Surface treatment method

Abstract

【Solution】 The present invention provides a method for coloring and surface-treating the surface of particulate materials such as sand (e.g., silica-based materials such as sand). The method comprises a) optionally heating the particulate material to a temperature of 30°C to 85°C; b) preparing an aqueous dispersion of a colorant, an alkoxysilane, a silyl alkanate, a polysiloxane, or a mixture thereof; c0) optionally treating the particulate material, c1) mixing the dispersion prepared in step b) with the particulate material of step a); c2) optionally adding an alkoxysilane, a silyl alkanate, a polysiloxane, or a mixture thereof; c3) heating the mixture at a temperature of 20°C to 80°C for 1 minute to 24 hours; and d) optionally mixing the treated sand formed in step c) with an aqueous dispersion of a colorant, an alkoxysilane, a silyl alkanate, a polysiloxane, or a mixture thereof. Steps a) (if used) and b) may be carried out simultaneously or sequentially, in any order. At least one step involves the use of an alkoxysilane, a silyl alkanate, and / or a polysiloxane. At least one step involves the use of a colorant. The aqueous dispersion in step d) may be the same as or different from that in step b). The present invention further provides a colored particulate material having at least one surface surface-modified with a colorant and at least one silylalkyl group or silylalkenyl group. The material can be produced by the method of the present invention. The present invention also provides a filled molding material comprising the colored particulate filler material.

Description

Technical Field

[0001] Technical Field of the Invention The present invention relates to the surface treatment of particulate materials. In particular, the present invention relates to a simple method for the surface treatment (e.g., hydrophobic surface treatment) of silica-based particulate materials such as sand. The present invention further relates to particulate materials subjected to such surface treatment, and to molding materials comprising such surface-treated particulate materials and at least one binder material.

Background Art

[0002] Background of the Invention Molding compositions typically include a binder material such as an organic polymer or a silicone binder, and an inert filler material such as a particulate mineral filler. The filler material provides bulk to the composition and modifies the feel and physical properties of the composition.

[0003] When formulating filled compositions such as molding compositions, it is important to consider the compatibility of the binder component and the filler component. In particular, if the adhesive force of the binder to the filler material is significantly lower than the cohesive force of the binder to itself, the filler may not remain stably incorporated within the binder. As a result, the filler may be lost from the composition, especially when handled or when in contact with certain other substances such as water.

[0004] The phenomenon of filler loss from molding compositions is usually more problematic with incompatible fillers, large filler particle sizes, and / or under extreme conditions such as high or low temperatures, high humidity, or contact with solvents such as moisture. This means that, in some cases, the type of filler and / or the use conditions are restricted due to the incompatibility between the filler and the binder.

[0005] Many common fillers, such as sand, glass, silica, and many ceramics, have a high silica (SiO2) content. These exhibit high compatibility with certain silicone-based binders, but do not necessarily show sufficient compatibility with all binders, especially those based on organic polymers. For this reason, difficulties may arise during the production of the composition, and / or the binder may be lost during daily use or use under high humidity or humidity contact conditions.

Summary of the Invention

Problems to be Solved by the Invention

[0006] Furthermore, filled compositions such as molding compositions are generally colored. Typically, the desired pigment deposition is achieved by coloring the binder composition. It would be advantageous if the filler material could be further colored to achieve a unique color pattern. Alternatively, since the binder is often used at a much lower concentration in the final filled composition, it would be advantageous to color the filler material instead of the binder material. However, it is often difficult to apply a stable colorant to the surface of the filler. For example, the resulting colored filler may suffer from pigment leakage when in contact with water.

Means for Solving the Problems

[0007] It would be a considerable advantage if a method could be found to enhance the compatibility of silica-containing particulate materials with a wide variety of binders, such as organic polymer binders and / or silicone-based binders. It would be even more advantageous if the treatment reduced the loss of filler from the filler material during use. It would be even more advantageous if the treatment reduced the amount of binder necessary to effectively and / or stably coat the filler. Such a method would be even more advantageous if it could use moderate conditions, short times, and / or mild reagents to facilitate manufacture. It would be even more advantageous if only a small amount (by weight) of surface treatment reagent were necessary to improve the properties of the particulate filler. It would be even more advantageous if the particulate filler could be surface-treated and colored simultaneously. Such coloring would advantageously be uniformly and effectively immobilized with little or no leaching (e.g., during use and / or in water).

Advantages of the Invention

[0008] Summary of the Invention The inventors have now demonstrated that the compatibility of particulate materials (especially silica-based fillers) with many binders, especially binders containing organic polymers and / or siloxane polymers, can be improved by surface treatment of the particulate materials with at least one alkoxysilane.

Modes for Carrying Out the Invention

[0009] In a first aspect, the present invention provides a method for surface-treating and optionally coloring at least one surface of a particulate material, the method comprising a) optionally heating the particulate material to a temperature of from 30 °C to 85 °C; b) preparing an aqueous dispersion of at least one material selected from colorants, at least one alkoxysilane, at least one silyl alkanate, at least one polysiloxane, and mixtures thereof; c1) mixing the dispersion prepared in step b) with the particulate material of step a); c2) Optionally adding at least one material selected from at least one alkoxysilane, at least one silyl alkanoate, at least one polysiloxane, and mixtures thereof; c3) Heating the mixture at a temperature from 20°C to 80°C for a period from 1 minute to 24 hours; and d) Optionally mixing the treated sand formed in step c) with at least one colorant and / or an aqueous dispersion of at least one alkoxysilane and / or at least one silyl alkanoate and / or at least one polysiloxane.

[0010] Here, step a) (when used) and step b) can be carried out simultaneously or sequentially in any order, where at least one step (e.g., at least one of steps b), c2), and / or d)) involves the use (e.g., addition) of a material selected from at least one alkoxysilane, at least one silyl alkanoate, and / or at least one polysiloxane. The aqueous dispersion in step d) may be the same as or different from that in step b), and at least one step (e.g., at least one of steps b), c2), and / or d)) may optionally contain a colorant.

[0011] As referred to herein, "step c" includes step c1), optionally step c2), and step c3) when the context permits. Step c) in any method herein may include any treatment of the particulate material with a basic solution (e.g., an alkali metal hydroxide solution). This can be considered as any step c0).

[0012] Therefore, the following two descriptions are considered equivalent: c) Mixing the dispersion prepared in step b) with the particulate material of step a) and heating the mixture at a temperature of 20 - 80°C for a period of 1 minute - 24 hours; and c1) Mixing the dispersion prepared in step b) with the particulate material of step a); and c3) A step of heating the mixture at a temperature of 20 to 80°C for 1 minute to 24 hours.

[0013] In another aspect, the present invention provides a method for surface treating at least one surface of a particulate material, the method comprising the following; a) A step of arbitrarily heating the particulate material to a temperature between ambient temperature (e.g., 20°C) and 85°C, for example, between 30°C and 85°C; b) A step of preparing an aqueous dispersion of at least one alkoxysilane and / or at least one silyl alkanoate; and c) A step of mixing the dispersion prepared in step b) with the particulate material and heating the mixture to a temperature between 20°C and 80°C for 1 minute to 24 hours; Here, step a) (when used) and step b) can be carried out simultaneously or sequentially in any order.

[0014] When no heat is applied in step a), this step consists of obtaining a suitable particulate material in all suitable embodiments. In one embodiment, the surface treatment is a hydrophobic surface treatment.

[0015] The method of the present invention can further be used for both surface treating (e.g., hydrophobizing) the surface of the particulate material and coloring its surface. In a corresponding aspect, the present invention thus provides a method as described in the first aspect for simultaneously surface treating and coloring the particulate material, the method further comprising the following; d) A step of mixing the treated particulate material formed in step c) with an aqueous dispersion of at least one colorant and optionally at least one alkoxysilane, at least one silyl alkanoate, and / or at least one polysiloxane.

[0016] Coloring and surface treatment (e.g., hydrophobization) can, according to a further aspect of the invention which provides a method for coloring and surface treating at least one surface of at least one particulate material, be carried out in a single step, and the method comprises the following; a) obtaining the particulate material (preferably, a non-surface-modified particulate material) and optionally heating it to a temperature between ambient temperature (e.g., 20 °C) and 85 °C (e.g., between 30 °C and 85 °C); b) preparing an aqueous dispersion of at least one alkoxysilane and / or at least one silyl alkanoate and at least one colorant; and c) mixing the dispersion prepared in step b) with the particulate material and heating the mixture to a temperature of 20 - 80 °C for 1 minute to 24 hours; wherein steps a) and b) can be carried out simultaneously or sequentially, in any order.

[0017] In a further aspect, the invention provides a method for coloring and surface treating at least one surface of at least one particulate material, the method comprising the following; a) optionally heating the particulate material to a temperature of 30 - 85 °C; b) preparing an aqueous dispersion of at least one colorant; and c0) optionally pretreating the particulate material with a basic solution c1) mixing the dispersion prepared in step b) with the particulate material of step a); c2) adding at least one material selected from at least one alkoxysilane, at least one silyl alkanoate, at least one polysiloxane, and mixtures thereof; and c3) heating the mixture at a temperature of 20 - 80 °C for 1 minute to 24 hours. Here, step a) (if used) and step b) can be carried out simultaneously or sequentially, in any order.

[0018] The materials produced by the method of the present invention are very useful for use as fillers, particularly in combination with polymeric binders, since the surface-treated particles have a high compatibility with many binders, particularly polymeric binders.

[0019] In a further aspect, the present invention provides a particulate material having at least one surface surface-modified with at least one silylalkyl or silylalkenyl group. Such particulate materials may also be further colored on at least one modified surface. Such modification and any coloring can be carried out as described herein.

[0020] In a further aspect, the present invention thus provides a particulate material having at least one treated (e.g., hydrophobized) surface formed or formable by treatment of at least one alkoxysilane in an aqueous dispersion. This will generally be at least one treated (e.g., hydrophobized) surface formed or formable by the methods described herein for all suitable aspects and embodiments of the present invention.

[0021] In a further aspect, the present invention thus provides a colored particulate material having at least one modified (e.g., hydrophobized) surface. This is preferably a surface-modified particulate material (such as sand) having a silica content of at least 50% by weight of the particulate material (e.g., as described herein). The colored particulate material can be formed or formable by any of the methods described herein.

[0022] In a further aspect, the present invention provides a filled molding material comprising at least one particulate filler material and at least one polymeric binder material, wherein the particulate filler material has at least one treated (e.g., hydrophobized) surface modified with at least one silylalkyl or silylalkenyl group (and preferably is also colored as described herein). Very suitable binder materials include, for example, siloxane polymers, polyesters (e.g., homopolymers or copolymers of polycaprolactone) and homopolymers or copolymers of polyvinyl acetate.

[0023] The molding material of the present invention is usually manually moldable at at least one temperature between 20 and 45 °C. The molding material is generally not an elastomer. The molding material may cure to a hard material at a temperature of, for example, 30 °C or lower (e.g., 15 to 30 °C), but generally does not solidify or cure (e.g., by chemical reaction) and softens again to be manually moldable when heated to at least one temperature between 20 and 45 °C.

[0024] In a further aspect, the present invention provides a method for improving the compatibility between a particulate material and a binder, the method comprising: a) optionally heating the particulate material to a temperature of 30 to 85 °C; b) preparing an aqueous dispersion of at least one alkoxysilane and / or at least one silyl alkanate; and c) mixing the dispersion prepared in step b) with the particulate material of step a) and heating the mixture to a temperature of 20 to 80 °C for 1 minute to 24 hours. Here, steps a) and b) may be carried out simultaneously or sequentially in any order.

[0025] The method may include a step of simultaneously coloring the particulate material.

[0026] In related aspects, the present invention provides a method for improving the compatibility of particulate materials with a binder and simultaneously coloring the materials, the method comprising: a) optionally heating the particulate material to a temperature of 30 to 85 °C; b) preparing an aqueous dispersion of at least one material selected from at least one alkoxysilane, at least one silyl alkanate, at least one polysiloxane, and a colorant; and c1) mixing the dispersion prepared in step b) with the particulate material of step a); c2) optionally adding at least one material selected from at least one alkoxysilane, at least one silyl alkanate, at least one polysiloxane, and mixtures thereof; c3) heating the mixture to a temperature of 20 to 80 °C for 1 minute to 24 hours; and d) optionally, mixing the treated sand formed in step c) with an aqueous dispersion of at least one colorant and / or at least one alkoxysilane and / or at least one silyl alkanate and / or at least one polysiloxane. Here, steps a) and b) may be carried out simultaneously or sequentially, in any order; at least one step (for example, at least one of steps b), c2) and / or d)) involves the use of a material selected from at least one alkoxysilane, at least one silyl alkanate, and / or at least one polysiloxane; the aqueous dispersion of step d) may be the same as or different from that of step b); and at least one step involves a colorant.

[0027] In yet a further aspect, the present invention accordingly provides a filled moulding material comprising at least one particulate filler material and at least one polymeric binder material, wherein the particulate filler material has at least one treated (e.g. hydrophobised) surface formed or formable by treatment with an aqueous dispersion of at least one alkoxysilane. Such treatment generally produces at least one treated (e.g. hydrophobised) surface formed or formable by any of the methods described herein for all suitable aspects and embodiments of the present invention. Highly suitable binder materials include, for example, siloxane polymers, polyesters (e.g. homopolymers or copolymers of polycaprolactone) and homopolymers or copolymers of polyvinyl acetate.

[0028] In yet a further aspect, the present invention provides a filled moulding material comprising at least one coloured particulate filler material and at least one polymeric binder material, wherein the coloured particulate filler material has at least one treated (e.g. hydrophobised) surface modified with at least one silylalkyl or silylalkenyl group and a colourant. The coloured particulate filler material is preferably a material formed or formable by any of the methods described herein in any suitable embodiment.

[0029] Detailed description of the invention Without being bound by theory, much of the immiscibility between silica-containing fillers and binders such as organic polymer binders is thought to be a result of the filler material having a hydrophilic surface. This may be due, at least in part, to the presence of silanol (Si-OH) groups on the particle surface. This is particularly applicable to materials containing at least one silica component, especially particles having at least partially silica on the surface.

[0030] The inventors have developed a method for modifying functional groups (such as silanol functional groups) on the surface of particulate materials so that the particle surface is more easily compatible with binders such as organic polymer binders and / or siloxane polymer binders. In one embodiment, the modification is a hydrophobic surface modification. In related embodiments, the particle surface becomes more hydrophobic and / or less hydrophilic after treatment than before treatment. In further embodiments, the treated surface has a higher compatibility with binder materials such as organic polymer binders and / or siloxane binders than the untreated surface. In further embodiments, the treated surface is resistant to leakage of any coloring dye (such as those described herein).

[0031] All suitable embodiments of the present invention utilize at least one alkoxysilane and / or at least one silyl alkanoate, and / or at least one polysiloxane (preferably at least one alkoxysilane and / or at least one silyl alkanoate), which is utilized in the form of a dispersion in a solvent. This is preferably as a dispersion in an aqueous solvent such as water (e.g., distilled water or deionized water). The preparation of the alkoxysilane dispersion is step b) of the method described herein and can be carried out before, after, or during the heating step a) described herein. In one embodiment, a mixture of at least two alkoxysilanes and / or silyl alkanoates is used. Mono- or di-alkoxysilanes may be used, but trialkoxysilanes form preferred embodiments. Similarly, silyl monoalkanoates or silyl dialkanoates may be used, but silyl trialkanoates form preferred embodiments.

[0032] In one embodiment, monoalkoxysilane and / or silyl monoalkanoate is used as the silyl component in step b) and / or step d).

[0033] In one embodiment, the silane used in the present invention may comprise, consist essentially of, or consist of a monofunctional silane (e.g., mono-alkoxysilane and / or mono-alkylsilane).

[0034] In one embodiment, the silane used in the present invention may comprise, consist essentially of, or consist of a difunctional silane (e.g., di-alkoxysilane and / or di-alkylsilane).

[0035] In a further embodiment, the silane used in the present invention may comprise, consist essentially of, or consist of a mixture of a monofunctional silane and a difunctional silane (e.g., a mixture of at least one di-alkoxysilane and / or di-alkylsilane and at least one mono-alkoxysilane and / or mono-alkylsilane).

[0036] In one embodiment of the present invention, at least one alkoxysilane comprises i) at least one alkoxyvinylsilane and ii) at least one alkoxyalkylsilane. These may be, for example, at least one trialkoxyvinylsilane and one trialkoxyalkylsilane.

[0037] In one embodiment of the present invention, at least one alkoxysilane comprises i) at least one alkoxyvinylsilane and ii) at least one alkoxyalkylsilane in a weight ratio of i) to ii) of 99:1 to 50:50. This may be, for example, a weight ratio between 98:2 and 70:30, or between 97:3 and 80:20.

[0038] Suitable alkoxysilanes for all embodiments of the present invention include silanes of the following formula i):

[0039]

Chemical formula

[0040] [Wherein, R1 is selected from H; CH3; a cyclic, branched or linear alkyl group having 2 to 12 carbon atoms; a branched or linear alkenyl group having 2 to 12 carbon atoms, and mixtures thereof; Each of R2, R3 and R4 is independently selected from H; CH3; a branched or linear alkyl group having 2 to 8 carbon atoms; and mixtures thereof.]

[0041] In one embodiment, R1 may be an alkenyl group, preferably a C2-C4 hydrocarbyl group having a terminal double bond. In certain embodiments, R1 may be a vinyl group.

[0042] In another embodiment, R1 may be a linear, branched or cyclic alkyl group having 2 to 12, preferably 2 to 8 carbon atoms. Branched hexyl or octyl groups such as trimethylpentyl groups form one preferred embodiment.

[0043] In another embodiment, R1 may be selected from H; CH3; a cyclic, branched or linear alkyl group having 2 to 12 carbon atoms; a C2-C12 alkyl or alkenyl group containing at least one oxygen-containing functional group (e.g., at least one ether bond and / or at least one epoxy group); and / or a C5-C10 aromatic group such as a substituted or unsubstituted phenyl ring.

[0044] In another embodiment, R1 may be selected from H; CH3; a cyclic, branched or linear alkyl group having 2 to 7 carbon atoms; a C2-C7 alkyl or alkenyl group containing at least one ether bond and / or at least one epoxy group.

[0045] In another embodiment, R1 may be selected from H; CH3; a cyclic, branched or linear alkyl group having 2 to 7 carbon atoms; and / or at least one C5-C7 aromatic group optionally substituted with at least one methyl group and / or ethyl group.

[0046] When a moiety is described as "substituted", this is preferably at least one CH3; C2-C7 cyclic, branched or linear alkyl group.

[0047] In one embodiment, each of R2-R4 may independently be H; CH3; a C2-C6 branched or linear alkyl group; and mixtures thereof. Particularly suitable as R2, R3 and R4 are a methyl group, an ethyl group and a propyl group. Each of R2-R4 may be independently selected (including from the options shown herein), but in one embodiment, each of R2-R4 may represent the same group. Thus, in one embodiment, each of R2 to R4 may be methyl, or each of R2 to R4 may be ethyl.

[0048] In a preferred embodiment applicable to any suitable aspect of the present invention, at least one alkoxysilane comprises i) a trialkoxyvinylsilane (e.g. C1-C4 alkoxy) and ii) a trialkoxytrimethylpentylsilane (e.g. C1-C4 alkoxy). In a more preferred embodiment, at least one alkoxysilane comprises i) trimethoxyvinylsilane and ii) triethoxytrimethylpentylsilane. The ratios described above for components i) and ii) are equally applicable to these embodiments.

[0049] In a further embodiment, triethoxytrimethylpentylsilane may be present in an amount of 1-50 wt%, such as 2-30 wt% or 5-15 wt%, of the total silane compounds used in the methods and other aspects of the present invention.

[0050] In a further embodiment, trimethoxyvinylsilane may be present in an amount of 50-99 wt%, such as 70-98 wt% or 85-95 wt%, of the total silane compounds used in the methods and other aspects of the present invention.

[0051] A further suitable silane material that can be used as all or part of the silane in the silane dispersion(s) may be at least one silyl alkanoate. This may be of the following formula ii):

[0052]

Chemical formula

[0053] In the formula, R5 is selected from C1-C6 alkyl groups, preferably a methyl group; Each of R6 and R7 is independently selected from R9, -O-R9 and -O-CO-R9 (wherein R9 is selected from H; CH3; C2-C12 cyclic, branched or linear alkyl groups), R8 is selected from H; CH3; C2-C12 cyclic, branched or linear alkyl groups; C2-C12 branched or linear alkenyl groups and mixtures thereof.

[0054] In one embodiment, R5 is methyl or ethyl, preferably methyl.

[0055] In one embodiment, both R7 groups are -O-R9 groups or -O-CO-R9 groups, preferably -O-CO-R9 groups.

[0056] In one embodiment, R9 is methyl or ethyl, preferably methyl.

[0057] In one embodiment, R8 is an alkenyl group, preferably a C2-C4 hydrocarbyl group having a terminal double bond. In one particular embodiment, R8 may be a vinyl group.

[0058] Silane compound(s) is generally utilized in the form of a dispersion, particularly an aqueous dispersion (e.g., in water such as distilled water or deionized water). The total silane content of the dispersion may be, for example, 0.1 to 50% by weight of the dispersion, preferably 0.5 to 30% by weight or 0.5 to 20% by weight, such as 1 to 10% by weight, 5 to 20% by weight or 5 to 15% by weight. Suitable dispersions may be of any effective type including suspensions, colloidal dispersions and / or solutions.

[0059] The total weight of the aqueous silane dispersion (including the water component) is generally made as low as possible while maintaining the ability to "wet" (substantially cover its surface) the particulate matter. In some embodiments, particularly for small-scale batches (e.g., less than 10 kg), the mass of the dispersion may be up to about 5%, or up to 10%, of the mass of the particulate material (e.g., sand). In other embodiments, particularly on a large scale such as 100 kg to 10,000 kg, the mass of the dispersion may be about 0.5% or less than 0.1% of the mass of the particulate material (e.g., sand). The inventors have surprisingly found that even an amount less than 1% by weight (e.g., 0.1 to 1%) is sufficient to substantially cover the surface of the particulate material (e.g., cover 75% or more, preferably 95% or more of the surface).

[0060] Various aspects of the present invention relate to surface coatings of particulate materials. These materials will in particular be materials comprising at least one metal oxide. Typical metal oxides constituting the particulate material (e.g. filler) include silica (SiO2), alumina (Al2O3), titania (TiO2), and mixtures of these with each other and other minerals. Preferred particulate materials include those having silicate and / or silica (SiO2) as constituent minerals. In one embodiment, at least 50% by weight (e.g. 50 - 100% by weight) of the particulate material is composed of SiO2 (e.g. silica and / or silicate measured as SiO2). This is preferably 60 - 99.9% or 70 - 95% (e.g., 75 - 90%) SiO2. In one particular embodiment, the particulate material can be formed of sand having an SiO2 content of 80 - 100% by weight, preferably 85 - 100% by weight, most preferably 90 - 99.9% by weight of SiO2, e.g. silica sand having 98.5 - 99.9% SiO2. Other forms of silica are also very suitable particulate materials.

[0061] Examples of materials containing SiO2 include silica (e.g., crystalline silica including quartz, tridymite, and cristobalite, silica gel and / or fumed silica), rocks (e.g., crushed stone), soda lime glass, borosilicate glass, silica sand, quartz sand, building sand, and related materials and all mixtures thereof. Clearly, the material is suitable for any manageable particle size, and thus, for example, the "silica sand" shown herein is used to denote a silica material having a particle size of about 0.05 to 2 mm (e.g., weight average particle size or d50 size) as is conventional for sand, but particles in the range of 0.05 to 0.004 mm considered "silt" and particles in the range of 0.004 to 0.001 mm (4 to 1 μm) considered "clay" are also suitable for use in the present invention. Similarly, a "pebble" size of about 2 mm to 10 mm can be used. These sizes are suitable for all particulate materials shown herein and not just for sand. For example, glass particles are also in the range of 1 μm to 10 mm, and particles of all other materials are the same. However, a typical "sand" size of about 50 μm to 2 mm is very suitable. In one embodiment, the particulate material is not of "nano" size (e.g., having a particle size of 100 nm or less). In related embodiments, the particulate material is not nanosilica. In related embodiments, the particulate material is not nanotitania.

[0062] The particulate material may have a "bimodal" or "multimodal" size distribution. For example, the particles may be composed of some particles of "clay" or "silt" size and some particles of "sand" or "pebble" size. This can be particularly suitable for filler applications of the particulate material since the small particles can be accommodated in the spaces between the large particles of the material. In one embodiment, in the case of a bimodal particle size distribution, the two peaks (maxima) of the particle size distribution curve occur at sizes where the larger particles are at least 2 times (e.g., 2 to 1000), preferably at least 3 times or at least 5 times larger than the smaller particles. This serves the "space filling" property. A corresponding ratio can be applied to multimodal distributions having more peaks.

[0063] In one embodiment, the particulate material is not a naturally occurring material such as a plant material or an animal material (i.e., a bio-derived material). For example, the particulate material is not wood or hemp fiber.

[0064] The amount of silane present corresponding to the surface of the particulate material in various methods of the present invention and thus in various aspects of the present invention is about 0.01 to 1% by weight of the particulate material.

[0065] In one embodiment, the amount of silane used in the method of the present invention and correspondingly the amount of silane present on the surface of the modified particles may range from about 1 to 200 mg of silane per square meter of particle surface area. This may be, for example, about 5 to 100 mg / m 2 or about 8 to 70 (e.g., 8 to 35) mg / m 2 and may be. Corresponding calculations can be performed for all aspects and embodiments of the present invention.

[0066] In the method of the present invention, step a) includes an optional step of preheating the particulate material. This step is not essential, but in many cases it has been found to improve the method. Without being bound by theory, this is thought to remove volatile substances from the surface of the material and help increase the reaction rate after the addition of silane. The particulate material can be used at room temperature (e.g., 20 °C or higher), and is usually 100 °C or lower. Generally, the particulate material is heated to a temperature of 30 to 85 °C, for example 40 to 75 °C. A range of 50 to 70 °C has been found to be very effective. Preferably, the particulate material is heated within these ranges and maintained at that temperature until ready to contact the alkoxysilane dispersion. If no heating is performed, step a) simply means obtaining the appropriate particulate material as needed.

[0067] Part b) of the method of the present invention involves the preparation of an aqueous dispersion of at least one alkoxysilane. Silanes suitable for all aspects of the present invention are discussed herein, and any suitable alkoxysilane or mixtures thereof may be used in any aspect or embodiment, provided it is technically feasible.

[0068] The concentration of the silane in the aqueous dispersion can be varied within a wide range while enabling effective surface treatment of the particulate material. For example, a silane concentration of at least 0.1 wt% in water may be effective, preferably at least 0.2% or 0.5%. However, concentrations up to 1%, for example up to 2%, up to 2.5%, or up to 5% can be used. Higher concentrations up to 10% or up to 20% are also suitable. Larger batch sizes generally preferably use less water and thus higher silane concentrations as mixing is easier on a large scale and water removal takes more time.

[0069] The formation of the silane dispersion may be carried out before, during, or after the heating step a). In one embodiment, the dispersion is made immediately before use to avoid decomposition of the silane material in water. In one embodiment, the silane dispersion can be mixed for about 10 - 180 minutes before use. This may be, for example, 20 - 120 minutes or 30 - 60 minutes.

[0070] In one embodiment, the silane dispersion can be prepared at a weakly acidic pH of 2 - 6, preferably pH 3 - 5, such as around pH 4. This will help reduce the decomposition of the silane before use. The pH can be adjusted as appropriate with any suitable acid or base material, although an acid such as an organic acid (e.g., acetic acid) is considered suitable. Adding acetic acid until the dispersion reaches pH 4 ± 0.5 is a highly suitable embodiment.

[0071] In one embodiment applicable to any suitable aspect of the present invention, the particulate material may be a metal hydroxide such as sodium hydroxide (e.g., NaOH (1M)) and may be treated with a basic solution before surface treatment. Treating the particulate material (i.e., sand) with a basic solution may result in better pigment immobilization and water resistance. When using epoxy silane for the surface treatment of sand, a method of basic treatment of sand before silane treatment is preferred.

[0072] The mixing of the silane dispersion and the heated particulate material is step c) of the method and is carried out after steps a) and b). This mixing may be at any effective temperature, but preferably at a temperature sufficient to remove water from the mixture, for example, between ambient temperature (e.g., 20 °C) and 100 °C. This is generally between 25 - 80 °C, for example 40 - 75 °C (e.g., 50 - 70 °C). The mixing and heating times can vary widely as they are usually sufficient to remove water from the mixture, but generally range from about 1 minute (preferably 5 minutes) to about 24 hours, preferably between 8 minutes and 1 hour (e.g., between 10 minutes and 40 minutes).

[0073] In addition to providing a surface treatment, the method of the present invention can be additionally used to color the particulate material. Typically, the colorant can be prepared as an aqueous solution or dispersion before adding the silane (e.g., silane dispersion) or simultaneously with the silane dispersion in step b) and can thus be mixed with the particulate filler in step c). Alternatively, an aqueous dispersion of the colorant may be added in an additional step d) after mixing the filler material with the silane dispersion. The aqueous dispersion of the colorant must be prepared in at least one of steps c) or d) and mixed with the particulate filler.

[0074] In a further embodiment, (e.g., when sand is not mixed with the colorant dispersion in step c)) the method described herein can include the following additional steps: d) Mix the treated sand formed in step c) (as described in any aspect or embodiment of this specification) with an aqueous dispersion of at least one colorant. Obviously, steps c) and d) can be combined in any combination as described in this specification and technically feasible.

[0075] Step d) generally follows a heating and / or drying step to "fix" the color on the particle surface. This step can use the same conditions as described for step c) of this specification in any embodiment.

[0076] In all embodiments, at least one silane material (e.g., any silane material described in this specification or any mixture thereof) is used in at least one step of the surface treatment method. Therefore, the method may be a method for providing a silylated particulate material (e.g., a colored silylated particulate material).

[0077] Colorants suitable for use in the method of the present invention include titanium white oxide, carbon black, organic pigments (e.g., metal complexes, nitrated, hydroxylated, and / or halogenated aromatic organic molecules), and inorganic pigments of any suitable color. Many suitable colorant materials are known in the art. In one embodiment, the colorant is not titanium dioxide. In related embodiments, the colorant does not contain titanium dioxide.

[0078] In one embodiment, the colorant is not a white colorant.

[0079] In one embodiment, the colorant is not a carbon colorant. Examples of carbon colorants include graphite, carbon black, graphene, graphene oxide, etc.

[0080] In one embodiment, the colorant is not a black colorant.

[0081] The coloring of the particulate material can also be used to produce a product that is colored overall, or to be used as a filler together with a colored or colorless binder material to provide a more white or more uniformly colored particulate material. Such methods can be used to improve the color intensity of the filled material or simply to make the material more uniform by compensating for the color variation of the starting filler particulate material. The amount of colorant used depends on the effect achieved and the strength of the pigment, but may be, for example, 0.01 to 1.5% by weight, for example 0.02 to 0.1% by weight of the particulate material. For certain colors, especially black and white, larger amounts of dye may be required. In such cases, 0.1 to 1.5%, for example 0.2 to 1% is the ideal level. For other colors and for lower black and white concentrations, 0.01 to 0.2%, for example 0.03 to 0.1% is sufficient.

[0082] Mixtures of dyes can clearly be used, including mixtures of any suitable combination of colors. In one embodiment, in order to obtain a particularly vivid effect, the TiO2 pigment can be used together with another color (preferably not black).

[0083] The coloring of the particulate material may be carried out in one step or two steps as described herein. When this is carried out in two steps, the aqueous dispersion of the colorant may be mixed with the silane material. This may be an alkoxysilane as described herein and / or a silyl alkanoate as described herein. Additionally or alternatively, a polysiloxane, such as an aminated polyalkylsiloxane like poly[3-((2-aminoethyl)amino)propyl]methyl(dimethyl)siloxane, may be used. The polysiloxane may be used in an amount of about 0.001 to 0.1% by weight (e.g., 0.001 to 0.1%) of the amount of the particulate material and may be present in the dispersion, for example, in an amount of 0.1 to 10% by weight, for example, about 1%. In any suitable embodiment or implementation, the coloring material as described herein may be "stable" against loss of color. When 50 g of the coloring material is contacted with 1 L of water for 5 minutes at 20 °C under magnetic stirring at 120 rpm and, when sedimented, the water sample shows an absorbance of less than 0.5 AU in a 1 cm path at the visible wavelength with the highest absorbance, the material is considered to be stable against discoloration. This is preferably less than 0.3 AU, more preferably less than 0.2 AU, or less than 0.1 AU in a 1 cm path at the visible wavelength with the highest absorbance. A practical test is that after stirring for a few minutes, the water is visually almost colorless.

[0084] The surface treatment particles of the present invention are very suitable for use as fillers in molding compositions. Such compositions typically also include at least one polymeric binder. Suitable binders include silicone-based binders, polyester-based binders, polyamide-based binders, and substituted aliphatic polymer-based binders. In particular, polyesters such as polycaprolactone (optionally copolymerized with lactic acid monomers), and substituted aliphatic polymers such as polyvinyl acetate (homopolymers or copolymers) can be mentioned. Silicone binders include polyalkylsiloxane binders, optionally crosslinked with materials such as alkylsilyl alkanoates. The binder can optionally include boron crosslinking, but preferably has a boron content of 1% by weight or less of the binder. The binder serves to hold the filler material (i.e., particulate material as described herein in any suitable aspect or embodiment) together into a formable material. However, even if the binder is a polysiloxane material, this is different from the surface-modified material of the present invention. In a preferred embodiment, the surface modification is covalently bonded to the surface of the particulate material (e.g., bonded to the Si-OH groups on the surface of the silicate or silica component). The binder preferably does not (or substantially does not) form a covalent bond with the particulate material, regardless of the presence or absence of the surface modification described herein. The binder is typically a polymeric material that can be dissolved or melted to at least partially coat the particulate material without directly bonding to the surface. In contrast, the "surface modification" by the silane materials described herein in particular can modify the surface of the material by chemical bonds, especially covalent bonds.

[0085] In one embodiment, the binder is a thermoplastic polymer. In related embodiments, the binder is not a curable or thermosetting polymer.

[0086] In one embodiment, the binder is not a fluorinated polymer. In a further embodiment, the binder is not polytetrafluoroethane (PTFE).

[0087] In one embodiment, the binder is not a phenolic resin. In one embodiment, the binder is not a homopolymer or copolymer of vinyl chloride and / or vinyl isobutyl ether.

[0088] It has been found that the particulate material surface-treated as described herein can be effectively coated with a binder using about 20% less binder material than is required to coat the untreated filler. This is thought to reflect a greater compatibility between the binder and the surface of the filler such that the binder spreads more readily over the surface.

[0089] Furthermore, it has been found that using a binder treated with a colorant in combination with a filler material treated with a colorant (such as those described herein) can produce a unique visual effect in the resulting filled molding composition.

[0090] In one embodiment, the binder is not an elastomer. For example, the binder is not rubber (such as natural rubber or synthetic rubber) (i.e., is not composed of more than 10%). In another embodiment, the binder is not spandex. In a further embodiment, the binder is not polyurethane.

[0091] In one embodiment, the molding material is not an elastomer. For example, when a 10 cm × 1 cm × 3 mm strip is stretched 20% at 25°C, it breaks within 10 minutes at 25°C or does not return to within 10% of its original length while stretched.

[0092] Binders typically contain additional components such as plasticizers and / or anti-tack agents, and can contain additional components such as pigments; brighteners; mica or coated mica; fragrances; preservatives; and / or flame retardants. Any combination of such additives can be used, but typically they are present at 5 wt% or less (e.g., 0.01 - 5%) of the total composition. This is preferably 2 wt% or less or 1 wt% or less.

[0093] As used herein, the terms "about", "approximate", "substantially", or "approximately" in connection with a numerical value or range generally indicate that the specified numerical value or range is preferred, but that such numerical values can vary to some extent without materially affecting the properties of the relevant material, composition, or similar product. One of ordinary skill in the art can readily determine how much such numerical values can be varied without impairing the important advantages of the present invention. As a general guideline, such numerical values or the two ends of such ranges can be varied by ±10%, preferably ±5%, more preferably ±1%. Corresponding meanings can also be attributed to a composition "consisting essentially of" a particular component, which composition may contain other components up to 10%, preferably up to 5%, most preferably up to 1% in addition to the specified component. Where a chemical group, chain, or other moiety is described as being optionally substituted herein, such substitution may be absent or one or more atoms (typically one or more hydrogens and / or carbons) of that moiety may be substituted with a halogen (e.g., F, Cl, Br, I) group, an oxygen-based moiety such as an ether, alcohol, ester carboxylic acid, or epoxide, a nitrogen-based group such as an amine, amide, nitrile, or nitro group, or a sulfur-based group such as a thiol, disulfide, or thioester. Such substitution may be carried out up to about 10 if context permits, but typically will be 3 or several substitutions, such as 1, 2, or 3 substitutions by independently selected substituents.

[0094] As used herein, "colorant" has its ordinary meaning and is a material that imparts color in the visible spectrum to a material. Such colorants typically absorb or reflect at least one wavelength in the visible spectrum (e.g., at least one wavelength between 800 and 400 nm). In any one embodiment, the colorant may have a color other than white. In any further embodiment, the colorant may have a color other than white or black. All color materials, including the processed particulate materials referred to herein, can be correspondingly interpreted.

[0095] The colorant used herein is preferably an organic or inorganic dye or pigment. Generally, the amount of the dye or pigment is at least 10% by weight (e.g., 10 - 100% by weight) of the colorant. The colorant may be soluble or insoluble in water and may include a proportion of a carrier material such as a polymer. However, the total amount of the dye and / or pigment in the colorant preferably amounts to at least 50% by weight, more preferably at least 70% by weight or at least 80% by weight. In some cases, 85% - 100% is preferred.

[0096] As used herein, "molding material" is a material that can be processed by hand at room temperature or at least one temperature between 20 and 45 °C (e.g., 20 - 42 °C or 30 °C - 45 °C). In one embodiment, the molding material does not set into a permanent shape (i.e., remains moldable) and can be remolded under the same conditions (e.g., a temperature of 20 - 45 °C). In one embodiment, the molding material becomes hard at temperatures of 30 °C or lower, but remains moldable at at least one temperature between 30 and 42 °C.

[0097] In a preferred embodiment, the "molding material" is a material suitable for children's play, particularly when the material can come into contact with water and be played with in water without any significant loss of any components.

[0098] The shaping material may be repeatedly shaped and reshaped. When the binder material is solid at room temperature (e.g., polyester), the shaping material can be heated and shaped one or repeatedly until the final shape is achieved, at which point the composition can be cooled. Cooling can be done simply by leaving the three-dimensional shape in ambient air or cooled air (e.g., inside a refrigerator or household freezer), or by immersing it in ambient water or cooled water. Ice water serves to essentially instantaneously "solidify" the composition of the present invention. Rapid solidification can also be achieved in a refrigerator or household freezer.

[0099] In one embodiment, the shaping material of any suitable aspect or embodiment of the present invention remains moldable at a suitable temperature (e.g., 25 - 90 °C or 35 - 42 °C). The composition of the present invention preferably does not "coagulate" or "harden". That is, the composition of the present invention does not form a hard material that cannot be reshaped by hand at a suitable temperature (e.g., 35 - 42 °C). As an example, the composition of the present invention does not harden by either a chemical reaction or loss of more than 10%.

[0100] Examples

[0101] [Table 1] JPEG2025524848000004.jpg210169

[0102] As used herein, d50 represents the sieve opening size through which 50% of the sand sample passes. Some of the following examples feature a colored particulate filler material. To test that the coloring is stable and there is no leakage from the particulate material, a test can be carried out to evaluate the immobilization of the coloring. In this test, the treated particulate material (about 2 g) is contacted with an aqueous dispersion such as pure water (about 40 mL) or dishwashing liquid (about 0.5 mL of liquid in 40 mL of water). The resulting suspension is stirred for several minutes (e.g., 5 minutes) using a magnetic stirrer bar, and the resulting aqueous phase is evaluated. If the aqueous phase remains substantially colorless after several minutes, the surface modification has effectively immobilized the pigment and prevented color leakage. Similar tests can be carried out with other solvents such as ethanol.

[0103] [Example 1a - Surface Modification of Sand with an Appropriate Amount and Blending of Silane] On a laboratory scale, surface - treated sand was prepared using the procedure described below as a standard. The pH value of the aqueous dispersion was adjusted to about 4, at which the silane reaction is minimized, using acetic acid. This results in a dispersion where the silane meets the silanol groups on the sand grain surface and the silane does not react before the aqueous phase evaporates. In the first examples (1a and 1b), a dilute (5 wt%) aqueous silane solution / dispersion was used, while in Example 1c, a treatment with a higher concentration of the dispersion was carried out.

[0104] First, a silane dispersion was prepared: - 5 g of silane was weighed. When using two or more silanes, they were first mixed in a beaker with a magnetic stirrer. - The silane (mixture) was added to an aqueous solution of 94.5 g of water and 0.5 g of HAc (24%) with vigorous stirring to form a solution, dispersion, or coarse dispersion (varying depending on the silane used). - Mixing (vigorously) was continued for about 30 - 60 minutes before contacting with the heated sand (described below).

[0105] Surface - treated sand was prepared: - 2.5 kg or 5 kg of sand (as below) was heated to 55 - 60 °C in a stainless-steel pot. - An aqueous silane dispersion (100 g - silane in about 5% water) was added to the hot sand under continuous stirring. - Mixing was continued until the moisture evaporated and the sand dried. The treatment was completed when the sand was dry. In laboratory-scale tests, the treatment time was only a few minutes.

[0106] The characteristics of the treated sand were determined by contacting the sand with pure water. Modification was confirmed by an increase in the hydrophobicity of the particles. This was evaluated by subjectively judging the wettability and contact angle when the sand was contacted with water. There is also a method of spreading the sand on a flat surface and placing a drop of water on the sand. If the water remains as a water droplet / lens on the sand without wetting the sand, it is judged that the surface modification was successful. As another method, there is a method of immersing the modified / treated sand in a large amount of water. If the immersed sand forms lumps and does not get wet, or if the sand grains are small (about 100 micrometers or less), it is judged that the treatment was successful as there is a possibility of floating on the water surface. The characteristics of a suboptimal treatment are that the sand gets wet, does not form lumps, and small sand grains sink. Table 2 shows selected experiments indicating that appropriate hydrophobicity can be obtained by balancing the selected silanes at appropriate addition amounts. Formulation D provides very good hydrophobicity at a low raw material consumption (silane ratio to sand of 0.1 wt%). In the following examples, in many cases, a silane mixture (10 wt% BS1701 and 90 wt% XL10) corresponding to Formulation D used at an addition level of 0.1 wt% was used. The "degree of hydrophobic modification of the sand surface" is calculated as the weight of the aliphatic part of the particle surface assuming that all silanes have reacted and bonded to the surface. As an example, assume that XL10 and GF62 provide vinyl groups (27 g / mol).

[0107]

Table 2

[0108] [Example 1b - Surface Modification of Various Sands] Various sands (GA39, B15, Mam1s, M32, B55) were modified according to the above formulation D. Since the sand grain sizes are different, the "degree of hydrophobic modification of the sand surface" varies even though the "silane on the sand" is constant at 0.1% by weight. The corresponding values are such that the d50 is approximately 91, 130, 205, 270, 500 micrometers, and the "degree of hydrophobicity on the sand surface" is 8, 11, 17, 23, 42 mg / m2. The latter is calculated as the weight of the aliphatic portion of the particle surface assuming that all the silane has reacted and bonded to the surface. As an example, assume that XL10 and GF62 provide vinyl groups (27 g / mol). The silane-treated sands are abbreviated as GA39(ST), B15(ST), Mam1s(ST), M32(ST), B55(ST).

[0109] All sands were successfully modified, and the silane reaction imparted hydrophobicity to the sands as determined by the above method (see Example 1).

[0110] For sand M32, it was observed that optimal results cannot be obtained when the temperature is below 50°C. Therefore, it is common to heat sand M32 5 - 10°C higher than the temperature used for other sands (such as Mam1s). This observation is rationalized by the hypothesis that as the temperature is increased, "some contamination" evaporates / removes from the surface of the sand grains.

[0111] [Example 1c - Large-scale experiment] The processing time on a production scale depends greatly on the time required to evaporate the water generated from the added silane solution / dispersion. Therefore, it is important to minimize the necessary water without compromising the results of the surface treatment by increasing the silane concentration in the aqueous solution / dispersion.

[0112] Mam1s sand was heated to 55 - 60°C in a jacketed steam-heated mixer. The batch size was 400 kg on a production scale.

[0113] The coarse aqueous silane dispersion was prepared by vigorously mixing for 30 to 60 minutes. The pH value was adjusted to approximately 4, at which the silane reaction is minimized, using acetic acid. This results in a dispersion in which the silane does not react before encountering the silanol groups on the sand grain surface and the aqueous phase evaporates.

[0114] Subsequently, the dispersion was added to pre-heated sand and mixing was continued until the water had evaporated. It was assumed that the treatment was complete when the sand was dry. The treatment time in large-scale production is about 5 to 30 minutes (varying depending on the amount of water used in the dispersion).

[0115] Table 3 shows the composition of the silane dispersions for the 400 kg test. These two types of silane dispersions were 5% by weight and 11% by weight respectively, and the characteristics of the sand evaluated by the above method gave good results. Version B has less content of silane (XL10 and BS1701) and water, and requires less treatment time, so it is recommended for large-scale production. The water content decreased by 74% compared to Version A, and the degree of modification decreased from 17 mg / m2 to 9 mg / m2.

[0116]

Table 3a

[0117]

Table 3b

[0118] [Example 1d - Water ratio on a large scale] Scale-up tests using the dispersion of Version A (see Example 1c) were carried out in 400 kg batches of various sand types (GA39, Mam1s, M32, B55). Good and acceptable results were obtained in all tests. This addition corresponds to approximately 7.6 L of water that has to be evaporated. Since it was found that it takes a long time to evaporate 7.6 L, the amount of water was reduced in subsequent tests as shown in Table 4 below.

[0119] Despite a significant reduction in water volume (and despite a reduction in processing time), the results do not appear to be affected.

[0120] 400 kg of sand M32 was modified with 0.1% silane (40 g of BS1701 and 360 g of XL10) to reduce the water content. This significantly shortened the processing time until the water evaporated. The starting temperature was targeted at about 65 °C.

[0121]

Table 4

[0122] Two large-scale tests were also conducted using Mam1s sand. The water / sand ratio decreased from 0.42% to 0.35%. The silane / sand ratios were 0.05% and 0.03%, and both concentrations showed good hydrophobicity.

[0123] The 0.03% treatment level can be used as the first-stage treatment before coloring. In the second-stage treatment of coloring, the ratio of colorant / sand can be 0.07%, which results in a total addition of 0.1% silane. See Example 3 below.

[0124] [Example 1e - Surface modification by an alternative method using epoxy silane] For some silanes such as epoxy silane, the immobilization of pigments and water resistance can be improved by an alternative method of surface treatment and coloring. In this alternative method, the sand is treated with a basic solution before mixing, and the colorant is added before the silane.

[0125] Exemplary alternative methods for modifying particulate fillers include the following: - Treat Mam1s (480 g) with 5 mL of NaOH (1 M) and let stand for about 30 minutes. - Mix Mam1s / NaOH with an aqueous solution of X-fast blue 7080 (0.3 g of X-fast in 5 mL of water). - Add 1.5 mL of silane (GF80) and mix carefully. - Let the sand rest for about 30 minutes. Then, heat the sand to 80 °C and mix until dry. To neutralize the NaOH, add 2 mL of HCl (9%) and mix carefully until dry.

[0126] After standing overnight, the leakage of the pigment from the sand was evaluated. The sand (2 g) was brought into contact with excess water (40 mL) and mixed with a magnetic stirrer bar. Only slight leakage was observed.

[0127] [Example 2a - Demonstrating the advantages of hydrophobic modification of sand fillers in a moldable creative material prepared with a polyvinyl acetate-co-vinyl laurate binder] Vinnapas B500 / 40VL was melted at about 100 °C to prepare the binder. The heating was stopped, and it was mixed in long-chain alcohol, and then medium-chain triglycerides (Grindsted MCT60) and triacetin were added: B500 / 40VL 52.6 g I20 36.5 g MCT60 4.6 g Triacetin 6.4 g

[0128] The prepared binder is mixed with the sand filler at about 30 °C: Binder 3.8 wt% Sand B55 or Sand B55 (ST) 96.2%

[0129] The compound made using untreated Sand B55 can be easily shaped by hand and is also convenient for children's play. When playing with water, the sand filler tends to fall out of the matrix. When playing with the material simultaneously, this phenomenon is accelerated during drying.

[0130] Prepare the corresponding materials. When using silane-treated sand B55, B55(ST), similar properties can be obtained in the dry state. When the materials are brought into contact with water, B55(ST) prevents unnecessary disintegration. Currently, it is possible to use the materials in a wet state, make contact with water, and play in water without significant loss of the sand filler.

[0131] [Example 2a(ii) - Demonstrating the advantages of hydrophobic modification of sand fillers using monofunctional silanes in a moldable creative material prepared with a polyvinyl acetate-co-vinyl laurate binder] Similar effects can also be obtained by mixing the same binder with sand treated with monofunctional silane at about 30 °C: Binder 5 wt% Mam1s (silane M3-ethoxy treatment): 95 wt%

[0132] The silane aqueous solution / dispersion was prepared according to a protocol very similar to Example 1a where the silane was M3-ethoxy: - Weighed 5 g of silane. - This silane was added to an aqueous solution of 94.5 g of water and 0.5 g of HAc (24%) with vigorous stirring to obtain a solution or dispersion. - Continued stirring (vigorously) for about 30 minutes.

[0133] The sand was first modified with about 0.05% silane: - Heated 480 g of sand Mam1s in a stainless steel pot to 55 - 60 °C. - Added 5 g of the aqueous silane dispersion to the hot sand with continuous stirring. - Continued mixing until the moisture evaporated and the sand dried.

[0134] Repeated the second step to perform surface modification of the sand with about 0.1% silane.

[0135] Subsequently, the surface-treated sand (95%) was mixed with a polyvinyl acetate-co-vinyl laurate binder (5%) to obtain a material that can be easily reshaped and used for children's play. Using the same binder and sand (Mam1s), a reference material without surface modification was also prepared. Both materials were exposed to water during play. The reference material lost most of the sand that had fallen off the binder during play, while the silane M3-ethoxy-modified material (Mam1s(ST)) was much more stable and had high water resistance. This indicates that monofunctional silane surface treatment is more effective in maintaining stability and enabling the formation of a moldable material that can withstand water.

[0136] [Example 2a(iii) - Demonstrating the advantages of hydrophobic modification of sand fillers using epoxy silane in a moldable creative material prepared using a polyvinyl acetate-co-vinyl laurate binder]

[0137] A similar effect is also achieved when the epoxy silane-modified sand of Example 1e is mixed with the above polyvinyl acetate-co-vinyl laurate binder (of Example 2a(ii)) at about 30 °C: Binder 5 wt% Mam1s (GF80 surface-treated as in Example 1e): 95 wt%

[0138] Compared to a material made of untreated sand where most of the sand filler is rapidly lost, the material made of sand treated with GF80 according to the method of Example 1e resists water play to a much greater extent.

[0139] [Example 2b - Demonstrating the advantages of hydrophobic modification in a molding material prepared with a polycaprolactone-based binder] The polymer PCL was melted at about 70 °C to prepare a binder. Heating was stopped and mixed with Benzoflex 988: PCL 5.4 g Benzoflex 988 9.6 g

[0140] The binder is mixed with the sand filler (sand M32 or M32(ST)) at about 50 °C and then with the anti-tack agent (AK10): Binder 15 g Sand M32 or M32(ST) 84 g AK10 1 g

[0141] Both compounds (based on sand M32 or silane-treated M32(ST)) are solid at room temperature and soften at about 40 °C. In the softened state, the shape of the material can be changed. When cooled, the material solidifies again.

[0142] When sand M32 is used as the filler, the material tends to demix and the filler drops out of the formulation when working in the warm state. Furthermore, warm water is a convenient way to heat the solid material so that the material becomes malleable. Unfortunately, when using unmodified sand M32 as the filler, the demixing of the formulation is accelerated and becomes prominent upon contact with water.

[0143] By using silane-treated M32(ST) as the filler instead of sand M32, demixing is suppressed, there is no significant loss of the filler, and the material can be used in contact with water without problems.

[0144] [Example 2c - Showing the advantages of hydrophobic modification in a molding material prepared with a polycaprolactone-based binder] When mixed with sand treated with the monofunctional silane solution of Example 2a(i), a similar effect is obtained with the same binder. The influence of the concentration of silane on the surface-treated sand and the mixing time of the aqueous silane dispersion was evaluated.

[0145] In addition to the aqueous silane dispersion / solution (Example 2a(i)) stirred for 30 minutes, an additional silane solution for M3-ethoxy was prepared and this was stirred for only 2 minutes. The resulting M3-ethoxysilane solution was used for the treatment of Mam1s (480 g) at different concentrations as shown in Table "5" below:

[0146]

Table 5

[0147] Using each of the treated sands in Table 5, a molding material using a PCL binder was prepared. A reference sample prepared with untreated Mam1 was also prepared. These five materials were molded and played in contact with warm water (about 40 °C).

[0148] The sample prepared with untreated sand (i.e., 0% M3-ethoxysilane) disintegrated immediately and lost the sand filler. Since the 0.1% sample prepared with the "30-minute" dispersion was the most resistant to treatment, it can be seen that the resistance is improved by increasing the mixing time of the aqueous dispersion. In the "2-minute" preparation, the 0.1% sample had the lowest resistance and the 0.4% sample had the highest resistance. This indicates that the resistance is improved by increasing the silane concentration of the surface-modified sand.

[0149] The examples further show that monofunctional silanes can provide enhanced properties to innovative materials prepared with various polymer-based binders.

[0150] [Example 3a - One-step coloring and immobilization of X-fast] Pigments / dyes that can be directly stirred into the aqueous silane dispersion can be conveniently used. As an example, there is X-fast from BASF, and there are several useful color versions: for example, Xfast Blue 7080, Xfast Green 8730, Xfast Magenta 4790, Xfast Orange 2931, Xfast Red 3860, Xfast Violet 5895, Xfast White 0025, Xfast Yellow 1256, Xfast Black 0066.

[0151]

Table 6a

[0152] In the initial test, 0.5 g of BS1701 and 4.5 g of XL10 were dispersed in 16.25 g of H2O containing 0.2 g of HAc (24%), and 3.10 g of X-fast was dissolved in 16.25 g of H2O. These two solutions were mixed to the final composition in Table 6a, and 3.9 g was added to 480 g of (unmodified) Mam1s at a temperature of about 50 °C and mixed until the water evaporated. As a result, the silane concentration of the sand was 0.10% and the X-fast concentration was 0.062%. Furthermore, it was brought into contact with the "painted" sand grains and a fastness test was conducted: - Water - Melted radicid 0406

[0153] The "painted" sand grains resisted contact without leaking into either polar or non-polar solvents. This indicates that the pigment / dye is immobilized. A subjective evaluation of the color strength is shown in Table 6b.

[0154]

Table 6b

[0155] Some sand versions with the characteristic of weak color strength (e.g., "orange" in Table 6b) could be successfully treated with twice the amount of the same dispersion (Table 6a). The higher the concentration of X-fast, the greater the increase in the color strength of the treated sand.

[0156] The color strength can also be increased by using a two-step surface treatment procedure as proposed in Example 1d without increasing the X-fast or silane concentration. In the first step, the sand is modified with a low level of silane, e.g., 0.03%. In the second step, in relation to the coloring corresponding to 0.062% of X-fast for the sand, the silane / sand ratio can be made 0.07%. This amounts to a total addition of 0.1% of silane and 0.062% of X-fast.

[0157] Using a two-step procedure rather than a one-step procedure where some sand grains are thought to have weak coloring and others strong coloring is thought to result in all sand grains in the batch having more similar coloring strength.

[0158] [Example 3b - Two-step coloring and immobilization of X-fast] In a second method, after the sand was first surface-treated, a pigmentation step was carried out. In the pigmentation (second) step, silane HC303E was tested as an immobilizing agent for X-fast agitation in pigment preparation. An aqueous mixture in Table 7 was prepared and mixed for about 1 hour (taking into account the possibility of reaction between HC303E and X-fast). This solution was added to already silane-treated Mam1s (0.1% of BS1701 and XL10) to a standard X-fast concentration of 0.062% (1.6 g of dispersion for 480 g of sand). Since HC303E is provided as a 17% aqueous solution, the HC303E concentration on the sand corresponds to about 0.0032%. When verified with the same test procedure as above, the results were generally good, and the pigment seems to strongly adhere to the surface of the sand grains.

[0159]

Table 7

[0160] [Example 3c - Two-step coloring and immobilization of X-fast with trimethoxyphenylsilane and triacetoxy(vinyl)silane] - The effect of surface treatment with trimethoxyphenylsilane and triacetoxy(vinyl)silane (GF62) on the coloring and immobilization of X-fast was evaluated according to a two-step method. The preparation of the silane solution / dispersion followed a protocol similar to that of Example 1a. 5 g of silane was weighed. - This silane was added to 64 g of water and an aqueous solution of 0.5 g of HAc (24%) with vigorous stirring to obtain a solution or dispersion. - Stirring (vigorously) was continued for about 30 - 60 minutes.

[0161] Subsequently, the surface-treated sand was prepared in a two-step process. In the first step, the sand was modified with approximately 0.05% silane. - 480 g of sand (Mam1s) was heated in a stainless steel pot to 55 - 60 °C. - 3.4 g of an aqueous silane dispersion was added to the hot sand under mixing. - Mixing was continued until the moisture evaporated and the sand dried. In the second step, 0.3 g of X-fast Blue 7080 was dissolved in 5 g of water, further mixed with 3.4 g of an aqueous silane dispersion, and a total of approximately 0.1% silane and 0.06% X-fast based on the weight of sand Mam1s were added to the sand: - The modified sand (described above) was heated in a stainless steel pot to approximately 55 - 60 °C. - While stirring continuously, the aqueous X-fast Blue 7080 / silane solution / dispersion was added to the hot sand. - Mixing was continued until the moisture evaporated and the sand dried. The resulting sand exhibited a fairly strong blue color, and there was almost no leakage of the pigment even when excessive water or ethanol was brought into contact with the sand during stirring with a magnetic bar.

[0162] [Example 3d - Two-step coloring and immobilization of X-fast with M3-ethoxysilane] An aqueous dispersion of M3-ethoxysilane of Example 2a was used for the surface treatment of sand: - 480 g of sand (Mam1s) was heated in a stainless steel pot to 55 - 60 °C. - 5 g of the silane M3-ethoxy dispersion was added to the hot sand under mixing. - Stirring (vigorously) was continued until drying.

[0163] After coloring, a sample was prepared by dissolving X-fast Blue 7080 (3 g) in water (30 g), 3.3 g of the resulting solution was added to the hot sand, and mixing was carried out until drying. Finally, an additional 5 g of the M3-ethoxy dispersion was added to the hot sand. The resulting sand contains approximately 0.1% silane and approximately 0.06% X-fast.

[0164] After drying, it was found that this colored sand had almost no leakage even when it came into contact with excess water, despite being vigorously stirred with a magnetic bar (2 g of sand was brought into contact with 40 mL of water). In the reference sample treated with only the X-fast solution (0.06%) without adding the silane solution, significant leakage was observed.

[0165] The challenge test was repeated with an aqueous solution containing water (40 mL) and dishwashing liquid (0.5 mL). The difference between the monofunctional silane-treated sample and the reference sample was very clear. The silane-treated sample had very slight pigment leakage, while the sand treated with only X-fast Blue 7080 lost most of its pigment when it came into contact with the aqueous solution.

[0166] This result indicates that the monofunctional silane also helps to immobilize the pigment on the surface of the particulate material.

[0167] [Example 3e - Two-step coloring and immobilization of X-fast on a larger scale] In this experiment, the scale is a typical laboratory scale (i.e., 480 g of sand), but the concentration of the silane and the concentration of the pigment are 10 times higher than in previous typical examples (i.e., compared to the typical addition amounts of 0.1% and 0.06% for silane and pigment respectively, currently 1% and 0.6%).

[0168] An aqueous silane solution of Example 3c was prepared, where the silane was trimethoxyphenylsilane - 32 g of the aqueous silane solution was added to 480 g of Mam1s preheated to 55 - 60 °C. - Mixing was continued until the water evaporated and the sand dried. On the other hand, 3 g of X-fast Blue 7080 was dissolved in 30 g of water. This solution was mixed with the remaining 37 g of the silane solution, and the resulting mixture was added to the hot sand. The materials were mixed until the water evaporated and the sand dried. As a result, about 1% of silane and about 0.6% of X-fast Blue adhered to the surface of the sand.

[0169] The obtained sand was strongly colored and remained almost uncolored for several minutes when brought into contact with excess water under stirring. Abrasion of the surface coloring layer was only observed when stirring was continued, and the aqueous phase gradually turned blue.

[0170] In a reference sample without silane that was only treated with an aqueous solution of X-fast, significant leakage was observed, and the excess aqueous phase immediately showed a strong blue color. This indicates that the pigment was effectively immobilized by the surface modification treatment.

[0171] [Example 4 - Low contamination from the cohesive sand-like molding material prepared with colored sand] A silicone binder "X" was prepared by cross-linking 397 g of C2T with 3.5 g of ES23. This reaction occurred while mixing the two components at a temperature of about 130 °C. The viscosity increased strongly due to cross-linking. The reaction ended after 3 hours.

[0172] 0.4 g of "X" and 1.8 g of CDS100 were added to a mixture of 1.2 g of K37 and 96 g of sand (specified below) at a temperature of about 60 °C. 0.4 g of HCl (9%) was added together with 0.3 g of radiacid 0406, melt-mixed, and then 0.1 g of I20 was added. As a final step, 0.2 g of SnS was added to the mixture. This resulted in a cohesive sand-like molding material useful for children's play.

[0173] Untreated Mam1s sand or the surface-treated and colored Mam1s sand from Example 3 was used for the sand. The contamination of the coloring material was subjectively evaluated. It was found that generally, there was little or very little contamination on the hands and the table from the moldable materials with bright colors.

[0174] Furthermore, the Mam1s-treated sand of Example 3c (containing trimethoxyphenylsilane or GF62) (95%) was mixed with the polycaprolactone binder of Example 2B (5%) to provide a re-moldable material having a strong blue color that does not stain hands during work. This material is useful for children's play. Thus, various silanes can be used to surface-modify sand to provide enhanced properties and coloring materials.

Claims

1. A method for coloring and surface treating at least one surface of a particulate material, comprising: wherein the method comprises: a) optionally heating the particulate material to a temperature between 30°C and 85°C; b) preparing at least one aqueous dispersion selected from a colorant, at least one alkoxysilane, at least one silyl alkanate, at least one polysiloxane, and mixtures thereof; c1) mixing the dispersion prepared in step b) with the particulate material of step a); c2) optionally adding at least one substance selected from at least one alkoxysilane, at least one silyl alkanate, at least one polysiloxane, and mixtures thereof; c3) heating the mixture to a temperature between 20°C and 80°C for between 1 minute and 24 hours; and d) optionally mixing the treated sand formed in step c) with an aqueous dispersion of at least one colorant and / or at least one alkoxysilane and / or at least one silyl alkanate and / or at least one polysiloxane, wherein steps a) (if used) and b) can be carried out simultaneously or sequentially, in any order; wherein at least one step comprises the use of a material selected from at least one alkoxysilane, at least one silyl alkanate, and / or at least one polysiloxane; wherein at least one step comprises the use of a colorant; and wherein the aqueous dispersion of step d) may be the same as or different from that of step b) method.

2. A method for coloring and surface treating (e.g., hydrophobic surface treating) at least one surface of a particulate material, the method comprising: a) optionally heating the particulate material to a temperature between 30°C and 85°C; b) preparing an aqueous dispersion of at least one alkoxysilane and / or at least one silyl alkanate; c) mixing the dispersion prepared in step b) with the particulate material of step a) and heating the mixture to a temperature between 20°C and 80°C for between 1 minute and 24 hours; d) mixing the treated sand formed in step c) with an aqueous dispersion of at least one colorant and optionally at least one alkoxysilane, at least one silyl alkanate and / or at least one polysiloxane comprising a method in which step a) (if used) and step b) can be carried out simultaneously or sequentially in any order **Claim 3** A method for coloring and surface-treating at least one surface of at least one particulate material, the method comprising a) optionally heating the particulate material to a temperature between 30°C and 85°C; b) preparing an aqueous dispersion of at least one alkoxysilane; and / or at least one silyl alkanate; optionally at least one polysiloxane; and at least one colorant; and c) mixing the dispersion prepared in step b) with the particulate material of step a) and heating the mixture to a temperature between 20°C and 80°C for between 1 minute and 24 hours; comprising a method in which step a) (if used) and step b) can be carried out simultaneously or sequentially in any order **Claim 4** A method for coloring and surface-treating at least one surface of at least one particulate material, the method comprising a) optionally heating the particulate material to a temperature between 30°C and 85°C; b) preparing an aqueous dispersion of at least one colorant: and c0) optionally pretreating the particulate material with a basic solution, c1) mixing the dispersion prepared in step b) with the particulate material of step a), c2) adding at least one substance selected from at least one alkoxysilane, at least one silyl alkanate, at least one polysiloxane and mixtures thereof; and c3) heating the mixture to a temperature between 20°C and 80°C for between 1 minute and 24 hours; comprising a method in which step a) (if used) and step b) can be carried out simultaneously or sequentially in any order **Claim 5** The method according to any of the preceding claims, wherein when present, the dispersions of steps b) and d) comprise 0.5 to 30% by weight of total silane and 70 to 99.5% by weight of water **Claim 6** The method according to any one of the preceding claims, wherein the weight ratio of the particulate material to the total silane is from 90 to 99.99% particulate material and from 0.01 to 10% total silane.

7. The method according to any one of the preceding claims, wherein the at least one alkoxysilane comprises at least one alkoxysilane of formula I. 【Chemical Formula 3】 [wherein, R 1 is a branched or linear alkyl group of H; CH 3 ; C 2 to C 12 ; a branched or linear alkenyl group of C 2 to C 8 ; a C 2 to C 12 alkyl or alkenyl group containing at least one ether bond and / or at least one epoxy group; and / or a C 5 to C 10 aromatic group; and is selected from mixtures thereof; R 2 and R 4 each of which is independently selected from H; CH 3 ; C 2 ~C 8 branched or linear alkyl groups; and mixtures thereof.]

8. The method according to any one of the preceding claims, wherein the at least one silyl alkanoate comprises at least one silyl alkanoate of formula II. 【Chemical Formula 4】 [wherein, R5 is selected from C1-C6 alkyl groups, preferably a methyl group; Each of R6 and R7 is independently selected from R9, -O-R9 and -O-CO-R9 (wherein R9 is H; CH 3 ; selected from cyclic, branched or linear alkyl groups having 2 to 12 carbon atoms), R8 is selected from H; CH 3 ; a cyclic, branched or linear alkyl group having 2 to 12 carbon atoms; a branched or linear alkenyl group having 2 to 12 carbon atoms, and mixtures thereof.]

9. The at least one alkoxysilane is i) at least one alkoxyvinylsilane and ii) at least one alkoxyalkyl The method according to any one of the preceding claims.

10. The at least one alkoxysilane is i) at least one alkoxyvinylsilane and ii) at least one alkoxyalkylsilane, with a weight ratio of i) to ii) from 99:1 to 50:50; The method according to any one of the preceding claims.

11. Step b) is i) at least one alkoxyvinylsilane and ii) at least one alkoxyalkylsilane, The method according to any one of the preceding claims, comprising mixing in an aqueous dispersion at a weight ratio of i) to ii) from 99:1 to 50:

50.

12. The method according to claim 11, wherein step b) further comprises a step of mixing a colorant.

13. The at least one alkoxysilane is i) trimethoxyvinylsilane and ii) triethoxytrimethylpentylsilane The method according to any one of the preceding claims.

14. The method of claim 13, wherein triethoxytrimethylpentylsilane is present in an amount of 5 to 15% by weight of the total silane compound.

15. The method of claim 13 or 14, wherein trimethoxyvinylsilane is present in an amount of 85 to 95% by weight of the total silane compound.

16. The method according to any one of the preceding claims, wherein the particulate material comprises at least one metal oxide, such as silica, titania and / or alumina.

17. The method according to any one of the preceding claims, wherein the particulate material comprises or consists of at least one material selected from silica, quartz, soda-lime glass, borosilicate glass, construction sand, silica sand, quartz sand, silica gel and / or fumed silica.

18. A method for improving the compatibility between a particulate material and a binder and simultaneously coloring the material, the method comprising: a) optionally heating the particulate material to a temperature between 30 °C and 85 °C; b) preparing an aqueous dispersant of at least one material selected from at least one alkoxysilane, at least one silyl alkanoate, at least one polysiloxane and a colorant; and c1) mixing the dispersion prepared in step b) with the particulate material of step a); c2) optionally adding at least one material selected from at least one alkoxysilane, at least one silyl alkanoate, at least one polysiloxane and mixtures thereof; c3) heating the mixture to a temperature between 20 °C and 80 °C for between 1 minute and 24 hours; and d) optionally mixing the treated sand formed in step c) with an aqueous dispersion of at least one colorant and / or at least one alkoxysilane and / or at least one silyl alkanoate and / or at least one polysiloxane comprising: Steps a) and b) may be carried out simultaneously or sequentially, in any order; at least one step (e.g., at least one of steps b), c2) and / or d)) comprises the use of a material selected from at least one alkoxysilane, at least one silyl alkanoate and / or at least one polysiloxane; the aqueous dispersion of step d) may be the same as or different from that of step b); and at least one step comprises a colorant, the method.

19. A method for improving the compatibility between a particulate material and a binder according to claim 16, the method comprising or consisting of the hydrophobic surface treatment according to any one of claims 1 to 15.

20. The method according to claim 18 or 19, wherein the binder comprises at least one polymer material.

21. The method according to claim 20, wherein the at least one polymer material is polyester, polyvinyl ester or polysiloxane.

22. The method according to claim 21, wherein the polyester material is polycaprolactone.

23. The method according to claim 21, wherein the polyvinyl ester material is polyvinyl acetate.

24. A particulate material having at least one surface surface-modified with at least one silylalkyl group or silylalkenyl group and at least one colorant.

25. The particulate material according to claim 24, wherein the particulate material is colored on the at least one modified surface.

26. A particulate material having at least one modified (e.g., hydrophobized) surface formed or capable of being formed by treatment with an aqueous dispersion of at least one alkoxysilane, wherein the at least one modified surface is further colored with a colorant.

27. The particulate material according to claim 24, having at least one modified (e.g., hydrophobized) surface formed or capable of being formed by the method according to any one of claims 1 to 23.

28. The particulate material according to any one of claims 24 to 27, which is a surface-modified sand having a silica content of 80% to 100% by weight and an average particle size of 0.05 to 2 mm.

29. A colored particulate material having at least one silyl-modified (e.g., hydrophobized) surface, preferably a surface-modified sand having a silica content of at least 50% by weight of the particulate material.

30. The colored particulate material according to claim 29, formed or capable of being formed by treatment with an aqueous dispersion of at least one alkoxysilane and at least one colorant.

31. The colored particulate material according to claim 29, formed or capable of being formed by the method according to any one of claims 1 to 23.

32. The colored particulate material according to claim 29, having at least one material selected from at least one alkoxysilane, at least one silyl alkanate, at least one polysiloxane and mixtures thereof and a colorant on at least one surface.

33. A filled molding material comprising at least one colored particulate filler material and at least one polymeric binder material, wherein the particulate filler material has at least one treated (e.g., hydrophobized) surface modified with at least one silylalkyl group or silylalkenyl group and at least one colorant, filled molding material.

34. A filled molding material comprising at least one colored particulate filler material and at least one polymeric binder material, wherein the particulate filler material has at least one treated (e.g., hydrophobized) surface formed or formable by treatment with an aqueous dispersion of at least one alkoxysilane.

35. A filled molding material according to claim 33 or 34, wherein the particulate filler material has at least one treated surface formed or formable by the method according to any one of claims 1 to 23. A filled molding material according to claim 33 or 34.

36. A filled forming material according to any one of claims 33 to 35, wherein the particulate material is surface-treated with an alkoxysilane in a weight ratio of silane of 0.01% to 1% with respect to the particulates. A filled forming material according to any one of claims 33 to 35.

37. A filled forming material according to any one of claims 33 to 36, wherein the colored particulate filler material has at least one treated surface formed or formable by the method according to any one of claims 1 to 23. A filled forming material according to any one of claims 33 to 36.

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