JP2503486B2 - Granular flaky glass - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention relates to a granular flake-shaped glass, and in particular, by solving the problems such as scattering at the time of opening the package, and improving the fluidity. , A granular glass flake having improved dispersibility in a composite material.

[Prior Art] Flake shaped glass is a glass flakes having an aspect ratio (particle diameter / thickness) of about 2 to 1000, and has been conventionally used as a reinforcing material for thermosetting resins or thermoplastic resins and as a filling material for anticorrosion linings. Widely used for other purposes.

For example, if a mixture of thermosetting resin and flake-shaped glass is troweled or spray-coated on a metal surface, etc., the flake-shaped glass is oriented in the coating film almost parallel to the coating surface, and the weight of the resin is 30% by weight. % Flake glass is mixed, about 30 to 40 flake glass layers are formed per 1 mm thickness of the coating film. As a result, the path length through which the water, oxygen, etc., penetrates the coating film and reaches the surface of the base material such as a metal is significantly lengthened, and corrosion is prevented.

Further, in a composite material in which a glass flake is mixed with a thermoplastic resin, tensile strength, bending strength, bending elastic modulus, heat deformation temperature, dimensional accuracy, etc. are improved due to the two-dimensional reinforcing effect of the glass flake, and a barrier. Property is also given, and a resin having excellent properties can be obtained. Molded products of resin reinforced with such glass flakes have a molding shrinkage ratio in the resin flow direction that is substantially equal to the molding shrinkage ratio in the direction perpendicular to the resin flow. The warpage of the product is extremely small.

Flake glass is generally supplied to a user after being packed in a paper bag, a drum, or the like in which kraft paper and polyvinyl are laminated. When the glass flakes are added to and kneaded with the thermoplastic resin for use by the user in reinforcing the thermoplastic resin, the flaky glass packaging is opened and the entire amount is administered to the supply hopper. Or, weigh out a part of the package and put it in the hopper.

[Problems to be Solved by the Invention] Conventionally, the glass flakes supplied as products are glass flakes having a thickness of several μm and a size (particle diameter) of 10 to 4000 μm, and a moisture content of 0.2% by weight. % Or less, most of the glass flakes are separated without adhering to each other, and are very easily scattered.

For this reason, when the user opens the flake-shaped glass package and takes out a part or all of the package and administers it to a hopper, etc., the flake-shaped glass scatters and adheres to the clothes of workers, Workers may inhale and the working environment deteriorates. In addition, the glass may be mixed in another process, and the yield of the glass flake is also reduced.

Further, since the glass flakes have low fluidity, there is a problem that bridging easily occurs in the hopper and the orifice.

[Means for Solving Problems] The present invention solves the above-mentioned conventional problems, and is a glass flake used for reinforcing a thermoplastic resin, which is opened in a package and put into a hopper or the like. It is intended to provide flake-shaped glass which hardly scatters and has good fluidity.

The granular flake glass of the present invention is a granular flake glass obtained by granulating flake glass with a binder, and the flake glass is a flake glass for reinforcing thermoplastic resin, The amount of the binder used is, relative to 100 parts by weight of the glass flakes, 0.2 parts by weight or more,
And, the granule size is 44μm sieve residue and 90μm passing through 5000μm sieve.
It is characterized in that the size is such that it is not less than wt%.

 Hereinafter, the present invention will be described in detail.

The granular flake glass of the present invention is obtained by adding a binder to flake glass and granulating the glass. If the amount of the binder used is 0.2 parts by weight or more with respect to 100 parts by weight of the glass flake, the anti-scattering effect can be obtained. In order to obtain a sufficiently low scattering rate with a good scattering prevention effect, it is preferable to use 0.5 parts by weight or more of the binder with respect to 100 parts by weight of the glass flake. When the amount of the binder used is too much and exceeds 10 parts by weight with respect to 100 parts by weight of the glass flake, dispersion of the glass flake may occur when melt-mixed with a thermoplastic resin or the like. Therefore, in the present invention, the amount of the binder used is
The amount is 0.2 parts by weight or more, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the glass flakes.

The binder used is not particularly limited as long as it can bond the glass flakes to each other, but a binder that does not adversely affect the matrix resin or the like when the glass flakes are used is selected.

Specific examples of the binder that can be used include polyvinyl acetate, polyacrylate, polyvinylpyrrolidone, addition polymers of olefins such as (acid-modified) polyethylene, (acid-modified) polypropylene and copolymers thereof, polyurethane, polyurea. And polycondensation polymers such as (un) saturated polyester, nylon and epoxy resin, ring-opening polymers such as nylon 6 and polyethyloxazoline, and addition condensation products such as urea formalin resin and phenol formalin resin. Can be mentioned.

An example of a method of granulating flaky glass using these binders to form granules will be described.

First, the binder is dissolved in an appropriate organic solvent to prepare a binder solution. Alternatively, the emulsion is appropriately diluted with water to prepare a binding solution.

While the flaky glass is being fluidized by a mixer such as a rotary disk mixer, a predetermined amount of binder solution is added by spraying or the like, and the mixture is stirred and mixed.

Next, the granulated glass flakes are obtained by drying in a mixer or taking out the glass flakes from the mixer and drying.

Granular flake-shaped glass is subjected to a weak impact to pass through a punching screen having holes of about 1 to 5 mmφ or a sieve wire mesh of about 1 to 5 mm for sizing. Note that this step can be omitted.

If the particle size of the granular flake glass thus produced is too small, the scattering prevention effect is low, and conversely, if it is too large, the uniform dispersibility in the matrix resin decreases.
In the present invention, the granular flake-shaped glass is sized so that 90% by weight or more of it is 44 μm sieve residue and passes through 5000 μm sieve.

By the way, the flake-shaped glass is used for a composite material, in order to increase the adhesive force with the matrix resin and to uniformly disperse the silane-based coupling agent, the titanium-based coupling agent, the zirconia-based coupling agent, etc. May be surface treated with agents.

In this case, the flake-shaped glass which has been surface-treated with these coupling agents in advance and dried, may be further mixed with the above binder solution for granulation, but in order to reduce the treatment step, the binder solution It is advantageous to mix the coupling agent with the flaky glass. As a result, the coupling agent treatment and the scattering prevention treatment according to the present invention can be performed in a single operation, which is extremely advantageous.

As the coupling agent used for the surface treatment of the glass flakes, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β-
Aminoethyl-γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane,
Examples thereof include silane coupling agents such as vinyltriethoxysilane and γ-methacryloxypropyltrimethoxysilane, titanium coupling agents, zirconia coupling agents and the like.

In addition to these coupling agents, various antistatic agents,
It is also effective to use a lubricant and a film-forming substance together.

In addition, as the flake-shaped glass granulated in the present invention, a flake-shaped glass that is usually provided can be applied, and for example, an average thickness of 0.5 to 7.0 μm and an average particle size of 5 to 5
Those having a thickness of 1000 μm and an aspect ratio of about 2 to 1000 are suitable.

As the composition of the glass flakes, so-called non-alkali silicate glass such as E glass and alkali-containing silicate glass such as C glass can be used. Examples of the latter include, for example, 60 to 75% by weight of SiO ₂ , and 8
Mainly contains ~ 20% R ₂ O (alkali metal oxides such as Na ₂ O and K ₂ O) (however, SiO ₂ + R ₂ O is 75 to 90%), and in addition, for example, CaO, MgO, B Examples thereof include alkali-containing silicate glass containing one kind or two kinds or more of ₂ O ₃ , Al ₂ O ₃ , ZnO, Fe ₂ O _{3, and the} like.

 Table 1 shows examples of preferred glass compositions.

The granular flake glass of the present invention is supplied to the user after being enclosed in a conventionally used kraft bag for packaging, a drum can, an Ito can or the like.

The granular flake glass of the present invention is used as a reinforcing material for thermoplastic resins such as nylon, saturated polyester, polycarbonate, polyacetal, polyphenylene oxide, polyphenylene sulfide, polyvinyl chloride, polystyrene, polypropylene and polyethylene. When the thermoplastic resin containing the granular flake glass of the present invention is extrusion-molded or injection-molded, the flakes are uniformly dispersed in the resin matrix.

[Function] The flaky glass of the present invention is a large number of glass flakes granulated with a binder into granules, and is extremely unlikely to scatter.

Further, the granular shape improves the degree of compression and uniformity, greatly improves the fluidity, and prevents the bridge in the hopper and the orifice. Moreover, since the fluidity is good as described above, the dispersibility in the matrix resin is also improved, and the properties such as strength of the obtained composite material are remarkably improved.

[Examples] Examples and comparative examples will be described below.

Example 1 and Comparative Example 1 4 kg of flake-shaped glass (CCF-048 manufactured by Nippon Glass Fiber Co., Ltd.) was placed in a rotary disk mixer (capacity 20), and 200 g of a binder solution having the following composition was added with stirring. Stir-mix for 3 minutes. Then, the glass flakes were taken out and dried in a hot air dryer.

Binder solution Urethane emulsion (solid content 50%): 80% by weight Water: 20% by weight The obtained glass flakes were in the form of granules having an average particle diameter of 600 μm.

With respect to this granular flake glass (Example 1), the scattering rate, the uniformity and the degree of compression were examined by the following methods, and the results are shown in Table 2.

In addition, for comparison, various properties of the flake-shaped glass (average particle size 100 μm) used for granulation were also examined,
The results are also shown in Table 2.

Scattering rate (%) A cylindrical main pipe that has a charging port at the upper end and a saucer for falling objects at the lower end, extends horizontally from the side of this main pipe, and is connected to an intake device via a filter. Using a scatterer equipped with a branch pipe, 10 g of glass flakes were dropped from the inlet at the upper end while inhaling air from the branch pipe. If the flake-shaped glass has a high scattering property, the amount of the flake-shaped glass extracted from the branch pipe together with the intake air and falling to the tray at the lower end is small. The lower the scatterability of the glass flake, the more likely it falls to the pan. Therefore, the weight W (g) of the flaky glass dropped on the saucer was measured, and the scattering rate was calculated by the following formula.

Uniformity 40% particle size on integrated screen (R ₁ ) and 90% particle size on integrated screen (R ₂ ) are calculated. Was calculated. The larger this value is, the wider the particle size distribution is, and the fluidity is generally lowered.

Compressibility (%) (Degree of Bulkiness) The volume density ρ _{1 in} a loosely packed state and the bulk density ρ ₂ in the case where tapping was added to this to make a dense packing were calculated by the following formula.

The degree of compaction is generally most closely related to the fluidity of the powder, and if the degree of compaction is greater than 20%, the fluidity is poor and a bridge is likely to occur.

From Table 2, the granular flake glass of the present invention is
It is clear that they are extremely unlikely to scatter, and that they have good fluidity and hardly cause bridges.

[Effects of the Invention] As described in detail above, the granular flake glass of the present invention hardly scatters when it is taken out from the package or the like during use.

Therefore, the working environment is improved, the handleability is improved, and the problem of yield reduction due to scattering is solved.

Further, the granular shape improves the degree of compression and uniformity, greatly improves the fluidity, and prevents the bridge in the hopper and the orifice. Moreover, because of the good flowability, the dispersibility in the matrix resin is improved, and the properties such as strength of the obtained composite material are remarkably improved.

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Claims (4)

(57) [Claims] 1. A granular flake-shaped glass obtained by granulating flake-shaped glass with a binder, wherein the flake-shaped glass is a flake-shaped glass for reinforcing thermoplastic resin, and the amount of the binder used is , 0.2 parts by weight or more per 100 parts by weight of the glass flakes, and the size of the granules is 44 μm sieve residue and 90% by weight passes through the 5000 μm sieve.
Granular flake-shaped glass characterized by having a size as described above. 2. The amount of the binder used is flake-shaped glass 100.
Claim 1 wherein 0.5 to 10 parts by weight relative to parts by weight
The glass flake in the form of granules according to item. 3. The granular flake glass according to claim 1 or 2, wherein the binder is a thermoplastic resin. 4. The granular flake glass according to any one of claims 1 to 3, wherein the binder contains a coupling agent.