degree by ozone generated during UV curing and matt and soft feel of the surface For the purpose of imparting texture functions such as feel, the surface of the wet film was covered with a PET film with irregularities, and high-hardness coated paper was manufactured using a UV curing machine.

Example 10.

The substrate used for coating was printing paper (thickness 120 μm), and after applying the UV curing coating solution prepared as in Example 9, prevention of curing degree deterioration due to ozone generated during UV curing and imparting a glossy function to the surface For this purpose, high-hardness coated paper was prepared by covering the wet film surface with an uneven PET film and using a UV curing machine.

Example 11.

14.5 parts by weight of Isobonyl Acrylate in the coating solution, 20.0 parts by weight of Phenol (EO) Acrylate in the coating solution, 5.0 parts by weight of Trimethylolpropane Triacrylate in the coating solution, 5.0 parts by weight of 6-functional group aliphatic urethane acrylate oligomer in the coating solution, 25.0 parts by weight of 10-functional group aliphatic urethane acrylate oligomer in the coating solution, and 2 functional group epoxy urethane acrylate oligomer in the coating solution 17.0 parts by weight, 10.0 parts by weight of silicone acrylate in the coating solution, 0.5 parts by weight of Airex 920 in the coating solution, 1-hydroxycyclohexyl phenyl ketone (1-hydroxycyclohexyl phenyl ketone, a photoinitiator for initiating photocuring according to UV irradiation) 1.5 parts by weight of hydroxycyclohexyl phenyl ketone in the coating solution and 1.5 parts by weight of diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide in the coating solution were added for 1 hour. After stirring while, a UV coating solution was prepared.

The substrate used for the coating was printed paper (thickness 120 ㎛), and after applying the UV curing coating solution prepared as described above, prevention of deterioration of curing degree by ozone generated during UV curing and matt and soft feel of the surface For the purpose of imparting texture functions such as feel, the surface of the wet film was covered with a PET film with irregularities, and high-hardness coated paper was manufactured using a UV curing machine.

Example 12.

The substrate used for coating was printing paper (thickness 120 μm), and after applying the UV curing coating solution prepared as in Example 11, prevention of curing degree deterioration due to ozone generated during UV curing and imparting a glossy function to the surface For this purpose, high-hardness coated paper was prepared by covering the wet film surface with an uneven PET film and using a UV curing machine.

Example 13.

14.5 parts by weight of Isobonyl Acrylate in the coating solution, 20.0 parts by weight of Phenol (EO) Acrylate in the coating solution, 5.0 parts by weight of Trimethylolpropane Triacrylate in the coating solution, 10.0 parts by weight of 6-functional group aliphatic urethane acrylate oligomer in the coating solution, 25.0 parts by weight of 10-functional group aliphatic urethane acrylate oligomer in the coating solution, and 2 functional group epoxy urethane acrylate oligomer in the coating solution 17.0 parts by weight, 5.0 parts by weight of silicone acrylate in the coating solution, 0.5 parts by weight of Airex 920 in the coating solution, 1-hydroxycyclohexyl phenyl ketone (1-hydroxycyclohexyl phenyl ketone, a photoinitiator for initiating photocuring according to UV irradiation) 1.5 parts by weight of hydroxycyclohexyl phenyl ketone in the coating solution and 1.5 parts by weight of diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide in the coating solution were added for 1 hour. After stirring while, a UV coating solution was prepared.

The substrate used for the coating was printed paper (thickness 120 ㎛), and after applying the UV curing coating solution prepared as described above, prevention of deterioration of curing degree by ozone generated during UV curing and matt and soft feel of the surface For the purpose of imparting texture functions such as feel, the surface of the wet film was covered with a PET film with irregularities, and high-hardness coated paper was manufactured using a UV curing machine.

Example 14.

The substrate used for coating was printing paper (thickness 120 μm), and after applying the UV curing coating solution prepared as in Example 13, prevention of curing degree deterioration due to ozone generated during UV curing and imparting a glossy function to the surface For this purpose, high-hardness coated paper was prepared by covering the wet film surface with an uneven PET film and using a UV curing machine.

Comparative Example 1.

14.5 parts by weight of the surface-modified alumina (Al2O3) dispersion in the coating solution, 10.0 parts by weight of Isobonyl Acrylate in the coating solution, 10.0 parts by weight of Phenol (EO) Acrylate in the coating solution, trimethylol Propane triacrylate (Trimethylolpropane Triacrylate) is 5.0 parts by weight of the coating solution, 6 functional group aliphatic urethane acrylate oligomer (Aliphatic Urethane Acrylate Oligomer) is 5.0 parts by weight of the coating solution, 10 functional group aliphatic urethane acrylate oligomer is 30.0 parts by weight of the coating solution, 2 23.0 parts by weight of functional group epoxy urethane acrylate oligomer in the coating solution, 0.5 parts by weight of Airex 920 in the coating solution, 1-hydroxycyclohexyl phenyl ketone (1 1.0 parts by weight of -hydroxycyclohexyl phenyl ketone in the coating solution and 1.0 parts by weight of diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide in the coating solution were added. After stirring for an hour, a UV coating solution was prepared.

The substrate used for the coating was printed paper (thickness 120 ㎛), and after applying the UV curing coating solution prepared as described above, prevention of deterioration of curing degree by ozone generated during UV curing and matt and soft feel of the surface For the purpose of imparting texture functions such as feel, the surface of the wet film was covered with a PET film with irregularities, and high-hardness coated paper was manufactured using a UV curing machine.

Comparative example 2.

The substrate used for coating was printing paper (thickness 120 μm), and after applying the UV curing coating solution prepared as in Comparative Example 1, prevention of curing degree deterioration due to ozone generated during UV curing and imparting a glossy function to the surface For this purpose, high-hardness coated paper was prepared by covering the wet film surface with an uneven PET film and using a UV curing machine.

Comparative Example 3.

14.5 parts by weight of Isobonyl Acrylate in the coating solution, 20.0 parts by weight of Phenol (EO) Acrylate in the coating solution, and 10.0 parts by weight of the hexafunctional aliphatic urethane acrylate oligomer in the coating solution Parts by weight, 30.0 parts by weight of 10 functional group aliphatic urethane acrylate oligomer in coating solution, 22.0 parts by weight of difunctional epoxy urethane acrylate oligomer in coating solution, 0.5 part by weight of Airex 920 in coating solution, according to UV irradiation 1.5 parts by weight of 1-hydroxycyclohexyl phenyl ketone, a photoinitiator for initiating photocuring, in the coating solution, diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide (Diphenyl (2, 4,6-trimethylbenzoyl)phosphine oxide) was added in 1.5 parts by weight to the coating solution and stirred for 1 hour to prepare a UV coating solution.

The substrate used for the coating was printed paper (thickness 120 ㎛), and after applying the UV curing coating solution prepared as described above, prevention of deterioration of curing degree by ozone generated during UV curing and matt and soft feel of the surface For the purpose of imparting texture functions such as feel, the surface of the wet film was covered with a PET film with irregularities, and high-hardness coated paper was manufactured using a UV curing machine.

Comparative Example 4.

The substrate used for coating was printing paper (thickness 120 μm), and after applying the UV curing coating solution prepared as in Comparative Example 3, prevention of deterioration in curing degree due to ozone generated during UV curing and imparting a glossy function to the surface For this purpose, high-hardness coated paper was prepared by covering the wet film surface with an uneven PET film and using a UV curing machine.

In the above examples and comparative examples, as shown in the matte coating UV curing conceptual diagram of FIG. 4, the coating liquid (coating composition of odd numbered examples and comparative examples) is applied to a substrate (paper or synthetic resin film) to obtain a matte surface. It is obtained by irradiating UV by laminating a film for laminating having a known mat surface on the coated surface after application.

Through this, the mat shape of the back side of the film for laminating is transferred to the surface of the coating layer of each corresponding Example and Comparative Example,

As a result, a matte coating surface like the SEM analysis picture on the right side of FIG. 4 is obtained, and the SEM picture of FIG.

In order to obtain the high-hardness UV coated paper according to the present invention, it is important to wet the pores (Open Pore) present on the surface of the base paper as the paper is used as the base material,

In this appropriate wetting, the viscosity of the high-hardness UV coating composition is important. Preferably, the viscosity of the composition is greater than 10 cPs and less than 10,000 cPs. (Open Pore) difficult to remove).

On the other hand, Figure 1 is a photograph of the high-hardness UV coating composition according to the present invention in lieu of a drawing for matte high-hardness coated paper, a photograph of the paper coated using the composition according to Example 3, and the composition using the matte effect film Corresponds to a photograph in which the hardness is measured after curing.

In addition, Figure 2 is a SEM analysis picture of the matte high hardness coated paper surface for the paper of FIG. 1, that is, a SEM analysis picture for Example 3, and all specimens having a glossiness of 3 or less, including Example 3, have similar surface shapes appeared to have

And Figure 3 is a photograph of the high-hardness UV coating composition according to the present invention as a substitute for a drawing for glossy high-hardness coated paper, a photograph of the paper coated using the composition according to Example 2, curing the composition using a glossy effect film Corresponds to the photograph after which the hardness was measured.

Furthermore, the present invention can apply the UV coated paper to various articles such as processed wood, building materials, furniture, various ornaments, and interior and exterior materials for automobiles.

In order to compare the physical properties of the above Examples and Comparative Examples, physical properties related to scratch resistance, glossiness, stain resistance and solvent resistance were measured, and the specific methods are as follows.

scratch resistance

For scratch resistance, a diamond tip of an Erichsen Scratch Tester (ISO 4586-2 / DIN EN 438-2) was used to measure the force at which scratches were generated.

Glossiness

After UV curing, the gloss of the surface of the specimen was measured at least three times at an angle of 60 ° according to ISO 2813 standard using BYK's micro-TRI-gloss, and then the average value and standard deviation were obtained.

Stain resistance and solvent resistance

According to the standard specification (KS M ISO 4586-2) for high-pressure veneer-thermosetting resin sheets, the results were classified as follows according to the results indicated in the measurement method.

1) Grade 5: No change in appearance

2) Grade 4: Minor change in gloss and/or color observed only at certain viewing angles

3) Grade 3: Moderate change in gloss and/or color

4) Grade 2: Significant change in gloss and/or color

5) Grade 1: Glossy surface warping and/or swelling

The measurement results of each physical property of the Examples and Comparative Examples are summarized in Tables 2 and 3 below.

Coating composition surface property evaluation result Property evaluation
Examples and Comparative Examples scratch resistance Gloss (60°) Example 1 2.0N 1.8 Example 2 2.0N 92.8 Example 3 4.0N 1.5 Example 4 4.0N 93.3 Example 5 3.5N 1.5 Example 6 3.5N 92.1 Example 7 3.5N 1.9 Example 8 3.5N 91.4 Example 9 3.0N 1.6 Example 10 3.0N 92.7 Example 11 3.0N 1.6 Example 12 3.0N 92.6 Example 13 2.0N 1.7 Example 14 2.0N 91.9 Comparative Example 1 1.5N 1.7 Comparative Example 2 1.5N 92.7 Comparative Example 3 0.5N 2.1 Comparative Example 4 0.5N 92.8

Regarding the evaluation of scratch resistance in Table 2, the high-hardness UV coating composition according to the present invention and the high-hardness UV-coated paper using the same essentially include silicon acrylate as a main component,

It is suitable for realizing high hardness to include a surface-modified alumina dispersion or a hexafunctional aliphatic urethane acrylate oligomer, or both, in a predetermined amount (Examples 1 & 2 and Examples 3 & 4, 5 & 6, As a result of comparing 7&8, 9&10).

Preferably, it contains 40 to 70 parts by weight of silicone acrylate based on 1 part by weight of the antifoaming agent,

It is preferable to include 20 to 50 parts by weight of the surface-modified alumina dispersion (when added) and 10 to 30 parts by weight (when added) of the hexafunctional aliphatic urethane acrylate oligomer (Examples 3, 4, 5, 6, 7, 8).

More preferably, it is preferable to include both 20 to 50 parts by weight of the surface-modified alumina dispersion and 10 to 30 parts by weight of the hexafunctional aliphatic urethane acrylate oligomer (Examples 3 and 4).

In addition, it is preferable that the photoinitiator is included in an amount of 6 to 8 parts by weight (as a result of comparison between Examples 1 & 2 and other examples).

Furthermore, it is preferable to include 20 to 30 parts by weight of a hexafunctional aliphatic urethane acrylate oligomer together with 40 to 70 parts by weight of silicone acrylate (when added) or 20 to 50 parts by weight of a surface-modified alumina dispersion (when added). (As a result of comparison of Examples 9 & 10 and Examples 3 & 4, 5 & 6, 7 & 8).

In addition, it is more preferable to include 20 to 30 parts by weight of a hexafunctional aliphatic urethane acrylate oligomer together with 40 to 70 parts by weight of silicone acrylate and 20 to 50 parts by weight of a surface-modified alumina dispersion (Examples 3 & 4 and Examples 5 & 6, as a result of comparison of 7&8).

Result of evaluation of solvent content and contamination resistance Examples and Comparative Examples


Property evaluation Example 1 or 2 Example 3 or 4 Example 5 or 6 Example 7 or 8 Example 9 or 10 Example 11 or 12 Example 13 or 14 Comparative Example 1 or 2 Comparative Example 3 or 4 Solvent Resistance - 95% Ethanol 5th grade 5th grade 5th grade 5th grade 5th grade 5th grade 5th grade 5th grade 5 star Solvent Resistance - Lacquer Thinner 5th grade 5th grade 5th grade 5th grade 5th grade 5th grade 5th grade 5th grade 4th grade Solvent Resistance - Petroleum Benzene 5th grade 5th grade 5th grade 5th grade 5th grade 5th grade 5th grade 4th grade Grade 3 Stain Resistance - Black Magic 5th grade 5th grade 5th grade 5th grade 5th grade 5th grade 5th grade 5th grade 5th grade Stain resistance - red crayon 5th grade 5th grade 5th grade 5th grade 5th grade 5th grade 5th grade 5th grade 5th grade Stain Resistance - Coffee 5th grade 5th grade 5th grade 5th grade 5th grade 5th grade 5th grade 4th grade Grade 3 Fouling Resistance - Soy Sauce 5th grade 5th grade 5th grade 5th grade 5th grade 5th grade 5th grade 5th grade 5th grade Stain Resistance - Mustard 5th grade 5th grade 5th grade 5th grade 5th grade 5th grade 5th grade 4th grade 4th grade Stain Resistance - Animal Butter 5th grade 5th grade 5th grade 5th grade 5th grade 5th grade 5th grade 5th grade 5th grade

In the above description, a commonly known technique in the high hardness UV coating composition and the high hardness UV coated paper using the same is omitted, but those skilled in the art can easily guess, infer, and reproduce it.

Claims (10)

A predetermined amount of an antifoaming agent and a photoinitiator,
A high-hardness UV coating composition comprising a surface-modified alumina dispersion or silicon acrylate, or both. According to claim 1,
Based on 1 part by weight of the antifoaming agent, 2 to 10 parts by weight of a photoinitiator, 20 to 50 parts by weight of a surface-modified alumina dispersion (when added), and 10 to 70 parts by weight of silicon acrylate (when added) Characterized in that it comprises A high-hardness UV coating composition. According to claim 2,
A high-hardness UV coating composition further comprising a polyfunctional urethane acrylate oligomer. According to claim 3,
A high-hardness UV coating composition, characterized in that the polyfunctional urethane acrylate oligomer is added in an amount of 20 to 100 parts by weight. According to claim 4,
A high-hardness UV coating composition, characterized in that the multifunctional urethane acrylate oligomer comprises a hexafunctional aliphatic urethane acrylate oligomer. According to claim 4,
A high-hardness UV coating composition, characterized in that the multifunctional urethane acrylate oligomer is composed of an aliphatic urethane acrylate oligomer and an epoxy urethane acrylate oligomer. According to any one of claims 1 to 6,
A high-hardness UV coating composition further comprising a crosslinking density improver. According to any one of claims 1 to 6,
A high-hardness UV coating composition further comprising a diluent. A high-hardness UV coated paper coated with the coating composition according to any one of claims 1 to 6. An article to which the high-hardness UV coated paper according to claim 9 is applied.

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