JP2005290051A - Reinforcing material for silicone emulsion - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a reinforcing material for a silicone emulsion excellent in strength, elongation and adhesiveness to various substrates. <P>SOLUTION: The surface-treated reinforcing material for a silicone emulsion is composed of particles surface-treated with an organic surface treatment agent, satisfies formulas (1)-(5) and has a hardness value based on a ten-step Mohs hardness tester of 6 or less: (1) 5 ≤Sw≤300 (m<SP>2</SP>/g), wherein Sw is a BET specific surface area; (2) 0.05≤As≤4.00 (mg/m<SP>2</SP>), wherein As is the reduction in weight by heating per unit specific surface area; (3) 0.02≤Dxs50≤3.00 (μm), wherein Dxs50 is the average particle size at 50% sum weight; (4) Dys≤10 (wt%), wherein Dys is the sum weight of the particle size higher than 5 μm; and 0<Smr≤3, wherein Smr is (Dxs10-Dxs90)/Dxs50, wherein Dxs10 is the average particle size at 10% sum weight measured from the large particle side (μm), and Dxs90 is the average particle size at 90% sum weight measured from the large particle side (μm). <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a reinforcing material for silicone emulsion that forms a rubber film by curing, and more particularly, when used in coating materials, paints, sealing materials, etc., it has excellent strength, elongation, adhesion to various substrates, and the like. The present invention relates to a reinforcing material for a silicone emulsion surface-treated with a specific organic surface treatment agent capable of forming a silicone emulsion to be a cured product.

  Conventionally, a silicone emulsion has been proposed or provided that forms a rubber film by curing after removing water. For example, an aqueous silicone emulsion composition comprising a hydroxylated diorganopolysiloxane, colloidal silica, an organic tin compound, or an organic amine compound has been proposed (see Patent Document 1). It is described that a coating agent that can be thickly coated at once can be formed by adding an extender of calcium carbonate, clay, mica, aluminum oxide, quartz, and zinc oxide to this emulsion composition. However, this composition has a drawback that it has poor adhesion to various substrates and causes a peeling phenomenon.

  Among the above-mentioned calcium carbonates, the carbon dioxide method is widely adopted as an industrial production method for precipitated calcium carbonate. This carbon dioxide method is a method of passing a carbon dioxide-containing gas (hereinafter referred to as carbon dioxide) through a calcium hydroxide aqueous suspension (hereinafter referred to as lime milk), or lime milk or calcium hydroxide in carbon dioxide gas. For example, spraying a mixed solution of precipitated calcium carbonate. Since precipitated calcium carbonate is produced in a water slurry, it is used as it is in a water slurry, or is powdered by dehydration, drying and pulverization by a conventional method.

  Precipitated calcium carbonate obtained by these methods has a very strong cohesion between primary particles, and many primary particles aggregate to form large secondary particles (coarse aggregates of primary particles). The slurry of secondary particles is said to be impossible to disperse to primary particles even if the slurry is vigorously stirred for a long time. When a reinforcing material containing a large number of aggregates of primary particles is used, good physical properties such as poor dispersion and reduced strength cannot be obtained due to the presence of coarse aggregates of primary particles. The compounding effect as in the case of the case is not obtained. Similarly, even when a reinforcing material containing a large number of aggregates is treated with a conventional inorganic or organic surface treatment agent, the dispersibility of the original primary particles cannot be exhibited.

  Up to now, many methods for mechanically dispersing these primary particle aggregates have been reported, and a method for strongly crushing and breaking using a ball mill, a sand grinder mill, an ultrasonic disperser or the like has been proposed. However, in such a method, since the grinding is performed using a strong energy, the aggregates are dispersed at the same time as the primary particles are ground, and as a result, the surface state is very unstable. In addition, it is difficult to say that this is a preferable method because particles that are smaller than the desired primary particle size and secondary particles that are incompletely dispersed are mixed, resulting in a broad distribution of particle sizes. In addition, even smaller particles are present, and undesired phenomena such as reaggregation due to their presence also occur. For these reasons, precipitated calcium carbonate, heavy calcium carbonate, gypsum, talc and the like have been used merely as extenders.

  In order to solve this problem, an emulsion composition containing calcium carbonate surface-treated with sodium polyacrylate is provided (see Patent Document 2). However, although this composition is improved in reaggregation itself, it cannot be said that the composition is sufficiently satisfactory in terms of strength and elongation.

  In any of these cases, various fillers represented by precipitated calcium carbonate, heavy calcium carbonate, clay, mica, aluminum oxide, quartz, and zinc oxide are used. Or, it is used only as an ultraviolet shielding agent or as a bulking agent, and colloidal silica or silica sol is used as a reinforcing material for improving physical properties such as strength and elongation.

In addition, the use of a hydroxyl group-containing organopolysiloxane emulsion, a reaction product of an aminofunctional silane and an acid anhydride (see Patent Document 3), an organopolysiloxane having two or more alkoxy groups or hydroxyl groups in one molecule Proposals have been made by improving resins and adding additives such as use (see Patent Document 4), use of ureido group-containing organoalkoxysilanes or partially hydrolyzed condensates thereof (see Patent Document 5). However, in these cases, there is a problem that the slipperiness of the coated surface becomes insufficient, and when another object comes into contact with the coated surface, strong shearing is applied to the contact portion, and the coated film itself is destroyed. It was.
In addition, the colloidal silica or silica sol used as a reinforcing material has a problem that the film tends to be hard and the film has poor flexibility.

Conventionally, colloidal silica and silica sol have been used for silicone emulsions. These are emulsion stabilizers for emulsions and have been used as reinforcing materials for imparting strength and elongation to a cured rubber coating. On the other hand, in the silicone emulsion, the poor adhesion is a problem, and various proposals have been made so far.
As a result of intensive studies, the present inventors have come to the conclusion that the cause of deterioration in adhesiveness is caused by the use of colloidal silica or silica sol. The reason for this is not necessarily clear, but the emulsion composition will flesh with water evaporation as it cures. It is inferred that the adhesiveness is lowered as a result. In addition, there is a problem that the flexibility of the rubber film is lowered, which is considered to be due to the hardness of the silica having a Mohs hardness of 7.

Therefore, it is considered that the improvement of adhesion and flexibility can be achieved by reducing or not using the amount of colloidal silica or silica sol, but instead of these, they have been used simply for the purpose of a bulking agent. Even when calcium carbonate or calcium phosphate was used, physical properties such as film strength such as strength and elongation could not be used as compared with the case where colloidal silica or silica sol was used.
JP 56-16553 A Japanese Patent Publication No. 6-39568 JP 58-101153 A JP-A-8-85760 JP-A-10-204294

  The present invention has been made in view of the above circumstances. That is, the present invention relates to a surface-treated reinforcing material for silicone emulsion that cures to form a rubber film, and forms not only excellent strength, elongation, adhesiveness to various base materials, but also forms a silicone marquee with excellent flexibility. It is an object of the present invention to provide a reinforcing material that is surface-treated with a specific organic surface treatment agent.

  As a result of intensive research to solve the above problems, the present inventors have performed surface treatment with a specific surface treatment agent, and by using a reinforcing material having a specific hardness, the amount of colloidal silica or silica sol used can be reduced. It has been found that it is possible to obtain a silicone emulsion that can be reduced or dispensed with, and not only has a film strength equal to or greater than that when using them, but also has excellent flexibility. .

That is, the present invention comprises particles surface-treated with an organic surface treatment agent, satisfies the following formulas (1) to (5), and has a hardness value of 6 or less based on a 10-step Mohs hardness tester. The feature is a surface treatment reinforcing material for silicone emulsion.
(1) 5 ≦ Sw ≦ 300 (m ² / g)
(2) 0.05 ≦ As ≦ 4.00 (mg / m ² )
(3) 0.02 ≦ Dxs50 ≦ 3.00 (μm)
(4) Dys ≦ 10 (wt%)
(5) 0 <Smr ≦ 3
Sw: BET specific surface area by nitrogen adsorption method (m ² / g) (single point measured value in NOV A4200 manufactured by Yuasa Ionics)
As: Heat loss per unit specific surface area calculated by the following formula (mg / m ² )
Amount of organic surface treatment agent (heat loss mg / g per gram of surface-treated reinforcing material at 200 to 500 ° C.) / Sw
Dxs50: 50% cumulative average particle diameter (μm) calculated from the large particle side in the particle size distribution in the diffraction formula (SALD-2000 manufactured by Shimadzu Corporation)
Dys: Cumulative weight (% by weight) of particle diameter exceeding 5 μm in particle size distribution
Smr: (Dxs10-Dxs90) / Dxs50 calculated particle sharpness index Dxs10: average particle size distribution in the laser diffraction formula (SALD-2000 manufactured by Shimadzu Corporation). Particle size (μm)
Dxs90: In particle size distribution in laser diffraction method (SALD-2000 manufactured by Shimadzu Corporation), cumulative weight 90% average particle diameter (μm) calculated from the large particle side

According to the surface treatment reinforcing material for a silicone emulsion of the present invention, a silicone emulsion excellent in strength, elongation, adhesion to various base materials, and flexibility can be provided.
For example, when the surface treatment reinforcing material for silicone emulsion of the present invention is added to a water-based coating material, it provides a water-based coating material that is excellent in strength, elongation, flexibility and adhesion to various substrates, When added to water-based paints, it provides water-based paints with excellent emulsification stability, curability and weather resistance, and when added to sealants, it has excellent strength, elongation and adhesion. Sealing material can be provided.

The present invention consists of particles surface-treated with an organic surface treating agent, satisfies the above formulas (1) to (5), and has a Mohs hardness of 6 or less (a hardness value based on a 10-step Mohs hardness meter) It is characterized by comprising.
Formula (1) indicates the BET specific surface area (m ² / g) of the surface treatment reinforcing material of the present invention by the nitrogen adsorption method, and serves as an index for knowing the primary particle diameter of the surface treatment reinforcing material for silicone emulsion. Regarding the BET specific surface area Sw, it is necessary that 5 ≦ Sw ≦ 300 (m ² / g), preferably 10 ≦ Sw ≦ 200 (m ² / g), more preferably 20 ≦ Sw ≦ 150 (m ² / G), more preferably 25 ≦ Sw ≦ 130 (m ² / g). If the specific surface area exceeds 300 m ² / g, the cohesive force between the primary particles becomes strong and behaves as an aggregate, which is not preferable. The amount of the organic surface treatment agent to be used is also required depending on the specific surface area. Therefore, it may be disadvantageous economically. In general, Sw is preferably as large as possible so that dispersibility can be maintained, but at present, dispersion exceeding 300 m ² / g is difficult. On the other hand, if it is less than 5 m ² / g, it becomes difficult to impart strength properties to the coating, or it is necessary to increase the number of blended parts in order to impart strength, resulting in a decrease in elongation and flexibility.
As a device for measuring the BET specific surface area, NOVA 4200 type manufactured by Yuasa Ionics Co., Ltd. was used. When the form of the surface treatment reinforcing material was slurry, the measurement was performed after drying at 100 ° C. and sufficiently removing moisture.

The formula (2) is the amount of the organic surface treatment agent per unit specific surface area of the surface treatment reinforcing material of the present invention. Regarding As, it is necessary that 0.05 ≦ As ≦ 4.00 (mg / m ² ). And preferably 0.1 ≦ As ≦ 3.0 (mg / m ² ), more preferably 0.2 ≦ As ≦ 2.0 (mg / m ² ).
When the amount of the organic surface treatment agent As per unit specific surface area exceeds 4.0 mg / m ² , the surface treatment agent is liberated due to excessive surface treatment agent, causing bleeding phenomenon and rough skin due to the surface treatment agent floating. Since it is necessary to use a surface treatment agent more than necessary, it is economically disadvantageous. Further, if it is less than 0.05 mg / m ^2, not only the effect of the surface treatment agent is not fully exhibited, but also the coating of the inorganic reinforcing material particles becomes insufficient and cannot be dispersed or reaggregated over time. , Because storage stability such as thickening is reduced.
The amount of the organic surface treatment agent per unit specific surface area (heat loss) was about 10 mm in the sample pan (platinum) having a surface treatment reinforcing material that had been dried in a dryer at 100 ° C. for 12 hours in advance. 100 mg was collected and used per gram of solid content of the surface treatment reinforcing material when the temperature was increased from room temperature to 510 ° C. at 15 ° C. per minute using a TG measuring device (THERMOFLEX TG8110 manufactured by Rigaku Corporation). A heat loss value (mg / g) of 200 to 500 ° C. is obtained, and this value is obtained by dividing by a BET specific surface area value.

The expressions (3), (4), and (5) serve as indexes for knowing the dispersion state in the emulsion composition of the reinforcing material obtained by surface-treating the organic surface treating agent. In the formula (3), Dxs50 is a 50% cumulative weight average particle diameter (μm) calculated from the large particle side in the particle size distribution in the laser diffraction method (SALD-2000 manufactured by Shimadzu Corporation). Formula (4) is the cumulative weight (% by weight) of particle diameters exceeding 5 μm in the above particle size distribution. The formula (5) is an index representing the sharpness of the surface treatment reinforcing material.
The particle size distribution was determined by weighing the following compounding materials (I) and (II) into a 140 ml mayonnaise bottle, adjusting the solid content concentration of the surface treatment reinforcing material to 1%, and stirring lightly with a stainless spoon. Then, it measures with the laser diffraction type particle size distribution analyzer (SALD-2000 by Shimadzu Corp.) using what was pre-dispersed with the ultrasonic disperser as a sample.
(I) Surface treatment reinforcing material sample (in terms of solid content) 0.5 g
(II) Water (Total amount of water contained in the surface treatment reinforcing material sample) 49.5 g
In particular, an ultrasonic disperser used as a pre-dispersion after adjusting with the above-described formulation as a pretreatment is preferably performed under certain conditions, and the ultrasonic disperser used in the examples of the present invention is US-300T (Japan). Using Seiki Seisakusho Co., Ltd.) and dispersed under constant conditions of 100 μA-60 seconds.

  In the above-mentioned particle size distribution, 0.02 ≦ Dxs50 ≦ 3.00 (μm) with respect to the cumulative weight 50% average particle diameter (μm) Dxs50 calculated from the large particle side of the surface treatment reinforcing material of the present invention of the formula (3). And preferably 0.02 ≦ Dxs50 ≦ 1.00 (μm), more preferably 0.02 ≦ Dxs50 ≦ 0.70 (μm), and still more preferably 0.02 ≦ Dxs50 ≦ 0.60. (Μm), most preferably 0.02 ≦ Dxs50 ≦ 0.50 (μm). When it exceeds 3.00 μm, physical properties such as coating strength such as strength and elongation are deteriorated. On the other hand, when it is smaller than 0.02 μm, the reaggregation force of primary or secondary particles is increased, and storage stability is decreased. Absent.

  In the particle size distribution described above, regarding the weight cumulative meter (wt%) Dys of the particle diameter exceeding 5 μm of the surface treatment reinforcing material of the present invention of the formula (4), it is necessary that Dys ≦ 10 (wt%). Preferably Dys ≦ 6 (% by weight), more preferably Dys ≦ 2 (% by weight). If the amount exceeds 10% by weight, the cohesiveness of the surface treatment reinforcing material is strong and not sufficiently dispersed. Therefore, when the reinforcing material is blended, undesired phenomena such as a decrease in film strength such as strength and elongation occur. To do.

  In the particle size distribution described above, the sharpness index Smr of the surface treatment reinforcing material of the present invention of the formula (5) needs to satisfy 0 <Smr ≦ 3, preferably 0.25 ≦ Smr ≦ 2.5, more preferably Is 0.5 ≦ Smr ≦ 2. In the case of Smr = 0, it can be said that it is in a monodispersed state, which is preferable in terms of strength but tends to deteriorate the adhesion. On the other hand, when Smr exceeds 3, the particle size distribution becomes broad, and undesirable phenomena such as a decrease in storage stability due to the presence of fine particles and a decrease in coating strength such as strength and elongation due to the presence of coarse particles occur.

The reinforcing material of the present invention is required to have a hardness value of 6 or less based on a 10-stage Mohs hardness tester. A Mohs hardness exceeding 6 is not preferable because the flexibility of the coating is lowered.
The substance having a Mohs hardness of 6 or less used in the present invention is not particularly limited, but may be precipitated calcium carbonate, heavy calcium carbonate, calcium phosphate, gypsum, talc, clay, mica, barium sulfate, aluminum hydroxide, aluminum silicate, etc. Inorganic particles are preferable, and used alone or in combination of two or more as necessary. When using natural minerals such as heavy calcium carbonate, talc, clay, mica, etc., a method of adjusting the particle size by wet pulverization is preferable in order to satisfy a specific particle size distribution range.
Of these, cubic, spherical calcite-type calcium carbonate, spherical vaterite-type calcium carbonate, or calcium phosphate is particularly preferable from the viewpoints of particle uniformity, particle dispersibility, and the like.

  Precipitated calcium carbonate is a carbonate that synthesizes precipitated calcium carbonate by reacting quick lime obtained by baking limestone at high temperature and water to adjust lime milk, and then conducting carbon dioxide gas generated during limestone baking in lime milk. It is precipitated calcium carbonate prepared by a chemical method such as a gas compounding method, a lime soda process in which sodium carbonate is reacted with lime milk, and a lime soda process in which sodium carbonate is reacted with calcium chloride. For example, when the precipitated calcium carbonate used in the present invention is produced by the carbon dioxide gas method, the following methods can be considered, but the method is not particularly limited to these methods.

(1) An ultrafine calcium carbonate aqueous suspension of less than 0.1 μm is prepared by a conventional method, the ultrafine calcium carbonate aqueous suspension is adjusted by pH control, and an aqueous dispersion of ultrafine calcium carbonate by pH control And conducting or dripping carbon dioxide gas and primary carbonated lime milk (lime milk that has been partially carbonated beforehand) into the ultrafine calcium carbonate aqueous dispersion so that the pH of the system is in a specific range, A method in which the particle size is grown sequentially with ultrafine calcium carbonate as the core.
(2) Lime milk is sprayed into carbon dioxide under specific conditions to perform a carbonation reaction, and an ultrafine calcium carbonate aqueous suspension of less than 0.1 μm is prepared, and a certain proportion of lime milk is added to the ultrafine calcium carbonate. After the mixture is mixed, the mixture is sprayed again into carbon dioxide gas, and this operation is repeated to grow the particle diameter sequentially with the ultrafine calcium carbonate as a nucleus.
(3) In the process of producing precipitated calcium carbonate by passing carbon dioxide through lime milk, a complex is formed by coordination with a salt or metal ion of strontium or barium in order to improve the degree of dispersion of the obtained calcium carbonate. To use the substance to be used in the carbonation step.
(4) By stirring the precipitated calcium carbonate aqueous suspension obtained by a conventional method and maintaining the pH of the system in a specific range using carbon dioxide and lime milk, the dispersibility of the precipitated calcium carbonate can be improved. How to squeeze.
(5) As a method of producing calcium carbonate having a relatively good dispersion state, carbon dioxide is conducted by conducting carbon dioxide in a methanol suspension of quick lime or slaked lime containing a specific amount of quick lime or slaked lime and a specific amount of water. A method of obtaining calcium carbonate particles having an arbitrary particle size by controlling the specific temperature, pH, electrical conductivity, etc. in the system during the carbonation reaction by performing a carbonization reaction.
(6) Among them, in the method of stirring a precipitated calcium carbonate aqueous suspension obtained by a conventional method and maintaining the pH of the system in a specific range using carbon dioxide and lime milk according to JP-A-08-249128. Calcium chelating agents such as malic acid, succinic acid, citric acid, adipic acid, oxalic acid and their alkali metal salts and polyvalent metal salts are added all at once before or during the introduction of carbon dioxide. Alternatively, a method of obtaining ultrafine precipitated calcium carbonate by adding in portions.

On the other hand, as a method for synthesizing calcium phosphate, for example, the following methods are conceivable, but are not particularly limited to these methods.
(1) By mixing and grinding calcium hydroxide powder and calcium hydrogen phosphate powder to cause a soft mechanochemical composite reaction to prepare a calcium phosphate precursor and heat-treating it at a temperature of 600 ° C. or higher. A method for preparing calcium phosphate powder.
(2) A wet method for adjusting calcium phosphate by mixing and reacting a calcium salt suspension and a phosphoric acid aqueous solution.
(3) In a mixing reaction of a calcium salt suspension and a phosphoric acid aqueous solution obtained by a conventional method, an organic acid having a carboxyl group, a phosphoric acid source, and an alkali metal source are added, and a method of preparing a mixed slurry, A method of obtaining highly dispersed and ultrafine calcium phosphate is preferred.
Examples of phosphoric acid herein include phosphoric acid and condensed phosphoric acid, and examples of condensed phosphoric acid include pyrophosphoric acid, tripolyphosphoric acid, tetrapolyphosphoric acid, pentapolyphosphoric acid, hexametaphosphoric acid, and the like. However, it can be used in combination of two or more. Also sodium phosphate, potassium salt and ammonium salt of phosphoric acid, sodium salt and potassium salt of condensed phosphoric acid, phosphoric acid and sodium salt, potassium salt, and a mixture of sodium salt, condensed phosphoric acid and sodium salt, potassium salt and sodium salt Examples of such phosphates can also be used, and these can be used alone or in combination of two or more.

Moreover, in the addition order of the organic acid which has a carboxyl group, a phosphoric acid source, and an alkali metal source, various methods are employable as follows.
(A) A precursor is prepared by mixing water, a polyvalent metal compound, an organic acid having a carboxyl group, and an alkali metal source, and finally a phosphoric acid source is added.
(B) A precursor obtained by mixing water, a polyvalent metal compound, a phosphoric acid source and an alkali metal source (or a phosphoric acid source / alkali metal source) is prepared, and finally an organic acid having a carboxyl group is added.
(C) A precursor obtained by mixing water, a polyvalent metal compound, and an organic acid having a carboxyl group is prepared, and a phosphoric acid source / alkali metal source is added to the precursor.
(D) A precursor is prepared by mixing water, a polyvalent metal compound, an organic acid having a carboxyl group, and a phosphoric acid source, and finally an alkali metal source is added.

Among these methods, in order to obtain a mixed slurry with better dispersibility, the method (3) is preferable, and the method (c) or (d) is more preferable.
Further, although the stoichiometric Ca / P molar ratio in calcium phosphate is 1.67, the calcium phosphate of the present invention is not limited to this, and there is no problem even if it is in the form of a composite of calcium salt and calcium phosphate.

  As the surface treatment reinforcing particles used in the present invention, particles having a good dispersion state are more effective. As a method of dispersing the aggregated particles in the calcium carbonate or calcium phosphate aqueous suspension obtained by a conventional method, the slurry is heated to an appropriate temperature (20 to 150 ° C.), and phosphorus and sulfur are contained during the aging method. There are methods such as adding substances etc. to suppress particle growth, wet dispersion methods using wet pulverizers, ultrasonic dispersion methods, methods of repeating dehydration and hydration while removing alkali, etc. A method may be used.

  The wet pulverization / dispersion method described above is not particularly limited with respect to the pulverizer and disperser used, but as the wet pulverizer, wet pulverizers such as dyno mill, sand mill, ball mill, nanomizer, microfluidizer, Ultima A roll mill such as an emulsifier / disperser such as an riser or homogenizer, an ultrasonic disperser, or a three roll mill can be preferably used.

  As described above, the particles used for the surface treatment reinforcing material of the present invention are adjusted, but when actually used, they are mixed and used in an aqueous medium, so the product form is an aqueous medium actually used. It may be a suspension that has been dispersed into it, or may be in the form of a dry powder in consideration of distribution costs, precipitation of the inorganic dispersant in the suspension, and the like. There are no particular restrictions on the type of the dryer, and various dryers are used.Preferably, a spray spray dryer or a droplet spray dryer such as a slurry dryer using a ceramic medium in a heated fluid state may be used. When the particle size is reduced, reaggregation due to drying may occur.

The organic surface treatment agents used in the present invention and their effects and roles on the surface treatment reinforcing material will be described in detail.
(I) in [Group A1] constituting the organic surface treatment agent (X1) is an α, β unsaturated monocarboxylic acid exemplified by acrylic acid, methacrylic acid, crotonic acid and the like, and these homopolymers And at least one salt (X1) selected from an alkali metal, alkaline earth metal, Al, Zn, ammonium, and amine, and a copolymer (hereinafter, both are referred to as a (co) polymer), It has the function of stabilizing the dispersion state in the aqueous solvent, which is the first condition of the surface treatment reinforcing material for silicone emulsion.
(II) is an α, β unsaturated dicarboxylic acid exemplified by maleic acid, itaconic acid, fumaric acid, etc., and these (co) polymers and salts thereof (X1) are water-based as in (I). Although it functions to disperse and stabilize the reinforcing material particles in the medium, it is particularly useful for fine reinforcing material particles of 0.3 μm or less.
(III) is hydroxyethylacrylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid (AMPS), sulfonated aliphatic dienes, chain olefins, cyclic olefins, styrene sulfonic acid, etc. The exemplified sulfo group-containing monomers, and these (co) polymers and salts thereof (X1) also have a function of stabilizing calcium carbonate particles in an aqueous medium in a dispersed state. By containing a group, steric hindrance is provided between the particles, which is preferable because it has an effect of preventing the particles from aggregating.
When reinforcing material particles not treated by (X1) are used, the particles cannot be sufficiently dispersed in an aqueous solvent. For example, when reinforcing particles that are not surface-treated by (X1) are used, the dispersion state becomes insufficient, so that when used in a silicone emulsion, physical properties such as the strength and elongation of the cured film have properties such as film strength. There was a problem getting worse.
However, it became possible to enhance the dispersibility of the particles in the aqueous solvent by subjecting the particles of the reinforcing material to the surface treatment of (X1).
(I), (II), and (III) can be arbitrarily selected according to the particle diameter of the reinforcing material used and the type of the silicone emulsion resin.

When the effect of the polymer selected from [Group A1] constituting (X1) is expected to be greater, a copolymer of monomers belonging to (I), (II) and (III) of [Group A1] is used. May be good. For example, the monomer belonging to (I) that exhibits hydrophilicity has a plurality of carboxyl groups inside the constituent copolymer, and thus has excellent adsorbability with the particles of the reinforcing material. A sufficient effect may not be expected in the particles of the reinforcing material. Usually, if the particles are small, the concentration cannot be increased when suspended in an aqueous solvent, but the dispersibility under high concentration is further increased by containing a monomer selected from (II) and (III). In order to improve physical properties such as film strength, the smaller the particles of the reinforcing material used, the more effective the dispersibility. Therefore, preferably, 0 to 300 parts by weight of the monomer belonging to (II) and 0 to 900 parts by weight of the monomer belonging to (III) with respect to 100 parts by weight of the monomer belonging to (I). good.
As described above, the component (II) is effective in a particularly fine region of the reinforcing material particles. Therefore, when handling in manufacturing is considered depending on the particle size of the reinforcing material, 0 part by weight is included in the copolymer. However, if it exceeds 300 parts by weight, the viscosity increases when a copolymer is obtained, sometimes causes gelation, and handling becomes difficult, and may be supported during use. For this reason, More preferably, it is 2-200 weight part with respect to 100 weight part of (I) component, More preferably, it is 5-100 weight part.
As described above, the component (III) is also effective because it is effective in the fine region of the reinforcing material particles, and has an effect of giving steric hindrance between the particles and preventing aggregation of the particles. Therefore, when handling in manufacturing is considered by the particle size of the reinforcing material, it may be 0 parts by weight or less in the copolymer, but if it exceeds 900 parts by weight, the viscosity increases when obtaining the copolymer, and sometimes gel May be difficult to handle and may be difficult to use during use. For this reason, it is more preferably 10 to 500 parts by weight, still more preferably 20 to 200 parts by weight with respect to 100 parts by weight of component (I).

As for the organic acid and alkali metal having a carboxyl group of (Z1), examples of the organic acid having a carboxyl group include malic acid, succinic acid, citric acid, adipic acid, fumaric acid, glutamic acid and alkali metal salts thereof. A polyvalent metal salt etc. can be illustrated, and each can be used alone or in combination of two or more. To obtain reinforcing particles with better dispersibility, select from citric acid, potassium citrate, sodium citrate, calcium citrate, magnesium citrate, ammonium iron citrate, iron citrate and ferrous sodium citrate At least one selected from the above is preferred.
Furthermore, examples of the alkali metal include sodium hydroxide, potassium hydroxide, sodium oxide, potassium oxide, sodium carbonate, sodium hydrogen carbonate, potassium carbonate and potassium hydrogen carbonate, and each can be used alone or in combination of two or more.

  Monomers in [Group A2] are (a) alkyl acrylates and alkyl methacrylates exemplified by methyl (meth) acrylate, ethyl, propyl, isoptyl, 2-ethylhexyl, etc., (b) methoxyethyl ( (Meth) acrylate, acrylate and methacrylate having an alkoxy group exemplified by ethoxyethyl (meth) acrylate and the like, (c) acrylate and methacrylate having a cyclohexyl group exemplified by cyclohexyl (meth) acrylate and the like, (d) 2-hydroxy Α, β monoethylenically unsaturated hydroxy ester exemplified by ethyl (meth) acrylate, etc., (e) polyalkylene exemplified by polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, etc. (F) Vinyl esters such as vinyl acetate and vinyl stearate, (g) Vinyl aromatics such as styrene vinyl toluene, (h) Unsaturation exemplified by acrylonitrile, methacrylonitrile, etc. Nitriles, (i) unsaturated dicarboxylic acid esters such as monomethyl maleate, dibutyl itaconate, (j) vinyl ethers exemplified by methyl vinyl ether, butyl vinyl ether, (k) conjugated dienes exemplified by butadiene, isoprene, l) a chain olefin, (m) a cyclic olefin, and a copolymer with a monomer in [Group A1], the single copolymer consisting of [Group A2] is efficient for reinforcing particles. It has the effect of effectively adhering things that are not well adsorbed. Further, the particles of the reinforcing material subjected to the surface treatment with the surface treatment agent having the composition have an effect of increasing the affinity with the silicone emulsion resin. As a result, the particles of the reinforcing material subjected to the surface treatment with the surface treatment agent having the above composition improve the affinity with the silicone emulsion resin and improve the physical properties of the cured film. What is necessary is just to select suitably from (a)-(m) so that it may become a surface treating agent which adapts to the silicone emulsion resin to be used.

  In particular, the polyalkylene gericol mono (meth) acrylate of (e) in [Group A2] is represented by the following formula:

(In the formula, R ₁ is hydrogen or a methyl group, Z is a ring-opened divalent C 2-4 alkylene oxide residue, n is an average number of 1-30, and R ₂ is a hydrogen group or A monovalent organic group derived from an alkyl group having 1 to 30 carbon atoms, an alkenyl group, an aryl group, an alkyl group having an aryl group as a substituent, a cyclic alkyl group, a cyclic alkenyl group or a heterocyclic compound.) By adding the above-specified components to R ₂ , the affinity between the reinforcing material particles and the silicone emulsion resin is improved at the time of coating formation, which helps to increase the physical properties of the cured coating.
Examples of this monomer include butoxypolyethylene glycol (meth) acrylate, butoxypolypropylene glycol (meth) acrylate, octyloxypolyethylene glycol (meth) acrylate, octyloxypolyethylene glycol-polypropylene glycol (meth) acrylate, phenoxypolyethylene glycol ( (Meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, naphthoxypolyethylene glycol (meth) acrylate, phenoxypolypropylene glycol (meth) acrylate, naphthoxypolyethylene glycol-polypropylene glycol (meth) acrylate, p-methylphenoxypolyethylene glycol (meta) ) Acrylate, pendyloxypolyethyleneglycol (Meth) acrylate, cyclohexoxypolyethyleneglycol (meth) acrylate, cyclopentenoxypolyethyleneglycol (meth) acrylate, pyridyloxypolyethyleneglycol (meth) acrylate, thienyloxypolyethyleneglycol (meth) acrylate, etc. It is derived from a hydrogen group or an alkyl group having 1 to 30 carbon atoms, an alkenyl group, an aryl group, an alkyl group having an aryl group as a substituent, a cyclic alkyl group, a cyclic alkenyl group, or a heterocyclic compound as a terminal group of the alkylene glycol chain. An example is a terminal ether type polyalkylene glycol mono (meth) acrylate having a monovalent organic group.

A copolymer obtained by copolymerizing a monomer that improves the affinity with the silicone emulsion resin as shown in [Group A2] with a monomer belonging to [Group A1] constituting (X1); By treating the salt (X12) into reinforcing material particles, the affinity between the reinforcing material particles and the silicone emulsion resin is improved, which helps to increase the physical properties of the cured coating. At the same time, the monomers belonging to [Group A2] are inherently lipophilic substances and are difficult to dissolve in water. When the surface treatment is performed on the particles of the reinforcing material, they must be processed in a dry manner or in an organic solvent. However, it is preferable because a water-soluble moiety such as (X1) is copolymerized to facilitate solubility in an aqueous solvent and facilitate the treatment of the reinforcing material into particles.
The constituent ratio of the copolymer of the monomer selected from [A1 group] and the monomer selected from [A2 group] constituting (X12) is constituted by the monomer selected from [A1 group]. It is preferable that the total amount of the polymerized portion constituted by the monomer selected from [Group A2] is 0.01 to 900 parts by weight with respect to 100 parts by weight of the total polymerized portion. If it is less than 0.01 parts by weight, the affinity with the silicone emulsion resin cannot be sufficiently exhibited, which is not preferable. On the other hand, when it exceeds 900 parts by weight, the copolymer itself is thickened and handling is possible. In addition, it is not preferable because the reinforcing particles cannot be efficiently processed. More preferably, it is 1-500 weight part, More preferably, it is 5-300 weight part, Especially preferably, it is 10-100 weight part.

  When the effect of the polymer selected from [Group A1] constituting (X1) in the copolymerization ratio in (X12) is expected to be greater, the unit belonging to (I), (II), and (III) of [Group A1] In some cases, a copolymer of a monomer may be used. For example, the monomer belonging to (I) that exhibits hydrophilicity has excellent adsorbing ability with the reinforcing material particles by having a plurality of carboxyl groups inside the constituting copolymer, but finer particles. In some cases, sufficient effect cannot be expected in the particles of the reinforcing material in the region. Usually, if the particles are small, the concentration cannot be increased when suspended in an aqueous solvent, but the dispersibility under high concentration can be improved by further containing a monomer selected from (II) and (III). When the physical properties such as the coating strength are to be improved, the smaller the carbon dioxide reinforcing particles used, the better the dispersibility. Therefore, preferably, 0 to 300 parts by weight of the monomer belonging to (II) and 0 to 900 parts by weight of the monomer belonging to (III) with respect to 100 parts by weight of the monomer belonging to (I). good. As described above, the component (II) has an effect on particularly fine regions of the reinforcing material particles. Therefore, when handling in manufacturing is considered depending on the particle diameter, the amount of the component may be 0 parts by weight. If the amount exceeds 300 parts by weight, the viscosity increases when a copolymer is obtained, sometimes causes gelation, making handling difficult, and may interfere with use. For this reason, More preferably, it is 2-200 weight part with respect to 100 weight part of (I) component, More preferably, it is 5-100 weight part. As described above, the component (III) is also preferable because it has an effect on particularly fine regions of the reinforcing material particles, and has an effect of giving steric hindrance between the particles and preventing aggregation of the particles. Therefore, when handling in manufacturing is considered depending on the particle size of the reinforcing material, the amount of the copolymer may be 0 parts by weight. However, if the amount exceeds 900 parts by weight, the viscosity increases when the copolymer is obtained, and sometimes gelates. May be difficult to handle and may be difficult to handle during use. For this reason, More preferably, it is 10-500 weight part with respect to 100 weight part of (I) component, More preferably, it is 20-200 weight part.

  As a method of obtaining a sulfo group-containing copolymer effective in a fine particle region, a method of polymerizing a monomer containing a sulfo group in advance as in (III) of (X1), (X12S), ( There is a method in which a sulfonateable monomer is polymerized and then sulfonated, as in A2S). The effect of the former and the latter as a treating agent is the same, and may be selected as appropriate during production. In the latter case, the constitutional ratio of the repeating unit monomer containing a sulfo group is preferably 5 to 95%, more preferably 10 to 80%, still more preferably 20 to 70% of the entire copolymer. If it is less than 5%, the effect of sulfonation may not be obtained. Conversely, if it exceeds 95%, the type of the reinforcing material and the particle size are in balance with the carboxylic acid-containing copolymer contained in the copolymer obtained. In some cases, the gelation occurs during the treatment, the viscosity increases, and the particle surface of the reinforcing material cannot be effectively treated.

  The respective (co) polymers comprising the organic surface treatment agents (X1), (X12), (X1S · X12S), and (A2S) are as described above, but these may be used as they are. Since these copolymers comprise an acid, neutralization or partial neutralization is preferred. The salt species to be neutralized are not particularly limited, and alkali metals, alkaline earth metals, Al, Zn, ammonium, amines, and the like can be used.

  In order to surface-treat the organic surface treatment agent more firmly on the surface of the reinforcing material particles, active functional groups (carboxyl group, sulfo group) having reactivity with the reinforcing material particles are contained in these surface treatment agents. Preferably it remains. When the reinforcing material is mechanically dispersed by a pulverizer or a disperser, the particles themselves may be pulverized if excessive dispersion force is applied in the process, and residual ions in the system may be eluted at that time. . If the eluted ions react with the functional group, the reactivity of the functional group is deactivated, and it may not be possible to cause a strong reaction with the particle surface of the reinforcing material. Therefore, a surface treatment agent in which the total amount of carboxyl groups neutralized by alkali metal, alkaline earth metal, Al, Zn, ammonium, amine, etc. is less than 100% of the total amount of all carboxyl groups in the copolymer, More preferably, a surface treatment agent of 90% or less is used. Furthermore, when the salt species is an ammonium salt, the terminal ammonium group is released by heat at room temperature or higher, and as a result, the number of active functional groups adsorbed to the reinforcing material particles increases, and the adsorptivity to the particle surface. Is more preferable. In particular, in the case of an ammonium salt, it may be 100% or more.

  The number average molecular weight (measured by gel osmotic pressure chromatograph) of each (co) polymer consisting of organic surface treatment agents (X1), (X12), (X1S · X12S), (A2S) is a component, component ratio, etc. Depending on the case, it is preferably 500 to 50,000, more preferably about 2000 to 30,000. If the number average molecular weight is less than 500, the adsorption rate tends to decrease. At the same time, in order to obtain a sufficient treatment effect, it is necessary to add a large amount, which is not economical. Moreover, when it exceeds 50,000, the production of the (co) polymer itself may be difficult, and the dispersibility of the surface-treated reinforcing material in the aqueous solvent may be poor and the viscosity may be increased. .

In the present invention, the method of surface-treating the organic surface treatment agents (X1), (X12), (X1S · X12S), and (A2S) into particles is roughly divided into the following two methods.
(1) Dry treatment method The particles are put into a treatment vessel having rotating blades such as a Henschel mixer, and the particles are vigorously stirred. A method of surface treatment. In this case, heating and cooling may be performed as necessary during processing.
(2) Wet treatment method Add a water diluent or organic solvent diluent of a surface treatment agent to a high concentration aqueous solvent suspension or water-containing cake of particles, and mix uniformly by stirring or the like to the particles. A method in which after the surface treatment agent is adsorbed, the slurry is dispersed using a continuous wet pulverizer such as a sand grinder before drying.
The object of the present invention can be achieved by adopting either of these two treatment methods. However, in order to achieve a higher degree of the object of the present invention by uniformly treating the particle surface with a surface treatment agent. The wet pulverization treatment (1) is preferred.
Further, the concentration of the surface treatment agent in the water dilution or the organic solvent dilution when the surface treatment is performed on the particles is not particularly limited, but it is preferably 10% by weight or more, more preferably 20%, for efficient surface treatment. % By weight or more, more preferably 25% by weight is suitable. The upper limit is preferably about 60% by weight because if the concentration is too high, the slurry viscosity increases and handling properties deteriorate, and an excess surface treatment agent is required.
The temperature at which the surface treatment is performed is not particularly limited, but the surface treatment may be performed at a temperature of at least 10 ° C. or more, preferably 20 ° C. or more in order to perform the surface treatment more firmly. The upper limit is preferably about 90 ° C. from the viewpoint of energy costs associated with temperature rise and reaggregation due to water evaporation.

  These (co) polymers can be obtained by a conventionally known method. For example, polymerization in a solvent such as water, an organic solvent, or a mixture of a water-soluble organic solvent and water can be mentioned. In this case, polymerization in an aqueous medium includes persulfate or persulfate as a polymerization initiator. Hydrogen oxide or the like is used, and an accelerator such as sodium bisulfite or ascorbic acid can be used. For polymerization in an organic solvent, an azo compound or an organic peroxide is used as a polymerization initiator, and an accelerator such as an amine compound can be used in combination. For polymerization in a mixed solvent of a water-soluble organic solvent and water, it can be appropriately selected from the above-mentioned various polymerization initiators or combinations of polymerization initiators and accelerators.

  By using the surfactant (Y) in combination with each (co) polymer comprising (X1), (X12), (X1S · X12S) and (A2S), the affinity with the emulsion resin is increased, There exists an effect | action which improves the emulsification stability of an emulsion. Further, by simultaneously treating with water-soluble (co) polymers such as (X1) and (X12) and (X12S) and (A2S), the solubility in aqueous solvents is facilitated, and the particles of the reinforcing material are added. Make processing easier. Furthermore, although the dry aggregation of the particles is strong only by the surface treatment with (X1), (X12), (X12S) and (A2S) alone, the dry aggregation can be prevented by the combined use with the surfactant.

  Examples of such a surfactant (Y) include anionic surfactants, zwitterionic surfactants, cationic surfactants, nonionic surfactants, and the like as listed below, preferably , Alkylbenzene sulfonic acid, polyoxyethylene alkyl ether sulfuric acid, sulfosuccinic acid, or the like, or alkali metal, alkaline earth metal, Al, Zn, ammonium, amine salt, or sulfonate type such as polyoxyalkyl sulfate ester A surfactant or a nonionic activator such as polyoxyethylene alkyl ether may be used, and these may be used alone or in combination of two or more as required.

(Anionic surfactant)
Carboxylate type:
(A) N-acyl amino acids obtained by condensation of higher fatty acids (C12 to C18) exemplified by N-acyl-N-amino acids and the like and amino acids, and (b) exemplified by polyoxyethylene alkyl ether carboxylic acids. N-acyl peptide sulfonate obtained by reacting a peptide exemplified by alkyl ether carboxylic acid, (c) N-acyl peptide and the like with fatty acid chloride:
(A) alkyl sulfonic acid exemplified by polyoxyethylene alkyl sulfonic acid, polyoxyethylene alkyl ether sulfuric acid, etc., (b) alkyl benzene sulfonic acid, (c) alkylene disulfonic acid, (d) alkyl naphthalene sulfonic acid, (e) Naphthalenesulfonate formalin condensate, (f) melamine sulfonate formalin polycondensate, (g) sulfosuccinic acid, (h) sulfosuccinic acid ester exemplified by dialkyl sulfosuccinic acid ester, (i) alkyl sulfoacetic acid, (j ) Α-olefin sulfonic acid sulfate salt type:
(A) Alkyl sulfate ester exemplified by polyoxyalkylsulfate ester, etc. (b) Alkyl ether sulfate ester exemplified by polyoxyethylene alkyl ether sulfate ester, (c) Polyoxyethylene alkylphenyl ether sulfate etc. Alkyl aryl ether sulfates, (d) alkyl aryl sulfates exemplified by polyoxyalkylphenyl sulfates, etc., (e) alkylamide sulfate phosphoric ester salts represented by fatty acid alkylolamide sulfates, etc .:
(A) Alkyl ether phosphates exemplified by polyoxyethylene alkyl ether phosphates, etc. (b) Alkyl phosphates exemplified by polyoxyethylene alkyl phosphates, etc. (c) Polyoxyethylene alkyl phenyl ether phosphates etc. Alkyl aryl ether phosphates exemplified by the above formulas, (d) alkyl aryl phosphates exemplified by polyoxyalkyl phenyl phosphates, etc.

(Zwitterionic surfactant)
(A) betaine, (b) aminocarboxylic acid, (c) imidazoline derivative,
(Cationic surfactant)
(A) aliphatic amine salt and its quaternary ammonium salt, (b) aromatic quaternary ammonium salt, (c) heterocyclic quaternary ammonium salt (nonionic activator)
(A) fluoroalkyl carboxylic acid, (b) perfluoroalkyl carboxylic acid, (c) perfluoroalkyl sulfonic acid, (d) alkyl ether, (e) alkyl allyl ether, (f) alkyl ester, (g) alkyl amine , (H) sorbitan derivatives, (i) polycyclic phenyl ethers, (j) fatty acid esters

  Surfactant (Y) is originally a lipophilic substance and is hardly soluble in water. Therefore, when the surface treatment is performed on the particles, the treatment is usually performed in a dry manner or in an organic solvent. By treating simultaneously with water-soluble (co) polymers such as (X1) and (X12) and (X12S) and (A2S), it is easy to dissolve in an aqueous solvent and to treat particles. . From the above viewpoints, (Y) having an HLB of 3 to 18 is more preferable. When the HLB is less than 3, the affinity of the reinforcing particles themselves with the resin tends to be poor, and as a result, the dispersibility tends to be poor when blended into the aqueous silicone emulsion. On the other hand, when it exceeds 18, the adhesion force of the surfactant itself to the particles of the reinforcing material is lowered, and it must be treated more than necessary, which may be economically disadvantageous.

  The combined ratio of the surface treatment agent (X1), (X12), (X1S · X12S), (A2S) and the surfactant (Y) is not particularly limited, but is preferably 1:99 to 99: 1, more preferably 5:95 to 95: 5, more preferably 10:90 to 90:10. If the surfactant (Y) exceeds 99, it is not effectively adsorbed on the particles, and the component (Y) that is eluted and remains in the aqueous solvent at the time of film formation becomes excessive, which increases the possibility of adversely affecting the physical properties of the film. On the contrary, if it is less than 1, the effect is not significantly different from the case of no addition, and (X1), (X12), (X1S · X12S), (A2S) and (Y) are used in combination. A sufficient effect cannot be obtained.

As the surfactant (Y), it is preferable to use a neutralized or partially neutralized surfactant. The salt species to be neutralized are not particularly limited, and alkali metals, alkaline earth metals, Al, Zn, ammonium, amines, halogen elements and the like can be used.
The surfactant (Y) is preferably one in which active functional groups (carboxyl group, sulfo group, phosphoric acid group, etc.) having reactivity with the reinforcing material particles remain. The active functional group remains, so that the adsorptivity with the particles is improved and is eluted in the aqueous solvent at the time of forming the coating, and the remaining surplus components are reduced, which is preferable from the viewpoint of physical properties of the coating. Therefore, the total amount of functional groups neutralized by alkali metal, alkaline earth metal, Al, Zn, ammonium, amine, halogen element, etc. is preferably less than 100% of the total amount of functional groups in the surfactant, More preferably, it is 90% or less. If it exceeds 100%, the amount of metal ions constituting the salt species brought into the system increases, which may lead to a decrease in physical properties, which is not preferable.

In the present invention, one or more surface treatment agents of (X1), (X12), (X1S · X12S), and (A2S) and each surfactant comprising (Y) are applied to the surface of the reinforcing material particles. The processing methods are roughly divided into the following two methods.
(1) Dry treatment method Reinforcing material particles are put into a processing vessel having rotating blades such as a Henschel mixer, the particles are vigorously stirred, and a water-diluted solution or a dilute organic solvent solution of a surfactant is dropped into the particles. A method of surface treatment by dry method. In this case, heating and cooling may be performed as necessary during processing.
(2) Wet treatment method Add a surfactant water dilution or organic solvent dilution to a high concentration aqueous solvent suspension or hydrous cake of reinforcing material particles, and mix evenly by stirring or the like. A method in which the surfactant is adsorbed on particles, and then the slurry is dispersed using a continuous wet grinder such as a sand grinder before drying.
The object of the present invention can be achieved by adopting either of these two treatment methods, but in order to achieve a higher degree of the object of the present invention by surface-treating the surfactant uniformly on the particle surface, The wet pulverization treatment (2) is preferred.
The temperature at which the surface treatment is performed is not particularly limited, but the surface treatment may be performed at a temperature of at least 10 ° C. or more, preferably 20 ° C. or more in order to perform the surface treatment more firmly. The upper limit is preferably about 90 ° C. from the viewpoint of energy costs associated with temperature rise and reaggregation due to water evaporation.
In addition, there is no restriction | limiting in particular about the particle size etc. of the particle | grains before surface treatment, for example, the particle | grains before surface treatment are in polyacrylic-acid sodium aqueous solution (Toa Gosei Co., Ltd. T-50 made into an active ingredient 0.001%). In the measurement of particle size and the like when pre-dispersed by an ultrasonic disperser, the surface treatment is performed after the particles satisfy the predetermined range described in the claims, thereby reducing changes in the particle size and the like before and after the surface treatment. In addition, after the particles and the surface treatment agent are mixed, the particles are dispersed using a dispersing device such as a wet pulverizer or an emulsifier / disperser (such as HG), and the particle size satisfies a predetermined range. In the case of manufacturing as described above, there is a tendency that the range of the particle size and the like after the surface treatment is dispersed is largely different before and after the surface treatment. Therefore, it is necessary to perform surface treatment in consideration of these.

  The surface-treated reinforcing material of the present invention obtained as described above is useful as a reinforcing material for silicone aqueous emulsions typified by adhesives, coating materials, sealing materials and the like. In other words, when the surface treatment reinforcing material of the present invention is used, physical properties such as film strength such as strength and elongation are not inferior to those when colloidal silica or silica sol is blended, and the amount used thereof can be reduced or not used. Adhesion and flexibility can also be improved.

  The amount of the surface treatment reinforcing material used in the present invention varies depending on its physical properties and use conditions and cannot be specified unconditionally. In many cases, it is 1 to 50 weight in terms of solid content in terms of solid content in silicone emulsion resin. %, Preferably 3 to 40% by weight, most preferably 5 to 30% by weight. The surface treatment reinforcing material of the present invention may be used in combination with a commercially available filler or reinforcing agent.

  There is no particular limitation on the silicone emulsion resin to which the surface treatment reinforcing material of the present invention can be applied. Specifically, hydroxyl group-containing (di) organopolysiloxane, alkenyl group-containing (di) organopolysiloxane, alkoxyl group-containing (Di) organopolysiloxane, hydroxyl group and alkenyl group-containing (di) organopolysiloxane, hydroxyl group and alkoxyl group-containing (di) organopolysiloxane, emulsion polymer of cyclic organosiloxane and functional group-containing organotrialkoxysilane, Siloxane block copolymer composed of dimethylsiloxane units and monophenylsiloxane units, siloxane polymer composed of vinylmethylsiloxane units and hydroxyl group-containing siloxane units, Si-H-containing organopolysiloxane Examples thereof include hydrogen siloxane blocked with an acid group, a reaction product of an organoalkoxysilane and an acid anhydride, and these can be used alone or in combination of two or more as required. Further, these are used in combination with one or more organic resins such as alkyd resin, epoxy resin, acrylic resin, acrylic silicone resin, phenol resin, fluororesin, polyester resin, chlorinated rubber resin, urethane resin, melamine resin and the like. It is also possible.

  In addition, the silicone emulsion blended with the surface treatment reinforcing material of the present invention includes, as other components, water, surfactant, curing catalyst, filler, reinforcing agent, adhesion-imparting agent, thickener, colorant, pH It is possible to arbitrarily add an antifoaming agent, etc., such as a regulator, preservative, and penetrant.

The surfactant here is for stably emulsifying the resin, and any of an anionic surfactant, a nonionic surfactant, and a cationic surfactant can be used. It is necessary that the surface treatment agent used for the reinforcing material is the same or nonionic. When different systems are used, the surfactant and the surface treatment agent may react to reduce the emulsion stability of the emulsion.
Anionic surfactants include alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, fatty acid salts, rosinates, dialkyl sulfosuccinates, hydroxyalkane sulfonates, alkane sulfonates, alkyl sulfate esters. , Alkylene sulfate ester salts, polyoxyethylene alkylaryl ether sulfates and the like.
Nonionic surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene alkyl aryl ethers such as polyoxyethylene nonylphenyl ether, and polyoxyethylene such as polyoxyethylene sorbitan monopalmitate. Examples include polyoxyethylene-added nonionic surfactants such as sorbitan fatty acid esters, oxyethylene-oxypropylene copolymers, polyhydric alcohol fatty acid partial esters, polyoxyethylenated polyhydric alcohol fatty acid esters, etc. it can.
Examples of the cationic surfactant include aliphatic amine salts, quaternary ammonium salts, alkylpyridinium salts and the like.
These may be used alone or in combination of two or more as required. Among these, alkylbenzene sulfonate, polyoxyethylene-added nonionic surfactant, and alkyl sulfate are particularly preferable. The amount of the surfactant used is not particularly limited. However, if the amount is insufficient, emulsification becomes difficult or the emulsion stability decreases, which is not preferable. On the other hand, if the amount is excessive, the curability and weather resistance of the film may be impaired, or the coating film In order to cause whitening of the resin and eventually cause deterioration of the cured film, it is preferably used in the range of 1 to 40% by weight, more preferably 2 to 30% by weight, in terms of solid content of the emulsion resin. .

  The curing catalyst is blended for crosslinking and curing the components of the silicone emulsion and is not particularly limited. Specifically, dibutyltin dilaurate, dibutyltin dioctate, dioctyltin dilaurate, dioctyltin diacetate, octylic acid Examples thereof include organic acid metal salts such as tin, zinc stearate, zinc octylate, zinc acetate and iron octylate, and amine compounds such as n-hexylamine and guanidine. These may be used alone or as needed. Used in combination of more than one species. The amount of the curing catalyst used is not particularly limited, but when it is insufficient, it cannot be cured sufficiently and the film strength is reduced, and when it is excessive, the remaining curing catalyst decreases the physical properties of the film. It is preferably used in the range of 0.01 to 10% by weight, more preferably 0.1 to 5% by weight.

The filler is represented by calcium carbonate / calcium phosphate / magnesium hydroxide / clay / mica / aluminum oxide / quartz / titanium dioxide / iron oxide, zinc oxide, and the reinforcing agent is colloidal silica, silica sol, Carbon black and the like can be exemplified, and those dispersed in water and those dispersed in a non-aqueous system can be used, but considering the stability of the emulsion, silica sol dispersed in water is preferable. Moreover, these are used individually or in combination of 2 or more types as needed.
These fillers can be used arbitrarily according to the intended use, and have a feature that high solid differentiation can be easily obtained by blending in a large amount. In many cases, it is preferably 0 to 150% by weight, more preferably 0 to 100% by weight in terms of solid content relative to the solid content of the emulsion resin, but there is no problem even if it is not used.
Further, since the reinforcing agent is blended for the purpose of imparting strength properties to the cured film, it may be used by blending the surface treatment reinforcing material of the present invention, but for improving the emulsion stability of the emulsion. It is preferably used in the range of 0 to 50% by weight, more preferably 0 to 30% by weight, based on the solid content of the emulsion resin.

  The adhesion-imparting agent is a component for improving the flexibility and adhesiveness of the film, and can be arbitrarily used. There are no particular restrictions on the adhesion-imparting agent, and specific examples include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltriethoxysilane, and γ-glycidoxy. Propylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-trimethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-methyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyl- Triethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-methyldiethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, N-cyclohexyl-γ-aminopropyltrimethoxysilane, γ-morpholinopropylmethyldimethoxysilane, etc. Can, they are used singly or in combination of two or more, if necessary. The amount of the adhesion-imparting agent is not particularly limited, but if it is excessive, the film becomes too hard or the flexibility is lowered, so that it can be used in the range of 0 to 20% by weight relative to the solid content of the silicone emulsion. Preferably, it is 0 to 10% by weight.

  Any thickening agent can be used as long as it can be used as a viscosity thickening agent for improving the stability of the silicone emulsion. Specifically, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxy Celluloses such as propylmethylcellulose and carboxymethylcellulose, polysaccharides such as guar gum and locust bean gum, animal proteins such as gelatin and casein, soluble starches, alginic acids, polyvinyl alcohol, and sodium polyacrylate Can be illustrated. Nonionic urethane block copolymers can also be used, which are associative to the emulsion particles and further improve the stability of the emulsion by forming a very uniform network of emulsion and thickener. These may be used alone or in combination of two or more as required. The amount of the thickener used is not particularly limited, but if it is excessive, the weather resistance of the cured film tends to decrease, and it is preferably used in the range of 0 to 10% by weight relative to the solid content of the emulsion. Preferably it is 0 to 5% by weight.

If necessary, the color can be adjusted by further including a colorant such as a pigment or a dye. Although it does not specifically limit as a pigment which can be used, for example, organic pigments, such as carbon black, quinacridone, naphthol red, cyanine blue, cyanine green, hansa yellow, inorganics, such as titanium oxide, barium sulfate, a petite, complex metal oxide The pigments are good, and these are used alone or in combination of two or more as required. The dispersion method of the pigment may be a commonly performed dispersion method, but a method of adding a pigment base in which the pigment has been dispersed in advance to the emulsion is preferable. In this case, a dispersion aid, a coupling agent, a wetting agent, a viscosity control agent, etc. May be included. In addition, the dye that can be used is not particularly limited, for example, azo, anthraquinone, indicoid, sulfide, triphenylmethane, xanthene, alizarin, acridine, quinoneimine, thiazole, methine, Nitro dyes and nitroso dyes can be exemplified, and these may be used alone or in combination of two or more as required.
The amount of the colorant used is not particularly limited because the colorability varies depending on the type of the colorant. However, when the amount is excessive, the durability of the cured film tends to decrease, and the amount of the colorant is 0 with respect to the solid content conversion of the whole emulsion composition. It is preferably used in the range of ˜40% by weight, more preferably 0 to 30% by weight.

As the pH adjuster, the appropriate pH range varies depending on the surfactant to be used, but it cannot be generally stated. However, when the surfactant to be used is an anionic surfactant, it is not particularly limited as long as it is an acidic substance. However, a strong acid having a low pH in a small amount is preferable, and examples thereof include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, alkyl sulfuric acid, alkylbenzene sulfonic acid, polyoxyethylene alkyl ether sulfuric acid, and the like. Used in combination with more than one species. The amount of the pH adjusting agent to be added may be an amount such that the pH of the emulsion is in the range of 1.0 to 7.0, and is preferably an amount such that the pH is 2.0 to 7.0.
Conversely, when the surfactant used is a cationic surfactant, it may be an alkaline substance, such as an alkali metal hydroxide such as potassium hydroxide, sodium hydroxide or lithium hydroxide, water Alkaline earth metal hydroxides such as calcium oxide and barium hydroxide, alkali metal carbonates such as potassium carbonate and sodium carbonate, ammonia, tetraammonium oxide, monomethylamine, monoethylamine, monopropylamine, monobutylamine, monopentanamine , Amines such as dimethylamine, diethylamine, trimethylamine, triethanolamine, ethylenediamine and the like, and these may be used alone or in combination of two or more as required. The amount of the pH adjusting agent to be added may be an amount such that the pH of the emulsion is in the range of 7.0 to 13.0, and is preferably an amount that results in a pH of 7.0 to 12.0.

  In addition to the above components, antiseptics, penetrants, etc., antifoaming agents, antibacterial agents, antioxidants, antistatic agents, ultraviolet absorbers, antifungal agents, etc. are also adversely affected by the effects of the present invention. Can be included within the range that does not give.

  The method for obtaining a silicone emulsion using each component as described above is not particularly limited as long as the apparatus used in this step is generally an emulsifier or a disperser. For example, a batch such as a homogenizer Such as continuous emulsifiers such as type emulsifiers, pipeline homomixers, colloid mills, fine flow mills, and optimizers; high-pressure emulsifiers such as microfluidizers and nanomizers; membrane emulsifiers such as membrane emulsifiers; Examples thereof include an ultrasonic emulsifier such as a vibration emulsifier and an ultrasonic homogenizer. The method of emulsifying using these machines can be illustrated, and the mixing order of each component during emulsification is not particularly limited.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, comparative examples, and application examples, but these do not limit the present invention. In the following description, “%” and “part” mean “% by weight” and “part by weight” unless otherwise specified.
Tables 1 and 2 show the surface treatment agents used, Table 3 shows the surfactants used, and Table 4 summarizes the physical properties of the surface treatment reinforcing materials obtained in the examples and comparative examples.

Example 1
The lime milk having a specific gravity of 1.060 is adjusted to 13 ° C., carbonic acid gas (27% CO ₂ ) of 30 liter / min is conducted per 1 kg of calcium hydroxide to conduct a carbonation reaction, and the system PH is 10.0. The carbonation reaction was stopped when Then, the calcium carbonate water suspension whose BET specific surface area is 11 m < ² > / g was obtained by age | cure | ripening for 3 days in the temperature range of 40-60 degreeC. Since the pH of the obtained calcium carbonate aqueous suspension is as high as 11.0, carbon dioxide gas is conducted to adjust the pH to 7.0, and then the calcium carbonate aqueous suspension is press-dehydrated, dried and pulverized for no treatment. Calcium carbonate powder was used. This calcium carbonate powder was put into a he-shell mixer (Mitsui Mining Co., Ltd.), and the treatment agent 1 shown in Table 1 was added to 1% with respect to the calcium carbonate solid content, and then mixed and stirred. The surface treatment calcium carbonate of Example 1 was obtained.
The obtained surface-treated calcium carbonate has a BET specific surface area Sw: 10.0 m ² / g, a thermal loss As per unit specific surface area As: 0.94 mg / m ² , a weight cumulative 50% average particle diameter Dxs 50: 1.10 μm, The cumulative total weight Dys of the particle diameter exceeding 5 μm was 6.5%, and the sharpness index Smr was 2.61.

Example 2
The lime milk having a specific gravity of 1.060 is adjusted to 13 ° C., carbonic acid gas (27% CO ₂ ) of 30 liter / min is conducted per 1 kg of calcium hydroxide to conduct a carbonation reaction, and the system PH is 10.0. The carbonation reaction was stopped when Then, the calcium carbonate water suspension whose BET specific surface area is 11 m < ² > / g was obtained by age | cure | ripening for 3 days in the temperature range of 40-60 degreeC. Since the pH of the obtained calcium carbonate aqueous suspension was as high as 10.5, after passing carbon dioxide and adjusting the pH to 7.0, the calcium carbonate aqueous suspension was press-dehydrated and the solid content was 61%. It was a press cake. To this press cake, the treatment agent 1 shown in Table 1 is added so as to be 1% with respect to the solid content of calcium carbonate, a predetermined amount of water is added, and a high-speed lab disper (manufactured by Special Machine Industries Co., Ltd.) Was used to obtain a surface-treated calcium carbonate slurry of Example 2.
The obtained surface-treated calcium carbonate slurry has a solid content concentration of 52.5%, a BET specific surface area Sw: 10.0 m ² / g, a thermal loss per unit specific surface area As: 0.99 mg / m ² , and a cumulative weight of 50%. The average particle diameter Dxs50 was 0.88 μm, the cumulative particle weight Dys of the particle diameter exceeding 5 μm was 5.5%, and the sharpness index Smr was 2.25.

Example 3
The surface-treated calcium carbonate slurry obtained in Example 2 was wet-ground using Dinomill (KD-1.4A: manufactured by Shinmaru Enterprise Co., Ltd.) as the secondary pulverization to obtain the surface-treated calcium carbonate slurry of Example 3. It was.
The obtained surface-treated calcium carbonate slurry has a solid content concentration of 52.5%, a BET specific surface area Sw: 10.5 m ² / g, a thermal loss per unit specific surface area As: 0.94 mg / m ² , and a cumulative weight of 50%. Average particle diameter Dxs50: 0.65 μm, cumulative particle weight Dys of particle diameter exceeding 5 μm: 0.2%, sharpness index Smr: 1.51.

Example 4
The surface-treated calcium carbonate slurry obtained in Example 3 was dried with a spray dryer (Ogawara Processing Machine Co., Ltd., high-speed disk type spray dryer L-8 type) to obtain the surface-treated calcium carbonate of Example 4. .
The obtained surface-treated calcium carbonate has a BET specific surface area Sw: 10.5 m ² / g, a heat loss per unit specific surface area As: 0.94 mg / m ² , and a weight cumulative 50% average particle diameter Dxs50: 0.68 μm. The cumulative weight Dys with a particle diameter exceeding 5 μm was 0.3%, and the sharpness index Smr was 1.53.

Comparative Example 1
The calcium carbonate aqueous suspension obtained in Example 1 was subjected to surface treatment with 2% commercial beef tallow fatty acid soap (Marcel soap manufactured by NOF Corporation) based on the solid content of calcium carbonate, dehydrated, dried and crushed for comparison. The surface-treated calcium carbonate of Example 1 was obtained.
The obtained surface-treated calcium carbonate has a BET specific surface area Sw: 8.8 m ² / g, a heat loss per unit specific surface area As: 1.82 mg / m ^{2, a} 50% cumulative weight average particle diameter Dxs50: 4.56 μm, The cumulative weight Dys of the particle diameter exceeding 5 μm was 25.5%, and the sharpness index Smr was 3.82.

Example 5
The lime milk having a specific gravity of 1.060 is adjusted to 13 ° C., carbonic acid gas (27% CO ₂ ) of 30 liter / min is conducted per 1 kg of calcium hydroxide to conduct a carbonation reaction, and the system PH is 10.0. The carbonation reaction was stopped when Then, the calcium carbonate water suspension whose BET specific surface area is 25 m < ² > / g was obtained by age | cure | ripening for 1 day in the temperature range of 40-60 degreeC. Since the pH of the obtained calcium carbonate aqueous suspension is as high as 10.5, the carbon dioxide gas was passed through to adjust the pH to 7.0, and then the calcium carbonate aqueous suspension was press dehydrated to obtain a solid content of 57%. It was a press cake. To this press cake, the treatment agent 1 shown in Table 1 is added so as to be 2% with respect to the solid content of calcium carbonate, a predetermined amount of water is added, and a high-speed lab disper (manufactured by Special Machine Industries Co., Ltd.) Was used to obtain a surface treated calcium carbonate slurry of Example 5.
The obtained surface-treated calcium carbonate slurry has a solid content concentration of 45.4%, a BET specific surface area Sw: 25 m ² / g, a heat loss per unit specific surface area As: 0.78 mg / m ² , and an average particle weight of 50%. Diameter Dxs50: 1.68 μm, cumulative particle weight Dys of particle diameter exceeding 5 μm: 9.8%, sharpness index Smr: 2.63.

Example 6
The surface-treated calcium carbonate slurry obtained in Example 5 was wet-ground using a dynomill (KD-1.4A: manufactured by Shinmaru Enterprise Co., Ltd.) as a secondary pulverization to obtain the surface-treated calcium carbonate slurry of Example 6. It was.
The obtained surface-treated calcium carbonate slurry has a solid content concentration of 45.4%, a BET specific surface area Sw: 27 m ² / g, a heat loss per unit specific surface area As: 0.73 mg / m ² , and an average particle weight of 50%. The diameter Dxs50 was 0.36 μm, the cumulative particle weight Dys of the particle diameter exceeding 5 μm was 0.1%, and the sharpness index Smr was 1.55.

Example 7
The surface-treated calcium carbonate slurry obtained in Example 6 was dried with a spray dryer (Ogawara Processing Machine Co., Ltd., high-speed disk type spray dryer L-8 type) to obtain the surface-treated calcium carbonate of Example 7. It was. The obtained surface-treated calcium carbonate has a BET specific surface area Sw: 27 m ² / g, a heat loss per unit specific surface area As: 0.73 mg / m ² , and a 50% cumulative weight average particle diameter Dxs50: 0.47 μm, 5 μm. The cumulative weight Dys of the particle diameter exceeding 0.7% and the sharpness index Smr: 1.98.

Example 8
A calcium carbonate aqueous suspension having a BET specific surface area of 40 m ² / g was obtained in the same manner as in Example 5 except that the specific gravity of lime milk to be used was adjusted to 1.020. Since the pH of the obtained calcium carbonate aqueous suspension was as high as 10.0, the carbon dioxide gas was passed through to adjust the pH to 7.0, and then the calcium carbonate aqueous suspension was press-dehydrated and the solid content was 51%. It was a press cake. To this press cake, the treatment agent 1 shown in Table 1 is added so as to be 2% with respect to the solid content of calcium carbonate, a predetermined amount of water is added, and a high-speed lab disper (manufactured by Special Machine Industries Co., Ltd.) Was subjected to wet pulverization using Dynomill (KD-1.4A: manufactured by Shinmaru Enterprise Co., Ltd.) as secondary pulverization to obtain a surface-treated calcium carbonate slurry of Example 8.
The obtained surface-treated calcium carbonate has a BET specific surface area Sw: 42 m ² / g, a heat loss As per unit specific surface area As: 0.47 mg / m ² , and a 50% cumulative weight average particle diameter Dxs50: 0.10 μm, 5 μm. The cumulative weight Dys of the particle diameter exceeding 0.0% and the sharpness index Smr was 1.70.

Comparative Example 2
The lime milk having a specific gravity of 1.045 is adjusted to 13 ° C., and 1.5% citric acid is previously adjusted to a 10% aqueous solution with respect to the calcium hydroxide solid content, and the lime milk is immediately before the carbonation reaction. Mixed with. Carbon dioxide (30% CO ₂ ) of 30 liters / minute of calcium hydroxide was passed through this slurry to conduct a carbonation reaction. When the pH of the system reached 10.0, the carbonation reaction was stopped. Then, the calcium carbonate water suspension whose BET specific surface area is 45 m < ² > / g was obtained by ageing | curing | ripening for 3 days in the temperature range of 40-60 degreeC. Since the pH of the obtained calcium carbonate aqueous suspension was as high as 11.0, the carbon dioxide gas was passed through to adjust the pH to 7.0, and then the calcium carbonate aqueous suspension was press-dehydrated and the solid content was 52%. It was a press cake. To this press cake, the treatment agent 1 shown in Table 1 is added so as to be 5% with respect to the solid content of calcium carbonate, a predetermined amount of water is added, and a high-speed lab disper (manufactured by Special Machine Industries Co., Ltd.) Was used to obtain a surface-treated calcium carbonate slurry of Comparative Example 2.
The obtained surface-treated calcium carbonate slurry has a solid content concentration of 35.6%, a BET specific surface area Sw: 45 m ² / g, a heat loss per unit specific surface area As: 1.06 mg / m ² , and an average particle weight of 50%. Diameter Dxs50: 1.56 μm, cumulative particle weight Dys of particle diameter exceeding 5 μm: 13.3%, sharpness index Smr: 2.49.

Example 9
The surface-treated calcium carbonate slurry obtained in Comparative Example 2 was wet-ground using a dynomill (KD-1.4A: manufactured by Shinmaru Enterprise Co., Ltd.) as the secondary pulverization to obtain the surface-treated calcium carbonate slurry of Example 9. It was.
The obtained surface-treated calcium carbonate slurry has a solid content concentration of 35.6%, a BET specific surface area Sw: 48 m ² / g, a heat loss per unit specific surface area As: 0.99 mg / m ² , and an average particle weight of 50%. Diameter Dxs50: 0.07 μm, cumulative particle weight of particle diameter exceeding 5 μm Dys: 0.0%, sharpness index Smr: 1.65

Example 10
A surface-treated calcium carbonate slurry of Example 10 was obtained in the same manner as in Example 9 except that the surface treatment agent (treatment agent 1 described in Table 1) used in Example 9 was changed to 2%.
The obtained surface-treated calcium carbonate slurry has a solid content concentration of 30.3%, a BET specific surface area Sw: 48 m ² / g, a heat loss As per unit specific surface area: 0.41 mg / m ² , and an average particle weight of 50%. Diameter Dxs50: 0.07 [mu] m, particle diameter exceeding 5 [mu] m, cumulative weight Dys: 0.0%, sharpness index Smr: 1.67

Example 11
The surface-treated calcium carbonate slurry obtained in Example 10 was dried with a spray dryer (Ogawara Processing Machine Co., Ltd., high-speed disk type spray dryer L-8 type) to obtain the surface-treated calcium carbonate of Example 11. It was. The obtained surface-treated calcium carbonate has a BET specific surface area Sw: 48 m ² / g, a thermal loss As per unit specific surface area: 0.41 mg / m ² , and a 50% cumulative weight average particle diameter Dxs50: 0.36 μm, 5 μm. The cumulative weight Dys of the particle diameter exceeding 0.0% and the sharpness index Smr: 2.46

Comparative Example 3
A surface-treated calcium carbonate slurry of Comparative Example 3 was obtained in the same manner as in Example 9 except that the surface treatment agent (treatment agent 1 described in Table 1) was changed to 25%.
The obtained surface-treated calcium carbonate slurry has a solid content concentration of 31.5%, a BET specific surface area Sw: 43 m ² / g, a thermal loss As per unit specific surface area: 4.65 mg / m ² , and an average particle weight of 50%. Diameter Dxs50: 0.09 μm Cumulative weight of particle diameter exceeding 5 μm Dys: 0.0%, Sharpness index Smr: 1.83

Comparative Example 4
A surface-treated calcium carbonate slurry of Comparative Example 4 was obtained in the same manner as in Example 9 except that the surface treatment agent (treatment agent 1 described in Table 1) was changed to 0.15%.
The obtained surface-treated calcium carbonate slurry has a solid content concentration of 21.5%, a BET specific surface area Sw: 49 m ² / g, a heat loss per unit specific surface area As: 0.03 mg / m ² , and an average particle weight of 50%. Diameter Dxs50: 0.51 μm, particle diameter exceeding 5 μm, cumulative weight Dys: 8.4%, sharpness index Smr: 3.18

Example 12
Lime milk with a specific gravity of 1.045 is adjusted to 13 ° C., and 3% citric acid is adjusted in advance to a 10% aqueous solution with respect to the calcium hydroxide solid content. Mixed. Carbon dioxide (30% CO ₂ ) of 30 liters / minute of calcium hydroxide was passed through this slurry to conduct a carbonation reaction. When the pH of the system reached 10.0, the carbonation reaction was stopped. After that, wet pulverization was performed using dynomill (KD-1.4A: manufactured by Shinmaru Enterprise Co., Ltd.) to obtain a calcium carbonate aqueous suspension having a BET specific surface area of 58 m ² / g. Since the pH of the obtained calcium carbonate is as high as 11.0 water suspension, after passing carbon dioxide and adjusting the pH to 7.0, the calcium carbonate water suspension is press-dehydrated and the solid content is 50%. It was a press cake. To this press cake, the treatment agent 1 listed in Table 1 is added to 3% of the calcium carbonate solid content, and a predetermined amount of water is added, and a high-speed lab disper (manufactured by Tokushu Kika Kogyo Co., Ltd.) Was used to obtain a surface-treated calcium carbonate slurry of Example 12.
The obtained surface-treated calcium carbonate slurry has a solid content concentration of 32.6%, a BET specific surface area Sw: 57 m ² / g, a heat loss per unit specific surface area As: 0.49 mg / m ² , and an average particle weight of 50%. The diameter Dxs50 was 0.07 μm, and the cumulative weight Dys of the particle diameter exceeding 5 μm was 0.0%, and the sharpness index Smr was 1.67.

Example 13
Lime milk with a specific gravity of 1.045 is adjusted to 13 ° C., 10% citric acid is adjusted in advance to a 10% aqueous solution with respect to calcium hydroxide solids, and mixed with lime milk immediately before the carbonation reaction. did. Carbon dioxide (30% CO ₂ ) of 30 liters / minute of calcium hydroxide was passed through this slurry to conduct a carbonation reaction. When the pH of the system reached 10.0, the carbonation reaction was stopped. Then, the calcium carbonate water suspension whose BET specific surface area is 95 m < ² > / g was obtained by ageing | curing | ripening for 3 days in the temperature range of 40-60 degreeC. Since the pH of the obtained calcium carbonate is as high as 11.0 aqueous suspension, after passing carbon dioxide gas and adjusting the pH to 7.0, the calcium carbonate aqueous suspension was press-dehydrated and the solid content was 45%. It was a press cake. To this press cake, the treatment agent 1 shown in Table 1 is added so as to be 5% with respect to the solid content of calcium carbonate, a predetermined amount of water is added, and a high-speed lab disper (manufactured by Special Machine Industries Co., Ltd.) Was further pulverized, and wet pulverization was performed using dynomill (KD-1.4A: manufactured by Shinmaru Enterprise Co., Ltd.) as secondary pulverization to obtain a surface-treated calcium carbonate slurry of Example 13.
The obtained surface-treated calcium carbonate slurry has a solid content concentration of 25.2%, a BET specific surface area Sw: 100 m ² / g, a thermal loss As per unit specific surface area: 0.48 mg / m ² , and an average particle weight of 50%. The diameter Dxs was 0.06 μm, the cumulative particle weight Dys of the particle diameter exceeding 5 μm was 0.0%, and the sharpness index Smr was 1.83.

Example 14
The surface-treated calcium carbonate slurry obtained in Example 13 was dried with a spray dryer (Ogawara Processing Machine Co., Ltd., high-speed disk-type spray dryer L-8 type) to obtain the surface-treated calcium carbonate of Example 14. It was. The obtained surface-treated calcium carbonate has a BET specific surface area Sw: 100 m ² / g, a heat loss As per unit specific surface area As: 0.48 mg / m ² , and a 50% cumulative weight average particle diameter Dxs50: 0.53 μm, 5 μm. Cumulative weight Dys of particle diameter exceeding 0.3%, sharpness index Smr: 2.62.

Example 15
Lime milk with a specific gravity of 1.045 is adjusted to 13 ° C., 4% malic acid is adjusted in advance to a 10% aqueous solution with respect to the calcium hydroxide solid content, and mixed with lime milk immediately before the carbonation reaction. did. Carbon dioxide (30% CO ₂ ) of 30 liters / minute of calcium hydroxide was passed through this slurry to conduct a carbonation reaction. When the pH of the system reached 10.0, the carbonation reaction was stopped. After that, wet pulverization was performed using dynomill (KD-1.4A: manufactured by Shinmaru Enterprise Co., Ltd.) to obtain a calcium carbonate aqueous suspension having a BET specific surface area of 58 m ² / g. Since the pH of the obtained calcium carbonate is as high as 11.0 water suspension, after passing carbon dioxide and adjusting the pH to 7.0, the calcium carbonate water suspension is press-dehydrated and the solid content is 50%. It was a press cake. To this press cake, the treatment agent 1 shown in Table 1 is added so as to be 20% with respect to the solid content of calcium carbonate, and a predetermined amount of water is added, and a high-speed lab disper (manufactured by Special Machine Industries Co., Ltd.) Was used to obtain a surface-treated calcium carbonate slurry of Example 15.
The obtained surface-treated calcium carbonate slurry has a solid content concentration of 31.6%, a BET specific surface area Sw: 52 m ² / g, a heat loss per unit specific surface area As: 3.21 mg / m ² , and an average particle weight of 50%. The diameter Dxs50 was 0.09 μm, the cumulative particle weight Dys of the particle diameter exceeding 5 μm was 0.0%, and the sharpness index Smr was 1.65.

Examples 16-42
The surface-treated calcium carbonate slurries of Examples 16 to 42 were prepared in the same manner as in Example 8 except that the surface treatment agents 2 to 28 listed in Table 1 were changed. Various physical properties of the obtained surface-treated calcium carbonate slurry are shown in Table 4.

Examples 42-48
Except for adding 0.3% of the surfactants 1 to 6 listed in Table 2 to the treating agent 1 listed in Table 1 in the same manner as in Example 7, 48 surface treated calcium carbonate slurries were prepared. Various physical properties of the obtained surface-treated calcium carbonate slurry are shown in Table 4.

Comparative Example 5
Heavy calcium carbonate (Super # 2000 manufactured by Maruo Calcium Co., Ltd.) was charged into a he-shell mixer (Mitsui Mining Co., Ltd.), and the treatment agent 1 shown in Table 1 was 0.2% based on the calcium carbonate solid content. Then, the mixture was stirred and the surface-treated calcium carbonate of Comparative Example 5 was obtained.
The obtained surface-treated calcium carbonate has a BET specific surface area Sw: 2.2 m ² / g, a thermal loss As per unit specific surface area As: 0.91 mg / m ² , a 50% cumulative weight average particle diameter Dxs: 1.42 μm, The cumulative weight Dys of the particle diameter exceeding 5 μm was 18.6%, and the sharpness index Smr was 3.11.

Example 49
After adding treatment agent 1 listed in Table 1 to heavy calcium carbonate (Super # 2000, manufactured by Maruo Calcium Co., Ltd.) so that the solid content of calcium carbonate is 0.5%, a predetermined amount of water is added, Slurry using a high-speed lab disper (manufactured by Tokushu Kika Kogyo Co., Ltd.), and wet pulverization using a dyno mill (KD-1.4A: manufactured by Shinmaru Enterprise Co., Ltd.) as a secondary pulverization example 49 surface treated calcium carbonate slurries were obtained.
The obtained surface-treated calcium carbonate has a solid content concentration of 48.2%, a BET specific surface area Sw: 12.2 m ² / g, a thermal loss As per unit specific surface area: 0.41 mg / m ² , and an average weight accumulation of 50%. The particle diameter Dxs was 0.80 μm, and the cumulative particle weight Dys of the particle diameter exceeding 5 μm was 5.6%, and the sharpness index Smr was 2.43.

Example 50
After adding talc (Talc SWE made by Nippon Talc Co., Ltd.) so that the treatment agent 1 listed in Table 1 is 1.5% of talc, a predetermined amount of water is added, and a high-speed lab disper (specialized machine) (Manufactured by Kogyo Co., Ltd.), and further subjected to wet pulverization using dynomill (KD-1.4A: manufactured by Shinmaru Enterprise Co., Ltd.) as secondary pulverization. Obtained.
The obtained surface-treated talc has a solid content concentration of 30.2%, a BET specific surface area Sw: 25.5 m ² / g, a thermal loss As per unit specific surface area: 0.58 mg / m ² , and an average particle weight of 50%. Diameter Dxs: 0.62 μm, cumulative particle weight of particle diameter exceeding 5 μm Dys: 4.1%, sharpness index Smr: 2.66

Example 51
After adding clay (SMC clay manufactured by Sanyo Clay Industry Co., Ltd.) so that the treating agent 1 shown in Table 1 is 0.5% with respect to the clay, a predetermined amount of water is added, and a high-speed lab disper (special machine) The surface-treated clay slurry of Example 51 was further slurried using a dynomill (KD-1.4A: manufactured by Shinmaru Enterprise Co., Ltd.) as a secondary pulverization. Got.
The obtained surface-treated clay has a solid content concentration of 36.2%, a BET specific surface area Sw: 11.2 m ² / g, a thermal loss As per unit specific surface area: 0.44 mg / m ² , and an average particle weight of 50%. The diameter Dxs was 0.80 μm, the cumulative particle weight Dys of the particle diameter exceeding 5 μm was 5.8%, and the sharpness index Smr was 2.49.

Example 52
After adding mica (Mica powder A-11 manufactured by Yamaguchi Mica Industry Co., Ltd.) so that the treatment agent 1 shown in Table 1 was 0.5% with respect to mica, a predetermined amount of water was added, and a high-speed laboratory was added. Slurry was performed using Disper (manufactured by Tokushu Kika Kogyo Co., Ltd.), and further wet pulverized using Dino Mill (KD-1.4A: manufactured by Shinmaru Enterprise Co., Ltd.) as secondary pulverization. A surface-treated mica slurry was obtained.
The obtained surface-treated mica has a solid content concentration of 37.8%, a BET specific surface area Sw: 11.1 m ² / g, a thermal loss As per unit specific surface area: 0.55 mg / m ² , and an average particle weight of 50%. Diameter Dxs: 0.80 μm, particle diameter exceeding 5 μm, cumulative weight Dys: 5.9%, sharpness index Smr: 2.78

Example 53
After adding barium sulfate (Varifine BF-20 manufactured by Sakai Chemical Industry Co., Ltd.) so that the treating agent 1 shown in Table 1 is 2.0% with respect to barium sulfate, a predetermined amount of water is added. Then, slurrying is performed using a high-speed lab disper (made by Special Machine Industries Co., Ltd.), and further, wet pulverization is performed using a dyno mill (KD-1.4A: manufactured by Shinmaru Enterprise Co., Ltd.) as secondary pulverization. A surface-treated barium sulfate slurry of Example 53 was obtained.
The obtained surface-treated barium sulfate slurry has a solid content concentration of 27.2%, a BET specific surface area Sw: 32.6 m ² / g, a thermal loss As per unit specific surface area: 0.60 mg / m ² , and a cumulative weight of 50%. Average particle diameter Dxs: 0.26 μm, cumulative particle weight Dys of particle diameter exceeding 5 μm: 0.2%, sharpness index Smr: 1.93.

Example 54
Water, calcium hydroxide and 50% citric acid are mixed and stirred to prepare a precursor, and a liquid prepared by mixing 30% phosphoric acid and 45% KOH in advance is added to the precursor and stirred sufficiently. And then dehydrated to obtain a calcium phosphate cake having a solid content of 40%. To the calcium phosphate cake, the treatment agent 1 shown in Table 1 is added so as to be 5% based on the solid content of calcium phosphate, water is further added, and a high-speed lab disper (manufactured by Special Machine Industries Co., Ltd.) is used. Surface treatment was performed to prepare a surface-treated calcium phosphate slurry of Example 54.
The molar ratio of each component during the reaction was calcium hydroxide: citric acid: phosphate ion: alkali metal = 6.7: 1.0: 4.4: 3.00.
The obtained surface-treated calcium phosphate slurry has a solid content concentration of 15.2%, a BET specific surface area Sw: 120.2 m ² / g, a thermal loss per unit specific surface area As: 0.83 mg / m ² , and an average particle weight of 50%. Diameter Dxs: 0.09 μm, cumulative particle weight of particle diameter exceeding 5 μm Dys: 0.0%, sharpness index Smr: 1.27

Example 55
A surface-treated calcium phosphate slurry of Example 55 was obtained in the same manner as in Example 98 except that the molar ratio of each component during the reaction was changed as follows. The molar ratio of each component during the reaction was calcium hydroxide: citric acid: phosphate ion: alkali metal = 20.0: 1.0: 12.0: 3.0.
The obtained surface-treated calcium phosphate slurry has a solid content of 10.3%, a BET specific surface area Sw: 98.3 m ² / g, a thermal loss per unit specific surface area As: 1.53 mg / m ² , and an average particle weight of 50%. Diameter Dxs: 0.10 μm, particle diameter exceeding 5 μm, cumulative weight Dys: 0.0%, sharpness index Smr: 1.44

Example 56
The surface-treated calcium phosphate slurry obtained in Example 55 was dried with a spray dryer (manufactured by Ogawara Koki Co., Ltd.), a high-speed disk type spray dryer L-8 type, to obtain the surface-treated calcium phosphate slurry of Example 56.
The obtained surface-treated calcium phosphate has a BET specific surface area Sw: 96.4 m ² / g, a heat loss per unit specific surface area As: 1.58 mg / m ² , and a weight cumulative 50% average particle diameter Dxs: 0.11 μm, 5 μm. The cumulative particle weight Dys was 0.0% and the sharpness index Smr was 1.57.

Example 57
The surface-treated calcium phosphate slurry of Example 57 was obtained in the same manner as in Example 54 except that the molar ratio of each component during the reaction was changed as follows, and the treatment agent 1 was changed to 10% with respect to the solid content of calcium phosphate. It was. The molar ratio of each component during the reaction was calcium hydroxide: citric acid: phosphate ion: alkali metal = 1.0: 1.0: 0.66: 3.0.
The obtained surface-treated calcium phosphate slurry has a solid content concentration of 7.3%, a BET specific surface area Sw: 212.3 m ² / g, a heat loss per unit specific surface area As: 0.71 mg / m ² , and a weight cumulative average of 50%. Particle diameter Dxs: 0.53 μm, cumulative weight Dys of particle diameter exceeding 5 μm: 0.0%, sharpness index Smr: 1.89.

Example 58
Add 25% potassium phosphate to 20% calcium chloride, stir, heat at 150 ° C. for 12 hours in an autoclave, dehydrate and concentrate, then add treatment agent 1 listed in Table 1 to 3% with respect to calcium phosphate As a result, a calcium phosphate slurry of Example 58 was obtained.
The molar ratio of each component during the reaction was calcium hydroxide: phosphate ion = 1.0: 0.6.
The obtained surface-treated calcium phosphate slurry has a solid content concentration of 24.4%, a BET specific surface area Sw: 85.6 m ² / g, a thermal loss As per unit specific surface area: 0.56 mg / m ² , and an average weight accumulation of 50%. Particle diameter Dxs: 0.25 μm, cumulative weight Dys of particle diameter exceeding 5 μm: 0.0%, sharpness index Smr: 1.75.

Comparative Example 6
A commercially available tricalcium phosphate (β-TCP: manufactured by Taihei Chemical Sangyo Co., Ltd.) was adjusted to a solid content of 20%, and the treatment agent 1 shown in Table 1 was further treated with 1% to obtain the surface-treated calcium phosphate slurry of Comparative Example 6. Obtained.
The obtained surface-treated calcium phosphate slurry has a solid content concentration of 10.2%, a BET specific surface area Sw: 5.5 m ² / g, a thermal loss per unit specific surface area As: 2.21 mg / m ² , and a weight cumulative average of 50%. The particle diameter Dxs was 3.22 μm, and the cumulative weight Dys of the particle diameter exceeding 5 μm was 22.4%, and the sharpness index Smr was 2.31.

Example 59
To the commercially available tricalcium phosphate (manufactured by Taihei Chemical Sangyo Co., Ltd.), the treatment agent 1 shown in Table 1 is added so as to be 3% with respect to the solid content of calcium phosphate, and a high-speed lab disper (Special Machine Industries Co., Ltd. )) And wet pulverized as a secondary pulverization using DYNOMILL (KD-1.4A: manufactured by Shinmaru Enterprise Co., Ltd.) to obtain a surface-treated calcium phosphate slurry of Example 59.
The obtained surface-treated calcium phosphate slurry has a solid content concentration of 20.4%, a BET specific surface area Sw: 68.5 m ² / g, a heat loss per unit specific surface area As: 0.73 mg / m ² , and an average weight accumulation of 50%. Particle diameter Dxs: 0.91 μm, cumulative particle weight Dys of particle diameter exceeding 5 μm: 0.0%, sharpness index Smr: 1.41.

Example 60
To the commercially available tricalcium phosphate (made by Yoneyama Chemical Co., Ltd.), the treatment agent 1 shown in Table 1 was added so as to be 3% with respect to the solid content of calcium phosphate. )), And wet pulverization as a secondary pulverization using a homogenizer (LAB1000: manufactured by APV) to obtain a surface-treated calcium phosphate slurry of Example 60.
The obtained surface-treated calcium phosphate slurry has a solid content concentration of 22.2%, a BET specific surface area Sw: 58.5 m ² / g, a heat loss As per unit specific surface area: 0.86 mg / m ² , and a total weight of 50%. Average particle diameter Dxs: 2.60 μm, cumulative weight Dys of particle diameter exceeding 5 μm: 9.5%, sharpness index Smr: 1.67.

Comparative Example 7
A surface-treated calcium phosphate slurry of Comparative Example 7 was prepared in the same manner as in Example 54 except that the treatment agent 1 shown in Table 1 was added to 30% of the calcium phosphate solid content.
The obtained surface-treated calcium phosphate slurry has a solid content concentration of 23.2%, a BET specific surface area Sw: 92.6 m ² / g, a heat loss per unit specific surface area As: 4.85 mg / m ² , and an average particle weight of 50%. Diameter Dxs: 0.10 μm, particle diameter exceeding 5 μm, cumulative weight Dys: 0.0%, sharpness index Smr: 1.78.

Examples 61-66
The surface-treated calcium phosphate slurries of Examples 61 to 66 were prepared in the same manner as in Example 55 except that the treatment agents listed in Table 1 were changed to 2, 3, 4, 5, 12, and 13.
Various physical properties of the obtained surface-treated calcium carbonate slurry are shown in Table 4.

Examples 67-69
Examples 67 to 69 are the same as Example 54 except that 1% of surfactants 1, 4, and 5 listed in Table 3 are added to treatment agent 1 shown in Table 1 in addition to the solid content of calcium phosphate. A surface-treated calcium phosphate slurry was prepared.
Various physical properties of the obtained surface-treated calcium phosphate slurry are shown in Table 4.

In order to confirm the effect of the surface treatment reinforcing material of the present invention, the surface treatment reinforcing material obtained in the above examples and comparative examples, and colloidal silica (Snowtex C manufactured by Nissan Chemical Co., Ltd.) as a comparative example were used. Water-based paints and sealants were made and evaluated.
The applied physical properties have been confirmed to vary greatly depending on the number of blended parts of the surface treatment reinforcing material of the present invention. Sw (m ² / g), As (mg / m ² ), Dxs 50 (μm), Dys (%) ), The effects of the present invention can be maximized.

(Table 1) continued 1

(Table 4) continued 1

Application examples 1 to 69, comparative application examples 1 to 7
Coating materials were prepared using the surface treatment reinforcing materials obtained in Examples 1 to 69 and Comparative Examples 1 to 7, and physical properties were evaluated.

Comparative application example 8
As a comparative application example, a coating material was prepared using colloidal silica (Snowtex C, manufactured by Nissan Chemical Co., Ltd.), and physical properties were evaluated.

Preparation of emulsion A 498 g of octamethylcyclotetrasiloxane, 2 g of triethoxyphenylsilane, 50 g of 10% sodium lauryl sulfate, and 50 g of 10% sodium dodecylbenzene sulfonic acid were quantified in a 2 liter beaker and evenly mixed with a homomixer. After emulsification, 400 g of water was gradually added for dilution, followed by two passes with a 30 MPa high-pressure homogenizer to obtain a uniform white emulsion. This emulsion was transferred to a 2 liter three-necked glass flask equipped with a stirrer, reflux condenser, and thermometer, polymerized at 50 ° C for 24 hours, and then aged at 10 ° C for 24 hours. Emulsion A for coating agent was prepared by neutralizing pH to 6.2 with 12 g of 10% strength aqueous sodium carbonate solution. Emulsion A was an organopolysiloxane having a solid content of 45.4% and a terminal hydroxyl group blocked.

Preparation of coating material 10 to 50% of the reinforcing materials of Examples 1 to 69 and Comparative Examples 1 to 7 as active ingredients with respect to 100 parts by weight of the active ingredients of emulsion A obtained by the above polymerization, or Therefore, colloidal silica (Snowtex C manufactured by Nissan Chemical Co., Ltd.) is added as an active ingredient at 10%, γ-glycidoxypropyltrimethoxysilane as an active ingredient is 5% as an active ingredient, and dodecylbenzenesulfonic acid is used as a curing catalyst in advance. 2 parts of dibutyltin dilaurate having a concentration of 10%, which had been emulsified in Step 1, as an active ingredient, and water for adjusting the solid content were added while stirring to prepare a coating material. The prepared coating material was evaluated based on the following test method. The test results are shown in Table 5.

Coating Material Test Method The coating material prepared by the above method is poured into a plastic tray having a length of 15 cm, a width of 10 cm, and a height of 2 cm so that the weight after drying becomes 10 g. By leaving for 48 hours in an atmosphere of 23 ° C. and 50% relative humidity, a rubber-like sheet having a thickness of about 1 mm was obtained.
(Break strength, elongation, and hardness test)
About this rubber-like sheet, about breaking strength, elongation, and hardness, according to JISK6249, adhesiveness was investigated by the following method.
(Adhesion test)
In the adhesion test, a rubber sheet is made into a material by making a 1mm sheet by the same method on five kinds of materials such as mortar, glass, wood, steel plate and nylon cloth. Was evaluated in the following four stages by pulling in the opposite direction and observing the state of the rubber sheet and the material at the time of breaking or peeling.
◎ ・ ・ ・ Excellent adhesion, not interfacial peeling, but the rubber sheet breaks.
○: Interfacial peeling occurs, but considerable force is required for peeling.
Δ: Interfacial peeling occurs, but a slightly smaller force than the above ○ may be used for peeling.
X: Interfacial peeling and peeling with slight force.
In the tensile test, a dumbbell was created using a dumbbell-shaped No. 3 type and tested with AUTOGRAPH AG-1 (manufactured by Shimadzu Corporation). Moreover, the hardness test was done with the C-type hardness tester (made by ASKER) for durometer hardness tests.

(Table 5) continued 1

Application Examples 70 to 138, Comparative Application Examples 9 to 15 Water-based paints using the surface treatment reinforcing materials obtained in Examples and Comparative Examples were prepared, and physical properties were evaluated.

Comparative application example 16
As a comparative application example, a water-based paint was prepared using colloidal silica (Snowtex C manufactured by Nissan Chemical Co., Ltd.).

Preparation of water-based paint 10% to 50% of the surface treatment reinforcing materials of Examples 1 to 69 and Comparative Examples 1 to 7 as active ingredients with respect to 100 parts of methyltrimethoxysilane, or colloidal silica for comparison (Nissan Chemical Co., Ltd.) After adding 10% of Snowtex C) as an active ingredient, 50 parts of methanol and water with solid content adjustment were added and hydrolyzed at room temperature to obtain a 30% methanol solution of orgaosiloxane partial hydrolyzate. . 5 parts of polyoxyethylene nonylphenyl ether was added to 100 parts of this 30% methanol solution, and after stirring uniformly, methanol was distilled off using a rotary evaporator. 100 parts of water was added to this while stirring, and then a 30 MPa homogenizer was passed in two passes to obtain a silicone emulsion. Further, 10 parts of water dispersible titanium oxide (STS-01 manufactured by Ishihara Sangyo Co., Ltd.) was added as an active ingredient under stirring to prepare a water-based paint. The prepared water-based paint was evaluated based on the following test method. The test results are shown in Table 6.

Water-based paint test method (emulsification stability)
The prepared water-based paint was visually observed for the emulsified state after 1 month and after 3 months, and determined as follows.
○: Uniform white emulsion without aggregated precipitates Δ ... Uniform white emulsion, but with a small amount of aggregated precipitates.
X: Heterogeneous phase separation has occurred and there is an aggregated precipitate.
(Curing test)
The prepared water-based paint was applied to the surface of a glass plate with a bar coater coating machine so that the dry coating thickness was 1 μm, and allowed to stand in an atmosphere of a temperature of 23 ° C. and a relative humidity of 50% for 24 hours, and then 150 ° C. Rub the test piece obtained by drying and curing for 30 minutes with the tip of the claw, and visually observe the cured film after rubbing. A mark with a scar left was marked with x.
(Weather resistance test)
The prepared water-based paint was applied to the surface of the glass plate with a bar coater coating machine so that the dry coating thickness was 2 μm, and allowed to stand in an atmosphere of a temperature of 23 ° C. and a relative humidity of 50% for 24 hours, and then 150 ° C. The test piece obtained by drying and curing at 30 minutes was subjected to an accelerated weathering test for 500 hours using a sunshine super long life weather meter (WEL-SUN-HC manufactured by Suga Test Instruments Co., Ltd.), and then the state of the coating film Was observed, and the case where there was no change was indicated as ◯, the case where slight deterioration was observed was indicated as Δ, and the case where deterioration was observed was indicated as ×.
(Color difference ΔE value)
After 0 hour and 500 hours of the weather resistance test, the Lab value of the surface of the test piece was measured with a color difference meter (Color Meter ZE2000 manufactured by Nippon Denshoku) to calculate ΔE.
ΔE is defined by the following equation, where the Lab value before the weather resistance test is L ₀ , A ₀ , b ₀ , and the Lab value after the weather resistance test is L ₅₀₀ , A ₅₀₀ , b ₅₀₀ in the following equation. Is.
ΔE = {(L ₀ −L ₅₀₀ ) ² + (A ₀ −A ₅₀₀ ) ² + (b ₀ −b ₅₀₀ ) ² } ^0.5

(Table 6) continued 1

Application examples 139 to 207, comparative application examples 17 to 23
Sealing materials were prepared using the surface-treated reinforcing materials obtained in Examples and Comparative Examples, and physical properties were evaluated.

Comparative Application Example 24
As a comparative application example, a sealing material was prepared using colloidal silica (Snowtex C manufactured by Nissan Chemical Co., Ltd.), and physical properties were evaluated.

Preparation of emulsion B After mixing 2 parts of sodium lauryl sulfate and 70 parts of water with 100 parts of hydroxyl group-blocked dimethylpolysiloxane having 30 repeating siloxane units, 2 passes of a homogenizer with a pressure of 30 MPa, To this was added 1 part of dodecylbenzenesulfonic acid as a polymerization initiator, emulsion polymerization was performed at room temperature for 16 hours, pH was adjusted to 7 with an aqueous sodium hydroxide solution, and an emulsion of hydroxyl-terminated dimethylpolysiloxane having a molecular weight of about 200,000. B was obtained.

Preparation of Sealant Based on 100 parts by weight of Emulsion B obtained by the above polymerization, Examples 1 to 69 and Comparative Examples 1 to 7 are used as reinforcing ingredients, and 10% to 50% as active ingredients, or a comparative control. Therefore, 10% of colloidal silica (Snowtex C manufactured by Nissan Chemical Co., Ltd.) was added and mixed as an active ingredient, a small amount of diethylamine was added to adjust to pH 11, and the mixture was aged at room temperature for 2 weeks. To 100 parts of this aged emulsion composition, 1 part of γ-glycidoxypropyltrimethoxysilane previously dissolved in the same amount of water was added and mixed to increase the solid content of the emulsion. 0.5 parts of sodium acrylate and 100 parts of calcium carbonate having an average particle diameter of 1 μm (Nanox # 30 manufactured by Maruo Calcium Co., Ltd.) were added and mixed to prepare a sealing material. The produced sealing material was evaluated based on the following test method. The test results are shown in Table 7.

Sealing material test method (tensile adhesion test)
The created silicone sealant was subjected to a tensile adhesion test (H-type test) in accordance with JIS A 1439.
A mortar plate was used as the adherend, and the specimen was cured for 28 days in an atmosphere at a temperature of 23 ° C. and a relative humidity of 50%, and in an atmosphere of a temperature of 30 ° C. and a relative humidity of 50% for 14 days.
About the created test piece, 150% modulus, breaking strength, elongation, and adhesion state were measured with AUTOGRAPH AG-1 (manufactured by Shimadzu Corporation).
(After the follow-up test H-type tensile test)
In the above tensile strength test, the sample was fixed for 7 days in an atmosphere at a temperature of 23 ° C. and a relative humidity of 50% in the stretched state by 50%, and the breaking strength (residual stress) was measured in the same manner.

(Table 7) continued 1

As described above, the surface-treated reinforcing material for silicone emulsion of the present invention provides a silicone emulsion excellent in strength, elongation, adhesion to various substrates, and flexibility.
For example, when added to water-based coating materials, it provides water-based coating materials with excellent strength, elongation, and flexibility, as well as excellent adhesion to various substrates, and when added to water-based paints, emulsification stability The water-based paint excellent in property, curability and weather resistance can be provided, and when added to a sealant, a sealant excellent in strength, elongation and adhesion can be provided.

Claims (9)

A silicone emulsion comprising particles surface-treated with an organic surface treatment agent, satisfying the following formulas (1) to (5) and having a hardness value of 6 or less based on a 10-stage Mohs hardness tester Surface treatment reinforcement.
(1) 5 ≦ Sw ≦ 300 (m ² / g)
(2) 0.05 ≦ As ≦ 4.00 (mg / m ² )
(3) 0.02 ≦ Dxs50 ≦ 3.00 (μm)
(4) Dys ≦ 10 (wt%)
(5) 0 <Smr ≦ 3
Sw: BET specific surface area by nitrogen adsorption method (m ² / g) (single point measured value in NOV A4200 manufactured by Yuasa Ionics)
As: Heat loss per unit specific surface area calculated by the following formula (mg / m ² )
Amount of organic surface treatment agent (heat loss mg / g per gram of surface-treated reinforcing material at 200 to 500 ° C.) / Sw
Dxs50: 50% cumulative average particle diameter (μm) calculated from the large particle side in the particle size distribution in the diffraction formula (SALD-2000 manufactured by Shimadzu Corporation)
Dys: Cumulative weight (% by weight) of particle diameter exceeding 5 μm in particle size distribution
Smr: (Dxs10-Dxs90) / Dxs50 calculated particle sharpness index Dxs10: average particle size distribution in the laser diffraction formula (SALD-2000 manufactured by Shimadzu Corporation). Particle size (μm)
Dxs90: In particle size distribution in laser diffraction method (SALD-2000 manufactured by Shimadzu Corporation), cumulative weight 90% average particle diameter (μm) calculated from the large particle side The organic surface treatment agent is selected from (co) polymers of at least one monomer selected from [Group A1] and / or its alkali metal, alkaline earth metal, Al, Zn, ammonium, and amine. The surface treatment reinforcing material for silicone emulsion according to claim 1, wherein the at least one salt (X1) and / or an organic acid having a carboxyl group and an alkali metal (Z1) are used.
[Group A1]
(I) α, β unsaturated monocarboxylic acid,
(II) α, β unsaturated dicarboxylic acid,
(III) Sulfo group-containing monomer The organic surface treatment agent is a copolymer of at least one monomer selected from [Group A1] and at least one monomer selected from [Group A2], and / or an alkali metal thereof, 2. The surface-treated reinforcing material for silicone emulsion according to claim 1, wherein the surface-treated reinforcing material for silicone emulsion is at least one salt (X12) selected from alkaline earth metals, Al, Zn, ammonium, and amines.
[Group A1]
(I) α, β unsaturated monocarboxylic acid,
(II) α, β unsaturated dicarboxylic acid,
(III) Sulfo group-containing monomer [Group A2]
(A) (meth) acrylic acid alkyl ester, (b) (meth) acrylic ether having an alkoxy group, (c) (meth) acrylate having a cyclohexyl group, (d) α, β monoethylenically unsaturated hydroxy ester, (E) polyalkylene glycol mono (meth) acrylate, (f) vinyl ester, (g) vinyl aromatic, (h) unsaturated nitrile, (i) unsaturated dicarboxylic acid ester, (j) vinyl ether, (k) Conjugated diene (l) chain olefin (m) cyclic olefin   The organic surface treating agent is a (co) polymer obtained by sulfonating the (co) polymer according to claim 2, a copolymer obtained by sulfonating the copolymer according to claim 3, and / or an alkali thereof. Sulfonation comprising at least one salt selected from metal, alkaline earth metal, Al, Zn, ammonium, amine (X1S · X12S) and / or [Group A2] The (co) polymer and / or at least one salt (A2S) selected from alkali metals, alkaline earth metals, Al, Zn, ammonium, and amines. Surface treatment reinforcement for silicone emulsion.   The organic surface treatment agent is at least one selected from (X1), (X12), (X1S · X12S), (A2S), a surfactant, and / or its alkali metal, alkaline earth metal, Al The surface treatment reinforcing material for silicone emulsion according to claim 1, which is at least one salt (Y) selected from Zn, ammonium, and amine.   The particles are at least one inorganic particle selected from precipitated calcium carbonate, heavy calcium carbonate, calcium phosphate, gypsum, talc, clay, mica, barium sulfate, aluminum hydroxide, and aluminum silicate. The surface treatment reinforcing material for silicone emulsion according to claim 1.   The surface treatment reinforcing material for silicone emulsion according to any one of claims 1 to 6, wherein the silicone emulsion is an aqueous coating material.   The surface treatment reinforcing material for a silicone emulsion according to any one of claims 1 to 6, wherein the silicone emulsion is a water-based adhesive. The surface treatment reinforcing material for a silicone emulsion according to any one of claims 1 to 6, wherein the silicone emulsion is an aqueous sealing material.