JPS5839176B2 - Inorganic additives for surface-modified organic materials - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to surface-modified inorganic additives for organic materials.

Inorganic substances have long been used as fillers, pigments, and reinforcing agents for polymers.

The surfaces of inorganic materials are hydrophilic in nature, so they are easily wetted by water and absorb water well.

However, the affinity between inorganic substances and polymers is inherently limited, and therefore, when polymers are highly loaded with inorganic substances, mechanical strength, especially impact strength, and processability are seriously impaired.

Furthermore, when an inorganic substance is dispersed in an organic liquid, there is a disadvantage that the dispersibility is generally poor.

In order to improve this inconvenience, the surface of the inorganic substance is prepared using the general formula % (where R is an aliphatic hydrocarbon group or aromatic hydrocarbon group having 1 to 12 carbon atoms, and R' is (methyl). A method of modifying with an organic aluminate represented by an acrylate group (n=1,2) (U.S. Pat. No. 3,905,93
Specification No. 6) has been proposed.

However, even with polymers filled with inorganic substances treated with the above-mentioned aluminates, mechanical strength such as impact strength and processability are not fully satisfied, and the above-mentioned aluminates are unstable against moisture. However, there are disadvantages such as restrictions on its use.

In view of the above circumstances, the present inventors have carried out intensive research to overcome such disadvantages, and have found that when an inorganic material is treated with a certain phosphorus-containing organic aluminate, the surface-modified organic material Even if the inorganic additive used in the polymer is highly loaded into the polymer, there is essentially no reduction in mechanical strength such as impact strength or processability, and the organic aluminate is stable against moisture. They discovered this and completed the present invention.

That is, the present invention refers to an organic group having the general formula 4 to 24 carbon atoms), B 0802R4, -08OR, or -0COR6, where R4 and R5 have 4 to 24 carbon atoms. Organic group, R6 represents an organic group having 2 to 50 carbon atoms.

) x+y+z=3, x=1.0~2.5, y=o~1
．． 0, z=0.5 to 1.5.

The present invention provides a surface-modified inorganic additive for organic substances that is treated with a phosphorus-containing organic aluminate represented by the following formula.

In carrying out the present invention, the general formula (wherein RI3 A 3 B 5 Z g X and y
(same as above) Impact strength etc. of a polymer molded body filled with a surface-modified inorganic additive for organic substances obtained by treating the surface of an inorganic substance with a phosphorus-containing organic aluminate expressed by The effect of slightly reducing the mechanical properties of the inorganic additive, or the same or more than that of the case without the additive, and the remarkable effect of minimizing the decline of the processability, or A remarkable effect of improving the dispersibility when dispersed in a medium is exhibited.

In the phosphorus-containing organic aluminate represented by the general formula (RIO)2Al(A)(B) used in the present invention, R1 is a hydrocarbon group having 1 to 8 carbon atoms, specifically methyl, ethyl
Alkyl groups such as n- and isopropyl, n-1iso-5ec= and t-butyl, amyl, hexyl, octyl, and 2-ethylhexyl, cyclic alkyl groups such as cyclopentyl and cyclohexyl, noaryl groups such as phenyl, benzyl, and tolyl, and vinyl groups. , aryl groups, etc., and particularly preferably an alkyl group having 3 to 5 carbon atoms is used.

R2 and R3 are organic groups having 4 to 24 carbon atoms, specifically alkyl groups such as butyl, amyl, hexyl, octyl, 2-ethylhexyl, decyl, dodecyl, and cyclic alkyl groups such as cyclopentyl and cyclohexyl. , phenyl, benzyl, tolyl, 5ec-hexylphenyl, dodecylphenyl, etc., or substituted with halo, amine, nitro, hydroxyl, carboxyl, epoxy ether, thioether, ester, cyano or hydroxy ether group, or substituted with oxygen, sulfur, nitrogen, etc. 4-2 containing heteroatoms in the chain
Examples include organic groups having 4 carbon atoms, and particularly preferred are alkyl groups having 8 to 16 carbon atoms.

Furthermore, B is -0802R4, -08OR, or -0CO
It is represented by R6, where R4 and R5 are organic groups having 4 to 24 carbon atoms, specifically alkyl groups such as butyl, amyl, hexyl, octyl, 2-ethylhexyl, dodecyl, phenyl, Examples include allyl groups such as tolyl, octylphenyl, and dotecylphenyl, and organic groups having 4 to 24 carbon atoms containing heteroatoms such as oxygen, sulfur, and nitrogen, and particularly preferably 8 to 24 carbon atoms.
An organic group having ~18 carbon atoms is used, furthermore R6 is an organic group having 2 to 50 carbon atoms,
Specifically, butyl, amyl, hexyl heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl hexadecyl heptadecyl octadecyl, nonadecyl, eicosyl,
Alkyl groups such as heneicosyl, tocosyl, trickle, and tetradecyl; cyclic alkyl groups such as cyclohexyl, cycloheptyl, and cyclooctyl; aryl groups such as phenyl and naphthyl; alkenyl groups such as vinyl, aryl, propenyl, hexenyl, dodecenyl, and hexadecenyl; , amino, nitrohydroxyl, carboxyl, epoxy, ether, 2 to 50 carbon atoms substituted with thioether, ester, cyano or hydroxyether groups, or containing heteroatoms such as oxygen, sulfur or nitrogen in the chain Among them, an alkyl group having 2 to 24 carbon atoms is particularly preferably used.

Also, x+y+2 is 3, 2 is 0.5-1.5, preferably 0.8-1.2, and X is 1.0-2.5, preferably 1.
．． 5-2.2, y=O-1.0, preferably 0-0.7
Indicates the range selected from.

If the range of the phosphorus-containing organic aluminate is outside the above range, a hydrophobic surface layer may not be sufficiently formed on the inorganic material, the compatibility between the inorganic material and the organic medium may become insufficient, or the surface of the inorganic material may be This is undesirable because it forms a molecular layer or wraps around the inorganic material, weakening the bond between the surface of the inorganic material and the organic continuous phase, and reducing the treatment effect.

Examples of the phosphorus-containing organic aluminate compounds of the present invention include: Organic aluminates represented by are preferred.

In the surface modification of an inorganic material using the phosphorus-containing organic aluminate of the present invention, the organic aluminate is used in an amount of at least o, i parts by weight or more, preferably 0.5 to 10 parts by weight, per 100 parts by weight of the inorganic material.

By modifying the surface of an inorganic substance with a phosphorus-containing organic aluminate, the reactive hydroxyl groups and/or adsorbed water present on the surface of the inorganic substance and the O of the phosphorus-containing organic aluminate can be removed.
A reaction occurs between the R, groups, and this reaction creates a bond between the inorganic material and the phosphorus-containing organic aluminate, and an organic hydrophobic surface layer is formed on the inorganic material. (molecular weight liquids or high molecular weight polymeric solids)), or the aggregated inorganic material is easily dispersed into individual particles, resulting in a homogeneous dispersion.

The inorganic material to be treated with the phosphorus-containing organic aluminate of the present invention must have reactive hydroxyl groups and/or adsorbed water on its surface.

Such inorganic substances include metals, clay, carbon black, calcium carbonate, barium sulfate, silica, mica, aluminum hydroxide, γ-alumina, magnesium hydroxide, calcium silicate, aluminum silicate, talc, glass, quartz, Examples include vermiculite, asbestos, metal compounds of zinc, magnesium, lead, calcium, and aluminum, iron scrap, sulfur, titanium dioxide, iron oxide, zinc chromate, zinc oxide, and ultramarine blue.

The shape of these inorganic substances is not particularly limited;
Further, particles having a particle size of 1 mm or less, preferably 0.1 to 500 μm are used.

The surface modification of an inorganic substance using the phosphorus-containing organic aluminate of the present invention may be carried out by mixing the phosphorus-containing organic aluminate and the inorganic substance by a dry or wet method, but a wet method is more preferable from the viewpoint of uniform mixing.

As the solvent used in the wet treatment, hydrocarbons such as naphtha, hexane, heptane, octane, octene, benzene, toluene, and xylene, or chlorinated hydrocarbons such as trichloroethylene, which do not react with the organic aluminate, are used.

The mixing temperature is not particularly limited, but is selected such that a reaction between the inorganic material and the organic aluminate occurs.

In dry mixing, it is preferable to use, for example, a Henschel mixer, a Hobart mixer, a Waring blender, or the like.

The surface-modified inorganic additive for organic substances as described above can be used as a filler for polymers as it is, or it can be polymerized in the presence of the surface-modified inorganic additive for organic substances, or it can be used as a filler for polymers. , printing inks, paints, abrasives, pastes for electronic materials, rubber, paper manufacturing, etc. = However, when inorganic substances are used as fillers for polymers, phosphorus-containing organic aluminates, inorganic It is also possible to mix substances and polymers directly.

Polymers include low density polyethylene, high density polyethylene, polystyrene, polypropylene, vinyl chloride, AB
Polymers such as S, polycarbonate, nylon resin, unsaturated polyester resin, epoxy resin, phenol resin, and rubber can be used.

The surface-treated inorganic additive or organic aluminate containing the unmodified inorganic material and the polymer are generally kneaded at a temperature above the second order rearrangement temperature of the polymer, preferably when the polymer is in a low melt viscosity state. temperature, for example 160 to 230°C for low density polyethylene, 19°C for high density polyethylene
The best processability is obtained in the temperature range of 0 to 250°C, 220 to 260°C for polystyrene, and 220 to 290°C for polypropylene.

The temperature at which it is mixed with other polymers is well known to those skilled in the art and can be determined with reference to known literature.

In addition, various mixing devices are used for mixing, such as a two-roll mill,
Banbury mixer 1 double concentric screws, counter-rotating or co-rotating twin screws, ZSK type unirners, etc. are used.

The amount of surface-modifying inorganic additives used as fillers, pigments, and reinforcing materials varies depending on the type of polymer and the required physical properties of the final product, but in general, the amount of inorganic additives for organic materials per 100 parts of polymer varies. 10-700 parts of additive, preferably 2
0 to 250 parts can be used.

As a result of the surface-modified inorganic additive for organic substances of the present invention having improved affinity for polymers or organic media, (1) rheological properties of dispersions of inorganic substances dispersed in organic media, especially Since the viscosity reduction effect is remarkable, it becomes possible to increase the filling rate of the inorganic dispersion into the organic medium.

(2) Since the affinity between the inorganic substance and the polymer is improved, the strength and other physical properties of the polymer are improved.

(3) Since the dispersibility is improved, dispersion is performed effectively, and it becomes possible to reduce the amount of emulsifier, color vehicle, etc. required.

(4) High loading of the inorganic filler into the polymer becomes possible.

(5) High loading of inorganic fillers can improve the flame retardancy and incineration properties of the polymer.

(6) The mixing time required for dispersion is shortened.

Effects like this are distantly related.

The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited thereto.

Example 1 1 amount of aluminum hydroxide having an average particle size of 1 μ as shown in Table 1 (C3H70).

, AlC0P(OC8H1□)2)2.1 The amount of phosphorus-containing organic aluminate shown in Table 1 was used.

Add 100 parts by weight of high-density polyethylene to this, tri-blend with a Henschel mixer, and cycle 4k for 3 minutes.
The mixture was mixed and ground in a panburi mixer at a ram pressure of g/cyiY and a temperature of 90°C.

The melt index of this powder was measured.

The pulverized product was then injection molded at 200° C., 300 kg/crit, ram forward direction, 10 seconds and a mold closing time of 15 seconds.

The Charpy (notched) impact strength of the thus obtained molded plate was measured.

The results are shown in Table 1.

For comparison, publicly known (l-C3H70).

, 9k12 (0COC(CH3) =CH2)2.
Using an organic aluminate represented by t, the melt index and impact strength were measured in the same manner as above.

The results are also shown in Table 1 as Experiment No. 10-12.

Table 1 shows that aluminum hydroxide surface-modified with the phosphorus-containing organic aluminate of the present invention is extremely useful as a filler for high-density polyethylene. When using (
This is clear from Experiment No. 1O-12).

Also, experiment number 6 Containing organic alumina represented by The same results as in Table 1 were obtained.

Example 2 The amount of phosphorus-containing organic aluminate shown in Table 2 was added to the amount of calcium carbonate shown in Table 2 having an average particle size of 1.5 μm and mixed uniformly.

100 parts by weight of low-density polyethylene was added to the above mixture, triblended using a Henschel mixer, mixed using a two-roll mill at a temperature of 170°C, pulverized, and then press-molded at 170°C.

The tensile strength, modulus, and elongation of the thus obtained molded plate were measured.

The results are shown in Table 2.

Table 2 shows that the low-density polyethylene filled with calcium carbonate whose surface has been modified with the phosphorus-containing organic aluminate of the present invention is superior to the case where unmodified calcium carbonate is used (experiment numbers 14 to 16). Duration and elongation are remarkable.

Furthermore, even if a phosphorus-containing organic aluminate is used, which is clearly shown to be improved in Experiment No. 18, the second
As shown in the table, the modulus and elongation were significantly improved.

Example 3 The amount of calcium carbonate shown in Table 3 having an average particle size of 1.0 μm was treated with the amount of phosphorus-containing organic aluminate shown in Table 3.

To this, 100 parts by weight of hard vinyl chloride resin, 5 parts by weight of tribasic lead sulfate, and 1 part by weight of lead stearate were added and mixed in a blender, kneaded and crushed in a twin-roll mill at 175°C, and then heated at 180°C. Press molded.

Table 3 shows the relative falling weight impact values of the molded plates thus obtained.

It is clear from Table 3 that the impact strength of hard polyvinyl chloride filled with calcium carbonate is improved by surface modification with the phosphorus-containing organic aluminate of the present invention.

In addition, even if the phosphorus-containing organic aluminate shown in Experiment No. 29 was used, the third
Results similar to those in the table were obtained.

Example 4 The amount of phosphorus-containing organic aluminate shown in Table 4 was dissolved in 100 parts by weight of naphthenic mineral oil, and 4 parts of aluminum hydroxide with an average particle size of 1 μm was dissolved.
The amounts shown in the table were mixed, and the Brookfield viscosity of the resulting dispersed product at 25°C was measured.

The results are shown in Table 4. Similar results were obtained by using a phosphorus-containing organic aluminate represented by instead of the phosphorus-containing organic aluminate shown in Experiment No. 36.

Example 5 In Example 4, the inorganic substance was kaolin (average particle size 2.
The same process was carried out except that 5μ) was used instead.

The results are shown in Table 5.

Tables 4 and 5 show that the viscosity of the mineral oil in which the inorganic filler is dispersed is significantly reduced by surface modification with the phosphorus-containing organic aluminate.

Claims (1)

[Claims] 1 General formula (R,0) 2 people #(A) x (B), [wherein R1
P is a carbon-hydrogen group having 1 to 8 carbon atoms, A is -OP(OR2)2 or O O 1111 -0}←P(OR3)2 (wherein R2 and R3 are 41 0H to 24 ), B10802R4, -08OR5 or -0CO
R6 (wherein R4 and R5 represent an organic group having 4 to 24 carbon atoms, R6 represents an organic group having 2 to 50 carbon atoms), x + y + z = 3, x = 1 .0~2.5
, y-0~1. Oz=0.5 to 1.5. A surface-modified inorganic additive for organic substances treated with a phosphorus-containing organic aluminate represented by 2. The phosphorus-containing organic aluminate is such that R1 is an alkyl group having 3 to 5 carbon atoms, R2 and R3 are an alkyl group having 8 to 16 carbon atoms, and R4 and R6 are 8 to 8 carbon atoms.
organic group with 18 carbon atoms, R6 is an alkyl group with 2 to 24 carbon atoms, z = 0.8 to 1.2, x
The surface-modified inorganic additive for organic substances according to claim 1, which is a phosphorus-containing organic aluminate in which y = 1.5 to 2.2 and y = o to 0.7. 3. The surface-modified inorganic additive for organic substances according to claim 1, wherein the phosphorus-containing organic aluminate is a phosphorus-containing organic aluminate selected from the following. 4. The surface-modified inorganic additive for organic substances according to claim 1, wherein 100 parts by weight of the inorganic substance is treated with 01 parts by weight or more of a phosphorus-containing organic aluminate. 5. The surface-modified inorganic additive for organic substances according to claim 1, wherein 100 parts by weight of the inorganic substance is treated with 0.5 to 10 parts by weight of a phosphorus-containing organic aluminate.