KR100955823B1 - Fluent and flowing compositions of acicular powder chemicals - Google Patents

Abstract

PURPOSE: An acicular powder chemical composition is provided to prevent a solid cake during a storage process, and a bridging at a hopper from generating without an expensive special equipment. CONSTITUTION: An acicular powder chemical composition is capable of improving the mobility and portability of the chemical composition while mixing the chemical composition with a polyolefin resin by flocking the chemical composition to have an average particle size over 30 micron through vibrating or compressing. The acicular powder chemical composition is either sorbitol acetal or xylitol acetal.

Description

FLUENT AND FLOWING COMPOSITIONS OF ACICULAR POWDER CHEMICALS}

The present invention relates to a needle-like powder chemical composition that improves fluidity and mobility by cross-linking the initial particles of the needle-like powder chemical by flocking.

Representative acicular structural chemicals include sorbitol acetal or xylitol acetal, which are used as a light-transmitting agent in polyolefin resin, and the initial particles of sorbitol acetal and xylitol acetal are ultrafine and have an average particle size of 15 μm. D ₉₇ is 30 µm or less, and bulk density 0.20 g / cm ³ It is as follows.

Representative examples of such sorbitol acetal or xylitol acetal are dibenzylidene sorbitol, 1,3: 2,4-bis-O- (benzylidene) -D-sorbitol, 1,3: 2,4-bis-O -(p-methylbenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (p-ethylbenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- ( p-isopropylbenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (2,4-dimethylbenzylidene) -D-sorbitol, 1,3: 2,4-bis-O -(3,4-dimethylbenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (3,5-dimethylbenzylidene) -D-sorbitol, 1,3: 2,4-bis -O- (2,4,5-trimethylbenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (p-chlorobenzylidene) -D-sorbitol, 1,3-O-benzyl Liden-2,4-O- (2,4-dimethylbenzylidene) -D-sorbitol, 1,3-O- (2,4-dimethylbenzylidene) -2,4-O-benzylidene-D-sorbitol , 1,3-O-benzylidene-2,4-O- (3,4-dimethylbenzylidene) -D-sorbitol, 1,3-O- (3,4-dimethylbenzylidene) -2,4- O-benzylidene-D-sorbitol and the like.

Sorbitol acetal or xylitol acetal, which is a needle-like powder chemical added to increase light transmission of a polyolefin resin, has been widely known and used for a long time in the plastic art.

The known art is described in US Pat. No. 4,016,118, Dizenzylidene sorbitol, US Pat. No. 4,314,039, di (alkylbenzylidene) sorbitol, US Pat. No. 4,371,645, di-substituted with one or more chlorine or bromine. Acetal sorbitol], [US Pat. No. 4,532,280, di (methyl or ethyl-substituted benzylidene) sorbitol], [US Pat. No. 4,845,137, dibenzylidene sorbitol derivatives with one or more sulfur containing substituents], [US patent No. 4,954,291, benzaldehyde substituted with dimethyl or trimethyl and sorbitol diacetal or xylitol diacetal distributions made unsubstituted benzaldehyde, US Pat. No. 5,049,605, Bis with substituents forming carbocycling 3,4-dialkylbenzylidene) sorbitol], [US Patent No. 3,721,682], [UK Patent Application GB 2,115,405A], [Japanese Patent Application Publication No. 85-157213 / 26], [Japanese Patent Application Publication No. 88-130662 / 19, incorporated herein by this reference.

The needle-like powder compound is usually stored in a hopper-type storage tank and then conveyed by a pipe (pipe) and a feed screw installed in the pipe to add to the polyolefin resin. However, in general, the needle-like powder compound is poor in mobility and fluidity, so that supply is not smooth, and thus, it cannot be quantitatively added. In order to compensate for these disadvantages, high-cost special facilities are installed as follows, or are mixed with other additives in granule masses, or foreign substances are added as additives to increase fluidity and mobility.

Japanese Patent Application Laid-Open No. 94-145431 and Korean Patent Registration No. 10-0183364 describe a method of improving the solubility in polyolefin resin by further ultrafine particles of powder of acicular-structure powder chemicals. However, in the case of ultrafine particulate needle powder chemicals, bridging occurs in a pipe or hopper through which the powder is moved, and the ultrafine particulate powder powder chemicals are mucus (strong adhesion between powders) during storage. And adhesiveness, the fluidity and mobility are inferior and there is a tendency to agglomerate to form a hard cake, which causes a big problem in operation. In addition, the effect is increased to be uniformly dispersed in the polyolefin resin, but is formed in the form of a cake is not uniformly mixed, there is a problem in the meterability and operability.

As a solution to this problem, there is a method of installing expensive special equipment, but it is uneconomically determined in the industry.

It is provided in US Pat. No. 6,673,856 and US Pat. No. 6,245,843 as a method of increasing the fluidity by being pre-mixed with other additives into pellets or granules to be provided to a polyolefin production facility. There is provided a method and apparatus for producing granular additives by mixing and compressing the additives of the additives with a carrier / binder.

However, in the case of adding other additives, the work utilization width is lowered due to the fixed use ratio between the additives, and there are problems such as product quality deterioration due to other additives, and compounding costs are additionally generated.

In addition, sorbitol acetal or xylitol acetal may be coated with an organic lubricant to improve fluidity (Korean Patent No. 2003-0049512), or higher fatty acids may be coated on a surface of a diacetal particle (Japanese Patent Publication No. 89-423, Japan). Japanese Patent Application Laid-Open No. 89-126352) and a method of coating a diacetal powder surface with carboxylic acid amide (Japanese Patent Publication No. 96-245843), but the melting point of the coating agent is relatively low or is stored due to secondary crystallization. Aggregation by fusion and the like is likely to occur, and no significant improvement in fluidity or mobility is found.

The present invention, which is invented to solve the above problems, generates bridging in a pipe or hopper in which acicular-structure powder chemicals are moved, or is viscous and sticky during storage, so that the cake and fluidity are not formed to form a hard cake. In order to improve, do not install expensive special equipment (equipment) to inject needle structure powder chemical into polyolefin resin, and do not mix with other additives into pellet or granules in advance, and add additives (solvent, organic lubricant) , Silica (SiO ₂ ) of hydrophilic powder, higher fatty acids, etc.) to improve the fluidity and mobility of the needle-like powder chemicals.

Needle structure powder chemical composition of the present invention to improve the fluidity and mobility of the present invention,

In the needle-shaped powder chemical composition for improving the fluidity and mobility of the needle-shaped powder chemical when the polyolefin resin and the needle-shaped powder chemical are mixed, the needle-shaped powder has a physical particle size of the average particle size. It is characterized by improving the fluidity and mobility by the floc (FLOCK) to be 30㎛ or more, the physical method uses any one or more of the method of vibration or compression or compression.

The average particle size is preferably 50 μm or more, and in the case of 100 μm or more, a lot of treatment costs and time are required, and production efficiency is lowered.

The acicular powder chemical is sorbitol acetal or xylitol acetal, specifically dibenzylidene sorbitol, 1,3: 2,4-bis-O- (benzylidene) -D-sorbitol, 1,3: 2 , 4-bis-O- (p-methylbenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (p-ethylbenzylidene) -D-sorbitol, 1,3: 2,4 -Bis-O- (p-isopropylbenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (2,4-dimethylbenzylidene) -D-sorbitol, 1,3: 2, 4-bis-O- (3,4-dimethylbenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (3,5-dimethylbenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (2,4,5-trimethylbenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (p-chlorobenzylidene) -D-sorbitol, 1, 3-O-benzylidene-2,4-O- (2,4-dimethylbenzylidene) -D-sorbitol, 1,3-O- (2,4-dimethylbenzylidene) -2,4-O-benzyl Liden-D-sorbitol, 1,3-O-benzylidene-2,4-O- (3,4-dimethylbenzylidene) -D-sorbitol, 1,3-O- (3,4-dimethylbenzylidene) Any one of -2,4-O-benzylidene-D-sorbitol, or a mixture of two or more thereof. All.

The flocked needle-like powder chemical is characterized in that d ₉₇ is 100 μm or more, and the density is 0.3 g / cm 3 or more.

Flocked needle-like powder chemical composition by crosslinking needle-like powder chemical in a physical manner as described above collides with polyolefin resin or pre-blend when mixed (mixed) with polyolefin resin To be evenly distributed.

In addition, it saves costs for special equipment (devices) in which needle-shaped powder chemicals are bridging in moving pipes or hoppers or aggregated into viscous and tacky adhesives during storage, so that no hard cake is formed. It is possible to do not mix with other additives into pellets or granules beforehand, so that the working range can be widened and further compounding cost can be saved.

In addition, there is an advantage that can increase the purity of the mixture by not adding an additive of the foreign material in order to improve the fluidity and mobility of the needle-like powder chemicals.

The terms or words used in this specification and claims are not to be construed as being limited to their ordinary or dictionary meanings, and the inventors may appropriately define the concept of terms in order to best describe their invention. It should be interpreted as meaning and concept corresponding to the technical idea of the present invention based on the principle that the present invention.

Therefore, the embodiments described in the specification and the drawings shown in the drawings are only the most preferred embodiment of the present invention and do not represent all of the technical content of the present invention, various modifications that can be replaced at the time of the present application It should be understood that there may be equivalents and variations.

As a result of research to solve the problem of fluidity and mobility, the ultrafine initial particles (average particle size is 15㎛ or less, d ₉₇ 30) produced during the synthesis and manufacture of the transparentizing agent, a needle-like powder chemical Μm or less, Bulk Density 0.20g / cm ³ or less) Flock by crosslinking the initial particles by various physical methods such as vibration, compression, or compression, so that the average particle size is 30㎛ or more, d ₉₇ Is 100 µm or more, and the bulk density is 0.30 g / cm 3 or more.

The Flocked needle-like powder chemical is blended into a polyolefin resin to produce a product that increases transparency without FISH EYES and bubbles, and the bulk density is 0.30 g at 0.20 g / cm 3 or less. It is changed to more than / cm 3 to reduce the volume (see FIG. 11) and to provide excellent properties of fluidity and mobility during process injection and transfer to polyolefin resins or during preparation of premixes (Master Batch, NDB, etc.).

Flocked needle-like powder chemicals that collide with the polyolefin resin during polyolefin resin blending automatically disperse and are dispersed evenly.

The initial particles produced during the synthesis of the needle-like powder chemical (composition), the transparentizing agent, are needle-shaped as shown in FIG. 1 and the average particle size is 15 μm or less, d ₉₇ 30 μm or less, and the density (Bulk Density). ) Less than 0.20 g / cm3 of transportability, bridging occurs in pipes or hoppers, and because they have mucus (strong adhesion between the powders) and tackiness during storage, they are inferior in fluidity and aggregate to form a hard cake It tends to cause a big problem in operation (see Figs. 7 and 9).

The present invention provides additional special properties for needle-like powder chemicals with an average particle size of 15 µm or less, d ₉₇ 30 µm or less, and bulk density of 0.20 g / cm 3 or less, by various physical methods such as vibration, compression, and compression. Compactness of particles of transparent needles, which are pure acicular powder chemicals (compositions), without the addition of equipment, prior to pelleting or granulation of other additives, and without the addition of additives of other foreign matter characteristics. In order to improve the mobility and fluidity by cross-linking to FLOCK (see Figs. 8 and 10).

The average particle size is 30-100 μm, preferably 50-80 μm, in consideration of the aspects of production management and fluid mobility, such as energy cost and work time reduction, when physically crosslinking flocs.

d ₉₇ is 100-300 micrometers, and a density of 0.30-0.60 g / cm <3> is preferable.

Flocked needle-like powder chemicals (compositions) as shown in FIG. 4 have improved fluidity and transportability, so that bridging, adhesion, and cake formation do not occur during storage and transport (see FIGS. 8 and 10). In addition, when added to a polyolefin resin, FLOCK is automatically disassembled due to a collision with the polyolefin resin during compounding and is evenly dispersed in the resin to maximize workability and transparency effect.

In addition, the flocculated needle-like powder chemicals (compositions) may be reduced in volume due to changes in the bulk density, thereby reducing logistics costs and loading efficiency (see FIG. 11).

The acicular powder chemical is sorbitol acetal or xylitol acetal, specifically dibenzylidene sorbitol, 1,3: 2,4-bis-O- (benzylidene) -D-sorbitol, 1,3: 2 , 4-bis-O- (p-methylbenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (p-ethylbenzylidene) -D-sorbitol, 1,3: 2,4 -Bis-O- (p-isopropylbenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (2,4-dimethylbenzylidene) -D-sorbitol, 1,3: 2, 4-bis-O- (3,4-dimethylbenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (3,5-dimethylbenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (2,4,5-trimethylbenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (p-chlorobenzylidene) -D-sorbitol, 1, 3-O-benzylidene-2,4-O- (2,4-dimethylbenzylidene) -D-sorbitol, 1,3-O- (2,4-dimethylbenzylidene) -2,4-O-benzyl Liden-D-sorbitol, 1,3-O-benzylidene-2,4-O- (3,4-dimethylbenzylidene) -D-sorbitol, 1,3-O- (3,4-dimethylbenzylidene) Any one of -2,4-O-benzylidene-D-sorbitol, or a mixture of two or more thereof is used.

EXAMPLE

The needle-like powder chemicals, bis (p-methylbenzylidene) sorbitol (MDBS) and bis (3,4-dimethylbenzylidene) sorbitol (DMDBS), are flocculated by physical methods. The initial state before) and the state after FLOCK were compared.

(1) particle shape

Needle structure powder chemicals (sorbitol acetal or xylitol acetal) The shape of the initial particles and the shape of the particles that have been flocculated to improve fluidity and mobility are photographed using the measuring device Dongwon Systems Digital Multi Image Microscope "DW-BM". Measured.

(2) Average particle size

The initial particle size of the needle-shaped powder chemical composition (sorbitol acetal or xylitol acetal) powder particles and the average particle size (μm) after flocking, d ₉₇ (μm) are laser diffraction / scattering particle size distributions manufactured by MALVERN. It measured using the measuring apparatus "Mastersizer Micro Ver.2.18".

(3) Production of Representative Acicular Structural Powder Chemical Compositions (Sorbitol Acetal, Xylitol Acetal) and Average Particle Size (µm), d ₉₇ (µm) and Density (Bulk Density, g /) after FLOCKization Cm 3) comparison result

 division Average particle (㎛) d ₉₇ (μm) Bulk Density (g / cm 3) Average Range Average Range Average Range Bis (p-methylbenzylidene) sorbitol Initial particle 10 4 to 6 20 19-21 0.18 0.16 ~ 0.19 FLOCK 55 43-73 201 179 ~ 224 0.42 0.35-0.50 Bis (3,4-dimethylbenzylidene) sorbitol Initial particle 10 7-16 31 28-34 0.20 0.19-0.21 FLOCK 50 45-64 197 188-220 0.41 0.36 ~ 0.49

(4) fluidity and mobility test

 Average particle size (㎛ d ₉₇ (μm)  Apparent density (g / cm3)  Fluidity and Mobility Test Fluidity and Mobility Test Results Stirring tank Feed screw 5 or less below 10 0.18 or less X X Bad below 10 30 or less 0.20 or less △ X Bad 20 or less 100 or less 0.25 or less △ △ Bad 30 or more More than 100 0.30 or more ○ ○ Good 50 or more More than 150 0.35 or more ○ ○ Good More than 70 More than 200 0.40 or more ○ ○ Good

 Remarks: Explanation:

      Defective X-Obstacle to fluidity and mobility due to large deposits of needle-like powder chemicals when observed

△ Medium-In case of observation, small amount of needle-like powder chemical adheres, which may interfere with fluidity and mobility.

○ Good-When there is very small amount of needle-like powder chemical attached during observation, but it does not cause problems in fluidity and mobility

1 is a photographic representation (40 times magnified) of an initial particle shape drawing of a needle-like powder chemical composition (sorbitol acetal, xylitol acetal).

FIG. 2 is a photographic representation (100-fold magnification) of the initial particle shape of a needle-shaped powder chemical composition (sorbitol acetal, xylitol acetal).

FIG. 3 is a photographic representation (400-fold magnification) of the initial particle shape of a needle-shaped powder chemical composition (sorbitol acetal, xylitol acetal).

FIG. 4 is a drawing substitute photograph (40 times magnified) after FLOCKization of the needle-like powder chemical composition (sorbitol acetal, xylitol acetal). FIG.

FIG. 5 is a drawing substitute photograph (100 times magnified) after FLOCKization of a needle-like powder chemical composition (sorbitol acetal, xylitol acetal). FIG.

FIG. 6 is a drawing substitute photograph (400 times magnified) after FLOCKization of acicular structure chemical composition (sorbitol acetal, xylitol acetal).

Figure 7 is a picture of the tank propeller substitute after the initial particle process of the needle-like powder chemical composition (sorbitol acetal, xylitol acetal).

Figure 8 is a substitute picture for the tank propeller drawing after the process of the needle-shaped powder chemical composition (sorbitol acetal, xylitol acetal) FLOCKization.

Figure 9 is a photograph of the transfer line screw diagram after the initial particle process injection of the needle-like powder chemical composition (sorbitol acetal, xylitol acetal).

10 is a photograph of the transfer line screw after the process injection after needle-shaped powder chemical composition (sorbitol acetal, xylitol acetal) FLOCKization.

FIG. 11 is a photograph showing the difference in apparent density after FLOCK and initial grains of acicular powder chemical composition (sorbitol acetal, xylitol acetal). FIG.

Claims (5)

In the needle-like powder chemical composition for improving the fluidity and mobility of the needle-like powder chemical when mixing the polyolefin resin and needle-like powder chemical, By improving the flowability and mobility by flocculating the needle-shaped powder by any one or more of physical methods of vibration, compression or compression so that the average particle size is 30㎛ or more. Needle structure powder chemical composition. The method of claim 1, The needle-like powder chemical composition of the needle-like powder chemical composition to improve the fluidity and mobility, characterized in that sorbitol acetal or xylitol acetal. The method according to claim 1 or 2, The needle-shaped powder chemical, Dibenzylidene sorbitol, 1,3: 2,4-bis-O- (benzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (p-methylbenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (p-ethylbenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (p-isopropylbenzylidene) -D-sorbitol, 1 , 3: 2,4-bis-O- (2,4-dimethylbenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (3,4-dimethylbenzylidene) -D-sorbitol , 1,3: 2,4-bis-O- (3,5-dimethylbenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (2,4,5-trimethylbenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (p-chlorobenzylidene) -D-sorbitol, 1,3-O-benzylidene-2,4-O- (2,4-dimethyl Benzylidene) -D-sorbitol, 1,3-O- (2,4-dimethylbenzylidene) -2,4-O-benzylidene-D-sorbitol, 1,3-O-benzylidene-2,4- O- (3,4-dimethylbenzylidene) -D-sorbitol, 1,3-O- (3,4-dimethylbenzylidene) -2,4-O-benzylidene-D-sorbitol, or 2 A needle-like powder chemical composition with improved fluidity and mobility, characterized by mixing more than one species. The method of claim 1, Wherein the floc (FLOCK) needle structure powder chemicals d ₉₇ is a needle structure powder chemical composition for improving fluidity and mobility, characterized in that more than 100㎛. delete

Images