KR20020007227A - Fine particle of aluminium hydroxide for filling resin and resin composition using the same - Google Patents

Abstract

PURPOSE: Provided are an aluminum hydroxide powder which is highly fillable in a resin with reducing viscosity and shortens the curing time when filled in thermosetting resin, and a resin composition using the aluminum hydroxide powder. CONSTITUTION: The aluminum hydroxide powder is characterized in that the composition ratio of: aluminum hydroxide powder(X) with a BET specific surface area of 1.0 m2/g or less and secondary particle size of 35-150 micro meter; aluminum hydroxide powder(Y) with a BET specific surface area of =1.0 m2/g or less and secondary particle size of 10-35 micro meter; and aluminum hydroxide powder(Z) with a BET specific surface area of 3.0 m2/g or less and secondary particle size of 0.5-10 micro meter, is enclosed by four points alpha, beta, gamma and delta in the three-component compositional diagram shown in figure 1 and also includes the peripheral line.

Description

Aluminum hydroxide powder for resin filling and resin composition using the same {FINE PARTICLE OF ALUMINIUM HYDROXIDE FOR FILLING RESIN AND RESIN COMPOSITION USING THE SAME}

The present invention relates to an aluminum hydroxide powder for resin filling used as flame retardant for plastics, rubber and the like, and a resin composition formed using the same.

Background Art Conventionally, aluminum hydroxide has been widely used as a filler for filling rubber and plastic. For example, thermoplastic resins, rubbers, and epoxy resins are used as colorant fillers for thermosetting resins such as unsaturated polyester resins and acrylic resins as flame retardants.

When aluminum hydroxide is used as a flame retardant, the more filling, the more flame retardant performance is improved, but if the filling amount is increased, the forming temperature is increased due to moldability or kneading torque rise, and aluminum hydroxide dehydrates and foams partly. have. In addition, the filling of the thermosetting resin also reduces the material cost by increasing the filling amount, but there is a problem that the molding workability is deteriorated and the curing speed is delayed.

In particular, resin compositions filled with unsaturated polyester resins or acrylic resins with aluminum hydroxide powder are artificial marbles, which are used in materials such as bus taps and kitchen counters, but exhibit a texture (weight) similar to that of natural marble. Must be filled with a large amount of aluminum hydroxide powder.

In order to solve such a problem, various techniques, for example, (1) a method of using a mixture of agglomerates having large primary particles or fine particles pulverized therein (Japanese Patent Publication No. 5-48782), ( 2) A method for obtaining aluminum hydroxide having a small specific surface area by pulverizing a fine particle or a limited amount of soda (Japanese Patent Publication No. 4-6648, Japanese Patent Publication No. 6-49573), and the like are disclosed. .

However, in the above (1), the granulation alone has the disadvantage of lowering the surface smoothness due to sedimentation during molding and lowering the molded body strength, and when used in combination with the fine particles, the curing time due to the increase of the specific surface area is long. There is a drawback to losing. Also in the case of (2), the increase in the specific surface area due to the pulverization and crushing of the aggregated particles has a long curing time, and when used alone, the particles are fine, so that the filling amount is limited.

Moreover, in order to improve the filling property with resin, surface treatment with fatty acid, a silane coupling agent, etc. is also frequently performed.

The present invention improves conventional aluminum hydroxide powders filled with resins such as plastics and rubbers under such circumstances, reduces the viscosity at the time of filling with resins, enables high filling, and is filled with thermosetting resins. In this case, an object of the present invention is to provide an aluminum hydroxide powder and a resin composition which can further shorten the curing time and further improve productivity.

The present inventors have conducted extensive studies to develop aluminum hydroxide having the above-described desirable properties, and as a result, at least a two-component blend (a binary system) of aluminum hydroxide powder having a secondary particle diameter and specific surface area present in a specific range, in particular, Preferably, the present inventors have found that the object can be achieved by three-component blending (ternary system), and have completed the present invention. That is, this invention provides the following invention.

FIG. 1 shows a three-element composition diagram of an aluminum hydroxide powder as an example of the present invention.

Fig. 2 shows a three-part composition diagram for aluminum hydroxide powder as an example of the present invention.

Fig. 3 shows a three-part composition diagram for aluminum hydroxide powder as an example of the embodiment.

(Explanation of the sign)

Composition ratio where α ---- X: Y: Z is 47.5: 25.0: 27.5

Composition ratio with β ---- X: Y: Z of 47.5: 50.0: 2.5

A composition ratio where γ ---- X: Y: Z is 82.5: 0.0: 17.5

Composition ratio where δ ---- X: Y: Z is 72.5: 0.0: 27.5

To measure the viscosity at 35 ° C. using a Brookfield viscometer when aluminum hydroxide powder was charged with 200 parts by weight of 100 parts by weight of unsaturated polyester resin (Ligorack 2004WM-2, manufactured by Showa Kobunshi Co., Ltd.). Aluminum hydroxide powder, which can be less than 200 poise, and 150 parts by weight of the powder is 100 parts by weight of other unsaturated polyester resin (polylite TP-123, manufactured by Dinib Ink Ink Chemical Co., Ltd.) and methyl ethyl ketone Viscosity measurement at 35 ° C. using a brookfield viscometer when filled with 2 parts by weight of oxide resin, the curing time until the viscosity can not be measured by curing the resin may be less than 20 minutes Aluminum hydroxide powder for resin filling, characterized by having.

(2) Aluminum hydroxide powder (X) having a BET specific surface area of 1.0 m 2 / g or less, its secondary particle diameter in the range of 35 to 150 μm, BET specific surface area of 1.0 m 2 / g or less, and its secondary particle diameter of 10 The mass composition ratio of aluminum hydroxide powder (Y) in the range of ˜35 μm, and aluminum hydroxide powder (Z) in which the BET specific surface area is 3.0 m 2 / g or less and the secondary particle diameter is in the range of 0.5 to 10 μm is determined. In the three-way composition diagram shown in FIG. 1 at 100 mass%, the point α (X: Y: Z = 47.5: 25.0: 27.5), the point β (X: Y: Z = 47.5: 50.0: 2.5), and the point γ ( X: Y: Z = 82.5: 0.0: 17.5) and point δ (X: Y: Z = 72.5: 0.0: 27.5), and are in the range of the mass composition ratio including the linear shape Aluminum hydroxide powder.

(3) Aluminum hydroxide powder (X) having a BET specific surface area of 1.0 m 2 / g or less and a secondary particle diameter of 35 to 150 µm, a BET specific surface area of 1.0 m 2 / g or less and a secondary particle diameter of 10 to The mass composition ratio of aluminum hydroxide powder (Y) in the range of 35 µm and aluminum hydroxide powder (Z) in which the BET specific surface area is 3.0 m 2 / g or less and the secondary particle diameter is in the range of 0.5 to 10 µm is 100. In the three-way composition diagram shown in FIG. 2 as mass%, point A (X: Y: Z = 50.0: 25.0: 25.0), point B (X: Y: Z = 50.0: 45.0: 5.0), and point C (X (Y: Z = 80.0: 0.0: 20.0), the point D (X: Y: Z = 75.0: 0.0: 25.0) is surrounded by four points and is in the range of the mass composition ratio including a shipboard Aluminum powder.

(4) The secondary particle diameter of the aluminum hydroxide powder (X) is in the range of 50 to 150 µm, the secondary particle diameter of the aluminum hydroxide powder (Y) is in the range of 10 to 25 µm, and the aluminum hydroxide powder (Z) The aluminum hydroxide powder as described in (2) or (3) whose secondary particle diameter is in the range of 0.5-8 micrometers.

(5) A resin composition containing the aluminum hydroxide powder according to any one of (1) to (4).

(6) The aluminum hydroxide powder, wherein the resin composition containing the aluminum hydroxide powder according to any one of (1) to (4) has a viscosity of less than 200 poise as measured at 35 ° C with a Brookfield viscometer. Resin composition comprising a.

(7) A resin composition comprising an aluminum hydroxide powder, wherein the resin composition containing the aluminum hydroxide powder according to any one of (1) to (4) is a resin composition for artificial marble formation.

(8) The resin composition containing the aluminum hydroxide powder according to any one of (1) to (4) contains at least one member selected from the group consisting of unsaturated polyester resins, acrylic resins, vinyl ester resins and epoxy resins. A resin composition containing aluminum hydroxide powder, characterized in that.

(9) A resin composition containing an aluminum hydroxide powder, wherein the resin composition containing the aluminum hydroxide powder according to any one of (1) to (4) is a cured resin composition.

Hereinafter, the present invention will be described in detail.

The aluminum hydroxide powder of the present invention is a resin composition in which 100 parts by weight of unsaturated polyester resin (Ligo Rack 204WM-2 manufactured by Showa Kobunshi Co., Ltd.) is filled with 200 parts by weight of aluminum hydroxide powder using a Brookfield viscometer. It is aluminum hydroxide powder which can be less than 200 poise in viscosity measurement at 35 degreeC, and 100 weight part of said other unsaturated polyester resins (polylite TP-123, the Dainippon Ink & Chemicals Co., Ltd. make). In a resin composition filled with 150 parts by weight of aluminum and 2 parts by weight of methyl ethyl ketone peroxide, the curing time until the viscosity cannot be measured by curing the resin at the time of viscosity measurement at 35 ° C. using a Brookfield viscometer is 20 Aluminum hydroxide powder for resin filling, characterized in that it has a characteristic that can be less than minutes.

Since the surface of the aluminum hydroxide powder is covered with many OH groups, the present inventors have found that when it is contained in a curable resin or the like, it inhibits the curing reaction of the curable resin and lengthens the curing reaction. The aluminum hydroxide powder which has was found.

The inventors of the present invention have made a careful study on the BET specific surface area, secondary particle diameter, filling composition, filling amount, and the like of aluminum hydroxide powder which does not significantly inhibit the curing reaction of the resin. The formulation ratio was found.

That is, the aluminum hydroxide powder of the present invention preferably has a secondary particle diameter of 35 to 150 µm, preferably 50 to 150 µm, and a specific surface area of 1.0 m 2 / g or less, preferably 0.5 by a nitrogen adsorption method (BET method). Granulated aluminum hydroxide powder (X) having a characteristic of m 2 / g or less, secondary particle diameter of 10 to 35 µm, preferably 10 to 25 µm, specific surface area of 1.0 m 2 / g or less, preferably 0.8 m 2 / g or less Neutral aluminum hydroxide powder (Y) having a characteristic of, and secondary particle diameter of 0.5 to 10㎛, preferably 0.5 to 8㎛, specific surface area of 3.0 m 2 / g or less preferably 2.0 m 2 / g or less In the case where the fine aluminum hydroxide powder Z is blended within a predetermined mass blending ratio, the viscosity is particularly reduced during resin filling, and the curing time during filling of the thermosetting resin is shortened.

The viscosity measurement at 35 degreeC by the Brookfield viscometer of this invention is performed based on JISK6901 and 4.4.1. That is, the rotor is rotated in the sample by the synchronous motor, and the viscosity resistance torque is measured by the spring balance. Specifically, the sample is placed in a 500 ml Vickers, and when the sample temperature reaches 35 ± 0.5 ° C., the rotor of the viscometer is immersed to the mark, fixed for about 5 minutes, and then the rotor is rotated for 3 minutes to read the value. Viscosity is obtained by multiplying the measured multiplier according to the rotor and rotation speed used.

The curing time until the viscosity measurement by the resin hardening of the present invention is impossible, after mixing 100 parts by weight of the unsaturated polyester resin of the present invention and 2 parts by weight of methyl ethyl ketone peroxide, the viscosity is measured by the above measuring method, The time until the rotation of the rotor stops and no viscosity measurement can be indicated.

Here, the range of the predetermined mass blending ratio is, for example, in the case of powder of ternary compounding, the granulated aluminum hydroxide powder (X), the neutral aluminum hydroxide powder (Y), and the fine aluminum hydroxide powder (Z) are all 100. In the three-way composition diagram shown in FIG. 1 as mass%, the point α (X: Y: Z = 47.5: 25.0: 27.5), the point β (X: Y: Z = 47.5: 50.0: 2.5), and the point γ (X The aluminum hydroxide powder surrounded by four points of Y: Z = 82.5: 0.0: 17.5) and point δ (X: Y: Z = 72.5: 0.0: 27.5) and blended within the range including the linear form (hereinafter, The compounding ratio is described in the order of X: Y: Z), More preferably, in the three-component composition ratio shown in Fig. 2, point A (50.0: 25.0: 25.0), point B (50.0: 45.0: 5.0), point It is surrounded by four points of C (80.0: 0.0: 20.5) and point D (75.0: 0.0: 25.0), and the mass compounding ratio within the range including the linear shape is good.

Viscosity is a Brookfield viscometer of a resin composition filled with 200 parts by mass of the aluminum hydroxide powder with respect to 100 parts by mass of a resin (for example, curable resin and unsaturated polyester resin). The viscosity at the time (unit is poise) is used.

In addition, hardening time is the resin composition which filled 150 mass parts of the aluminum hydroxide powders, and 2 mass parts of radical generating agents, such as a methyl ethyl ketone peroxide compound, with respect to 100 mass parts of curable resins (for example, unsaturated polyester resin). When viscosity is measured at 35 degreeC with a Brookfield viscometer, it can evaluate by the time until it becomes impossible to measure a viscosity by resin hardening.

Aluminum hydroxide used in the present invention is alumina trihydrate represented by the general formula _{Al 2 O 3 · 3H 2 O} , the purity is not particularly limited.

Granulated aluminum hydroxide powder (X) used in the present invention is agglomerated particles precipitated by the Bayer method, the secondary particle diameter is 35 ~ 150㎛, preferably 50 ~ 150㎛, measured by nitrogen adsorption method (BET method) The specific surface area is 1.0 m 2 / g or less, preferably 0.5 m 2 / g or less. If the secondary particle diameter is smaller than 35 µm, the neutral aluminum hydroxide powder (Y) to be described later is close to the particle diameter, so that the effect of reducing the viscosity at the time of particle blending is low. If the secondary particle diameter is larger than 150 mu m, the strength when the resin is filled is remarkably lowered, which is not preferable. If the specific surface area is larger than 1.0 m 2 / g, the curing time when the resin is filled is long, which is not preferable.

The secondary particle diameter refers to the particle diameter when the aluminum hydroxide powders aggregate to form aggregates, aggregates, or binders. The measurement of the secondary particle diameter uses a conventional sieve separation, an optical microscope, a coulter counter, and a leisure scattering diffraction method. Among these, it is preferable to use the laser scattering diffraction method especially.

Neutral aluminum hydroxide powder (Y) used in the present invention is not particularly limited to the type of aggregates of the granulated aluminum hydroxide powder (X), but decomposition or crushing to the primary particles using a known dry or wet grinding machine, or aluminum acid alkali After adding the said aggregate to a solution and making it slurry, it can obtain by melt | dissolving a part of aggregated particles and chemically decomposing and crushing to a primary particle by raising this slurry to 60-90 degreeC. The secondary particle diameter is 10 to 35 m, preferably 10 to 25 m, and the specific surface area is 1.0 m 2 / g or less, preferably 0.8 m 2 / g or less. If the secondary particle diameter is smaller than 10 mu m, the particle size of the aluminum hydroxide (Z) to be described later is close to the particle diameter, so that the effect of reducing the viscosity at the time of particle blending is low. If the secondary particle diameter is larger than 35 µm, the granulated aluminum hydroxide powder (X) described above is close to the particle diameter, so the effect of reducing the viscosity at the time of particle blending is low. Moreover, when specific surface area is larger than 1.0 m <2> / g, the hardening time at the time of filling with resin becomes long, and it is unpreferable.

The fine aluminum hydroxide powder Z used in the present invention is not specifically limited to agglomerates of agglomerated particles having a smaller secondary particle diameter than the granulated aluminum hydroxide powder X obtained by the via method, but a dry or wet grinding machine of the prior art is not particularly limited. The primary particles are decomposed and crushed, or the aggregate is added to an aluminum acid alkali solution to form a slurry, and then the slurry is heated to 60 to 90 ° C. to partially dissolve the aggregated particles and chemically decompose and destroy the primary particles. You can get it by The secondary particle diameter is 0.5 to 10 m, preferably 0.5 to 8 m, and the specific surface area is 3.0 m 2 / g or less, preferably 2.0 m 2 / g or less. If the secondary particle diameter is larger than 10 mu m, the neutral aluminum hydroxide powder (Y) described above is close to the particle diameter, so the effect of reducing the viscosity at the time of particle blending is low. If the secondary particle diameter is smaller than 0.5 mu m, the handling properties are significantly deteriorated, which is not preferable. Moreover, when specific surface area is larger than 3.0 m <2> / g, the hardening time at the time of filling with resin becomes long, and it is unpreferable.

The present invention also provides a resin composition containing aluminum hydroxide powder having the above characteristics. In addition, the resin composition containing the aluminum hydroxide powder of this invention should just be less than 200 poise when measured at 35 degreeC in a Brookfield viscometer, and is not restrict | limited to a composition. Any resin that can satisfy this viscosity condition can be used without limitation.

In the present invention, for example, when filling a resin with a tertiary aluminum hydroxide powder (powder containing three components of X, Y and Z), the resin is not limited as described above. And xylene formaldehyde resins, guanamine resins, diaryl phthalate resins, phenol resins, franh resins, polyimide resins, melamine resins, urea resins and the like. Preferably, unsaturated polyester resins, acrylic resins, vinyl ester resins, epoxy resins and the like are used.

The resin composition of the present invention is preferably a resin composition for artificial marble forming. For example, at least one selected from the group consisting of unsaturated polyester resins, acrylic resins, vinyl ester resins, and epoxy resins may be used as the resin for artificial marble forming. .

The compounding method of the aluminum hydroxide powder may be a conventionally known method such as an air blender, a V-type blender, a locking blender, a Henschel mixer, and is not particularly limited.

In addition, the aluminum hydroxide powder of this invention may use what surface-treated by the conventionally well-known method, It is not limited to the method.

The present invention also provides a cured product of the curable resin composition containing the aluminum hydroxide powder.

(Example)

Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to these Examples at all.

(Examples 1 to 5)

Granulated aluminum hydroxide powder (X) with a secondary particle diameter of 84 μm, specific surface area of 0.2 m 2 / g, neutral particle aluminum hydroxide with a secondary particle diameter of 16.5 μm, surface area of 0.5 m 2 / g (Y), secondary particle diameter of 5.9 μm, specific surface area At least two components of the granulated aluminum hydroxide powder (Z) of 1.6 m 2 / g were mixed for 10 minutes in a V-type blender at the composition ratio shown in Table 1 to obtain a particle-mixed aluminum hydroxide powder.

200 parts by mass of the above-mentioned powdered aluminum hydroxide powder and 100 parts by mass of a commercially available unsaturated polyester resin (Ligo Rack 2004WM-2, manufactured by Showa Kobunshi Co., Ltd.) were used to obtain a viscosity at 35 ° C. with a Brookfield viscometer. Measured. In addition, 100 parts by mass of commercially available unsaturated polyester resin (manufactured by Polylite TP-123 Dinib Ink & Chemicals Co., Ltd.) was added to 150 parts by mass of the above-mentioned powdered aluminum hydroxide powder, and a methyl ethyl ketone compound (Trigo 2 parts by mass of Knox 63 Kayakuangjo Co., Ltd. was added thereto, and the viscosity was continuously measured at 35 ° C. with a Brookfield viscometer to measure the time from start of measurement until measurement was impossible by resin curing, that is, curing time. did.

(Comparative Examples 1 to 12)

After mixing at least 2 components similar to Examples 1-5 by the composition ratio shown in Table 1, it evaluated similarly to Examples 1-5.

(Comparative Example 13)

Except for using neutral aluminum hydroxide powder (Y2) having a secondary particle diameter of 16.4 µm and a specific surface area of 1.4 m 2 / g, the same composition as in Example 1 was carried out using the particle-mixed aluminum hydroxide powder mixed in the same manner as in Example 1 and the other components. Evaluation was performed.

(Comparative Example 14)

Evaluation similar to Example 1 using the particle | grain composite aluminum hydroxide powder similarly mixed with Example 1 and a composition ratio and all other components except having used the granular aluminum hydroxide powder (Z2) of 6.4 micrometers of secondary particle diameters, and a specific surface area of 3.2m <2> / g. Carried out.

The mass composition ratio of the aluminum hydroxide powders (X, Y, Z) used in the said Example and the comparative example is shown in FIG.

As can be seen from Table 1, by blending aluminum hydroxide powder having a specific secondary particle diameter and specific surface area at a specific ratio, when filled in a resin such as plastic or rubber, the viscosity is reduced and high filling is possible. When the thermosetting resin is filled, the curing time is very short, and the productivity can be further improved. Therefore, the aluminum hydroxide powder shown in the present invention has a great industrial effect in the sense that the properties required for resin filling can be improved.

Claims (9)

To measure the viscosity at 35 ° C. using a Brookfield viscometer when aluminum hydroxide powder was charged with 200 parts by weight of 100 parts by weight of unsaturated polyester resin (Ligorack 2004WM-2, manufactured by Showa Kobunshi Co., Ltd.). Aluminum hydroxide powder, which can be less than 200 poise, and 150 parts by weight of the powder is 100 parts by weight of other unsaturated polyester resin (polylite TP-123, manufactured by Dinib Ink Ink Chemical Co., Ltd.) and methyl ethyl ketone Viscosity measurement at 35 ° C. using a brookfield viscometer when filled with 2 parts by weight of oxide resin, the curing time until the viscosity can not be measured by curing the resin may be less than 20 minutes Aluminum hydroxide powder for resin filling, characterized by having. Aluminum hydroxide powder (X) having a BET specific surface area of 1.0 m 2 / g or less and a secondary particle diameter of 35 to 150 μm, a BET specific surface area of 1.0 m 2 / g or less and a secondary particle diameter of 10 to 35 μm The mass composition ratio of the aluminum hydroxide powder (Y) in the range and the aluminum hydroxide powder (Z) in which the BET specific surface area is 3.0 m 2 / g or less and the secondary particle diameter is in the range of 0.5 to 10 µm is 100% by mass. In the ternary composition diagram shown in FIG. 1, the point α (X: Y: Z = 47.5: 25.0: 27.5), the point β (X: Y: Z = 47.5: 50.0: 2.5), and the point γ (X: Y: An aluminum hydroxide powder, which is surrounded by four points of Z = 82.5: 0.0: 17.5) and point δ (X: Y: Z = 72.5: 0.0: 27.5) and is in a range of mass composition ratio including a linear shape. Aluminum hydroxide powder (X) having a BET specific surface area of 1.0 m 2 / g or less and a secondary particle diameter of 35 to 150 μm, a BET specific surface area of 1.0 m 2 / g or less and a secondary particle diameter of 10 to 35 μm The mass composition ratio of the aluminum hydroxide powder (Y) in the range and the aluminum hydroxide powder (Z) in which the BET specific surface area is 3.0 m 2 / g or less and the secondary particle diameter is in the range of 0.5 to 10 µm is 100% by mass. In the ternary composition diagram shown in Fig. 2, point A (X: Y: Z = 50.0: 25.0: 25.0), point B (X: Y: Z = 50.0: 45.0: 5.0), and point C (X: Y: An aluminum hydroxide powder, which is surrounded by four points of Z = 80.0: 0.0: 20.0) and point D (X: Y: Z = 75.0: 0.0: 25.0) and is in a range of mass composition ratio including a linear shape. The secondary particle diameter of the aluminum hydroxide powder (X) is in the range of 50-150 micrometers, The secondary particle diameter of the aluminum hydroxide powder (Y) is in the range of 10-25 micrometers, An aluminum hydroxide powder, wherein the secondary particle diameter of the aluminum hydroxide powder Z is in the range of 0.5 to 8 µm. The resin composition containing the aluminum hydroxide powder in any one of Claims 1-4. The resin composition containing the aluminum hydroxide powder according to any one of claims 1 to 4 has a viscosity of less than 200 poise when measured at 35 ° C with a Brookfield viscometer, containing aluminum hydroxide powder. Resin composition. A resin composition containing an aluminum hydroxide powder, wherein the resin composition containing the aluminum hydroxide powder according to any one of claims 1 to 4 is a resin composition for artificial marble formation. The resin composition containing the aluminum hydroxide powder according to any one of claims 1 to 4 contains at least one member selected from the group consisting of unsaturated polyester resins, acrylic resins, vinyl ester resins, and epoxy resins. A resin composition containing aluminum hydroxide powder. The resin composition containing the aluminum hydroxide powder as described in any one of Claims 1-4 is hardening resin composition, The resin composition containing the aluminum hydroxide powder characterized by the above-mentioned.