KR20130077142A - Luminescent artificial marble - Google Patents

Abstract

PURPOSE: A phosphorescent artificial marble with excellent phosphorescent effect is provided to minimize the content of the phosphorescent pigment by using an unsaturated polyester resin, and a silica-containing compound and a phosphorescent pigment in the optimal rate. CONSTITUTION: A phosphorescent artificial marble comprises 7-10 weight% of a polyester resin (A), 85-91 weight% of a silica-containing compound (B), and 2-5 weight% of a phosphorescent pigment (C). The phosphorescent artificial marble has maximum luminance over 110mcd / m^2 and maintains the brightness over 7mcd / m for more than 1 hour. The silica-containing compound (B) includes a natural stone particle (B1) 50-80 weight% and an inorganic filler (B2) 20-50 weight% against silica-containing compound 100 weight%. The average particle diameter of the natural stone particle (B1) is 0.1-9.0mm. The inorganic filler (B2) is the silica powder with the average particle diameter is 20 μm or less. The average particle diameter of the phosphorescent pigment (C) is 6-150 μm.

Description

Luminescent Artificial Marble

The present invention relates to a photoluminescent artificial marble. More specifically, the present invention is made by adding a photoluminescent pigment to a resin-based reinforced natural stone composed of an unsaturated polyester resin, a silica-containing compound artificially expressing the overall photoluminescent effect in the dark while maintaining the texture and appearance of the existing artificial marble in the bright place It's about marble.

Natural stone, such as granite and marble, has been used as an architectural decoration material since ancient times because of its beautiful surface pattern. Recently, it has been spotlighted as a material of high quality texture, and its demand in the fields of flooring, wall, counter top, etc. Is increasing significantly. As a result, expensive natural stones alone cannot meet the demand, and as a result, various kinds of artificial stones were developed.

Artificial stone is vacuum-compressed compound made of general artificial stone manufactured by adding various mixed materials such as inorganic filler, colorant, hardener to acrylic or unsaturated polyester base resin, and inorganic (silica-based) natural mineral and binder resin. It is classified as a resin-based reinforcement natural stone (called "Engineering stone") which is molded to express the texture of natural stone as it is.

The resin-reinforced natural stone can be manufactured to exhibit a variety of colors and textures according to the type of natural minerals to be mixed, the color of the resin or pigment, the stirring process, etc. Since the natural minerals as the main raw material is much better than natural artificial stone In recent years, the demand has increased greatly.

The resin-reinforced natural stone prepared as described above may be manufactured in a single color, or may be made to have a multicolor tone by mixing a resin mixture having different colors by adding pigments of different colors, respectively, in a mixer, or using chips to have a natural stone texture. Doing.

However, the color, pattern, and pattern of the conventional resin-reinforced natural stone as described above has been used for a long time, and there is a problem that it is insufficient to satisfy the consumer's desire for the production of various textures, and does not escape the monotonous feeling. .

In an attempt to improve the function and performance of such artificial marble, attempts have been made to impart a luminescent function to the artificial marble using a luminous material such as a phosphorescent material or an luminescent material such as an ultraviolet light emitting material that emits light with ultraviolet absorption. .

However, the existing photoluminescent artificial marble was a method of creating a texture by coating a photoluminescent pigment on the surface or by using a photoluminescent chip. When the photoluminescent chip is used, no uniform photoluminescence can be exhibited, and when the photoluminescent pigment is coated on the surface, there is a problem in that it cannot be used for a long time due to the floor or surface hardness of many people.

On the other hand, the conventional photoluminescent artificial marble was not enough to be suitable for a variety of applications of the luminous performance. In other words, in terms of luminous performance, there was a problem that the initial luminance, i.e., for 15 minutes, which is considered necessary for evacuation induction during power failure, did not occur clearly. It was only one hour that light emission could be maintained up to a luminance of 3mcd / m 2.

In addition, the conventional photoluminescent artificial marble is used in excess of the photoluminescent pigment to achieve sufficient photoluminescent performance. However, photoluminescent pigments are expensive materials, and if they are used excessively, they can be a major obstacle to commercialization due to an increase in manufacturing cost. Therefore, it has been required to achieve sufficient photoluminescence while minimizing the use of photoluminescent pigments.

Therefore, the inventors have recognized the above problems and studied the appropriate mixing ratio, and as a result, artificial marble which can achieve various photoluminescence properties with sufficient brightness for a long time while minimizing the content of the photoluminescent pigment, and create various patterns on the floor and walls It is early to develop.

An object of the present invention is to provide an artificial marble having excellent photoluminescent effect.

Another object of the present invention is to provide an artificial marble which lasts a long time the photoluminescent effect.

Another object of the present invention is to provide an artificial marble having an excellent photoluminescent effect while minimizing the content of the photoluminescent pigment.

Another object of the present invention is to provide an artificial marble having an excellent photoluminescent effect without reducing the surface hardness.

Still another object of the present invention is to provide an artificial marble having excellent photoluminescent effect that can implement various interior patterns.

The above and other objects of the present invention can be achieved by the present invention described below.

In order to solve the above problems, the present invention, in one embodiment, may include (A) unsaturated polyester resin, (B) silica-containing compound, and (C) photoluminescent pigment, the highest brightness is 110 mcd / m 2 or more It provides a synthetic marble silver having a total photoluminescence lasting for more than 1 hour the brightness of 7 mcd / m 2 or more.

In another embodiment of the present invention, the artificial marble comprises 7 to 10% by weight of unsaturated polyester resin (A), 85 to 91% by weight of silica-containing compound (B) and 2 to 5% by weight of photoluminescent pigment (C). It is characterized by.

As another embodiment of the present invention, the silica-containing compound (B) comprises 50 to 80% by weight of the natural stone particles (B1) and 20 to 50% by weight of the inorganic filler (B2) relative to 100% by weight of the silica-containing compound It features.

As another embodiment of the present invention, the natural stone particles (B1) comprises 15 to 93% by weight of silica sand (b1) and 7 to 85% by weight of quartz chip (b2) based on 100% by weight of natural stone particles (B1) It is characterized by.

As another embodiment of the present invention, it is preferable that the average particle diameter of the silica sand (b1) is 0.1 ~ 1.2mm, the average particle diameter of the quartz chip (b2) is 1.2 ~ 9.0mm. Moreover, it is preferable that the said inorganic filler (B2) is a silica powder whose average particle diameter is 20 micrometers or less.

As another embodiment of the present invention, the artificial marble is based on 100 parts by weight of the composition consisting of the unsaturated polyester resin (A), the silica-containing compound (B) and the photoluminescent pigment (C) 0.1 / organic pigment (D) 0.1 It may further comprise 1 part by weight.

The artificial marble of the present invention has an excellent photoluminescent effect while minimizing the content of the photoluminescent pigment, and can provide an artificial marble that can implement various special patterns on the floor and walls.

1 is a photograph of the photoluminescent artificial marble of the present invention in natural lighting and dark room.
Figure 2 is a photograph showing the photoluminescent effect of artificial marble according to the content of the photoluminescent pigment.
Figure 3 is a photograph showing the photoluminescent effect of the artificial marble according to the average particle diameter of the natural stone particles.

Hereinafter, the present invention will be described in detail.

Accumulation  Artificial marble

The photoluminescent artificial marble of the present invention is produced including (A) an unsaturated polyester resin, (B) a silica-containing compound and (C) a photoluminescent pigment. The artificial marble of the present invention has a maximum brightness of 110 mcd / m 2 or more, and can maintain a brightness of 7 mcd / m 2 or more for 1 hour or more.

The artificial marble may be prepared including 7 to 10% by weight of unsaturated polyester resin (A), 85 to 91% by weight of silica-containing compound (B) and 2 to 5% by weight of photoluminescent pigment (C).

Hereinafter, each component constituting the photoluminescent artificial marble of the present invention will be described in detail.

(A) unsaturated polyester resin

In the present invention, the resin component surrounds natural stone particles and inorganic fillers that form the skeleton of artificial marble, serves to bind the whole together with a crosslinking agent, and provides elastic or tensile strength when artificial marble is formed. .

The present invention is characterized by using an unsaturated polyester resin (UPE resin; Unsaturated PolyEster resin) having excellent binding strength with natural stone particles and the like as the resin component.

Unsaturated polyester resins used in the present invention are commonly known in the art and as esterification products of polyacids and polyalcohols, the polyacid and / or polyalcohol compounds comprise unsaturated moieties.

As the polyacid, polycarboxylic acid, polycarboxylic anhydride, polycarboxylic acid halide, polycarboxylic acid ester may be used, and specific examples of the unsaturated polycarboxylic acid may include maleic acid, maleic anhydride, fumaric acid, Chloromaleic acid, ethyl maleic acid, itaconic acid, citraconic acid, geronic acid, lirochinic acid, mesaconic acid, aconic acid, ecythylene polycarboxylic acid or mixtures thereof may be used. In addition, phthalic acid, isophthalic acid, terephthalic acid, succinic acid or mixtures thereof commonly used in the preparation of the polyester resin can be used.

Examples of the polyhydric alcohols include dihydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,6-hexanediol, neopentyl glycol, and 1,4-cyclohexanediol, and glycerin. Trihydric alcohols, such as pentaerythritol, tetrahydric alcohols, etc., or a mixture thereof can be used. In addition, specific examples of the unsaturated polyhydric alcohol may use butenediol, pentendiol, allyl or vinyl glycerol ether, allyl or vinyl pentaerythritol, or mixtures thereof.

It is preferable to use the unsaturated polyester resin whose molecular weight is 70,000-100,000. This is because the larger the molecular weight of the unsaturated polyester resin is, the better the bonding strength with the natural stone particles can effectively fix the natural stone particles exposed to the outside even if a part of the resin is scrapped in the polishing process. If the molecular weight of the unsaturated polyester resin is less than 70,000 may drop out of the natural stone particles on the surface of the artificial marble, and if it exceeds 100,000 has a disadvantage that the viscosity is too large to mix well with the natural stone particles.

In the present invention, the unsaturated polyester resin may be used 7.0 to 10.0% by weight based on the total weight. If the unsaturated polyester resin is included in less than 7.0% by weight, the bonding strength with the natural stone particles may be lowered, and when it exceeds 10.0% by weight, the appearance and texture of the natural stone may be lost.

(B) silica containing compound

The silica-containing compound (B) of the present invention may be included in an amount of 85 to 91% by weight based on 100% by weight of a composition containing an unsaturated polyester resin (A), a silica-containing compound (B), and a photoluminescent pigment (C). This is because by including a silica-containing compound in a high content as in the above range, the appearance and texture close to natural stone can be formed.

The silica-containing compound (B) of the present invention may include 50 to 80% by weight of the natural stone particles (B1) and 20 to 50% by weight of the inorganic filler (B2) based on 100% by weight of the silica-containing compound.

(B1) natural stone particles

The artificial marble of the present invention essentially contains natural stone particles in order to form an appearance and texture close to natural stone.

The natural stone particles may use various kinds of inorganic aggregates obtained from nature, but it is preferable to use natural stone particles having transparency in order to increase the photoluminescent effect. The reason for using transparent natural stone particles is that they promote dispersion or diffuse reflection inside artificial marble, which helps most of the phosphorescent pigments absorb light energy.

As the natural stone particles having transparency, natural stone particles made of silica sand, quartz chips, crystals or mixtures thereof may be used.

It is possible to use minerals of various sizes as the natural stone particles, it is preferable to use particles having an average particle diameter of 0.1 ~ 9.0 mm. In the case of using natural stone particles having an average particle diameter of less than 0.1 mm in the formulation of the present invention, the time for reaching a luminance of 3 mcd / m 2 is only 0.5 to 1 hour. Although the phosphorescent performance can be improved by increasing the blending ratio of the phosphorescent pigment, since the phosphorescent pigment is relatively expensive, the economical efficiency may be reduced due to the increase of the raw material cost when the usage amount is increased. On the other hand, when the average particle diameter exceeds 9.0 mm may cause a problem that the strength of the artificial marble is lowered.

In particular, in the present invention, as the natural stone particles (B1), it is preferable to use a mixture of silica sand (b1) and quartz chip (b2) having a different average particle diameter, the average particle diameter of the silica sand is 0.1 ~ 1.2mm, quartz chip The average particle diameter of is more preferably 1.2 to 9.0mm.

Such silica sand and quartz chips have the best natural stone texture when they contain 15 to 93% by weight of silica sand (b1) and 7 to 85% by weight of quartz chips (b2) with respect to 100% by weight of the natural stone particles (B1). It is preferable in view of effectiveness and cost.

In the present invention, the natural stone particles (B1) may comprise 50 to 80% by weight relative to the total 100% by weight of the silica-containing compound (B), it is preferable in terms of the photoluminescence effect and cost.

(B2) inorganic filler

The present invention may further include an inorganic filler having a smaller average particle diameter than the natural stone particles. These inorganic fillers serve to minimize the amount of resin components used in the overall mixing of the artificial marble, thereby making it possible to maintain the appearance and texture of the natural marble as much as possible and contribute to the densification of the artificial marble.

Examples of the inorganic filler (B2) may be silica powder, aluminum hydroxide, glass powder, quartz powder, calcium carbonate, and the like, most preferably using silica powder of natural stone.

It is most preferable that the average particle diameter of the said inorganic filler (B2) is 20 micrometers or less.

In the present invention, the inorganic filler (B2) may be included in 20 to 50% by weight based on 100% by weight of the total silica-containing compound (B). If the content of the inorganic filler is less than 20% by weight, there is a problem in that the molding of the product is not good, if the content of the inorganic filler exceeds 50% by weight, the content of the unsaturated polyester resin (A) is increased to the physical properties on the surface of the product This can be lowered.

(C) Phosphorescent pigment

The photoluminescent pigment imparting the photoluminescent property to the artificial marble of the present invention can be used without limitation as long as it is a conventional photoluminescent pigment, but it is preferable to use a strontium aluminate pigment or a zinc sulfide pigment.

It is preferable to use the phosphorescent pigment having an average particle diameter of 6 ~ 150 ㎛. When the average particle diameter of the photoluminescent pigment is less than 6 μm, the light emission performance may be reduced, and when the average particle diameter is more than 150 μm, the time of light irradiation for initial saturation is long.

On the other hand, since the phosphorescent pigment is an expensive material, it is important to maximize the luminous performance of the artificial marble while minimizing the use ratio of the phosphorescent pigment. In the present invention, it is preferable to use the phosphorescent pigment at 2.0 to 5.0% by weight based on the total weight. . In the compounding ratio of the present invention, when the phosphorescent pigment is used at less than 2.0% by weight, sufficient photoluminescence effect may not be exhibited. When the phosphorescent pigment is used at an amount exceeding 5.0% by weight, it is not preferable in terms of economics. You cannot expect an improvement.

(D) Oil / Inorganic pigment

In the present invention, the organic / inorganic pigments are used for introducing a color representing the photostability. As the organic / inorganic pigment, azo-based, phthalocyanine-based may be used, and 0.1 to 1 parts by weight based on 100 parts by weight of the composition consisting of an unsaturated polyester resin (A), a silica-containing compound (B) and a photoluminescent pigment (C) It is preferable to use as.

(E) Other additives

In the present invention, a curing agent (e1) may be used to cure the artificial marble, and a curing accelerator (e2) may be used to promote curing. The curing agent is preferably used in an amount of 0.1 to 0.2 parts by weight and the curing accelerator in an amount of 0.01 to 0.02 parts by weight based on 100 parts by weight of the composition consisting of an unsaturated polyester resin (A), a silica-containing compound (B) and a photoluminescent pigment (C). Do.

In addition, a crosslinking agent (e3) may be used to bond the unsaturated polyester resin of the present invention with natural stone particles and an inorganic filler. It is preferable to use a silane crosslinking agent as the crosslinking agent, and to use 0.05 to 0.1 parts by weight based on 100 parts by weight of the composition consisting of an unsaturated polyester resin (A), a silica-containing compound (B) and a photoluminescent pigment (C). desirable.

Hereinafter, preferred embodiments of the present invention will be described. However, the following examples are only a preferred embodiment of the present invention, and the present invention is not limited by the following examples.

Example

Preparation of sample

(A) unsaturated polyester

Aekyung Chemical M900 artificial marble (UPE) resin was used.

(B) silica containing compound

(B1) natural stone particles

(b1) silica sand

Silica sand having an average particle size of 0.1-1.2 mm was used.

(b2) quartz chips

Quartz chips with 1.2 ~ 9.0 mm average particle diameter of 21st century silica were used.

(B2) inorganic filler

Silica powder having an average particle diameter of 12 μm of silica in the 21st century was used.

(C) photoluminescent pigment

Uk Sung Chemical Co., Ltd. PL-120 photoluminescent pigment was used.

(D) Oil / Inorganic pigment

The TR92 pigment of Wooshin Pigment Corporation was used.

(F) Other additives

(f1) Luperox P TBPB was used as a curing agent.

(f2) Cyanide 6% -Cobalt was used as a curing accelerator.

(f3) A Gudam (WD70) silane coupling agent was used as the crosslinking agent.

Property evaluation method

(1) Maximum luminance: After irradiating 200 lux for 20 minutes with DN65 commercial light source, the initial luminance after 5 minutes was measured.

(2) Minimum luminance: After irradiating 200 lux for 20 minutes with a DN65 commercial light source, luminance after 60 minutes was measured.

(3) Natural stone texture: Visually inspected whether artificial marble forms a texture close to natural stone and classified as good or bad.

(4) Surface Hardness (Barcol): Barcol hardness was measured by applying the ASTM D 2583 measuring method.

Example  And Comparative example

Example 1

7% by weight of unsaturated polyester resin, 13% by weight of silica sand, 55% by weight of quartz chip, 23% by weight of silica powder, 2% by weight of phosphorescent pigment, 0.1% by weight of organic / inorganic pigments, 0.2% by weight of curing agent, 0.02% by weight of curing accelerator , 0.1% by weight of the silane-based crosslinking agent was measured by physical properties of the artificial marble prepared by curing and the results are shown in Table 2 below.

Example 2 and Comparative Examples 1 to 5

It was prepared in the same manner as in Example 1 except for using the content of Table 1.

As shown in Table 2, Examples 1 and 2 have a natural stone texture and do not decrease the surface hardness, it is excellent in the initial luminance, it can be seen that the photoluminescent effect lasts for a long time.

On the other hand, in Comparative Example 1 using less photoluminescent pigment, it can be seen that the photoluminescence deteriorates. In Comparative Example 2 using an excess photoluminescent pigment, the photoluminescent property is excellent but the texture of natural stone is reduced. In addition, in Comparative Example 3 using only silica sand as the natural stone particles and Comparative Example 4 using only quartz chips as the natural stone particles, it was confirmed that both the photoluminescence and the natural stone texture were deteriorated. In the case of the comparative example 5 which used the excess amount of unsaturated polyester-type resin, not only photoluminescence but natural stone texture and surface hardness fell.

Claims (14)

(A) unsaturated polyester resin;
(B) silica containing compounds; And
(C) phosphorescent pigments;
A synthetic marble having a total photoluminescent property comprising a, wherein the highest luminance is 110 mcd / m 2 or more, and the luminance is 7 mcd / m 2 or more.
The artificial marble according to claim 1, wherein the artificial marble comprises 7 to 10% by weight of an unsaturated polyester resin (A), 85 to 91% by weight of a silica-containing compound (B) and 2 to 5% by weight of a photoluminescent pigment (C). Artificial marble having a total photoluminescent property.
The method according to claim 1, wherein the silica-containing compound (B) comprises 50 to 80% by weight of the natural stone particles (B1) and 20 to 50% by weight of the inorganic filler (B2) Artificial marble with full condensation.
The artificial marble having a total photoluminescence property according to claim 3, wherein the average particle diameter of the natural stone particles (B1) is 0.1 to 9.0 mm.
The method according to claim 3, wherein the natural stone particles (B1) comprises 15 to 93% by weight of silica sand (b1) and 7 to 85% by weight of quartz chips (b2) based on 100% by weight of natural stone particles (B1). Artificial marble with full photoluminescence.
The artificial marble having total photoluminescence property according to claim 5, wherein the silica sand (b1) has an average particle diameter of 0.1 to 1.2 mm.
The artificial marble of claim 5, wherein the quartz chip (b2) has an average particle diameter of 1.2 mm to 9.0 mm.
The artificial marble having total photoluminescence property according to claim 3, wherein the inorganic filler (B2) is silica powder having an average particle diameter of 20 µm or less.
The artificial marble having a total photoluminescence property according to claim 1, wherein the average particle diameter of the photoluminescent pigment (C) is 6 to 150 µm.
According to claim 1, The artificial marble is based on 100 parts by weight of the composition consisting of the unsaturated polyester resin (A), silica-containing compound (B) and the photoluminescent pigment (C) 0.1 to 1 weight of organic / inorganic pigment (D) Artificial marble having a total photoluminescent property, characterized in that it further comprises a wealth.
According to claim 1, wherein the artificial marble is 0.1 to 0.2 parts by weight of a curing agent (e1) and curing based on 100 parts by weight of the composition consisting of the unsaturated polyester resin (A), silica-containing compound (B) and photoluminescent pigment (C) Accelerator (e2) Artificial marble having a total photoluminescent property, characterized in that it further comprises 0.01 to 0.02 parts by weight.
12. The artificial marble of claim 11, wherein the curing agent (e1) is tert-butyl peroxy benzoate (TBPB).
12. The artificial marble of claim 11, wherein the curing accelerator (e2) is 6% -coblat.
According to claim 1, wherein the artificial marble is 0.05 to 0.1 parts by weight of the silane-based crosslinking agent (e3) based on 100 parts by weight of the composition consisting of the unsaturated polyester resin (A), silica-containing compound (B) and photoluminescent pigment (C) Artificial marble having a natural stone texture and total photoluminescence, characterized in that it further comprises.

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