KR102161333B1 - Packaging container for cationic polymerization composition and the packaging using the same - Google Patents

Abstract

The present invention relates to a packaging container for a cationic polymerizable composition and a packaging method using the same, characterized in that the cationic polymerizable composition and air are accommodated.

Description

A packaging container for a cationic polymerizable composition and a packaging method using the same {PACKAGING CONTAINER FOR CATIONIC POLYMERIZATION COMPOSITION AND THE PACKAGING USING THE SAME}

The present invention relates to a packaging container for a cationic polymerizable composition and a packaging method using the same, and more specifically, a packaging container for a cationic polymerizable composition capable of securing the aging stability of the cationic polymerizable composition for forming a bezel pattern, and It relates to a packaging method using this.

Metal wiring for driving the device is located around display devices such as TVs and monitors. Conventionally, a separate plastic case (bezel) was assembled to cover this, but recently, a method of directly printing a bezel pattern using a printing method such as inkjet has been used.

Recently used bezel pattern printing composition is using a cationic polymerizable composition that has excellent adhesion properties to a glass substrate. When the cationic polymerizable composition is stored in a container, the contents are deteriorated due to visible or ultraviolet light, or stored for a long time. However, the container is deformed by leaving it at a high temperature, causing problems such as evaporation of the solvent and leakage of the contents.

Such a cationic polymerizable composition suffers from a polymerization disorder due to moisture (moisture), but does not receive a polymerization disorder due to air, and thus polymerization cannot be prevented even if air is included in the container, resulting in a problem of thickening.

KR 10-2014-0072070 A

In order to solve the problems of the prior art, the present invention provides a packaging form of a cationic polymerizable composition that can be improved by injecting air when a thickening phenomenon occurs in a container storing the cationic polymerizable composition. It is aimed at.

In order to solve the above problem,

The present invention provides a packaging container for a cationic polymerizable composition, characterized in that the cationic polymerizable composition containing an iodonium salt photopolymerization initiator and air are accommodated.

In addition, the present invention provides a method for packaging a cationic polymerizable composition, characterized in that the cationic polymerizable composition containing an iodonium salt photopolymerization initiator and air are accommodated.

According to the present invention, in storing the cationic polymerizable composition in the packaging container, a packaging container capable of securing stability over time during storage by improving the occurrence of problems such as thickening in the container by air injection And there is an effect that can provide a method using the same.

1 is a schematic diagram showing a packaging container according to the present invention.

The inventors of the present invention have discovered through various attempts that when thickening occurs in the cationic polymerizable composition, if a special photopolymerization initiator is used, the stability of the cationic polymerizable composition can be secured by air injection.

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

The present invention provides a packaging container of a cationic polymerizable composition, characterized in that air and a cationic polymerizable composition containing an iodonium salt photopolymerization initiator are accommodated, as shown in FIG. 1.

In the present invention, the packaging container is such that the packaging container includes at least one blocking layer that blocks at least one of solvent, gas, visible light, and energy rays, so that deterioration and discoloration of the contents can be prevented. have. To this end, in order to improve gas barrier properties or moisture permeability, a pouch shape having two or more layers including the above barrier layer may be used, and preferably, an aluminum pouch film may be used as the barrier layer.

The material of the packaging container is not particularly limited as long as it can block at least one of solvent, gas, visible light, and energy ray, but preferably any one or more selected from the group consisting of synthetic resin, glass, or metal can be used. have.

In the packaging container of the present invention, air may be naturally mixed into the packaging container when the cationic polymerizable composition is injected without going through a separate air injection process. The air may be used regardless of dry air or wet air, but it is preferable not to contain nitrogen in order to prevent the thickening of the composition.

In the packaging container of the present invention, the amount of air contained in the packaging container is preferably contained in an amount of 20 to 100% by volume based on 100% by volume of the cationic polymerizable composition to be filled. When the amount of air is less than 20% by volume, the stability of the cationic polymerizable composition is insufficient, and when the amount of air exceeds 100% by volume, packaging efficiency is lowered, and there is a problem that bubbles are easily generated during transportation.

In the packaging container of the present invention, the cationic polymerizable composition contained in the packaging container may be a cationic polymerizable composition for bezel pattern printing.

In general, a radical polymerizable composition and a cationic polymerizable composition can be mainly used for the ultraviolet curable ink composition. In the case of a radical polymerizable composition, it is not suitable for curing a thin film because it suffers from curing disorder by oxygen. Due to the large shrinkage, the adhesion to the glass substrate is low, which is not suitable for forming a bezel pattern. On the other hand, in the case of a cationic polymerizable composition, it is advantageous for curing a thin film because the curing shrinkage is generally low and the effect of oxygen is small.

In the present invention, the cationic polymerizable composition may specifically include a colorant, an epoxy resin, an oxetane resin, and a photopolymerization initiator, and the content ratio of the epoxy resin: oxetane resin is 1:0.5 to 1:4 days I can.

The cationic polymerizable composition used in the present invention contains an epoxy resin as a cationic curing component. The epoxy resin is specifically selected from a bisphenol type epoxy resin, a novolac type epoxy resin, a glycidyl ester type epoxy resin, a glycidyl amine type epoxy resin, a linear aliphatic epoxy resin, a biphenyl type epoxy resin, and an alicyclic epoxy compound. It may be one or a mixture of two.

The alicyclic epoxy compound may mean a compound containing one or more epoxidized aliphatic cyclic groups.

In the alicyclic epoxy compound containing an epoxidized aliphatic cyclic group, the epoxidized aliphatic cyclic group refers to an epoxy group bonded to the alicyclic ring, for example, 3,4-epoxycyclopentyl group, 3,4-epoxy Cyclohexyl group, 3,4-epoxycyclopentylmethyl group, 3,4-epoxycyclohexylmethyl group, 2-(3,4-epoxycyclopentyl)ethyl group, 2-(3,4-epoxycyclohexyl)ethyl group, 3- Functional groups, such as a (3,4-epoxycyclophenyl)propyl group or a 3-(3,4-epoxycyclohexyl)propyl group, can be illustrated. In the above, the hydrogen atom constituting the alicyclic ring may be optionally substituted with a substituent such as an alkyl group. As the alicyclic epoxy compound, for example, a compound specifically exemplified below may be used, but the epoxy compound that may be used is not limited to the following types.

For example, dicyclopentadiene dioxide, cyclohexene oxide, 4-vinyl-1,2-epoxy-4-vinylcyclohexene, vinylcyclohexene dioxide, limonene monooxide, limonene dioxide, (3,4-epoxycyclohexyl)methyl- 3,4-epoxycyclohexanecarboxylate, 3-vinylcyclohexene oxide, bis(2,3-epoxycyclopentyl) ether, bis(3,4-epoxycyclohexylmethyl) adipate, bis(3,4- Epoxy-6-methylcyclohexylmethyl) adipate, (3,4-epoxycyclohexyl) methyl alcohol, (3,4-epoxy-6-methylcyclohexyl) methyl-3,4-epoxy-6-methylcyclohexane Carboxylate, ethylene glycol bis (3,4-epoxycyclohexyl) ether, 3,4-epoxycyclohexenecarboxylic acid ethylene glycol diester, (3,4-epoxycyclohexyl) ethyltrimethoxysilane, Daicel Corporation Celoxide 8000 manufactured by the company can be used.

The content of the epoxy resin is preferably 5 to 60% by weight, more preferably 10 to 30% by weight based on the total weight of the cationic polymerizable composition. When it exceeds 60% by weight, the viscosity of the composition increases, and when it is less than 5% by weight, the curing sensitivity decreases.

The cationic polymerizable composition contains an oxetane resin as another cationic polymerizable monomer.

The oxetane resin is a compound having a four-membered cyclic ether group in its molecular structure, and may function to lower the viscosity of the cationic cured ink composition (for example, less than 50 cPs at 25°C).

Specifically, 3-ethyl-3-hydroxymethyl oxetane, 1,4-bis[(3-ethyl-3-oxetanyl)methoxymethyl]benzene, 3-ethyl-3-(phenoxymethyl) Oxetane, di[(3-ethyl-3-oxetanyl)methyl]ether, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-cyclohexyloxymethyl oxetane or Phenol novolac oxetane and the like may be exemplified. As the oxetane compound, for example, "Allonoxetane OXT-101", "Allonoxetane OXT-121", "Allonoxetane OXT-211", "Allonoxetane OXT-221" by Toagosei, or "Alonoxetane OXT-212" or the like can be used. These can be used alone or in combination of two or more.

The content of the oxetane resin is preferably 15 to 80% by weight, more preferably 40 to 60% by weight based on the total weight of the cationic polymerizable composition. If it exceeds 80% by weight, the curing sensitivity is low, and if it is less than 15% by weight, the viscosity increases and the coatability decreases.

In addition, the oxetane resin of the present invention can be used, including an oxetane compound having one oxetane ring and an oxetane compound having two oxetane rings. When the oxetane compound having one oxetane ring and the oxetane compound having two oxetane rings are used together, the viscosity and flexibility of the film can be controlled. When two types of oxetane compounds are used together as described above, an oxetane compound having one oxetane ring: the content range of the oxetane compound having two oxetane rings is in the range of 1:16 to 1:3. It is preferable to use.

In addition, the present invention is characterized in that the content ratio of the epoxy resin: oxetane resin is 1:0.5 ~ 1:4. When the ratio of the epoxy compound and the oxetane compound exceeds 1:4, the coating property of the composition is excellent, but the curing sensitivity may be lowered as the viscosity of the composition is low. Accordingly, coating properties may be deteriorated.

The ink composition of the present invention uses an iodonium salt photopolymerization initiator as a cationic photopolymerization initiator. In the case of sulfonium salts conventionally used as cationic photopolymerization initiators, the solubility in epoxy compounds, oxetane compounds, binders or solvents is relatively insufficient, the curing sensitivity of the polymerization reaction is low, and the wavelength of the active energy ray for the polymerization reaction is There are limited drawbacks.

On the other hand, in the case of using an iodonium salt, the solubility in epoxy, oxetane, binder or solvent is excellent, curing sensitivity is high, and the wavelength selection of the active energy ray is relatively free, but as described above, stability during storage is poor. Because it falls, it needs to be improved.

The content of the iodonium salt photopolymerization initiator may include 0.5 to 15% by weight based on the total weight of the cationic polymerizable composition. When the content of the iodonium salt photopolymerization initiator is less than 0.5% by weight, the curing reaction is not sufficient, and when the content of the iodonium salt photopolymerization initiator is less than 15% by weight, the curing reaction may not be dissolved or the viscosity may increase, resulting in a decrease in coating properties.

The iodonium salt photopolymerization initiator causes a curing reaction in which a monomer having an unsaturated double bond contained in the ink reacts to form a polymer during an ultraviolet curing process, and a photosensitizer may be used depending on polymerization efficiency.

For example, the photopolymerization initiator may have an anion represented by SbF ₆ -, AsF ₆ -, BF ₆ -, (C ₆ F ₅ ) ₄ B-, PF ₆ -or RfnF _6-n , but is limited thereto. It does not become.

The photopolymerization initiator is preferably contained in an amount of 1 to 15% by weight, more preferably 2 to 10% by weight, based on the total weight of the cationic polymerizable composition. If the content of the photopolymerization initiator is less than 1% by weight, the curing reaction is not sufficient, and if it is more than 15% by weight, all of them are not dissolved or the viscosity increases, resulting in a decrease in coating properties.

The cationic polymerizable composition may have a thickening ratio of 200% or less after 30 to 90 days at 5 to 50°C, depending on the composition as described above. As the thickening rate is adjusted within the above range, the viscosity of the cationic polymerizable composition is not significantly changed over time, so that the stability of the cationic polymerizable composition can be maintained.

The cationic polymerizable composition contains a colorant.

As the colorant, one or more pigments, dyes, or mixtures thereof may be used, and there is no particular limitation as long as the color can be expressed as required.

As a specific example of the present invention, carbon black, graphite, metal oxide, organic black pigment, etc. may be used as the black pigment.

Examples of carbon black include Cysto 5HIISAF-HS, Cysto KH, Cysto 3HHAF-HS, Cysto NH, Cysto 3M, Cysto 300HAF-LS, Cysto 116HMMAF-HS, Cysto 116MAF, Cysto FMFEF-HS. , Systo SOFEF, Systo VGPF, Systo SVHSRF-HS and Systo SSRF (Donghae Carbon Co., Ltd.); Diagram Black II, Diagram Black N339, Diagram Black SH, Diagram Black H, Diagram LH, Diagram HA, Diagram SF, Diagram N550M, Diagram M, Diagram E, Diagram G, Diagram R, Diagram N760M, Diagram LR, #2700, # 2600, #2400, #2350, #2300, #2200, #1000, #980, #900, MCF88, #52, #50, #47, #45, #45L, #25, #CF9, #95, # 3030, #3050, MA7, MA77, MA8, MA11, MA100, MA40, OIL7B, OIL9B, OIL11B, OIL30B and OIL31B (Mitsubishi Chemical Corporation); PRINTEX-U, PRINTEX-V, PRINTEX-140U, PRINTEX-140V, PRINTEX-95, PRINTEX-85, PRINTEX-75, PRINTEX-55, PRINTEX-45, PRINTEX-300, PRINTEX-35, PRINTEX-25, PRINTEX- 200, PRINTEX-40, PRINTEX-30, PRINTEX-3, PRINTEX-A, SPECIAL BLACK-550, SPECIAL BLACK-350, SPECIAL BLACK-250, SPECIAL BLACK-100, and LAMP BLACK-101 (Daegu Corporation); RAVEN-1100ULTRA, RAVEN-1080ULTRA, RAVEN-1060ULTRA, RAVEN-1040, RAVEN-1035, RAVEN-1020, RAVEN-1000, RAVEN-890H, RAVEN-890, RAVEN-880ULTRA, RAVEN-860ULTRA, RAVEN-850, RAVEN- 820, RAVEN-790ULTRA, RAVEN-780ULTRA, RAVEN-760ULTRA, RAVEN-520, RAVEN-500, RAVEN-460, RAVEN-450, RAVEN-430ULTRA, RAVEN-420, RAVEN-410, RAVEN-2500ULTRA, RAVEN-2000, RAVEN-1500, RAVEN-1255, RAVEN-1250, RAVEN-1200, RAVEN-1190ULTRA, and RAVEN-1170 (Colombia Carbon Co., Ltd.), or mixtures thereof.

As the organic black pigment, aniline black, lactam black, or perylene black series may be used, but is not limited thereto.

In the present invention, the cationic polymerizable composition is cured by irradiation with ultraviolet (for example, 250 or 450 nm), more preferably, long-wavelength ultraviolet (for example, 360 nm to 410 nm) to have a certain level of OD (Optical Density). It is characterized by that. To this end, the content of the colorant is preferably 1 to 15% by weight, more preferably 3 to 10% by weight based on the total weight of the cationic polymerizable composition. When the content of the colorant is less than 1% by weight, an OD equivalent to that of the bezel does not appear, and when the content of the colorant is more than 15% by weight, an excess colorant may not be dispersed in the ink and a precipitate may be formed.

In addition, the present invention is a packaging method for a cationic polymerizable composition using the packaging container, wherein the cationic polymerizable composition containing an iodonium salt photopolymerization initiator and air are accommodated. Provides a way.

In the packaging method of the present invention, a detailed description of the packaging container, the cationic polymerizable composition, and air is as described in the packaging container of the cationic polymerizable composition of the present invention.

Hereinafter, the present invention will be described in detail by way of examples. The following examples are for explaining the present invention, and the scope of the present invention includes the ranges described in the following claims and their substitutions and modifications, and is not limited to the scope of the examples.

Example

[Examples 1 to 5 and Comparative Examples 1 to 4]

99 parts by weight of a cationic polymerizable ink composition for bezel pattern (LG-751M, manufactured by LG Chem) was mixed with 1 part by weight of a photopolymerization initiator of a diaryliodonium salt as shown in Table 1 below. Thereafter, the composition was injected so that a certain amount of air was present in a glass bottle or a container made of synthetic resin as shown in Table 1 below, and stability was evaluated. When the composition and air were injected into the container, it was carried out in a clean room with a relative humidity of 50% or a dry room with a relative humidity of 0%.

Example One 2 3 4 5 Furtherance Light polymerization
Initiator Omnicat 440 (IGM resin) Rhodosil2074
(Blue Star Silicone) Igacure
250 (BASF) WPI-170
(Made by Wako) WPI-170
(Made by Wako) 1 part by weight 1 part by weight 1 part by weight 1 part by weight 1 part by weight Packing Container type glass bottle glass bottle Synthetic resin bottle Synthetic resin
film glass bottle Type of gas Psychrometric Psychrometric Psychrometric Dry air Dry air Base injection amount 60% by volume 90% by volume 40% by volume 25% by volume 90% by volume Comparative example One 2 3 4 Furtherance Light polymerization
Initiator Omnicat 440 (IGM resin) Omnicat 440 (IGM resin) Omnicat 440 (IGM resin) Omnicat 440 (IGM resin) 1 part by weight 1 part by weight 1 part by weight 1 part by weight Packing Container type glass bottle glass bottle Synthetic resin bottle glass bottle Type of gas Psychrometric nitrogen Dry air Psychrometric Base injection amount Not injected 50% by volume 10% by volume 120% by volume

[Photopolymerization initiator]

Diaryliodonium salt: Omnicat 440 (IGM resin), Rhodosil 2074 (manufactured by Blue Star Silicone), Igacure 250 (manufactured by BASF), WPI-170 (manufactured by Wako)

[Material of packaging container]

Glass bottle: Glass vial test bottle with a rated capacity of 20cc (manufactured by Kwangjin Chemical)

Synthetic resin bottle: A test bottle made of polypropylene with a rated capacity of 60cc (manufactured by Nalgene)

Synthetic resin film: Pouch bag made of polyethylene terephthalate/aluminum/nylon/ultra-low density polyethylene structure with a rated capacity of 1000cc (manufactured by NITE)

[Type of packaging gas]

Moist air: normal air with 50% relative humidity

Dry air: dry air with 0% relative humidity

Nitrogen: nitrogen gas (100% purity)

[Measurement of gas injection amount]

The gas injection amount was expressed as the fraction (%) of the volume occupied by the gas relative to the ink volume. In the glass bottle and the synthetic resin bottle, the maximum volume that can be injected without overflowing the composition was calculated as the total volume, and the volume limit of the injected composition was calculated as the volume of air. The synthetic resin pouch was calculated by comparing the volume of water that overflowed from the water tank by the pouch before the composition was injected and the volume of water that overflowed from the water tank by the pouch before the composition was injected, using Archimedes' principle.

<Experimental Example 1>: Thickening rate

For the packaging containers of Examples 1 to 5 and Comparative Examples 1 to 4, each container was stored in a convection oven maintained at 45° C. for January to 3 months.

The viscosity of the composition in each container was measured using a Viscometer DV-2 (Brookfield) at 25 degrees Celsius. The increase in viscosity based on the initial viscosity (viscosity increase/initial viscosity) was calculated, classified as follows, and the results are shown in Table 2.

* When solidified by reaction: solidified

*Over 200%: X

* In the case of 50% to 200%: △

*In case of 10% to 50%: ○

*If less than 10%: ◎

Example One 2 3 4 5 Stability packaging After January ◎ ◎ ◎ ◎ ◎ February ◎ ◎ ◎ ◎ ◎ March ○ ◎ ○ △ ◎ Comparative example One 2 3 4 Stability packaging After January ◎ ◎ ◎ ◎ February X △ △ ◎ March rigidity rigidity rigidity ◎

From the results of Table 2 above,

According to the packaging containers of Examples 1 to 5 according to the present invention, it was confirmed that the viscosity of the cationic polymerizable composition was maintained because the change in viscosity was not large over time.

On the other hand, in the case of Comparative Examples 1 and 3, a rapid change in viscosity occurred from the elapse of 2 months, and the composition was hardened after 3 months.

In the case of Comparative Example 2, 50% by volume of nitrogen gas was injected, but unlike when air was injected, the effect of suppressing the thickening did not appear, and the composition solidified within 3 months. When 120% of air was injected as in the case of Comparative Example 4, thickening did not appear even after a maximum of 3 months, but packaging was not economical because more air was present than ink in the packaging container.

Claims (18)

Cationic polymerizable composition containing an iodonium salt photopolymerization initiator and air are accommodated, and the air is contained in an amount of 90 to 100% by volume based on 100% by volume of the cationic polymerizable composition, and is made of a glass material Packaging container of the cationic polymerizable composition. The method according to claim 1,
The packaging container is a packaging container of a cationic polymerizable composition, characterized in that it comprises at least one layer of blocking layer for blocking at least one of solvent, gas, visible light and energy rays. delete The method according to claim 2,
The packaging container of the cationic polymerizable composition, characterized in that the blocking layer is an aluminum pouch film. delete delete The method according to claim 1,
The cationic polymerizable composition is a packaging container, characterized in that for printing a bezel pattern. The method according to claim 1,
The cationic polymerizable composition comprises a colorant, an epoxy resin, an oxetane resin and an iodonium salt photoinitiator,
Packaging container, characterized in that the content ratio of the epoxy resin: oxetane resin is 1:0.5 ~ 1:4. The method of claim 8,
The oxetane resin is a packaging container comprising an oxetane compound having one oxetane ring and an oxetane compound having two oxetane rings. The method of claim 9,
The packaging container, characterized in that the content ratio of the oxetane compound having one oxetane ring: the oxetane compound having two oxetane rings is 1:16 to 1:3. The method of claim 8,
The content of the epoxy resin is a packaging container, characterized in that 5 to 60% by weight based on the total weight of the cationic polymerizable composition. The method of claim 8,
The content of the oxetane resin is a packaging container, characterized in that 15 to 80% by weight based on the total weight of the cationic polymerizable composition. The method of claim 8,
Packaging container, characterized in that the content of the iodonium salt photopolymerization initiator is 0.5 to 15% by weight based on the total weight of the cationic polymerizable composition. The method of claim 13,
The cationic polymerizable composition has a thickness of 200% or less after 30 to 90 days at 5 to 50°C. The method of claim 8,
The content of the colorant is a packaging container, characterized in that 1 to 15% by weight based on the total weight of the cationic polymerizable composition. The method of claim 8,
The cationic polymerizable composition is a packaging container, characterized in that cured by absorbing ultraviolet rays in a wavelength range of 250 nm to 450 nm. The method of claim 16,
The cationic polymerizable composition is a packaging container, characterized in that cured by absorbing ultraviolet rays in a wavelength range of 360 nm to 410 nm. A cationic polymerizable composition containing an iodonium salt photopolymerization initiator and air are accommodated in a glass packaging container,
The air is a packaging method of a cationic polymerizable composition, characterized in that contained in 90 to 100% by volume based on 100% by volume of the cationic polymerizable composition.

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