KR20030032818A - Method for preparing epoxy resin containing photochromic compound and chameleon compound, and forms coated with the same - Google Patents

Abstract

PURPOSE: A method for preparing an epoxy resin containing a photochromic compound and a chameleon compound and molded product coated with the epoxy resin are provided, to improve the concentration of color and to enable the photochromic compound and the chameleon compound to be infiltrated into the epoxy resin uniformly. CONSTITUTION: The method comprises the steps of mixing 0.5-3 g of a photochromic compound and 0.1-1 g of a chameleon compound with a solvent mixture consisting of 500-700 g of toluene and 100-300 g of methylene chloride; mixing 400-600 g of the obtained mixture with 1,000 g of a thermosetting bisphenol-based epoxy resin with a softening point of 160-300 deg.C and a molecular weight of 300-4,000; mixing 200-400 g of the obtained mixture with 500 g of a thermosetting bisphenol-based epoxy resin with a softening point of 160-300 deg.C and a molecular weight of 300-4,000; and curing the obtained mixture, and drying the cured one at a temperature of 70-80 deg.C for 3-4 hours. Preferably the photochromic compound is naphtopyrane-based compound; and the chameleon compound changes the color at a temperature range of -10 to 65 deg.C.

Description

Method for preparing epoxy resin containing photochromic compound and chameleon compound and molded article coated thereon {Method for preparing epoxy resin containing photochromic compound and chameleon compound, and forms coated with the same}

The present invention relates to a method for producing an epoxy resin containing a photochromic compound and a chameleon compound and to a molded article coated with the epoxy resin. More specifically, the photochromic compound and a chameleon compound are uniformly mixed with an epoxy resin to form a resin. The present invention relates to a method for producing an epoxy resin containing a photochromic compound and a chameleon compound that can change color and shorten curing time and pot life in a manufacturing process, and a molded article coated with the epoxy resin.

In general, photochromatism refers to a reversible photochromic phenomenon caused by a compound that changes color under ultraviolet rays such as sunlight or artificial lighting including ultraviolet rays and returns to a colorless and transparent color under UV blocking or in the dark.

These photochromic materials exist in a double-bottom state that absorbs ultraviolet light strongly and absorbs visible light strongly. Thus, the photochromic material is colored when exposed to ultraviolet rays and then converted into a colorless transparent state when blocked by ultraviolet rays. It is a compound that provides a variety of colors depending on the presence or absence of ultraviolet rays, as a kind of benzopyran-based compound (Korean Patent Application No. 98-018556), naphthopyran-based compound (Korean Patent Publication No. 99-0170432 ), A spiroxazine-based compound, and a spiropyran-based compound (Korean Patent Application No. 90-701930).

Until now, such photochromic compounds have been mainly used in glass such as automobiles and buildings, or have been used in the manufacture of ophthalmic glass such as sunglass or glass or plastic lenses. For example, Korean Patent Publication No. 94-07779 provides a product having an organic photochromic material in a plastic matrix such as a photochromic ophthalmic lens and a car roof skylight.

Recently, cosmetic products and coating agents (Korean Patent Application Nos. 99-06814 and 99-048421), such as cosmetics or nail polish (Korean Patent Application No. 99-06813), which focus on photochromic properties of photochromic compounds, The use of compounds is expanding.

Meanwhile, until now, such photochromic compounds are used to provide various colors. In the manufacture of products, the photochromic compounds are incorporated into raw materials, or these compounds are dissolved in a solvent together with a polymer and then coated. It has been used by a method of forming a film.

For example, in Korean Patent Application No. 2001-1402, 20 to 30% by weight of resin, 1 to 3% by weight of camphor, 4 to 6% by weight of dibutyl phthalate, 4 to 6% by weight of ethyl acetate, 12 to 18% by weight of toluene , 12-18 wt% butyl acetate, 4-6 wt% isopropyl alcohol, 10-12 wt% cellulose acetate butyrate, 0.1-0.3 wt% polyethylene wax, 8-12 wt% methyl isobutyl ketone, methyl isoethyl ketone 10 A photochromic trinket accessory coating / printer composition comprising from 15 wt% to 0.5 wt% of a photochromic compound is disclosed.

In addition, Korean Patent Publication No. 2001-84405 discloses a solution obtained by dissolving a spiropyrane photochromic compound in a toluene / alcohol mixed solvent in a resin granule at 0.05 to 48 hours at 0.05 to 48 hours, and then 160 to 300. Disclosed is a method for producing a photochromic resin molded product which is heated to a temperature and molded.

In addition, Korean Patent Application No. 2001-29435 discloses 30 to 50 parts by weight of methyl ethyl ketone, 10 to 20 parts by weight of toluene, 10 to 20 parts by weight of xylene, 5 to 10 parts by weight of ethyl acetate, and 5 to 10 parts by weight of isopropyl alcohol. After mixing the fragrance 0.001-5 parts by weight and the photochromic compound 0.1-20 parts by weight, 50-100 parts by weight of the resin was added and immersed for 1 to 24 hours, and after stirring uniformly, the solvent was dried and primary grinding Then, a method for producing a master batch of a photochromic resin molding which is rapidly cooled after heating is disclosed.

On the other hand, the chameleon compound is a compound exhibiting color in response to the ambient temperature, also referred to as thermochromic dye. Such chameleon compounds are Korean Utility Model Application No. 96-23453 (Far Infrared Radiation and Temperature Sensing Device for Wearing Goods), Korean Utility Model Application No. 98-25822 (Insulation Cap for Wire Connection) or Korean Patent Application No. 2000- It has been used simply by adding it to the target resin as in 25073 (thermochromic hair coating or dye composition).

However, the coating layer of the moldings provided by this method is more excellent in spite of the excellent discoloration characteristics of the photochromic compound and chameleon compound due to problems such as easy peeling or detachment of the photochromic compound or chameleon compound particles. There have been many limitations in the use, such as being unable to use variously in a wide range of fields requiring the formation of a smooth and uniform coating layer.

In addition, the resin molding provided by the above method was not only poor in durability, but also had a disadvantage that the photochromic compound or chameleon compound did not uniformly penetrate the resin. In addition, there is no example in which the photochromic compound and the chameleon compound were simultaneously infiltrated into a resin, particularly an epoxy resin.

Therefore, in the present invention, as a result of extensive research in order to solve the above problems, lower alcohols and lower acetates in the mixed organic solvent used as the solvent of the photochromic compound destroys the molecular structure of the photochromic compound, thereby causing problems in durability. In the organic solvent except for this, a mixed organic solvent and a penetration method capable of penetrating the chameleon compound to the epoxy resin under a certain condition at a high concentration were found, and the present invention was completed based on this.

Accordingly, it is an object of the present invention to provide a method for producing an epoxy resin containing a photochromic compound and a chameleon compound, which is excellent in durability of the photochromic and chameleon resin moldings and is capable of uniformly penetrating the photochromic compound and chameleon compound into the epoxy resin. To provide.

Another object of the present invention is to provide a molded article coated with the photochromic and chameleon epoxy resin obtained from the above method.

The method for producing an epoxy resin containing the photochromic compound and chameleon compound of the present invention for achieving the above object is 0.5 g to 3 g of a photochromic compound and a chameleon compound in a mixed organic solvent composed of 500 g to 700 g of toluene and 100 g to 300 g of methylene chloride. Providing a first mixture in which 0.1-1 g is mixed; Adding 400-600 g of the first mixture to 1,000 g of a thermosetting bisphenol-type epoxy resin having a softening point of 160 to 300 ° C. and a molecular weight of 300 to 4,000 to provide a second mixture; Providing a third mixture obtained by mixing 200-400 g of the second mixture with 500 g of a thermosetting bisphenol-type epoxy resin having a softening point of 160-300 ° C. and a molecular weight of 300-4,000; And adding a curing agent to the third mixture, and then drying at 70 to 80 ° C. for 3 to 4 hours.

The molding for achieving another object of the present invention is applied to a sticker, a cell phone accessory, a sunglass, an artificial nail-shaped sticker, a garment, a shoe, a hat, a key ring, etc. to apply the epoxy resin obtained from the above method to a fancy sticker, various designs and the like. Get it done.

Looking at the present invention in more detail as follows.

As described above, the method for producing an epoxy resin of the present invention is a mixture of a mixed organic solvent consisting of toluene and methylene chloride, a photochromic compound and a chameleon compound first, and then, at room temperature in a thermosetting bisphenol type epoxy resin having a specific softening point and molecular weight. The mixture, which has been infiltrated for an appropriate period of time, and the new thermosetting bisphenol type epoxy resin are mixed, then cured and dried.

According to the present invention, lower alcohols such as isopropyl alcohol and lower acetates such as ethyl acetate, butyl acetate and the like in the mixed organic solvent used as the solvent of the photochromic compound and chameleon compound are molecules of the photochromic compound. The structure was destroyed to reduce the color durability of the photochromic resin molding. In the present invention, the use of these in the mixed organic solvent was excluded. In addition, a combination was found in which the chameleon compound could be dissolved to easily penetrate the epoxy resin.

In the present invention, a preferred mixed organic solvent for dissolving 0.5 g to 3 g of the photochromic compound and 0.1 to 1 g of the chameleon compound is composed of 500 g to 700 g of toluene and 100 g to 300 g of methylene chloride.

In particular, in the present invention, 100 g to 300 g of methylene chloride may be used as a mixed organic solvent, and the methylene chloride has not been used as a solvent of a photochromic compound and a chameleon compound.

If the amount of the methylene chloride is less than 100g, there is a tendency to color the resin surface due to supersaturation of the color, and if it exceeds 300g, the concentration of the color is low and it is difficult to penetrate uniformly.

The photochromic compound suitable for the present invention is preferably a naphthopyran-based compound, and the chameleon compound (thermochromic dye) may be contained as a monochromatic dye or a mixture of two or more kinds of pigments having different colors, and also discolored at a specific temperature. It may be contained as a monochromatic pigment | dye, 2 or more types of pigment mixtures discoloring at the same temperature, or 2 or more types of pigment mixtures discoloring at different temperature.

In the color of the chameleon compound, representative ones currently being developed are black, red, blue, yellow, green, orange, magenta, and magenta. Sky blue and violet.

In addition, in the discoloration temperature of the chameleon compound, one of the ones currently being developed may change within a temperature range of -10 ° C to 65 ° C. For example, a chameleon compound expressing a color in response to a temperature such as -10, -5, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, or 65 ° C Discolorable pigments) are known. Of these, suitable for use in the present invention are discoloration at ambient temperature.

Chameleon compounds have been developed in various forms. Among these products, consideration should be given to compatibility with photochromic compounds, solubility in organic solvents, and safety in penetration into epoxy resins. Whether or not.

Although not particularly limited, the chameleon compound suitable for application to the epoxy resin of the present invention contains an electron-donating material and an electron-accepting material in the microcapsule, and when they are heated, they are independent entities. It is a microcapsule type thermochromic pigment that causes a reaction and expresses a specific color. Currently, microcapsule type thermochromic pigments have been developed that have an average particle size of several microns and do not destroy capsules even under severe conditions.

In the present invention, such microcapsule type thermochromic pigment may be blended in a dry state (powder state) or an aqueous slurry state. In the case of blending in the aqueous slurry state, the content of the microcapsule discoloring pigment in the aqueous slurry is preferably 10 to 60% by weight based on the solid content.

On the other hand, the epoxy resin used in the present invention is a thermosetting bisphenol type epoxy resin, the molecular weight of which is preferably 300 to 4,000, and the softening point is preferably 160 to 300 ° C. If the molecular weight is less than 300, the difference in discoloration according to the presence or absence of sunlight is not largely known. If the molecular weight exceeds 4,000, the discoloration rate due to sunlight tends to be lowered. If the softening point is less than 160 ° C, the pot life is too short. When it exceeds 300 degreeC, hardening time will become too long.

Meanwhile, according to the present invention, a second mixture is obtained by adding a part of an epoxy resin to a first mixture in which a photochromic compound and a chameleon compound are dissolved in a solvent. Then, the new epoxy resin and the second mixture are mixed.

Thus, by mixing the photochromic compound, chameleon compound and epoxy resin in two stages, an even concentration distribution of the photochromic compound and a viscosity maintaining effect of the epoxy resin can be obtained.

Next, an amine curing agent is added to the epoxy resin containing the photochromic compound and the chameleon compound, and then applied to the printed matter and dried at 70 to 80 ° C. for 3 to 4 hours.

As such, the thermosetting bisphenol-type epoxy resin according to the present invention can shorten the curing time and the pot life, and can penetrate both the photochromic compound and the chameleon compound at a high concentration. In addition, by drying at 70 ~ 80 ℃ can make chameleon and photochromic properties and can produce an epoxy resin excellent in stability and heat resistance.

Therefore, the conventional epoxy products can not give a change in color (functionality) by the method of coating and drying on the picture or letters, and the drying time was long, but the photochromic and chameleon epoxy resins according to the present invention have a chameleon color indoors. It can then be converted to ultraviolet color outdoors to produce the functional epoxy desired by the consumer.

As described above, in the present invention, the mixed organic solvent, the photochromic compound, and the chameleon compound are liquefied together, mixed into the epoxy resin uniformly in two steps, and then cured and dried to uniformly infiltrate the photochromic compound and the chameleon compound into the resin. The color heat resistance and color durability of the resin can be maintained.

The photochromic and chameleon resin obtained from the above method can be applied to a molded product (product) and dried on a drying stand maintained at 60 to 70 ° C to obtain a product. The molded article may be, but is not limited to, stickers, cell phone accessories, sunglasses, artificial nail-shaped stickers, clothing, shoes, hats, key rings, etc. to be applied to fancy stickers, various designs, and the like.

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

Example 1

In a 500 L Henschel mixer, 600 g of toluene, 200 g of methylene chloride, 1 g of photochromic compound (Photochromic) and 0.5 g of chameleon compound (Japanese Prism, Chameleon: Blue Sky) were mixed at 600 rpm for 10 minutes. 500 g of the mixture was mixed with 1,000 g of a thermosetting epoxy resin (Deonyoung Chemical, GH202) having a softening point of 200 ° C. and an average molecular weight of about 2,000 for 20 minutes at 900 rpm.

To 300 g of the mixture, 500 g of a new softening point of 160 ° C. and an average molecular weight of about 2,000 were mixed at 500 rpm for 30 minutes at 900 rpm, and 800 g of an amine curing agent (Samsung Epoxy) was added thereto. It cured at 8 degreeC. This was applied to the printed matter and dried for 3 to 4 hours at a temperature of 70 to 80 ° C.

Example 2

The same procedure was followed except that 0.02 g of a light stabilizer (Japan Shin-Etsu Co., Ltd. PL50) was further added to the final mixture of Example 1.

Comparative Example 1

The epoxy resin was carried out in the same manner as in Example 1 except that a thermosetting epoxy resin having a softening point of 350 ° C. and an average molecular weight of about 5,000 was used.

According to Examples 1 and 2 and Comparative Example 1, the discoloration rate and the degree of discoloration were determined by the sensory test when the epoxy was exposed to the room and sunlight. The results are shown in Table 1 below. In addition, using a daylight fastness measuring instrument, the conditions of 40 ℃, relative humidity 40% and using a UV lamp as a light source was determined by the sensory test the speed of change and the degree of change of color by UV irradiation and irradiation time and the results are shown in Table 1 It was.

division Example 1 and Example 2 Comparative example color Functionality (Indoor: Chameleon, Outdoor: Photochromic) Left Drying time 3 to 4 hours More than 6 hours Curing time 7-8 hours at 20 ℃ 24 hours at 20 ℃ Pot life ¹⁾ (100g) 30 minutes (100g) 30 minutes or more Drying temperature 70 ℃ ~ 80 ℃ 80 ℃ UV protection 96% 60% decolorization Good usually

1) Pot life: time to start to harden after mixing the main material and hardener

As described above, the method of the present invention uses a mixed organic solvent composed of toluene and methylene chloride as a mixed organic solvent used as a solvent for the photochromic compound and chameleon compound, and penetrates into a thermosetting bisphenol type epoxy resin having a specific softening point and molecular weight. Through the infiltration process and the drying process, the photochromic compound can be uniformly infiltrated into the epoxy resin to express a uniform color and high concentration color.

In addition, the method of the present invention can shorten the curing time and pot life by selecting a thermosetting bisphenol-type epoxy resin as the main epoxy resin, and excellent effect on the color change (change from chameleon color to photochromic color outdoors) There is).

Claims (5)

Providing a first mixture of 0.5 g to 3 g of a photochromic compound and 0.1 to 1 g of a chameleon compound in a mixed organic solvent composed of 500 g to 700 g of toluene and 100 g to 300 g of methylene chloride; Adding 400-600 g of the first mixture to 1,000 g of a thermosetting bisphenol-type epoxy resin having a softening point of 160 to 300 ° C. and a molecular weight of 300 to 4,000 to provide a second mixture; Providing a third mixture obtained by mixing 200-400 g of the second mixture with 500 g of a thermosetting bisphenol-type epoxy resin having a softening point of 160-300 ° C. and a molecular weight of 300-4,000; And Adding a curing agent to the third mixture, and then drying for 3 to 4 hours at 70 ~ 80 ℃; manufacturing method of epoxy resin containing a photochromic compound and chameleon compound. The method of claim 1, wherein the photochromic compound is a naphthopyran-based compound. The method of claim 1, wherein the chameleon compound is -10 ℃ as a mixture of one or two or more selected from the group consisting of black, red, blue, yellow, green, orange, magenta, sky blue and violet color pigments Discoloration in the temperature range of 65 ℃. A molded article coated with an epoxy resin containing a photochromic compound and a chameleon compound obtained from the method of any one of claims 1 to 3. The molded article according to claim 4, wherein the molded article is a fancy sticker, a sticker, a cell phone accessory, a sunglass, an artificial nail-shaped sticker, a garment, a shoe, a hat, or a key ring.