KR20010087478A - Oriental lacquer formulations with improved electrical properties and method for curing the same - Google Patents

Abstract

PURPOSE: Provided are a lacquer composition having improved electric property and a curing method thereof for producing a lacquer film having conductivity and excellent coating property. CONSTITUTION: The lacquer composition, having a surface resistance value of 1011-1010 ohm, comprises 65-99wt% of lacquer, 0.5-30wt% of a compound (formula 1) for giving the conductivity, and 0.01-5wt% of a photoinitiator, wherein R1, R2, R5, and R6 are identically or differently hydrogen, methyl, or ethyl, R3 and R4 are identically or differently hydrogen, methyl, ethyl, propyl, or butyl, n is an integer of 1-10, and X- is CH3SO3, CH3SO4, or C2H5SO4. And the curing method comprises the steps of; curing the lacquer at an ordinary temperature under a humidity of 70-80%; irradiating UV for 5-25 seconds.

Description

Oriental lacquer formulations with improved electrical properties and method for curing the same

The present invention relates to a lacquer composition with improved electrical properties and a curing method thereof, and more particularly, a compound represented by the following Chemical Formula 1 for the purpose of forming a lacquer coating film having excellent conductivity of 10 ¹¹ to ^{10 10} Ω and other general properties. And a functional lacquer composition comprising a photoinitiator and a curing method thereof.

Wherein R ₁ , R ₂ , R ₅ and R ₆ are the same or different from each other, and are selected from the group consisting of hydrogen, methyl and ethyl groups, and R ₃ and R ₄ are the same or different from each other, hydrogen, methyl, ethyl, propyl and Selected from the group consisting of butyl groups, n is an integer from 1 to 10 and X ⁻ is an organic acid selected from the group consisting of CH ₃ SO ₃ , CH ₃ SO ₄ and C ₂ H ₅ SO ₄ .

Conventional natural paints mainly include ocher powder, wood powder, rubber components, rosin, linseed oil, dama resin, citrus oil, lacquer and the like in the coating composition.

Among them, lacquer is a natural paint taken from lacquer trees and is widely applied to crafts and wooden furniture because of its elegant luster and durability. It is also an environmentally friendly paint because it does not use organic solvents.

As an example of using such a lacquer as a paint, Korean Patent No. 40256 describes a lacquer composition containing photosafely treated fine particles having a particle size distribution of 0.01 to 20 micrometers, and in Korean Patent Application No. 87-5754. Application of lacquer or catshoe in the manufacture of ceramics describes the ease of post-processing such as gloss and stray light treatment. Korean Patent Application No. 95-24759 describes lacquer, clay powder and rice paste lacquer in the manufacture of dry board. A method of applying and drying is disclosed, and Korean Patent Application No. 97-80807 describes a transfer solution for painting containing 60 to 80% by weight of lacquer paint, and Korean Patent Application No. 98-40096 describes high quality woodworking. The application of lacquer to articles is said to have the effect of increasing the preservation and value of high-quality wood crafts by giving the pattern a brilliant and beautiful luster.

However, while lacquer has the advantages as described above, the surface is too hard, the drying speed is very slow, there is an operational drawback that must pay close attention to the drying management of temperature, humidity. Because of these disadvantages and very expensive features, lacquer is very poorly used as an industrial paint.

On the other hand, Japanese Patent No. 78-112651 describes the drying and physical properties of the cloth according to the conditions of temperature, humidity, air and oxygen, and Japanese Patent Application No. 81-26657 by applying polyphenol oxidase to lacquer Japanese Laid-Open Patent Publication No. 88-259207 describes that the application of isocyanate to lacquer liquid improves its physical properties and improves the drying of the lacquer. However, the above-described prior arts have the advantage that the drying and physical properties of the lacquer are improved, while the inherent properties of the lacquer are deteriorated. For example, the problem is that the soft luster disappears.

Accordingly, the present inventors intend to expand the scope of application of the lacquer coating method to electric, electronic and modern coatings as well as to the high value-added technology area by improving the electrical characteristics of the lacquer coating, as well as the inheritance and development of traditional technologies. As a result of extensive research, it has been found that the use of a lacquer composition in which a conductive functional compound and a photoinitiator are mixed with a lacquer solution improves the conductivity and overall coating properties of a coating film, and the present invention has been completed based on this.

Accordingly, the present invention is to provide a lacquer composition with improved conductivity and excellent coating properties.

In addition, another object of the present invention is to improve the curing reactivity of the conductive functional compound using the composition to impart a permanent electrical properties and at the same time to provide a curing method for producing a lacquer coating excellent coating properties required as other paints To provide.

The composition of the present invention for achieving the above object comprises 65 to 99% by weight of lacquer, 0.5 to 30% by weight conductive functional compound represented by the formula (1) and 0.01 to 5% by weight photoinitiator.

Formula 1

Wherein R ₁ , R ₂ , R ₅ and R ₆ are the same or different from each other and are selected from the group consisting of hydrogen, methyl and ethyl groups, and R ₃ and R ₄ are the same or different from each other in hydrogen, methyl, ethyl, propyl and butyl Selected from the group consisting of groups, n is an integer from 1 to 10, and X ⁻ is an organic acid selected from the group consisting of CH ₃ SO ₃ , CH ₃ SO ₄ and C ₂ H ₅ SO ₄ .

The method of curing the lacquer composition of the present invention for achieving the above another object consists of curing the composition under normal temperature and humidity of 70 to 80%, and then irradiating UV within 5 to 25 seconds.

1 is a graph showing the curing reactivity of the composition according to the present invention.

2 is a spectrum showing the results of surface analysis of the composition according to the present invention.

Hereinafter, the present invention will be described in more detail.

The lacquer is slightly different in composition depending on the region of origin, such as Korea, China, Japan, Southeast Asia, etc., in the present invention can be applied regardless of the region.

The conductive functional compound used in the present invention is represented by the following formula (1), it was used that contains a quaternary ammonium salt. The compound is conventionally mainly used in the field of ultraviolet coating or silicone hard coating, and in the present invention, hydroxypropyl acrylate is added while reacting to 70 ° C by adding piperazine, glycidyl methacrylate and 4-methoxyphenol. After stirring, dimethyl sulfate was mixed to give the final product. The amount of the compound used may be up to 0.5-30% by weight of the entire lacquer composition, but preferably in the range of 5-27% by weight, and exhibited excellent effects. If the amount of the compound used is less than 0.5% by weight, the conductive effect cannot be expected, and when the amount is used in excess of 30% by weight, the physical properties peculiar to lacquer deteriorate and curing reactivity decreases.

Formula 1

Wherein R ₁ , R ₂ , R ₅ and R ₆ are the same or different from each other and are selected from the group consisting of hydrogen, methyl and ethyl groups, and R ₃ and R ₄ are the same or different from each other in the hydrogen methyl, ethyl, propyl and butyl groups N is an integer from 1 to 10, and X ⁻ is an organic acid selected from the group consisting of CH ₃ SO ₃ , CH ₃ SO ₄ and C ₂ H ₅ SO ₄ .

The photoinitiator contained in the lacquer composition of the present invention includes a short wavelength photoinitiator and a long wavelength photoinitiator. In the present invention, in order to improve the curing reactivity and the final coating properties due to the synergistic effect, the mixture is used in an appropriate ratio. The short wavelength photoinitiators include benzyldimethyl ketal, hydroxy cyclohexyl phenyl and 2-hydroxy-2-methyl-1-phenyl-propane-1one (2-hydroxy-2-methyl- 1-phenyl-propane-1one) and one or more selected from the group consisting of, the long-wavelength photoinitiator to acylphosphine oxide (APO), diethoxy acetophenone (diethoxy acetophenone) and 2-chlorothioxane One or more selected from the group consisting of tons (2-chlorothioxanethon). On the other hand, the photoinitiator mixture is used 0.01 to 5% by weight, preferably in the range of 0.04 to 3% by weight is most suitable. If the total content of the photoinitiator is less than 0.01% by weight, the curing reactivity of the conductive function imparting compound is lowered, and when used in excess of 5% by weight, the coating properties of the lacquer coating film are lowered, and the economical efficiency is inferior because the photoinitiator is expensive. there is a problem.

The lacquer coating film of which the electrical characteristic of this invention was improved is manufactured by the following hardening methods.

After coating the lacquer composition of the present invention to a thickness of 45㎛, it is cured at room temperature for 24 hours under a humidity of 70 to 80%, and then irradiated with UV in the range of 5 to 25 seconds through UV curing, the electrical properties are An improved lacquer coating is formed.

In this case, when the curing humidity is less than 70%, the activity of the enzyme is weakened may cause a problem that the curing reactivity is delayed, if it exceeds 80%, the problem of wrinkles on the surface may occur while the curing proceeds quickly on the surface .

The curing method of the present invention undergoes ultraviolet curing, which is intended to provide the effect of improving the curing reactivity of the conductive functional compound contained in the final lacquer coating film, and if the ultraviolet irradiation time is less than 5 seconds, The hardening reaction may be degraded and the problem of permanently maintaining electrical characteristics may occur. If the curing time exceeds 25 seconds, the enzyme in the lacquer loses its activity due to high heat, which may delay the curing reactivity of the lacquer. Can be.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the scope of the present invention is not limited to the following Examples.

Production Example

The conductive functional compound represented by Chemical Formula 1 used in the present invention is a piperazine (0.1 mol) and glycidyl methacrylate (0.2 mol), and 4-methoxy phenol 0.4g while reacting to 70 ℃ 62.6 g of oxypropyl acrylate was added and stirred, followed by mixing dimethyl sulfate to obtain a final product.

Example 1

Japanese otaek 90% by weight, in the formula _{1 R = CH 3, n =} 1 and X ^- electricity = CH ₃ SO ₄ was stirred for 8% by weight, 1.5% by weight of a photoinitiator for the short wavelength, 0.5% by weight of a long wavelength photoinitiator for at room temperature After preparing a lacquer composition with improved mechanical properties, coating it to a PET film with a thickness of 45 μm, first curing at room temperature and 75% humidity for 24 hours, and then irradiating with UV for 10 seconds to improve electrical properties A coating film was prepared.

Examples 2-8

After preparing a lacquer composition according to the blending ratio of Table 1, except that the UV irradiation time shown in Table 1 was carried out in the same manner as in Example 1 to prepare a lacquer coating of the present invention.

Comparative Example 1

Chinese otaek 99.5% by weight, in Formula 1, R = H, n = 1 and X ^- and = CH ₃ SO ₃ was stirred for 0.195 wt%, photoinitiator 0.005% for long wave length at room temperature producing the electrical characteristics improved lacquer composition Then, it was coated on a PET film with a thickness of 45㎛, first cured at room temperature and 75% humidity for 24 hours, and then irradiated with ultraviolet light for 15 seconds to prepare a lacquer coating with improved electrical properties.

Comparative Examples 2 to 3

After the lacquer composition was prepared according to the blending ratio of Table 1, the lacquer coating of the present invention was prepared in the same manner as in Comparative Example 1 except for the UV irradiation time shown in Table 1.

The final physical properties of the lacquer coating film prepared using the lacquer compositions of Examples 1 to 8 and Comparative Examples 1 to 4 were measured by the following items and methods, and the results are shown in Table 2 below.

<Measurement item and measuring method>

(1) Surface resistance: Measure the surface resistance using the Surface Resistivity meter of PINION Products Corporation.

(2) Pencil hardness: Measured according to JIS D0202 (using UNI-PENCIL).

(3) Curing reactivity: Measured by the following equation (1).

Where I _{990, t = 2h} is the absorption intensity measured at 990cm ^-1 wavelength after 2 hours drying, I _{990, t = 2h} is the absorption intensity initially measured at 990cm ^-1 wavelength, and T _{t = 2h} is 2 Time value after time drying, T _{t = 0h} is the initial time value.

Components and amounts of lacquer composition (% by weight) division Lacquer composition (% by weight) UV curing Lacquer Conductivity giving compound Photoinitiator UV irradiation time (seconds) For short wavelength ¹ Long wavelength ² Control 100 - - - - Example 1 90 8 1.5 0.5 10 Example 2 85 14 0.5 0.5 8 Example 3 77 21 0.5 1.5 12 Example 4 82 17 0.3 0.7 15 Example 5 86 13 0.6 0.4 13 Example 6 86 13 0.8 0.2 20 Example 7 79 20 0.5 0.5 18 Example 8 77 22 0.7 0.3 22 Comparative Example 1 99.5 0.195 - 0.005 15 Comparative Example 2 85 14 One - 8 Comparative Example 3 86 13 - One 20 Comparative Example 4 86 13 0.8 0.2 3

1. Short-wavelength photoinitiator: Igacure 184, Igacure 651, etc. of Shiva Chemical Specialty Inc. may be used, and Igacure 184 was used in the present invention.

2. Long-wavelength photoinitiator: Igacure 907, Igacure369, TPO, etc. of Shiva Chemical Specialty Co. may be used, and TPO was used in the present invention.

Physical property evaluation result of lacquer coating film division Surface resistance (Ω) Pencil hardness Glossiness Curable Control 3.5 × 10 ¹³ HB 65 0.0004 Example 1 5.8 × 10 ¹¹ HB 62 0.0003 Example 2 3.2 × 10 ¹¹ 1H 67 0.0005 Example 3 5.5 × 10 ¹⁰ HB 64 0.0003 Example 4 8.1 × 10 ¹⁰ HB 68 0.0002 Example 5 1.4 × 10 ¹¹ 1H 62 0.0009 Example 6 2.7 × 10 ¹⁰ HB 66 0.0006 Example 7 4.3 × 10 ¹⁰ 1H 65 0.0010 Example 8 6.8 × 10 ¹⁰ 1H 63 0.0010 Comparative Example 1 9.2 × 10 ¹³ 1B 61 0.00009 Comparative Example 2 3.9 × 10 ¹³ 3B 38 0.00005 Comparative Example 3 4.8 × 10 ¹³ 1B 58 0.00006 Comparative Example 4 6.1 × 10 ¹³ 1B 55 0.00001

As can be seen from the evaluation results of Table 2 above, 0.5-30% by weight of a conductive functional compound was mixed with the lacquer, and a short wavelength photoinitiator and a long wavelength photoinitiator were added at a ratio of 0.01-5% by weight of the photoinitiator. It was possible to obtain a surface resistance value of 10 ¹¹ to ^{10 10} Ω without degrading the lacquer intrinsic properties.

In addition, it was possible to control the surface resistance value and curing reactivity by adjusting the compounding amount of the conductive function imparting compound, and at the same time can improve the coating properties of the lacquer coating film according to the type and content of the photoinitiator.

1 is a graph illustrating the change in absorption strength of 993 cm ^-1 changed over time by coating the lacquer composition of the present invention and curing for 8 hours using 2926 cm ^-1 as an internal standard band. Measured. As a result, in the case of the composition prepared in the present invention, the curing rate was observed between 0.0002 and 0.0010 in the content of 0.5 to 30% by weight of the conductive functional compound. On the other hand, when the content of the conductive function compound more than 30% by weight or the content of the photoinitiator is added less than 0.01% by weight, the curing rate was observed at 0.0002 or less.

Figure 2 is the result of observing the surface of the lacquer coating film prepared by coating the lacquer composition of the present invention according to the type of photoinitiator using FT-IR / ATR. As observed in the figure, when a long wavelength photoinitiator was mixed and used in an appropriate ratio than when the short wavelength photoinitiator was used alone, the absorption band of 812cm ^-1 represented by the acrylic group disappeared much more. In addition, it can be seen from these results that when the short wavelength photoinitiator and the long wavelength photoinitiator are mixed and used, the curing reactivity is improved by the synergy effect, and the final coating properties are improved.

As described above, the lacquer composition with improved electrical properties according to the present invention is expected to increase the industrial utilization of the lacquer coating method by imparting conductivity to the lacquer coating and improving curing reactivity and other coating properties.

Claims (5)

Lacquer composition with improved electrical properties, characterized in that it comprises 65 to 99% by weight of lacquer, 0.5 to 30% by weight of a conductive functional compound represented by the following formula (1) and 0.01 to 5% by weight of a photoinitiator. Formula 1 Wherein R ₁ , R ₂ , R ₅ and R ₆ are the same or different from each other and are selected from the group consisting of hydrogen, methyl and ethyl groups, and R ₃ and R ₄ are the same or different from each other in hydrogen, methyl, ethyl, propyl and butyl Selected from the group consisting of groups, n is an integer from 1 to 10, and X ⁻ is an organic acid selected from the group consisting of CH ₃ SO ₃ , CH ₃ SO ₄ and C ₂ H ₅ SO ₄ . The composition according to claim 1, wherein the composition has a surface resistance value of 10 ¹¹ to ^{10 10} Ω. The composition of claim 1, wherein the photoinitiator is used by mixing a short wavelength photoinitiator and a long wavelength photoinitiator. The method of claim 3, wherein the short wavelength photoinitiator is selected from the group consisting of benzyldimethyl ketal, hydroxy cyclohexyl phenyl and 2-hydroxy-2-methyl-1-phenyl-propane-1one, The long wavelength photoinitiator is a composition, characterized in that one or more selected from the group consisting of acylphosphine oxide, diethoxy acetophenone and 2-chlorothioxanthone. After curing the composition according to any one of claims 1 to 4 at room temperature and humidity of 70 to 80%, UV is irradiated within the range of 5 to 25 seconds of the lacquer composition with improved electrical properties, characterized in that Curing method.