KR20210010416A - Artificial stone - Google Patents

Abstract

The present application relates to an artificial stone and a curable composition. The present application can provide: the curable composition which can manufacture the artificial stone having excellent moldability and physical properties suitable for molding into the artificial stone, having excellent optical properties, being free to give color, etc., having excellent physical properties such as scratch resistance, and thus having excellent light resistance; and the artificial stone manufactured by the curable composition.

Description

Artificial stone {Artificial stone}

This application relates to an artificial stone and a curable composition.

Artificial stone, such as artificial marble, is used for various purposes, including interior materials and building materials.

In the industry, artificial stone is largely classified into MMA series and E stone series. MMA-based artificial stone refers to an artificial stone formed mainly by casting using a material in which a filler is mixed with an acrylic polymer such as PMMA (poly(methyl methacrylate)). On the other hand, E stone is an abbreviation of engineered stone, and refers to an artificial stone mainly manufactured by a press method using a material in which a filler is mixed with an unsaturated polyester (UPE) binder resin.

For any type of artificial stone, it is important to ensure transparency and appropriate color. For example, if the artificial stone is opaque or has an unnecessary color, the intended effect such as a decorative effect is greatly reduced, or it is difficult to add a desired color to the artificial stone.

In addition, artificial stone is required to have light resistance. Artificial stone is often used outdoors, and for example, yellowing should be prevented when exposed to ultraviolet rays.

In order to solve this problem, conventionally, a method of mixing an artificial stone with a sunscreen such as titanium dioxide, an ultraviolet absorber or a radical stabilizer has been used. However, the titanium dioxide or the like blended in the artificial stone makes the artificial stone opaque due to its own color and makes it difficult to control the color of the artificial stone.

As another method, a method of manufacturing artificial stone using an epoxidized linseed oil called bio-resin is also known. However, the above method also requires a large amount of white pigment to be applied due to the inherent yellowness of the binder used, and it is difficult to control the color of the artificial stone.

In this application, a curable composition capable of manufacturing artificial stone having excellent moldability and physical properties suitable for artificial stone molding, excellent optical properties, free imparting of color, etc., excellent physical properties such as scratch resistance, and excellent light resistance, and It is an object to provide an artificial stone made of such a curable composition.

The physical properties mentioned in the present application are those measured at room temperature unless otherwise specified. The term room temperature is a natural temperature that is not reduced or warmed, for example, any temperature in the range of about 10°C to 30°C, any temperature in the range of 20°C to 30°C, 23°C or 25°C It can mean temperature.

The present application provides a curable composition. The curable composition may be a so-called heat curable composition. That is, the curable composition may be cured by application of heat.

The curable composition can be used in various applications. In one example, the curable composition may have moldability and physical properties suitable for manufacturing artificial stone such as artificial marble. Therefore, the curable composition may be a curable composition for artificial stone. The artificial stone made of the curable composition has excellent optical properties such as transparency and color, is free to impart color, etc., has excellent physical properties such as scratch resistance, and has excellent light resistance.

The curable composition may include a polyol component and an isocyanate component, and may also include a filler together with the above.

The term polyol component refers to a component consisting of one polyol or a mixture of two or more polyols, and the term isocyanate component refers to a component consisting of one isocyanate compound or a mixture of two or more isocyanate compounds. That is, when one kind of polyol in the curable composition is present, the polyol component is one kind of polyol, and if two or more kinds of polyols are present, the polyol component is a mixture of the two or more polyols. In addition, when there is one isocyanate compound in the curable composition, the isocyanate component is that one isocyanate compound, and if two or more isocyanate compounds are present, the isocyanate component is a mixture of the two or more isocyanate compounds.

The polyol component and the isocyanate component may undergo a curing reaction to form a so-called polyurethane. Accordingly, the components of the curable composition including the polyol component and the isocyanate component, and excluding the filler may be referred to as a polyurethane binder component.

Accordingly, in the curable composition for forming the artificial stone, the component including the polyol component and the isocyanate component, excluding the filler, may be referred to as a binder component.

The polyol component may include a so-called bifunctional polyol (which may also be called a glycol) and a polyfunctional polyol. In the above, the bifunctional polyol refers to a compound having two hydroxy groups (OH), and the polyfunctional polyol refers to a compound having three or more hydroxy groups (OH). The polyfunctional polyol may have, for example, trifunctional to 10 functional. The polyfunctional polyol may be 9 functional or less, 8 functional or less, 7 functional or less, 6 functional or less, 5 or 4 functional or less, in one example. In one example, the polyfunctional polyol may be a trifunctional polyol.

Through the application of the two types of polyols, the curable composition has moldability suitable for manufacturing artificial stone, and after curing, it is possible to increase the strength and surface hardness of the artificial stone by imparting a high curing density to the artificial stone. Further, the use of the two types of polyols contributes to improvement of light resistance and weather resistance.

The type of polyol that can be applied in the present application is not particularly limited. For example, the bifunctional polyol is ethylene glycol, diethylene glycol, triethylene glycol, pentaethylene glycol, polyethylene glycol, tetra Ethylene glycol (Tetraethylene glycol), 1,6-hexanediol (1,6- Hexanediol), 1,5-pentanediol (1,5-pentanediol), 1,4-pentanediol (1,4-pentanediol), 1 ,3-pentanediol (1,3-pentanediol), 1,2-pentanediol (1,2-pentanediol), 1,2-butanediol (1,2-butanediol), 1,3-butanediol (1,3- butanediol), 1,4-butanediol, 1,7-heptanediol, 1,6-heptanediol, 2,3-heptanediol (2,3-heptanediol), 1,4-heptanediol, 1,2-heptanediol, 1,3-heptanediol, or An aliphatic polyol (glycol) having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms such as 3,5-heptanediol may be used.

The polyfunctional polyols include trimethylolpropane, trimethylolpropane ethoxylate, trimethylolmethane, trimethylolethane, trimethylolpropane monoallyl ether, trimethylolpropane, triethylolpropane. , 1,2,4-butanetriol, glycerol, pentaerythritol, dipentaerythritol, trimethylolphosphine, or the like may be used.

In order to secure appropriate physical properties, as the polyol component, a component containing 80 mol% or more of a polyol having a molecular weight of 500 g/mol or less (hereinafter, may be referred to as a low molecular weight polyol) may be used.

In another example, the molecular weight of the low molecular weight polyol is 480 g/mol or less, 460 g/mol or less, 440 g/mol or less, 420 g/mol or less, 400 g/mol or less, 380 g/mol or less, 360 g/mol Or less, 340 g/mol or less, 320 g/mol or less, 300 g/mol or less, 280 g/mol or less, 260 g/mol or less, 240 g/mol or less, 220 g/mol or less, 200 g/mol or less, 180 g/mol or less, 160 g/mol or less, or 140 g/mol or less, 50 g/mol or more, 52 g/mol or more, 54 g/mol or more, 56 g/mol or more, 58 g/mol or more, 60 g/mol or more, 72 g/mol or more, 74 g/mol or more, 76 g/mol or more, 78 g/mol or more, 80 g/mol or more, 82 g/mol or more, 84 g/mol or more, 86 g/ mol or more, 88 g/mol or more, 90 g/mol or more, 92 g/mol or more, 94 g/mol or more, 96 g/mol or more, 98 g/mol or more, 100 g/mol or more, 110 g/mol or more , 120 g/mol or more, or 130 g/mol or more.

In one example, the content of the low molecular weight polyol in the polyol component is 82 mol% or more, 84 mol% or more, 86 mol% or more, 88 mol% or more, 90 mol% or more, 92 mol% or more, 94 mol% or more, 96 mol % Or more or 98 mol% or more, and the content may be 100 mol% or less.

In order to ensure proper physical properties, as the polyol component, a component containing 80 mol% or more of a non-aromatic polyol may be used. The non-aromatic polyol is a non-aromatic polyol, and the non-aromatic polyol may be a non-aromatic non-cyclic polyol in one example.

In one example, the content of the non-aromatic polyol in the polyol component is 82 mol% or more, 84 mol% or more, 86 mol% or more, 88 mol% or more, 90 mol% or more, 92 mol% or more, 94 mol% or more, 96 mol % Or more or 98 mol% or more, and the content may be 100 mol% or less.

Meanwhile, the polyol component may include 25 to 55 mol% of the bifunctional polyol. In another example, the ratio is 27 mol% or more, 29 mol% or more, 31 mol% or more, 33 mol% or more, 35 mol% or more, 37 mol% or more or 39 mol% or more, or 53 mol% or less, 51 mol% It may be about 49 mol% or less, 47 mol% or less, 45 mol% or less, 43 mol% or less, or 41 mol% or less.

The ratio (P2/PM) of the number of moles of the bifunctional polyol (P2) to the number of moles (PM) of the polyfunctional polyol in the polyol component of the curable composition may be in the range of 0.2 to 1.5. In another example, the ratio is 0.25 or more, 0.3 or more, 0.35 or more, 0.4 or more, 0.45 or more, 0.5 or more, 0.55 or more, 0.6 or more, or 0.65 or more, or 1.4 or less, 1.3 or less, 1.2 or less, 1.1 or less, 1.0 or less, 0.95 It may be about 0.9 or less, 0.85 or less, 0.8 or less, 0.75 or less, or 0.7 or less.

As the polyol forming the polyol component, a variety of known polyols may be applied as described above, but the polyol component applied such that the non-aromatic polyols having the molecular weight satisfies the above ratio is combined with an isocyanate component to be described below to achieve the desired effect here. Can be further maximized.

In the present application, as the isocyanate component, a component including a bifunctional isocyanate compound and a trifunctional or higher polyfunctional isocyanate compound may be used.

The term bifunctional isocyanate compound refers to a compound having two isocyanate groups, and a polyfunctional isocyanate compound refers to a compound having trifunctional or higher, that is, three or more isocyanate groups. The polyfunctional isocyanate compound may be, for example, trifunctional to 10 functional. The polyfunctional isocyanate compound may be 9 functional or less, 8 functional or less, 7 functional or less, 6 functional or less, 5 functional or less, or tetrafunctional or less in one example. In one example, the polyfunctional isocyanate compound may be a trifunctional isocyanate compound.

Through the application of the two isocyanate compounds, the curable composition has moldability suitable for manufacturing artificial stone, and after curing, the strength and surface hardness of the artificial stone can be increased by imparting a high curing density to the artificial stone. In addition, the use of the above two isocyanate compounds contributes to improvement of light resistance and weather resistance.

The kind of the isocyanate compound that can be applied in the present application is not particularly limited. For example, as the bifunctional isocyanate compound, isoboroone diisocyanate (IPDI), 2,2,4-trimethylhexane-1,6-diisocyanate (TMDI), or 4,4'-methylenedicyclo Hexyl diisocyanate (H12-MDI) or the like, or hydrogenated aromatic diisocyanate may be used. Examples of the aromatic diisocyanate include xylene diisocyanate, diphenylmethane diisocyanate, tetramethylxylene diisocyanate, methylenediphenyl diisocyanate, or naphthalene diisocyanate, but are not limited thereto.

In one example, as such a bifunctional isocyanate compound, a compound represented by the following Formula 1 may be used.

[Formula 1]

In Formula 1, L ₁ to L ₄ are each independently a single bond or an alkylene group having 1 to 20 carbon atoms.

In Formula 1, L ₁ and L ₂ are each independently a single bond or an alkylene group, but at least one may be an alkylene group. In this case, when only one of L ₁ and L ₂ is an alkylene group, the number of carbon atoms in the alkylene group may be in the range of 1 to 20, 2 to 20, 3 to 20, 3 to 16, 3 to 12, or 3 to 8. . In addition, when both L ₁ and L ₂ are alkylene groups, the total number of carbon atoms of the alkylene group may be in the range of 1 to 20, 2 to 20, 3 to 20, 3 to 16, 3 to 12, or 3 to 8.

In one example, any one of L ₁ and L ₂ may be an alkylene group having 1 to 2 carbon atoms, and the other may be an alkylene group having 3 to 20, 3 to 16, 3 to 12, 3 to 8 or 3 to 4 carbon atoms have.

Meanwhile, in Formula 1, L ₃ and L ₄ may each independently be a single bond or an alkylene group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms.

The alkylene group of Formula 1 may be straight or branched, and may be optionally substituted with one or more substituents other than an isocyanate group.

In addition, the polyfunctional isocyanate compound is hexamethylene diisocyanate isocyanurate (HDI isocyanurate), hexamethylene diisocyanate imino oxadiazine dione (HDI-imino oxadiazine dione), hexamethylene diisocyanate biuret trimer (HDI biuret trimer) ), hexamethylene diisocyanate trimer (HDI trimer), hexamethylene diisocyanate biuret (HDI biuret), hexamethylene diisocyanate uretdione (HDI uretdione), or hexamethylene diisocyanate (HDI) and/or isophorone diisocyanate (IPDI) ) May be blended with a trimmer or the like, but is not limited thereto.

These ingredients are variously known in the art. For example, as the hexamethylene diisocyanate trimer (HDI trimer), Asahi Kasei's Duranate TUL-100, Duranate TLA-100, Duranate TKA-100, Duranate TSA-100 or Duranate TSE-100, or Covestro's Desmodur N3300, Desmodur A known compound such as N3900 or Desmodur N3600 may be used, and a known compound such as Duranate 24A-100 from Asahi Kasei or Desmodur N100 or Desmodur N3200 from Covestro may be used as the hexamethylene diisocyanate biuret (HDI biuret). , As the hexamethylene diisocyanate ureddione (HDI uretdione), a compound known as Covestro's Desmodur N3400 or Desmodur XP2840 may be used, and the hexamethylene diisocyanate (HDI) and isophorone diisocyanate (IPDI) are blended. As a trimmer, a compound known as Covestro's Desmodur XP2838 or the like can be used.

In order to secure appropriate physical properties, as the isocyanate compound component, a component containing 80 mol% or more of an isocyanate compound having a molecular weight of 1000 g/mol or less (hereinafter, may be referred to as a low molecular weight isocyanate compound) may be used.

In another example, the molecular weight of the low molecular weight isocyanate compound is 950 g/mol or less, 900 g/mol or less, 850 g/mol or less, 800 g/mol or less, 750 g/mol or less, 700 g/mol or less, 650 g/ mol or less, 600 g/mol or less, 550 g/mol or less, 500 g/mol or less, 450 g/mol or less, 400 g/mol or less, 350 g/mol or less, 300 g/mol or less, 250 g/mol or less Or 200 g/mol or less, 50 g/mol or more, 100 g/mol or more, 150 g/mol or more, 200 g/mol or more, 250 g/mol or more, 300 g/mol or more, 350 g/mol or more, It may be about 400 g/mol or more or 450 g/mol or more.

The content of the low molecular weight isocyanate compound in the isocyanate compound component is 82 mol% or more, 84 mol% or more, 86 mol% or more, 88 mol% or more, 90 mol% or more, 92 mol% or more, 94 mol% or more, It may be 96 mol% or more or 98 mol% or more, and the content may be 100 mol% or less.

In order to secure appropriate physical properties, as the isocyanate compound component, a component containing 80 mol% or more of a non-aromatic isocyanate compound may be used. The non-aromatic isocyanate compound is an isocyanate compound that is not aromatic. For example, as the bifunctional isocyanate compound, when the non-aromatic isocyanate compound is applied, a non-aromatic cyclic compound (so-called alicyclic compound) may be used as the isocyanate compound, and in that case, the compound is represented by the formula It may be a compound of 1. Further, when the polyfunctional isocyanate compound is a non-aromatic isocyanate compound, the compound may be cyclic or non-cyclic.

The content of the non-aromatic isocyanate compound in the isocyanate compound component is 82 mol% or more, 84 mol% or more, 86 mol% or more, 88 mol% or more, 90 mol% or more, 92 mol% or more, 94 mol% or more, It may be 96 mol% or more or 98 mol% or more, and the content may be 100 mol% or less.

The isocyanate compound component may include 55 to 90 mol% of the bifunctional isocyanate compound. In another example, the ratio is 57 mol% or more, 59 mol% or more, 61 mol% or more, 63 mol% or more, 65 mol% or more, 67 mol% or more, 69 mol% or more, or 71 mol% or more, or 88 mol% It may be about 86 mol% or less, 84 mol% or less, 82 mol% or less, 80 mol% or less, 78 mol% or less, 76 mol% or less, 74 mol% or less, 72 mol% or less, or 70 mol% or less.

The ratio (P2/PM) of the number of moles (N2) of the bifunctional isocyanate compound to the number of moles (NM) of the polyfunctional isocyanate compound in the isocyanate compound component of the curable composition may be in the range of 1.5 to 5. In another example, the ratio is 1.7 or more, 1.9 or more, 2.1 or more, 2.3 or more, or 2.5 or more, or 4.8 or less, 4.6 or less, 4.4 or less, 4.2 or less, 4.0 or less, 3.8 or less, 3.6 or less, 3.4 or less, 3.2 or less, 3.0 It may be about 2.8 or less, 2.6 or less, 2.4 or less, 2.2 or less, or 2.0 or less.

As the isocyanate compound forming the isocyanate compound component, various known isocyanate compounds may be applied as described above, but the isocyanate compound component applied so that the non-aromatic isocyanate compounds having the molecular weight satisfies the above ratio is combined with the polyol component to the present application. The desired effect can be further maximized.

The blending ratio between the polyol component and the isocyanate component in the curable composition of the present application is not particularly limited, for example, the number of moles of the isocyanate compound in the isocyanate component (N) of the number of moles (P) of the polyol compound in the polyol component The ratio (P/N) to may be adjusted to be in the range of 0.4 to 1.5. The ratio (P/N) is 0.45 or more, 0.5 or more, 0.55 or more, 0.6 or more, 0.65 or more, 0.7 or more, 0.75 or more, 0.8 or more, or 0.85 or more, 1.4 or less, 1.3 or less, 1.2 or less, 1.1 or less in other examples , 1.0 or less, 0.95 or less, 0.9 or less, 0.85 or less, or may be about 0.8 or less.

In another example, in the curable composition, the polyol so that the ratio (OH/NCO) of the total number of moles of hydroxyl groups (OH) in the polyol component to the number of moles (NCO) of all isocyanate groups in the isocyanate component (OH/NCO) is in the range of 0.5 to 1.5. And an isocyanate component may be blended. The ratio (OH/NCO) is, in another example, 0.55 or more, 0.6 or more, 0.65 or more, 0.7 or more, 0.75 or more, 0.8 or more, 0.85 or more, or 0.9 or more, or 1.4 or less, 1.3 or less, 1.2 or less, 1.1 or less, 1.0 It may be less than or equal to 0.95 or less.

In another example, the binder component may include 20 to 60 parts by weight of a polyol component based on 100 parts by weight of the isocyanate component. The term parts by weight is the ratio of the weight between the components. Specifically, the ratio of the polyol component is 22 parts by weight or more, 24 parts by weight or more, 26 parts by weight or more, 28 parts by weight or more, 30 parts by weight or more, 32 parts by weight or more, or 34 parts by weight or more based on 100 parts by weight of the isocyanate component. Or, 58 parts by weight or less, 56 parts by weight or less, 54 parts by weight or less, 52 parts by weight or less, 50 parts by weight or less, 48 parts by weight or less, 46 parts by weight or less, 45 parts by weight or less, 44 parts by weight or less, 42 parts by weight It may be about 40 parts by weight or less, 38 parts by weight or less, or about 36 parts by weight or less.

In the above range, it is possible to provide a curable composition capable of forming an artificial stone that exhibits excellent moldability and workability before curing, has excellent transparency or color characteristics after curing, and has excellent light resistance to prevent yellowing due to ultraviolet rays. have.

The curable composition of the present application may include a filler together with the component. As a filler that can be applied, a well-known filler, for example, a well-known filler applied in the manufacture of artificial stone may be applied without any particular limitation.

For example, a so-called quartz-based filler or a filler such as aluminum hydroxide may be applied as the filler.

In one example, a mixture of a filler including so-called quartz sand and quartz powder may be applied as the quartz-based filler.

The terms quartz sand and quartz powder are types of masonry fillers classified according to the size of the particles.

For example, the term quartz sand refers to a quartz-based filler having a particle size of approximately 0.01 mm to 2 mm. The particle size of the quartz sand may be 0.02 mm or more, 0.03 mm or more, 0.04 mm or more, 0.05 mm or more, or 0.06 mm or more in another example. In addition, the particle size of the quartz sand is 1.9 mm or less, 1.8 mm or less, 1.7 mm or less, 1.6 mm or less, 1.5 mm or less, 1.4 mm or less, 1.3 mm or less, 1.2 mm or less, 1.1 mm or less, 1.0 mm or less, 0.9 mm or less, 0.8 mm or less, 0.7 mm or less, 0.6 mm or less, 0.5 mm or less, 0.4 mm or less, or 0.3 mm or less. In one example, as the quartz sand, a mixture of quartz sand having a particle size of 0.3 mm or less or less than 0.3 mm within the above-described range and quartz sand having a particle size of 0.3 mm or more or more than 0.3 mm within the above-described range may be used. I can.

Meanwhile, the term quartz powder refers to a quartz-based filler having a particle size of 250 to 400 mesh. The particle size in this case means a quartz-based filler that passes through a sieve of 250 to 400 mesh. For example, the size of the quartz powder may be 270 mesh to 380 mesh, 290 mesh to 360 mesh, 310 mesh to 340 mesh, or 320 mesh to 330 mesh. The mesh refers to the number of holes included in a 1 inch sieve, and may be expressed in units representing the size of solid particles.

The method of measuring the particle size of the quartz-based filler is not particularly limited. The particle size of the filler can be measured by applying a known method of measuring the particle size for artificial stone, and in the above method, the size of the particles is measured using a sieve with a defined mesh size.

By applying the quartz-based filler so as to have the distribution of the particle size as described above, it is possible to exhibit an aesthetic feeling similar to that of a natural stone along with physical properties such as excellent scratch resistance.

In one example, the quartz powder may be used in an amount of 25 to 60 parts by weight based on 100 parts by weight of the quartz sand. In another example, the quartz powder is 30 parts by weight or more, 35 parts by weight or more, 40 parts by weight or more, 45 parts by weight or more, 57 parts by weight or less, 54 parts by weight or less, 51 parts by weight or less, or It may be up to 49 parts by weight.

In addition, the weight ratio of the quartz sand based on the total weight of the filler may be about 50 to 90% by weight in one example. In another example, the ratio is 52% by weight or more, 54% by weight or more, 56% by weight or more, 58% by weight or more, 60% by weight or more, 62% by weight or more, 64% by weight or more, or 66% by weight or more, or 85% by weight It may be about 80% by weight or less, 75% by weight or less, or 70% by weight or less.

In addition, as the quartz sand, a mixture of quartz sand having a particle size of 0.3 mm or less or less than 0.3 mm (hereinafter, small quartz sand) and quartz sand having a particle size of 0.3 mm or more or more than 0.3 mm (hereinafter, large quartz sand) When applied, 25 to 60 parts by weight of the large quartz sand relative to 100 parts by weight of the small quartz sand may be used. The ratio of the quartz sand is, in another example, 30 parts by weight or more, 35 parts by weight or more, 40 parts by weight or more, or 45 parts by weight or more, or 57 parts by weight or less, 54 parts by weight or less, 51 parts by weight or less, or 49 parts by weight It may be below.

The curable composition may include the filler component in an amount of 70 to 95% by weight based on the total weight of the curable composition. In another example, the ratio is 72% or more, 74% or more, 76% or more, 78% or more, 80% or more, 82% or more, 84% or more, 86% or more, or 88% or more by weight. Or, it may be about 93% by weight or less or 91% by weight or less.

In the curable composition, the total weight part of the polyol component and the isocyanate component may be in the range of 5 to 30 parts by weight based on 100 parts by weight of the filler.

The total part by weight of the polyol component and the isocyanate component (parts by weight of the binder component) may be 7 parts by weight or more, 9 parts by weight or more, 11 parts by weight or more, or 12 parts by weight or more, based on 100 parts by weight of the filler, and 28 parts by weight. It may be parts by weight or less, 26 parts by weight or less, 24 parts by weight or less, 22 parts by weight or less, 20 parts by weight or less, 18 parts by weight or less, 16 parts by weight or less, 14 parts by weight or less, or 13 parts by weight or less.

Through this ratio, it is possible to provide a curable composition that more efficiently satisfies the desired properties.

The curable composition may contain the necessary additional ingredients together with the above ingredients. For example, the curable composition may further include a catalyst for curing the polyol component and the isocyanate component. As the catalyst, a known catalyst (for example, a urethane reaction catalyst) may be used without particular limitation. For example, a so-called tertiary amine may be used as the catalyst.

The ratio of the catalyst is not particularly limited, and may be used as a catalyst amount. For example, the catalyst may be included in an amount of 1 part by weight or less based on 100 parts by weight of the isocyanate component. The catalyst may be included in an amount of 0.8 parts by weight or less, 0.6 parts by weight or less, 0.4 parts by weight or less, 0.2 parts by weight or less, or 0 parts by weight based on 100 parts by weight of the isocyanate component. The catalyst may be included within the above-described range, thereby accelerating the curing reaction time. For example, the curing reaction may be completed within 1 hour at 120°C. In addition, it is possible to secure a time for controlling the shape of the curable composition to the desired shape before initiation of the curing reaction under the content of the catalyst, and excellent optical properties and color sense of the cured product can be maintained.

In one example, a catalyst that does not contain metal may be used as the catalyst. That is, as the catalyst, a metal catalyst or an organo-metal hybrid catalyst may not be used, thereby solving problems such as bubble generation due to overcuring.

The tertiary amine is a compound in which three hydrogen atoms of ammonia are substituted with a hydrocarbon group, and imidazole, N,N-dimethylaminopyridine, N-methylmorpholine, triethanolamine, N-cocomorpholine 2,2' -Consisting of dimorpholinyldiethyl ether, N,N'-bis-[3-(dimethylamino)propyl]urea, N,N-dimethylcyclohexylamine and 2,4,6-tris(dimethylaminomethyl)phenol One or more compounds selected from the group may be used, but the type of catalyst applicable is not limited thereto.

In addition to the above, the curable composition may freely contain various known necessary components.

The curable composition may be prepared by appropriately mixing the above-described components. For example, the isocyanate component and the polyol component, which are binder components, may be first blended, and then blended with a filler component to prepare a curable composition.

This application is also directed to artificial stone, such as artificial marble. The artificial stone can be prepared by curing the curable composition described above. Therefore, the artificial stone may be a cured product of the curable composition.

The method of manufacturing artificial stone by curing the curable composition is not particularly limited, and a method of manufacturing artificial stone in general, for example, a curing method using a casting process or a curing method using a press process may be applied. . The curable composition of the present application exhibits moldability and curability suitable for manufacturing artificial stone as described above.

In addition, the artificial stone formed by the curable composition may exhibit a texture that accompanies natural stone, has excellent optical properties, can freely implement a desired color as needed, and also has excellent various mechanical properties.

For example, the artificial stone may have a flexural strength of 30 MPa to 80 MPa according to KS F 4739. The flexural strength refers to the maximum stress until fracture of the cured product due to a bending load. Specifically, the cured product may have a flexural strength of 40 MPa to 75 MPa, or 50 MPa to 70 MPa.

The artificial stone may have a compressive strength of 170 MPa to 300 MPa according to KS F 2519. The compressive strength means the maximum stress until failure when the cured product is subjected to a compressive force. Specifically, the compressive strength of the cured product may be in the range of 200 MPa to 240 MPa or 210 MPa to 230 MPa.

The binder component (ie, the component of the curable composition including the polyol component and the isocyanate component, and excluding the filler) applied to the artificial stone may be cured to exhibit excellent optical transparency. For example, the cured product of the binder component may exhibit a transmittance of 90% or more. In another example, the transmittance may be 90.5% or more, 91% or more, 95% or less, 94% or less, 93% or less, or 92% or less. The transmittance is a transmittance measured using a D65 standard light source, and is a transmittance measured in the thickness direction for an artificial stone having a thickness of 5 mm.

In addition, the artificial stone may exhibit excellent color characteristics, and for example, the value of L* in the CIE Lab color coordinate may be 90 or more. The L* may be a value related to the initial color of the artificial stone immediately after manufacture. The CIE Lab color coordinate is a color value defined by the International Commission on Illumination, and L* in the color coordinate is a numerical value representing brightness. The lower limit of L* is 0, the upper limit is 100, and 0 means black, and as the value of L* increases, it means that the color is white or close to the color of the light source. The L* value may be 90.5 or more, 91 or more, 98 or less, 95 or less, or 93 or less in another example.

In the present application, L*, a*, and b* values in CIE Lab color coordinates are values measured using a known CIE LAB color difference meter. That is, the L*, a*, and b* values are values measured using a light source mounted on a CIE LAB color difference meter (Spectro-guide, BYK).

The artificial stone may have a b* value in the range of -1.0 to 3.5 in the CIE Lab. The b* value is a value representing the degree of yellow and blue color of the artificial stone, and as the value increases, the object exhibits a color closer to yellow. Conversely, as the value decreases, the object It means showing a color closer to blue than this.

The b* value in the initial state may be 3.3 or less or 3.0 or less, -0.7 or more, 0.4 or more, or 0 or more in another example.

The artificial stone may exhibit excellent light resistance, in particular, resistance to ultraviolet rays.

For example, even after the artificial stone is exposed to ultraviolet rays having a wavelength of about 340 nm for 1000 hours with an intensity of 0.6 W/m ² , the change amount ΔE of the color change index may be maintained below a certain level. For example, the artificial stone may have an absolute value of a change amount ΔE of 3 or less in a color change index before and after exposure to ultraviolet rays having a wavelength of about 340 nm for 1000 hours with an intensity of 0.6 W/m ² .

The amount of change ΔE of the color change index can be measured by Equation 1 below.

[Equation 1]

△E = (△L* ² + △a* ² + △b* ² ) ^1/2

In Equation 1, ΔL*, Δa*, and Δb* are values determined by the following Equations 2 to 4, respectively.

[Equation 2]

△L* = La*-Li*

In Equation 2, La* is the L* value in the CIE Lab color coordinate of the artificial stone immediately after exposure to ultraviolet rays of about 340 nm wavelength with an intensity of 0.6 W/m ² for 1000 hours, and Li* is the artificial stone immediately before exposure to the ultraviolet rays. It is the L* value in the CIE Lab color coordinates.

[Equation 3]

△a* = aa*-ai*

In Equation 3, aa* is a* value in CIE Lab color coordinates of the artificial stone immediately after exposure to ultraviolet rays of about 340 nm wavelength with an intensity of 0.6 W/m ² for 1000 hours, and ai* is the artificial stone immediately before exposure to the ultraviolet rays. It is a* value in the CIE Lab color coordinate of

[Equation 4]

△b* = ba*-bi*

In Equation 2, ba* is the b* value in the CIE Lab color coordinates of the artificial stone immediately after exposure to ultraviolet rays of about 340 nm wavelength with an intensity of 0.6 W/m ² for 1000 hours, and bi* is the artificial stone immediately before exposure to the ultraviolet rays. It is the b* value in the CIE Lab color coordinates.

In Equations 1 to 4, the meanings of L* and b* are as described above. In addition, a* is a physical quantity representing the degree of red and green, and as the value increases, the object represents a color closer to red, and a lower value indicates a color closer to green.

The artificial stone may also have Δb* of Equation 4 in the range of -1.5 to 3.0 or -1.5 to 1.5. In addition, Δb* may be -1 or more, -0.5 or more, 2.5 or less, or 2 or less in another example.

In the above range, the artificial stone can exhibit excellent optical transparency and color, and if necessary, the color of the pigment added to the artificial stone is expressed, so that the color can be adjusted freely. In the above, the values of L*, a*, and b* representing the color of artificial stone are color characteristics in a state in which pigments or dyes that implement other colors other than the above-described binder component and filler component are not included.

The shape of the artificial stone as described above is selected according to the purpose and is not particularly limited, and dimensions such as thickness are not limited to being adjusted according to the purpose.

In this application, a curable composition capable of manufacturing artificial stone having excellent moldability and physical properties suitable for artificial stone molding, excellent optical properties, free imparting of color, etc., excellent physical properties such as scratch resistance, and excellent light resistance, and It is possible to provide an artificial stone made of such a curable composition.

1 and 2 are images of artificial stone prepared with the curable composition of Example 1 immediately before and immediately after exposure to ultraviolet rays for 1000 hours, respectively.
3 and 4 are images of artificial stone prepared with the curable composition of Comparative Example 1 immediately before and immediately after exposure to ultraviolet rays for 1000 hours, respectively.
5 and 6 are images of artificial stone prepared with the curable composition of Comparative Example 2 immediately before and immediately after exposure to ultraviolet rays for 1000 hours, respectively.

The present application will be described in detail through the following examples, but the scope of the present application is not limited by the following examples.

1. Formability evaluation

The curable composition prepared in Examples or Comparative Examples is put into a mold for artificial stone, and the upper plate of the mold is vibrated for 1 minute and 30 seconds using a vibrator under vacuum conditions, and compression is applied to form a plate. Subsequently, each of the upper and lower plates was set to a temperature of 120° C. with an upper and lower plate hot press type oven, and then thermally cured for 1 hour. After completion of curing, the cured product is cooled to room temperature, taken out from the mold, cut in all directions, and polished to produce artificial stone. When artificial stone is stably manufactured through the above process, formability is evaluated as PASS, and when artificial stone cannot be manufactured due to phase separation, high or low viscosity, it is evaluated as NG.

2. Transparency evaluation

The binder (mixture of resin components before being mixed with the quartz filler) prepared in Examples or Comparative Examples is cured by holding at a temperature of 120° C. for about 1 hour to form a plate-shaped cured product having a thickness of about 5 mm. Subsequently, a CM-5 spectrophotometer (Konica minolta) and a D65 standard light source were used to evaluate the transmittance (transparency) and the b* value of the CIE Lab color coordinate of the transmitted light. The meaning of the b* value is the same as the text.

3. Evaluation of scratch resistance

The plate-shaped cured product formed in the same manner as the transparency evaluation was evaluated for scratch resistance through the Ericsson test.

The Ericsson test is a surface strength test performed using the Erichsen's Scratch Hardness tester 413, and if it satisfies the standard value of 1.4N or higher, it is judged as PASS, and if it is less than 1.4N, it is determined as NG. Judge. As for the test method, after fixing the specimen to the tester, increase the weight by 0.1N from 0 using a diamond tip and a weight, and check that the surface is scratched. Measure the weight of the weight when the scratch is visible.

4. Light durability evaluation

An artificial stone was prepared by applying the curable composition of the Example or Comparative Example to the method in the above moldability evaluation. The manufactured artificial stone was exposed to ultraviolet rays of 340 nm wavelength with an intensity of 0.6 W/m ² using QUV equipment (QUV, Q-LAB), and the temperature inside the equipment was maintained at 50°C.

Using the CIE LAB color difference meter (Spectro-guide, BYK), L*, a* and b* values of the CIE Lab color space are measured, respectively. The definitions of the L*, a* and b* values are the same as in the text. The L*, a*, and b* values before and after exposure to ultraviolet rays are obtained, respectively, and ΔL*, Δa*, and Δb* values are obtained through the difference in values before and after exposure to ultraviolet rays.

Thereafter, the obtained value is substituted into Equation A below to obtain a color change value ΔE.

[Equation A]

△E = (△L* ² + △a* ² + △b* ² ) ^1/2

Example 1

Hydrogenated xylene diisocyanate (Takenate-600, Mitsui Chemical) (molecular weight: about 194.24 g/mol) 37% by weight, HDI isocyanurate trimer (Desmodur N3300, Covestro) (molecular weight: About 504.6 g/mol) 36 wt%, trimethylolpropane (molecular weight: about 134.17 g/mol) 17 wt%, diethylene glycol (molecular weight: about 106.12 g/mol) 9 wt% and tertiary amine (1-Methylimidazole) 1% by weight was mixed at room temperature to prepare a mixture (binder).

As a filler, a quartz filler was prepared. The quartz-based filler includes 41% by weight of quartz sand having an average particle size of about 0.1 mm to 0.3 mm, 19% by weight of quartz sand having an average particle size of about 0.3 mm to 0.7 mm, and quartz powder having an average particle size of about 325 mesh. It was prepared by mixing 29% by weight.

A curable composition was prepared by uniformly mixing the binder and the quartz-based filler in a weight ratio of 89:11 (binder: quartz-based filler).

Example 2

A curable composition was prepared in the same manner as in Example 1, except that isoborone diisocyanate (IPDI) (molecular weight: about 222.3 g/mol) was used instead of hydrogenated xylene diisocyanate when preparing the binder.

Example 3

A curable composition was prepared in the same manner as in Example 1, except that hexamethylene diisocyanate biuret (HDI biuret) (Desmodur N3200 from Covestro) (molecular weight: 478.59 g/mol) was used instead of HDI isocyanurate when preparing the binder. I did.

Comparative Example 1

As a binder, a curable composition was prepared in the same manner as in Example 1, except that unsaturated polyester for an engineered stone was used.

Comparative Example 2

As a binder, an epoxidized linseed oil (Arkema) 55% by weight, a hexahydro-4-methylphthalic anhydride curing agent (Aldrich) 41% by weight and a polyol solution in which 1-methylimidazole is dissolved 4% by weight A curable composition was prepared in the same manner as in Example 1, except that a bioresin in the form of a mixture in which% was mixed at room temperature was used.

Comparative Example 3

A curable composition was prepared in the same manner as in Example 1, except that hydrogenated xylene diisocyanate was not used and the amount of HDI isocyanurate was 74% by weight.

Comparative Example 4

A curable composition was prepared in the same manner as in Example 1, except that HDI isocyanurate was not used in the preparation of the binder, and the amount of hydrogenated xylene diisocyanate was 74% by weight.

Bifunctional polyols (diethylene glycol), polyfunctional polyols (trimethylolpropane), bifunctional isocyanate compounds (hydrogenated xylene diisocyanate, isoborone diisocyanate) applied in Examples 1 to 3 and Comparative Examples 3 to 6, respectively, and The relationship, such as the number of moles of the trifunctional isocyanate compound (HDI isocyanurate, HDI burette), is summarized in Table 1 below and described.

Example Comparative example One 2 3 3 4 Polyol DEG 0.08 0.08 0.08 0.08 0.08 TMP 0.13 0.13 0.13 0.13 0.13 NCO
compound HXDN 0.19 0 0.19 0 0.38 IPDI 0 0.17 0 0 0 HDII 0.07 0.07 0 0.14 0 HDIB 0 0 0.08 0 0 OH/NCO 0.92 1.01 0.91 1.27 0.73 P2/PM 0.67 0.67 0.67 0.67 0.67 N2/NM 2.67 2.33 2.53 0 - P/N 0.81 0.89 0.8 1.46 0.56 NCO compound: Isocyanate compound
DEG: Molar ratio of diethylene glycol in the binder
TMP: Molar ratio of trimethylolpropane in the binder
HXDN: Molar ratio of hydrogenated xylene diisocyanate in the binder
IPDI: Molar ratio of isoborone diisocyanate in binder
HDII: Molar ratio of HDI isocyanurate in binder
HDIB: Mole ratio in the binder of HDI burette
OH/NCO: molar ratio of all hydroxy groups in the polyol component to all isocyanate groups in the NCO compound
P2/PM: ratio of the number of moles of the difunctional polyol to the number of moles of the polyfunctional polyol
N2/NM: The ratio of the number of moles of the bifunctional NCO compound to the number of moles of the polyfunctional NCO compound
P/N: the ratio of the number of moles of the polyol to the number of moles of the NCO compound

The evaluation results for the curable compositions of Examples and Comparative Examples are summarized in Tables 2 and 3 below. However, in the case of Comparative Examples 3 and 4, since the artificial stone was not properly manufactured for reasons such as phase separation, high viscosity, low viscosity, or low hardness, it became NG in formability, so other physical properties could not be evaluated.

Example One 2 3 Formability PASS PASS PASS Transmittance(%) 91.2 90.4 89.1 B* in CIE Lab color space 0.57 1.21 1.42 Scratch resistance PASS PASS PASS

Comparative example One 2 3 4 Formability PASS PASS NG NG Contribution (%) 87.9 89.8 - - B* in CIE Lab color space -0.05 4.5 - - Scratch resistance PASS PASS - -

The light durability evaluation results for the curable compositions of Examples and Comparative Examples are summarized in Table 4 below. However, in the case of Comparative Examples 3 and 4, since the artificial stone was not properly manufactured for reasons such as phase separation, high viscosity, low viscosity, or low hardness, it became NG in formability, so other physical properties could not be evaluated.

Example
Comparative example
One 2 3 One 2 CIE Lab characteristics just before UV exposure L* 91.07 80.28 78.65 89.78 88.31 a* 0 -0.11 -0.08 -0.15 -0.15 b* 2.42 2.32 3.33 3.85 6.91 CIE Lab characteristics immediately after 1000 hours exposure to UV L* 91.41 80.22 80.09 88.55 92.14 a* -0.40 -0.55 -0.47 -1.11 -0.26 b* 3.49 3.87 5.24 19.61 5.16 △E 1.19 1.61 2.42 15.84 4.21 △b* 1.07 1.55 1.91 15.76 -1.75

From Table 4, it can be seen that the artificial stone prepared with the curable composition of the example exhibits a larger L* value compared to the comparative example in the initial state, thus showing a brighter color, and a color closer to white through a lower b* value. In addition, it can be seen that color change and yellowing are suppressed even after exposure to ultraviolet rays.

1 is an image of an artificial stone made of the curable composition of Example 1 before UV exposure, FIG. 2 is an image of the artificial stone after 1000 hours exposure to UV light, and FIG. 3 is an image of the curable composition of Comparative Example 1 before UV exposure. An image of an artificial stone, FIG. 4 is an image of the artificial stone after exposure to ultraviolet light for 1000 hours, FIG. 5 is an image of an artificial stone made of the curable composition of Comparative Example 2 before UV exposure, and FIG. 6 is the image after exposure to ultraviolet light for 1000 hours. It is an image of artificial stone.

Claims (20)

Polyol component; An isocyanate component including a bifunctional non-aromatic isocyanate compound and a trifunctional or higher polyfunctional non-aromatic isocyanate compound; And artificial stone which is a cured product of the curable composition containing a filler. The artificial stone according to claim 1, wherein the polyol component contains 80 mol% or more of a polyol having a molecular weight of 500 g/mol or less. The artificial stone of claim 1, wherein the polyol component contains 80 mol% or more of a non-aromatic polyol. The artificial stone according to claim 3, wherein the non-aromatic polyol is a non-aromatic non-cyclic polyol. The artificial stone according to claim 1, wherein the polyol component contains a bifunctional polyol and a trifunctional or higher polyfunctional polyol. The artificial stone according to claim 5, wherein the polyol component contains 25 to 55 mol% of a bifunctional polyol. The artificial stone according to claim 5, wherein a ratio (P2/PM) of the number of moles of the bifunctional polyol (P2) to the number of moles of the polyfunctional polyol (PM) in the curable composition is in the range of 0.2 to 1.5. The artificial stone according to claim 1, wherein the isocyanate component contains 80 mol% or more of an isocyanate compound having a molecular weight of 1,000 g/mol or less. The artificial stone according to claim 1, wherein the isocyanate component contains 80 mol% or more of a non-aromatic isocyanate compound. The artificial stone according to claim 1, wherein the bifunctional non-aromatic polyol is represented by the following formula (1):
[Formula 1]

In Chemical Formula 1, L ₁ to L ₄ are each independently a single bond or a linear or branched alkylene group having 1 to 20 carbon atoms. The artificial stone according to claim 1, wherein the isocyanate component contains 55 to 90 mol% of a bifunctional non-aromatic isocyanate compound. The artificial stone according to claim 1, wherein the ratio (N2/NM) of the number of moles (N2) of the bifunctional non-aromatic isocyanate compound to the number of moles (NM) of the polyfunctional non-aromatic isocyanate compound in the curable composition is in the range of 1.5 to 5. The artificial stone according to claim 1, wherein the ratio (P/N) of the number of moles (P) of the polyol compound in the polyol component to the number of moles (N) of the isocyanate compound in the isocyanate component in the curable composition is in the range of 0.4 to 1.5. The artificial stone according to claim 1, wherein the ratio (OH/NCO) of the total number of moles of hydroxyl groups (OH) in the polyol component to the number of moles (NCO) of all isocyanate groups in the isocyanate component in the curable composition is in the range of 0.8 to 1.2. The artificial stone according to claim 1, wherein the filler is a quartz filler. The artificial stone of claim 1, wherein the curable composition contains a filler in an amount of 70 to 95% by weight. The artificial stone according to claim 1, wherein the total weight part of the polyol component and the isocyanate component in the curable composition is in the range of 5 to 30 parts by weight based on 100 parts by weight of the filler. The artificial stone according to claim 1, wherein Δb* in Equation 4 below is in the range of -1.5 to 3:
[Equation 4]
△b* = ba*-bi*
In Equation 4, ba* is b* value in the CIE Lab color coordinates of the artificial stone immediately after exposure to ultraviolet light for 1000 hours, and bi* is b in the CIE Lab color coordinates of the artificial stone immediately before exposure to UV light for 1000 hours. *Value. The artificial stone according to claim 1, wherein the absolute value of the change amount ΔE of the color change index before and after exposure to ultraviolet rays for 1000 hours is 3 or less. Polyol component;
An isocyanate component including a bifunctional non-aromatic isocyanate compound and a trifunctional or higher polyfunctional non-aromatic isocyanate compound; And
Artificial stone which is a cured product of a curable composition containing a filler.

Images