KR20150137587A - Photocurable Resin Composition for Manufacturing Photocured Tansparant Chips for Artificial Marble - Google Patents

Abstract

The present invention discloses a manufacturing method of a photocurable transparent chip for an artificial marble. Specifically, the present invention discloses a manufacturing method of a photocurable transparent chip for an artificial marble, which comprises the steps of: (a) manufacturing a resin composition for manufacturing a photocurable transparent chip for an artificial marble including a base resin selected from unsaturated polyester and an acrylate oligomer, a monomer which is a reactive diluting agent, and a photoinitiator; (b) obtaining a cured body by irradiating the resin composition with light and photocuring; and (c) crushing the cured body.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0002] The present invention relates to a photocurable resin composition for manufacturing artificial marbles,

The present invention relates to a method of manufacturing a photo-curable transparent chip for artificial marble.

Marbles used as interior and exterior materials include natural marble and artificial marble. Natural marble is a stone taken directly from a quarry. Artificial marble is made by mixing natural minerals with synthetic resin and showing natural beauty of natural marble.

Natural marble is regarded as the finest material to decorate the space with its exquisite appearance, but its use is limited because it is limited in quantity, and it is expensive to process and transport. In order to overcome the disadvantages of such natural marble, artificial marble is widely used these days. Artificial marble has lower cost and weight than natural marble, and has the advantage of being able to express unique colors freely.

Artificial marble generally refers to artificial composites that combine natural marble chips or minerals with acrylic or unsaturated polyester resins, and add various additives or pigments thereto to realize the texture of natural marble. In general, artificial marbles are classified into acrylic artificial marble and unsaturated polyester artificial marble depending on the type of the resin.

Acrylic artificial marble has excellent appearance, good workability, light weight and excellent strength compared with natural marble, and is widely used as various interior materials including counters and tables. However, there are technical limitations in expressing various patterns compared with natural marble or granite with the monochromatic chip combination generally known.

At this time, a pigment or a chip is used as means for expressing the appearance of the artificial marble. However, most artificial marbles known to date have a combination of monochromatic and opaque chips to realize the appearance effect, and such processing is limited to implement a pattern similar to natural marble or granite.

It is therefore desirable to use transparent chips to overcome these limitations and to impart a more refined impression of natural marble or granite-like patterns to artificial marble.

Such a transparent chip for artificial marble has been produced by thermally curing an acrylic resin or an unsaturated polyester resin at a high temperature.

Such a thermosetting method does not sufficiently cure due to insufficient heat to cure if the thickness of the molded body for the transparent chip is reduced, and if the thickness of the cured layer is made thick, cracks may occur in the cured product due to exothermic reaction, It is necessary to adjust the molded body to a certain thickness in order to heat harden.

In addition, since the heat curing method for producing a transparent chip requires a heat source for curing, it is not environmentally friendly, and it takes a lot of time to cure the transparent chip sufficiently, resulting in poor productivity.

It is an object of the present invention to provide a resin composition for producing a photocurable transparent chip for artificial marble.

It is another object of the present invention to provide a method for producing a photo-curable transparent chip for artificial marble using the resin composition.

Other and further objects of the present invention will be described below.

In one aspect, the present invention relates to a resin composition for producing a photo-curable transparent chip for artificial marble.

As shown in the following examples and experiments, the inventors of the present invention have found that when a brominated epoxy acrylate oligomer as a base resin, Irgacure 184 as a short wavelength initiator, Darocur TPO as a long wavelength initiator, and / Or a long wavelength initiator Irgacure 819 and Irganox 1076 as an antioxidant was poured into a tray to a predetermined thickness and photocured with a high pressure mercury lamp to form a film having a thickness of 1 mm, When a cured product of 20 mm, 30 mm, 40 mm, 50 mm, 60 mm, 70 mm and 80 mm was produced using Duroker TPO or Irgacure 819 as a long wavelength initiator alone or Irgacure 184 as a short wavelength initiator, In the case of using only Irgacure 184, which is a short wavelength initiator, the thickness of the cured product is not less than 40 mm It was confirmed that no bottom is not cured (i.e., all but the hardened case of 1mm to 30mm cured to its lower 40mm to 80mm In the case of the cured product is lower that the curing was not).

Further, the inventors of the present invention have found that the use of a brominated epoxy acrylate oligomer, which is the same base resin used in the photocuring method, and the use of di (4-tertiary-butylcyclohexyl) peroxydicarbonate, tertiary-butylperoxy- Peroxide, and / or bis (4-tertiary-butylcyclohexyl) peroxydicarbonate with an antioxidant, Irganox 1076, at 70 ° C for 20 minutes to 30 minutes When the obtained cured product was compared with the above-mentioned photo-cured product, the cured product was not cured at a thickness of 10 mm or 20 mm. When the cured product was thick, the cured product was yellowed and cracked.

Generally, a transparent chip for artificial marble is prepared by curing an acrylic resin or an unsaturated polyester resin to produce a cured product having a uniform thickness, then crushing the cured product to a size of 0.1 to 20 mm, or if necessary, use.

Therefore, in order to manufacture a transparent chip, it is necessary to prepare a cured product having a certain thickness.

The present invention is characterized in that a photocuring method is used instead of the conventional thermosetting method in the production of such a cured body, and thus a problem caused by the thermosetting method, such as a long curing time and a small thickness of the cured body, It is possible to overcome the fact that the reaction is weak so that no curing occurs and that a yellowing or cracking phenomenon occurs when the thickness of the cured product is large. Further, according to the present invention using the photo-curing method, the cooling time after the production of the molded article required when the thermosetting method is adopted is not required.

(I) a base resin selected from an acrylate oligomer and an unsaturated polyester, (ii) a monomer as a reactive diluent, and (iii) a photoinitiator as a photoinitiator. .

In the resin composition of the present invention, the acrylate oligomer may be an epoxy acrylate, a halogenated epoxy acrylate, a urethane acrylate, or a polyester acrylate oligomer.

The reason for using such an acrylate oligomer and an unsaturated polyester in the present invention is not only to have a reactor which is cured by a photoreaction but also to be excellent in adhesiveness and corrosion resistance particularly in the case of epoxy and unsaturated polyester series.

The acrylate oligomer having photosensitivity by introducing an acrylic group for such a photoreaction is used in many business fields due to the energy saving and environment friendly characteristics required in the modern society, and it is difficult to apply the acrylate oligomer to a complicated shaped structure Although it has a disadvantage of high price, it is a liquid form which uses a reactive acrylic monomer instead of a solvent as a diluent, and thus can prevent environmental problems caused by air pollution There is an advantage not to cause it.

Because of these advantages, UV-curable coatings and adhesives are widely used for top coating and bonding applications such as wood, plastic, flooring, and metal. Recently, as environmental problems have arisen, their applications and demand have rapidly increased And is generally used in many cases.

In the present invention, at least one selected from the group consisting of unsaturated polyester, epoxy acrylate, halogenated epoxy acrylate, urethane acrylate and polyester acrylate oligomer is used. Of these, halogenated epoxy acrylates are preferred because they have a high specific gravity, excellent adhesive strength to substrates, and a high refractive index to give a feeling of luxury. In the present invention, acrylate oligomers other than halogenated epoxy acrylate oligomers can be used. Among these halogenated epoxy acrylate oligomers, halogenated epoxy acrylate oligomers can be prepared by reacting halogenated epoxy resin with acrylic acid or methacrylic acid.

As one example of the present invention, bisphenol A or phenol-formaldehyde novolak type may be used as the halogenated epoxy resin.

The content of the photopolymerizable acrylate oligomer is preferably 60 to 90% by weight, and if it exceeds 90% by weight, imperfect curing occurs. Therefore, the photopolymerizable acrylate oligomer tends to be polymerized non-uniformly during shrinkage and light polymerization, resulting in cracking after curing.

In the present invention, the monomer as the reactive diluent is preferably selected from the group consisting of methyl (meth) acrylate, ethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, dodecyl (Meth) acrylate, benzyl (meth) acrylate, chlorophenyl (meth) acrylate, methoxyphenyl (meth) acrylate, Propylene glycol (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1, 2-propylene glycol di Butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, Methacrylate, triethylene glycol (Meth) acrylate, dipentaerythritol tri (meth) acrylate, dipropylene glycol di (meth) acrylate, diallyl terephthalate, diallyl phthalate, diallyl carbonate, trimethylolpropane tri Pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (metha) acrylate, ethoxyethoxyethyl acrylate, epoxy acrylate of glycidyl methacrylic acid, 1,6-hexanediol di (meth) (Meth) acrylate, styrene, halogenated styrene, vinyl toluene, divinylbenzene, alpha methyl styrene, bisphenol A di (meth) acrylate, (Meth) acrylate, ethoxylated bisphenol A (meth) acrylate, and mixtures thereof, at least one selected from the group consisting of Can be used.

The monomer as a reactive diluent used in the present invention is important for improving the hardness, strength, chemical resistance, water resistance, and the like of the artificial marble in producing the artificial marble with the light-curing transparent chip for artificial marble of the present invention, Preferably 30 to 30% by weight, and more preferably 10 to 30% by weight. When the amount is less than 5 parts by weight, cracks may occur. When the amount is more than 30 parts by weight, a product having high strength can not be obtained.

The photoinitiator used in the present invention serves to initiate photo-curing in the exposed portion of the resin composition, and both a short-wavelength photoinitiator exhibiting light absorption in the range of 200-350 nm and a long-wavelength photoinitiator exhibiting light absorption in the range of 300-480 nm . When a short-wavelength photoinitiator is used, it is advantageous in producing a cured product of a thick thickness, and when a long-wavelength photoinitiator is used, it is advantageous in producing a cured product of a thick thickness. However, if the thickness of the cured product is too thin, the productivity is decreased, and the particle diameter of the transparent chip obtained by crushing the cured product is too small, which is not preferable, so that the use of a long wavelength photoinitiator is preferable. When a long wavelength photoinitiator is used, long wavelength photoinitiator may be used alone, but it may be mixed with a short wavelength photoinitiator and a proper composition ratio (long wavelength photoinitiator: short wavelength photoinitiator = 1: 0.1 ~ 2.0 weight ratio).

When a photoinitiator is mixed and used, it is preferable to use two or more photoinitiators having different absorption wavelength regions. This is because it can efficiently utilize the light energy generated from the light source and increase the curing rate.

As short-wavelength photoinitiators, any of those known in the art may be used, and examples thereof include 1-hydroxy-cyclohexyl-phenylketone, 2-hydroxy-2-methyl- Methylbenzoylformate,?,? - dimethoxy -? - phenylacetophenone, 2-benzoyl- Methyl-1- [4- (methylcio) phenyl] -2- (4-morpholino) Propanone. Examples of products currently available on the market include Irgacure 184, Darocur 1173, Irgacure 2959, Darocur MBF, Irgacure 651, Irgacure 369 and Irgacure 907 from BASF.

The long wavelength photoinitiator may be any known one, and examples thereof include 2-benzyl-2-dimethylamino-1-butanone, diphenyl (2,4,6-trimethylbenzoyl) -phosphine oxide, bis (6-trimethylbenzoyl) -phenylphosphine oxide, benzyldimethyl ketal, 2,4,6-trimethylbenzophenone, oligo (2-hydroxy- Methoxy-1,2-diphenylethan-1-one, 1-hydroxy-cyclohexyl phenyl ketone, 2-hydroxy- (2, 6-dichlorobenzoyl) - diethyl thioxanthone, 3,3-dimethyl-4-methoxy-benzophenone, ethyl p-dimethyl aninobenzoate, isoamyl p- (2,6-dichlorobenzoyl) -4-ethoxyphenylphosphine oxide, bis (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, bis 6-dichlorobenzoyl) -4-propylphenylphosphine oxide, bis (2,6- Trimethylpentylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and the like. Commercially available products include Irgacure 819, Irgacure 369, Irgacure 2020 , Irgacure 2022, Irgacure 2100, Irgacure 784, Lucirin TPO, Darocur 4265, and the like.

The photoinitiator may be contained in the resin composition of the present invention in an amount of 0.01 to 10% by weight. When the content of the photoinitiator is less than 0.01% by weight, sufficient curing may not occur. When the content of the photoinitiator exceeds 10% by weight, the weather resistance may be lowered due to the unreacted initiator.

The resin composition of the present invention may further comprise a chain transfer agent. As shown in the following examples and experimental examples, when the chain transfer agent is additionally used, the thickness of the cured product becomes thick, the heat generated during curing can be effectively controlled, and the bubbles and cracks due to the exothermic reaction can be effectively controlled .

The chain transfer agent may be any organic compound including a thiol group (-SH group) without any particular limitation. In addition to the thiol group-containing compound, alpha methyl styrene dimer and the like may also be used.

Specifically, alkyl mercaptans such as ethyl mercaptan, butyl mercaptan, hexyl mercaptan or dodecyl mercaptan; Thiophenols such as phenyl mercaptan or benzyl mercaptan; Carboxyl group-containing mercaptans such as thioglycolic acid, 3-mercapto propionic acid or thiosalicylic acid; Hydroxyl group-containing mercaptans such as 2-mercapto ethanol or 3-mercapto-1,2-propanediol; Or mercaptans having two or more of the above functional groups in combination such as pentaerythritol tertracis (3-mercapto) propionate, or the like, or a mixture of two or more thereof Can be used.

On the other hand, as shown in the following Examples and Experimental Examples, when a compound having only one thiol group in the molecule, that is, a monofunctional chain transfer agent, is used in the chain transfer agent, there is a disadvantage in that the hardness of the cured product is lowered due to lower molecular weight after photo- When a multifunctional chain transfer agent having two or more functional groups (thiol groups) in the molecule is used, it is also possible to solve the problem that the hardness, which is a disadvantage in using a monofunctional chain transfer agent, is lowered by inducing steric cross-linking. Therefore, it is preferable to use a multifunctional chain transfer agent.

As the multifunctional chain transfer agent that can be used, any one known in the art can be used, and examples thereof include 1,5-pentanediol, 1,6-hexanedithiol, ethylene glycol bis (3-mercaptobutyrate) (3-mercaptobutyrate), diethylene glycol bis (3-mercaptobutyrate), butanediol bis (3-mercaptobutyrate), octanediol bis (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), dipentaerythol hexacis (3-mercaptobutyrate), ethylene glycol bis (2-mercaptopropionate), propylene glycol bis Mercaptopropionate), diethylene glycol bis (2-mercaptopropionate), butanediol bis (2-mercaptopropionate), octanediol bis (2-mercaptopropionate) (2-mercaptopropionate), pentaerythritol tetrakis (2-mercaptopropionate), dipentaerythritol hexakis (2-mercaptopropionate), ethylene glycol bis (3-mercapto (3-mercaptoisobutyrate), butanediol bis (3-mercaptoisobutyrate), octanediol bis (3-mercaptopropionate) (3-mercaptoisobutyrate), pentaerythritol tetrakis (3-mercaptoisobutyrate), dipentaerythol hexacis (3-mercaptoisobutyrate) , Ethylene glycol bis (2-mercaptoisobutyrate), propylene glycol bis (2-mercaptoisobutyrate), diethylene glycol bis (2-mercaptoisobutyrate), butanediol bis Butyrate), octanediol (2-mercaptoisobutyrate), trimethylolpropane tris (2-mercaptoisobutyrate), pentaerythritol tetrakis (2-mercaptoisobutyrate), dipentaerythritol hexakis Propyleneglycol bis (4-mercaptoisovalerate), diethylene glycol bis (4-mercaptovalerate), butanediol bis (4-mercaptobalate), ethylene glycol bis (4-mercaptovalerato), pentaerythritol tetrakis (4-mercaptovalerate), dipentaerythol hexacis (4-mercaptovalerate) Propylene glycol bis (3-mercaptovalerate), diethylene glycol bis (3-mercaptovalerate), butanediol bis (3-mercaptovalerate), ethylene glycol bis -Mercaptovalerate), octanediol bis (3- Mercaptovalerate), trimethylolpropane tris (3-mercaptovalerate), pentaerythritol tetrakis (3-mercaptovalerate), dipentaerythritol hexakis (3-mercaptovalerate), hydrogenated bisphenol A (3-mercaptobutyrate), bisphenol A dihydroxyethyl ether-3-mercaptobutyrate, 4,4 '- (9-fluorenylidene) bis (2-phenoxyethyl 3-phenylpropionate), propylene glycol bis (3-mercapto-3-phenylpropionate), diethylene glycol bis (3-mercapto-3-phenylpropionate) 3-phenylpropionate), butanediol bis (3-mercapto-3-phenylpropionate), octanediol bis (3-mercapto- Phenyl propionate), tris-2- (3-mercapto-3-phenylpropionate) ethyl isocyanurate, pentaerythritol Pentaerythritol tetra there may be mentioned tetrakis (3-mercapto-3-phenyl propionate), pentaerythrityl di stall hexahydro tetrakis (3-mercapto-3-phenyl propionate) and the like.

As the chain transfer agent, at least one monofunctional chain transfer agent and at least one multifunctional chain transfer agent known in the art can be used alone or in combination of two or more kinds. The chain transfer agent may be contained in the resin composition of the present invention in an amount of 0.01 to 10.0% by weight, preferably 0.01 to 5.0% by weight. When it is 0.01% by weight or less, it is difficult to exhibit the intended effect, % Can have an undesirable effect on the reaction rate and the reaction stability.

The resin composition of the present invention may further contain additives such as an antioxidant, an inorganic filler, a coupling agent, a pigment, a crosslinking agent, a UV stabilizer, a defoamer, a light diffusing agent, a polymerization inhibitor, a curing modifier, an antistatic agent, a flame retardant, have.

These additives are well known in the art and may be added in an appropriate amount to suit the intended use of the additive. Herein, the addition in an appropriate amount means that the additive is added in an amount sufficient to achieve the purpose of adding the additive in an amount not lowering the other physical properties of the cured product.

For example, antioxidants and phenolic antioxidants are known as antioxidants. These antioxidants may be added to the resin composition of the present invention in the range of 0.01 to 10 parts by weight based on 100 parts by weight of the resin composition of the present invention.

Further, for example, inorganic fillers are added for the purpose of increasing the specific gravity of the transparent chips, and aluminum hydroxide, calcium hydroxide and the like are known, and such inorganic fillers can be added in the range of 10 to 80 parts by weight based on 100 parts by weight of the resin composition of the present invention .

Further, for example, a coupling agent is added to increase the bonding strength between the resin and the inorganic filler, and silicate anhydride is known, and may be added in the range of 0.01 to 5 parts by weight based on 100 parts by weight of the resin composition of the present invention. A suitable pigment known in the art may be selected according to the color (iron oxide pigment for reddish brown color and iron hydroxide pigment for yellow color) in the range of 0.01 to 5 parts by weight based on 100 parts by weight of the resin composition of the present invention Can be added. In the case of the crosslinking agent, tetraethylene glycol, ethylene glycol dimethacrylate and the like may be used, and may be added in the range of 0.01 to 5 parts by weight based on 100 parts by weight of the resin composition of the present invention. The selection of suitable additives, such as anti-foaming agents, ultraviolet stabilizers, and the like, are within the ordinary skill in the art as long as they are based on techniques known in the art.

The method for producing a photocurable transparent chip for marble according to the present invention comprises the steps of: (a) preparing a resin composition as described above; (b) irradiating the resin composition with light to obtain a cured product by photo- ), And crushing the cured product.

In the method of the present invention, after the step (a) of preparing the resin composition, a step of removing the bubbles of the resin composition may be further included. Removal of air bubbles may be accomplished by leaving under a pressure condition lower than atmospheric pressure or by heating to an appropriate temperature (50 to 90 ° C). Since the resin composition of the present invention does not contain a thermosetting initiator, the bubbles may be removed by heating differently from the thermosetting resin composition.

There is no particular limitation on the light source that can be used in the light curing in the step (b), and a high-pressure mercury lamp, a metal halide lamp, an LED lamp, or the like can be used. At the time of this photo-photo-curing time it can be determined in accordance within the ordinary skills of one of ordinary skill in the art depending on the thickness of the light quantity or the cured body, the degree embodiment, 2 minutes to 3 minutes, and the amount of light of 1200 mJ / cm ² below the light To obtain a cured product.

The thickness of the cured product (c) may range from 1 to 70 mm. If it is more than 70 mm, hardening of the lower portion of the hardened body may not occur and cracks may occur due to non-uniformity of hardening. This is because, as shown in the following examples, when the thickness of the cured product is 80 mm, the lower uncured portions are generated even when the long wavelength initiator is used.

Preferably, the thickness of the cured body is 20 mm or more. If the thickness of the cured product is too thin, the productivity is low and the particle size of the transparent chips is too small, which is not suitable for the production of artificial marble.

It is preferable that the crushing step (c) is performed so that the particle size of the crushed material (i.e., the transparent chip) is in the range of 0.1 to 20 mm, and the crushed material may be classified if necessary.

As described above, according to the present invention, a photo-curable transparent chip resin composition for artificial marbles and a method for producing the photo-curable transparent chip can be provided.

The present invention relates to a method for producing transparent chips for artificial marble, which uses a photo-curing system instead of the conventional thermal curing system to produce a transparent cured product for artificial marble. In the case where the curing time is long, It is possible to overcome the point that the internal exothermic reaction is weak and no curing occurs, and the yellowing or cracking phenomenon occurs when the thickness of the cured product is large. Further, according to the present invention, the productivity is improved because the working time is short.

Hereinafter, the present invention will be described with reference to examples. However, the scope of the present invention is not limited to these embodiments.

< Example > Photocuring Transparent chip  Produce

&Lt; Example 1 > Synthesis of brominated epoxy acrylate Preparation of oligomers

67.8% by weight of a bisphenol-A brominated epoxy resin (YDB-400, manufactured by Kokudo Chemical Co., Ltd.) was added to a four-necked flask equipped with a stirrer, a thermometer, a dropping device and a charge cooler, heated and melted, Lt; / RTI &gt; 0.01% by weight of an antioxidant Irganox 1010 as a polymerization inhibitor, 0.01% by weight of hydroquinone monomethyl ether as a polymerization inhibitor, and 12.81% by weight of acrylic acid and 0.3% by weight of triethylamine were mixed in a dropping apparatus within 1 minute The mixed solution was subjected to dropping reaction. Using the exotherm, the temperature of the reactant was raised to 110 캜 to prepare a brominated epoxy acrylate having an acid value of 5 or less.

The brominated epoxy acrylate prepared above was cooled to 90 DEG C and diluted with methyl methacrylate to 19.07 wt% to prepare a brominated epoxy acrylate oligomer.

&Lt; Example 2 > Preparation of photocurable resin solution

Using the brominated epoxy acrylate oligomer prepared in Example 1, a photo-curing resin solution was prepared by the components and contents shown in Tables 1 and 2 below.

The use of a chain transfer agent using a short-wavelength photoinitiator (Irgacure 184) and / or a long-wavelength photoinitiator (TPO, Irgacure 819) in combination with a polyfunctional chain transfer agent (PEMP) The use of a monodisperse (Dodecyl mercaptane) or polyfunctional (PEMP) chain transfer agent in the resin composition shown in Table 2 below was used to control the heat generation And the flexural strength of the cured product.

Components and content of photocurable resin solution division Production Example 1 Production Example 2 Production Example 3 Production Example 4 &Lt; Example 1 > 98.4 98.4 97.9 98.9 Irgacure 184 0.2 0.2 One - TPO 0.3 - - Irgacure 819 - 0.3 - 0.1 Irganox 1076 One One One One PEMP 0.1 0.1 0.1 - Sum 100 100 100 100 * Irgacure 184: 1-Hydroxy-cyclohexyl-phenyl-ketone (Basf)
* TPO: Diphenyl (2,4,6-trimethylbenzoyl) -phosphine oxide (Basf)
* Irgacure 819: Phosphine oxide, phenyl bis (2,4,6-trimethyl benzoyl) (Basf)
* Irganox 1076: Octadecyl-3- (3,5-di-tert.butyl-4-hydroxyphenyl) -propionate (Ciba)
* PEMP: Penntaerythritol tetrakis (3-mercaptopropionate)

Components and content of photocurable resin solution division Production Example 5 Production Example 6 Production Example 7 Production Example 8 &Lt; Example 1 > 99.6 99.2 99.7 99.2 TPO 0.3 0.3 0.3 0.3 PEMP 0.1 0.5 - - Dodecyl Mercaptane - - - 0.5 Sum 100 100 100 100 * TPO: Diphenyl (2,4,6-trimethylbenzoyl) -phosphine oxide (Basf)
* PEMP: Penntaerythritol tetrakis (3-mercaptopropionate)

&Lt; Example 3 > Preparation of photocured product

The photocurable resin solution prepared in Example 2 was poured into a tray to a predetermined thickness and the high pressure was cured at a light intensity of 1200 mJ / cm ² in an ultraviolet curing apparatus using a lamp to prepare a cured product for producing transparent chips for artificial marble.

< Comparative Example > Thermoset  Produce

Using the brominated epoxy acrylate oligomer prepared in Example 1, a thermosetting resin solution was prepared with the components and contents shown in Table 3 below. The thermosetting resin composition was vacuum-defoamed at 730 mmHg for 5 minutes, poured into a tray, and heated and cured at 70 DEG C to prepare a cured product for producing transparent chips for artificial marble.

Composition and content of thermosetting resin solution division Comparative Example 1 Comparative Example 2 Comparative Example 3 Synthetic example 99.8 99.3 98.8 Perkadox 16 0.1 - 0.1 Trigonox 21 0.1 - 0.1 Benzoyl peroxide - 0.2 - Bis (4-tertiary-butylcyclohexyl) peroxydicarbonate - 0.5 Irganox 1076 One Sum 100 100 100

< Experimental Example  1> The photo- Thermoset  Comparison of physical properties

The physical properties of the cured products prepared in the above Examples and Comparative Examples were compared as shown in Table 4 below.

Comparison of physical properties between photocurable and thermoset Production Example 1 Production Example 2 Production Example 3 Production Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Hardening method Photocuring Photocuring Photocuring Photocuring Heat curing Heat curing Heat curing Curing temperature Room temperature Room temperature Room temperature Room temperature 70 ℃ 70 ℃ 70 ℃ Curing time - - - - 20 minutes 30 minutes 60 minutes Curing Thickness 1mm Cured Cured Cured Cured No hardening No hardening No hardening Hardening thickness 10mm Cured Cured Cured Cured No hardening No hardening No hardening Curing thickness 20mm Cured Cured Cured Cured Cured Cured No hardening Hardening thickness
30mm Cured Cured Cured Cured Cured Cured No hardening Hardening thickness
40mm Cured Cured bottom
Uncured Cured Cured
Yellow Cured
Yellow
Cracking No hardening Hardening thickness
50mm Cured Cured bottom
Uncured Cured Cured
Yellow
Cracking Cured
Yellow
Cracking Cured
Yellow
Cracking Hardening thickness
60mm Cured Cured bottom
Uncured Cured
Yellow
Cracking Cured
Yellow
Cracking Cured
Yellow
Cracking Cured
Yellow
Cracking Hardening thickness
70mm Cured Cured bottom
Uncured Cured
Yellow
Cracking Cured
Yellow
Cracking Cured
Yellow
Cracking Cured
Yellow
Cracking Hardening thickness
80mm Lower uncured Lower uncured bottom
Uncured Cured
Yellow
Cracking Cured
Yellow
Cracking Cured
Yellow
Cracking Cured
Yellow
Cracking

As shown in Table 4, in the case of Production Example 3, only a short wavelength initiator (Irgacure 184) was used, resulting in a lower uncured portion. This seems to be due to the fact that energy is consumed at the upper part of the specimen and the energy is not transferred to the lower part. Also, even when a long wavelength initiator is used (Production Examples 1 and 2), when the hardening thickness is 80 mm or more, the lower uncured portions are generated in all production examples, and it is preferable to control the thickness to 70 mm when the transparent chip is manufactured through photo- . In the case of Production Example 4, in which no chain transfer agent (PEMP) was used, curing was performed to the lower part, but yellowing occurred and cracks occurred due to the inability to control the internal exothermic reaction.

In the case of the thermosetting (Comparative Examples 1 to 3), when the thickness is thin, it is not cured and when the thickness is thick, yellowing phenomenon and crack are generated.

< Experimental Example  2> Used To the chain transfer agent  Following Of the light cured body  Comparison of physical properties

Cracks, yellowing occurrence, heat generation temperature and flexural strength of the photocurable compositions prepared in Production Examples 5 to 8 were measured and shown in Table 5 below. Here, the flexural strength was measured by ASTM D-790 method, and the heating temperature was checked with a heat label.

division Production Example 5 Production Example 6 Production Example 7 Production Example 8 Thickness of the cured body 70mm 70mm 70mm 70mm Heating temperature (℃) 88 ~ 93 77 ~ 82 160 or more 82 ~ 88 Flexural strength (kg / cm ² ) 1321 1291 1289 958 Average transmittance (visible light,%) 88 85 81 82 Crack and yellowing occurred radish radish U radish

As shown in the results of Table 5 above, it can be seen that the PEMP, which is a multifunctional chain transfer agent, is used to control the heat generation while the bending strength is high. This seems to be due to the induction of crosslinking in the case of polyfunctional chain transfer agents. When the chain transfer agent was not used, cracks and protrusion occurred due to a high temperature of heat generation. In the case of using a monofunctional chain transfer agent, cracks and yellowing did not occur but a cured product with low strength was obtained.

Claims (10)

(a) a resin composition for the manufacture of a photocurable transparent chip for artificial marble comprising a base resin selected from unsaturated polyester and acrylate oligomers, a monomer as a reactive diluent, and a photoinitiator.
The method according to claim 1,
Wherein the base resin is contained in an amount of 60 to 90% by weight, the reactive diluent monomer is contained in an amount of 5 to 30% by weight, and the photoinitiator is included in an amount of 0.01 to 10% Resin composition.

The method according to claim 1,
Wherein the acrylate oligomer is at least one selected from the group consisting of an epoxy acrylate resin, a halogenated epoxy acrylate resin, a urethane acrylate resin, and a polyester acrylate resin. .
The method according to claim 1,
The reactive diluent monomer may be selected from the group consisting of methyl (meth) acrylate, ethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, oxyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (Meth) acrylate, methoxycarbonyl (meth) acrylate, methylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate, phenyl Propylene glycol (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,3-propylene glycol (meth) acrylate, (Meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,5-pentanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, diethylene glycol di Triethylene glycol di (meth) acrylate (Meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, diethylene glycol di (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethoxyethoxyethyl acrylate, epoxy acrylate of glycidyl methacrylic acid, 1,6-hexanediol di (meth) acrylate, glycerin tri Acrylate, styrene, halogenated styrene, vinyltoluene, divinylbenzene, alpha methylstyrene, bisphenol A di (meth) acrylate, poly (Meth) acrylate, a mixture thereof, and a mixture thereof. Lee seokyong sight resin composition for manufacturing transparent chips burned.
The method according to claim 1,
Wherein the photoinitiator is at least one of a long-wavelength photoinitiator and a short-wavelength photoinitiator.
6. The method of claim 5,
The long wavelength photoinitiator may be 2-benzyl-2-dimethylamino-1-butanone, diphenyl (2,4,6-trimethylbenzoyl) -phosphine oxide, bis (2,4,6-trimethylbenzoyl) (2-hydroxy-2-methyl-1- (4- (methylvinyl) phenylpropane), 2,2-dimethoxy-1,2 2-methyl-1-phenylpropan-1-one, 2,4-diethylthioxanthone, 3,3 (2,6-dichlorobenzoyl) -phenylphosphine oxide, bis (2,6-dichlorobenzoyl) -phenylphosphine oxide, bis (2,6-dichlorobenzoyl) -4-ethoxyphenylphosphine oxide, bis (2,6-dichlorobenzoyl) -4-propylphenoxide Phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide It represents at least one member selected from the group consisting of diphenylphosphine oxide pin, - 2,4,6-trimethylbenzoyl
The short wavelength photoinitiator may be selected from the group consisting of 1-hydroxy-cyclohexyl-phenyl ketone, 2-hydroxy-2-methyl- (2-benzoyl-2- (dimethylamino) -1- [4- (4-methylphenylsulfanyl) (4-morpholinyl) phenyl] -1-butanone and 2-methyl-1- [4- By weight based on the total weight of the composition.
The method according to claim 1,
Wherein the resin composition further comprises a chain transfer agent. &Lt; RTI ID = 0.0 &gt; 11. &lt; / RTI &gt;
The method according to claim 1,
The chain transfer agent is a polyfunctional chain transfer agent,
The multifunctional chain transfer agent is selected from the group consisting of 1,5-pentanedithiol, 1,6-hexanedithiol, ethylene glycol bis (3-mercaptobutyrate), propylene glycol bis (3-mercaptobutyrate), diethylene glycol bis Mercaptobutyrate), butanediol bis (3-mercaptobutyrate), octanediol bis (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis ), Dipentaerythritol hexacis (3-mercaptobutyrate), ethylene glycol bis (2-mercaptopropionate), propylene glycol bis (2-mercaptopropionate), diethylene glycol bis Mercaptopropionate), butanediol bis (2-mercaptopropionate), octanediol bis (2-mercaptopropionate), trimethylolpropane tris (2-mercaptopropionate), pentaerythritol tetrakis (2-mercapto (3-mercaptoisobutyrate), propylene glycol bis (3-mercaptoisobutyrate), diethylene glycol bis (3-mercaptoisobutyrate), dipentaerythritol hexa 3-mercaptoisobutyrate), butanediol bis (3-mercaptoisobutyrate), octanediol bis (3-mercaptoisobutyrate), trimethylolpropane tris (3-mercaptoisobutyrate) (2-mercaptoisobutyrate), propylene glycol bis (2-mercaptoisobutyrate), erythritol tetrakis (3-mercaptoisobutyrate), dipentaerythol hexacis Diisobutyrate), diethylene glycol bis (2-mercaptoisobutyrate), butanediol bis (2-mercaptoisobutyrate), octanediol bis (2-mercaptoisobutyrate), trimethylolpropane tris 2-mercaptoisobutyrate ), Pentaerythritol tetrakis (2-mercaptoisobutyrate), dipentaerythritol hexakis (2-mercaptoisobutyrate), ethylene glycol bis (4-mercaptovalerate), propylene glycol bis (4-mercaptovalerate), butanediol bis (4-mercaptovalerate), octanediol bis (4-mercaptovalerate), trimethylolpropane tris (4 (4-mercaptovalerate), ethylene glycol bis (3-mercaptovalerate), propylene glycol bis (3-mercaptovalerate), pentaerythritol tetrakis (3-mercaptovalerate), diethylene glycol bis (3-mercaptovalerate), butanediol bis (3-mercaptovalerate), octanediol bis (3-mercaptovalerate), trimethylolpropane tris (3-mercaptovalerate), pentaerythritol (3-mercaptovalerate), dipentaerythritol hexaquis (3-mercaptovalerate), hydrogenated bisphenol A bis (3-mercaptobutyrate), bisphenol A dihydroxyethyl ether-3-mercapto Butyrate, 4,4'- (9-fluorenylidene) bis (2-phenoxyethyl (3-mercaptobutyrate)), ethylene glycol bis (3-mercapto-3-phenylpropionate), propylene glycol 3-phenylpropionate), diethylene glycol bis (3-mercapto-3-phenylpropionate), butanediol bis (3-mercapto-3-phenylpropionate) (3-mercapto-3-phenylpropionate), trimethylolpropane tris (3-mercapto-3-phenylpropionate), tris-2- Pentaerythritol tetrakis (3-mercapto-3-phenylpropionate) and dipentaerythole hexakis (3- Le mercaptomethyl-3-phenyl propionate) resin composition for producing artificial marble photocurable transparent chips, characterized in that at least one member selected from. The method according to claim 1,
The resin composition further comprises a chain transfer agent
Wherein the cured product has a thickness of 1 to 70 mm.
A photocured product for producing a photocurable transparent chip for artificial marble, which is obtained by irradiating light to the resin composition according to any one of claims 1 to 9 and photo-curing the same.