JPS5945906A - Inorganic oxide particle composition - Google Patents

Abstract

PURPOSE:To provide the titled composition having excellent reinforcing effect and dispersion-promoting effect, by treating the surface of inorganic oxide particles with a mixture of a specific organopolysiloxane compound and an organic silane compound. CONSTITUTION:(A) 10-90wt% of the organopolysiloxane compound of formula I (X is group of formula II and/or formula III, and at least one of X is group of formula II; R<1> is H or <=5C univalent hydrocarbon group; l is 1-100; a is 1-20) is mixed with (B) 90-10wt% of an organic silane compound of formula IV(R<2> is organic group containing C bonded directly to Si and having functional substituent group; R<3> is R<2> or univalent hydrocarbon group; Y is hydrolyzable group; b is 0 or 1), and the mixture is dissolved in a solvent. Inorganic oxide particles (e.g. alumina particles) are mixed with the above solution, and dried at 130-150 deg.C to obtain the objective composition comprising the inorganic oxide particle coated with 0.05-10wt% of said mixture.

Description

[Detailed description of the invention]

The present invention provides a plastic composition, an elastomer side 11 composition, a coating n[acid and a tiered oxide powder treated with an organosilicon compound, which can be easily used. A, l [μm to acid. The purpose of inorganic oxide powder is to reduce the cost of composite materials such as plastic compositions, elastomer compositions, coating materials, adhesive compositions, etc., and also to facilitate processability and improve physical properties. RJJ is very widely used to improve it for special applications. However, it is known that (!!(!) oxide powders usually reduce the Pq mechanical and electrical properties of these compositions, and sometimes increase water absorption. In order to improve defects, the particle surface is generally
(Modification by treatment with a silane compound has been carried out (/l: "Komei No. 55-8097").
1AW S silane compound is a filler, a pigment, etc.
Powder powder and fibers (e.g. glass 1)
．． It is used in the surface treatment of floor desks (strings, aluminum C1 red and steel fibers). In general, an organic silane compound can enhance the chemical bond between the 48 ra/chemical-free powder base material and an organic substance, thereby improving the electrical contact between the two. however,
Depending on the type of oxide powder, organic silane compounds (4%) may have a pronounced W effect on the surface, while others may have no effect or have no effect at all. For example, natural silica such as sand, quartz, and tubaculite; synthetic silica such as wet process silica, colloidal silica, and silica aerogel; kaolin, mica, Merck,
Natural silicates such as wollastonite and asbestos; Synthetic silicates such as silicate calcium and hexaquarium: alumina, water-containing alumina, titanium oxide, zinc oxide, iron oxide,
Metal oxides and oxides such as magnesium oxide; effective against metals such as aluminum, bronze, and copper. On the other hand, for carbonate groups, sulfates, sulfites and carbon black of alkaline earth metals such as calcium carbonate, magnesium carbonate, calcium sulfate, zirium sulfate, tulsium sulfite, etc., Table α■ using organic silane compounds is used. Although there is almost no immediate effect, even if there is, it is known that the effect is small.Furthermore, the silane compound does not bring any sound effects other than improving the contact Only very rarely. A specific exception is the use of vinyl or methacrylic silanes to improve to some extent the dispersion of hydrated alumina in unsaturated polyester resin systems. Thus, If the treatment with silanized material is 4H
+ By Pak Chi of the strictly controlled powder! jL! There are cases in which it produces a 7"l effect, and cases in which it rarely produces an effect, but even if it does, it only appears to a small extent.2) Therefore, force;
(I Hij knowledge of organic oxide powder u'I C + mi no i
What is desired is a surface treatment that can be used for a variety of purposes, and that can also contain several 5r-1-x L molecular weights (1" and 4'". Monotoa Z) C: 1 of 2
The combination with Luganobori Shirogisan has been widely used in the past as mentioned above (!!
It has been found that the combination of a strong effect and a dispersion promoting effect on powder 11- is effective.Furthermore, this combination has the effect of increasing the treatment effect of organosilane compounds. However, it was found that it has an excellent reinforcing effect and dispersion promoting effect on carbonates, sulfates, and sulfites, which are the most common alkali metals, but this was unexpected. The purpose of the present invention is to obtain an excellent complementary material by using an inorganic oxide powder, which has been widely used in the past, as a base material and modifying the particle surface with a certain amount of organopolysiloxane and an organosilane compound. :'The purpose is to provide a composition that has both the Ij effect and the dispersion promoting effect.In particular, alkaline earths such as calcium and magnesium, which have almost no surface treatment effect with organic silane compounds,
47PA carbonate, sulfate, and 161r acid salt are used as a base, and the particle surface is similarly modified.

[v] provides a composition with excellent reinforcing effects and dispersion promoting effects. In other words, the present invention defines the surface of a phaseless oxide particle using the general formula % () (where X is 0% ((CH3)tSiO]tR'
t Taha 03/f, R'. All Xs do not have to be the same, and may be a mixture of the two groups listed above. However, at least 10% ((CH3)tS i O
] must be zR'. R1 is a hydrocarbon group having a carbon number of 5υ or less. t is 1 to 1oo. a is 1-20. ) By treating with a mixture consisting of an organopolysiloxane compound and an organic silane compound shown in It depends. In the present invention, inorganic oxide powder means any sawn solid material having either bound or free hydroxyl groups or chemisorbed or covalently bound oxygen on its atomized surface. Therefore, the inorganic oxide particles include all types of inorganic oxide particles as described above. Metals such as aluminum, bronze, pot 1, steel, etc.
Since its surface is oxidized, it can be considered to have a moltenide surface according to the present invention. The organic oxide particles of the present invention are suitable materials for use in various rod molding or coating processes such as injection molding lamination, transfer molding, compression molding, coating, and casting. Additionally, if the bleached oxide powder material is classified as a filler or pigment, it may or may not be a reinforcing material. The organopolysiloxane compound used in the present invention can be synthesized by the method described in Japanese Patent Application No. 56-166527. That is,
Alkyl polysilicate selected from hexaethoxydisiloxane, octaethoxytrisiloxane, decaethoxytetrasiloxane (ethyl silicate 40, manufactured by Nippon Colcoat), etc. Tetraethyl silicate (ethyl silicate 28, manufactured by Nippon Colcoat) and cyclotetradimethylsiloxane, cyclo A cyclic dinonal siloxane selected from pentadimethylsiloxane and the like can be obtained by heating and stirring in a porous atmosphere in a polar organic compound to which an alkali catalyst has been added. As an alkali agent. Potassium hydroxide, sodium hydroxide, etc. are 1! You can use it. As the polar organic compound, tetrahydrofuran, dinonalformamide, dinotylacetamide, hexamethylphosphamide, dimethylsulfoxide, phosphine oxide, etc. can be used. In addition, organic silane compounds are so-called silane coupling agents, and have the general formula % (21 (wherein, R1 contains a carbon atom directly bonded to a silicon atom, and a functional %i substituent). R3 is a group selected from the group consisting of the above R2 and 14Hi hydrocarbon groups. Y is a hydrolyzable group. b is 0 or 1. The formula (
The silane coupling agent in 2) includes vinyltriethoxysilane, vinyltritoxysilane, and vinyltris(2).
-methoxyethoxy)silane, γ-methacryloxyp L
L-pyrtrimethoxy/ran, β~(5,4-epoxycyclohexyl)-ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxy/ran, γ-mercaptopropyltrimethoxysilane, γ-aminobrobiltriethoxysilane There are silane, N-β-(aminoether)-γ-aminopropyltrimethoxysilane, etc., but these are just examples. The silane coupling agent may be appropriately selected from one having an optimal organic group depending on the type of synthetic resin and elastomer used to fill the inorganic oxide powder. dua jlJ M compound powder, the usage date of the mixture consisting of organopolysiloxane and organic silane compound represented by formula (1) is OD 5 to 10.0 Hi%, preferably 0.1 to 5.0 Parts by weight. Usage is 0
If it is less than 0.05 parts by weight, the mechanical strength of the composite material, l) I+, and resistance properties will be insufficient, and if it is more than 10.0 parts by weight, the inorganic filler will aggregate and the rice grains will This tends to be undesirable. It is also disadvantageous in terms of cost. The content of the organopolysiloxane represented by formula m in the mixture consisting of the organopolysiloxane represented by formula 0> and the organosilane compound is 10 to 90% by weight, preferably 30 to 70% by weight. The content of organoborisiloxane represented by formula (1) in the mixture is less than 10 Mrt% (and especially when alkaline earth metal charcoal is treated against salts, sulfates, and 61C salts) This is undesirable because the effect tends to be almost lost.Also, even if the amount exceeds 90, the reinforcing effect decreases. (2) is treated with a mixture consisting of a silane coupling agent, and the treatment method is, for example, conventional (,111; 4i'i). The following examples further illustrate the invention, but are not intended to limit the scope of the invention. Table of organopolysiloxane compounds
Described in . Table ■ CH. Hs Hs C) Is Hs Hs Hs Hs Hs CH. CH. The inorganic oxide powder was treated in the following manner. A predetermined amount of inorganic oxide powder was placed in a Henschel mixer, and while stirring uniformly, a mixture consisting of the organopolysiloxane listed in Table 1 and the silane coupling agent represented by formula (2) was mixed with ethanol or ethanol. A liquid solution consisting of toluene was sieved from the separating funnel for 5 minutes. After the dropping was completed, the mixture was stirred uniformly for another 10 minutes, transferred to a tray, and dried at 130° to 150° C. for 1 hour. Example 1 Hydrated alumina was treated with a mixture of organopolysiloxane B and γ-methacryloxypropyltrimethoxysilane (A-174) having F fL2 as shown in Table 1. Compound B and A-1 for hydrated alumina 1 [10 parts]
The amount of the mixture used (phf) from 74 and the mixing ratio of Compound B and A-174 in the mixture (by wt
) f Shown in Table 1. As a reference example, untreated aqueous alumina was used. 175 parts of these fillers, 55 parts of unsaturated polyester resin, 5 parts of the first layer of brominated polyester (40% purple), 30 parts of low shrinkage resin, 10 parts of styrene monomer, 4 parts of zinc stearate, t-butyl perbenzoate. 1.5s, Sb
, o, 3w15, Mgoo, 8 strands and 25 1-inch glass fibers were kneaded and comparative evaluations of moldability and physical properties were performed. The results are shown in Table 1. - Table 1 It can be seen that Example 1-1 is superior to Comparative Example 1-2 and Reference Example 1-3 in terms of initial paste appearance, moldability such as fluidity, mechanical properties, and electrical properties. Example 2 Irrigation alumina was treated with a mixture of organopolysiloxane C and gamma-methacryloxypropyltrimethoxysilane (A-174) listed in Table I. Amount of mixture used for irrigation alumina ion part (phf)
Table 2 shows the mixing ratio (by wt) in the mixture. As a reference example, untreated alumina was used. 150 parts of these fillers and 100 parts of acrylic monomer were mixed to determine a viscosity of 1iil+. Next, 0.2 part of benzyl peroxide was added to this mixture, and then 1117 flIll (contact pressure) was added at 25°C.
It was cured at 00.degree. C. for 2 hours, and two test pieces of Pli were prepared. The test results are shown in Table 2. It can be seen that Actual Muha Example 2-1 is more effective in reducing viscosity and improving mechanical properties than Comparative Example 2-2 and Reference Example 2-3. As in Comparative Example 2-2, when the amount of treated grains exceeds 1a, o (g)% by weight, there is a tendency for the grains to become coarse. Table 2 Example 6 For quartz powder, organopolysiloxane E and γ-glycidoxyglobyl trimethoxysilane (
A-187). quartz powder 100
Table 3 shows the amount of the mixture used per part (phf) and the mixing ratio in the mixture (by wt). As a reference example, untreated quartz powder was used. 18 parts of these optical fillers were mixed with 100 parts of epoxy resin, 65 parts of tetrahydrophthalic anhydride, 16 parts of benzyldimethylamine, and 1 part of gold at 120°C for 16 hours and then at 180°C for 1 hour (i'J! The results are shown in Table 3. Table 3 Examples 6-1 and 5-2 are the same as Comparative Examples 3-5 and 6-
It can be seen that compared to No. 4, it is effective in improving the electrical characteristics after boiling. It can be assumed that this improvement in electrical properties is due to stronger adhesion at the interface between the quartz powder and the epoxy resin. Example 4 Aluminum powder was treated with a mixture of organopolysiloxane A and γ-glycidoxypropyltrimethoxysilane (A-187) listed in Table I. Use of the mixture for 100 aluminum powders
(phf ) and the mixing ratio in the mixture (by w
t) are shown in Table 4. As a reference example, untreated aluminum powder was used. 200 parts of these fillers, 100 parts of the epoxy side and 4 parts of imidazole were mixed and cured at 60° C. for 8 hours to prepare a test piece. The test results are shown in Table 4. Example 4-1 has improved O'i +4 characteristics compared to Comparative Example 4-2 and Reference Example 4-6. Organopolysiloxane D and vinyltriethoxysilane (A-151)
treated with a mixture consisting of Hydrated alumina 1 o o f
Table 5 shows the m (phf) of the mixture used for lys and the mixing ratio (bywt) in the mixture. As a reference example, untreated hydrated alumina was used. 60 hl of these fillers were kneaded with 591'il'i of polyethylene resin (DQDJ-1868 manufactured by Nippon Unicar Co., Ltd.) and α-dicumyl peroxide, and the physical properties of the press-molded product were compared. The results are shown in Table 5. Examples 5-1 and 5-2 were compared to Comparative Example 5-3 and Reference Example 5.
It can be seen that not only the mechanical properties but also the flame retardant properties are improved compared to -4. Table 5 Example 6 Wollastonite was treated with a mixture consisting of organopolysiloxane F and r-aminopropyltriethoxysilane (A-1100) listed in C5 Table I. Use of the mixture per 100 parts of wollastonite * (ph
f) and the mixing ratio in the mixture (by wt)
Table 64 shows: As a reference example, untreated wollastonite was used. 50 parts of these fillers and nylon 6
Table 6 shows the results of comparing the physical properties of kneaded and press-molded products with 100 parts of resin. Example 6-1 is Comparative Example 6
-2 and Reference Example 6-3, especially warm water immersion fjt
Later mechanical properties are improved. Table 6 Example 7 Mica was treated with a mixture of organopolysiloxane E described in I and r-glycidoxypropyltrimethoxysilane (A-187). Mica 1
Table 7 shows the usage of the mixture (phf) and the mixing ratio (bywt) in the mixture for 00 cities. b As an example, untreated mica was used. 30 of these fillers and 100 of PBT resin were mixed and press-molded and the physical properties were compared and shown in Tables 6 and 7. Example 7-1 has better mechanical properties than Comparative Example 7-'2 and Reference Example 7-3. Table 7 Example 8 Heavy calcium carbonate was treated with a mixture consisting of organopolysiloxane B and N-β-(amino/ethyl)-r-aminopropyltrimethoxysilane (A-1120) listed in Table 1. did. Table 8 shows the amount of the -4-based mixture used per 100 parts of heavy calcium carbonate (phf) and the mixing ratio (bywt) in the mixture. As a reference example, untreated heavy calcium carbonate was used. 40 parts of these fillers and 100 parts of nylon 6.6 resin were kneaded and press-molded, and the results of comparing the physical properties are shown in Table 8. Example 8-1 has superior mechanical properties compared to Comparative Example 8-2 and Reference Example 8-3, and in particular, A-1120
The mechanical properties are improved compared to Comparative Example 8-2, which was treated alone. Table 8 Example 9 For silica, organopolysiloxane F listed in Table I and r-mercaptopropyltrimethoxysilane (A
-189). Silica'1o
Table 9 shows the amount of the mixture used (phf) and the mixing ratio (by wt) in the mixture relative to o B-6. As a reference example, untreated silica was used. 50 parts of these fillers, 100 frA of natural rubber, 1 sulfur compound
Table 9 shows the results of comparing the physical properties of the vulcanized rubber by kneading 1 vulcanization accelerator, 2.4 g of sulfur, 4 parts of zinc M, 3 parts of stearic acid, and 5 parts of process oil. Example 9
-1 has improved mechanical properties compared to Comparative Example 9-2.2-3 and Reference Example 9-4. It was treated with a mixture consisting of polysiloxane A and r-aminopropyltrie)oxysilane (A, -1100). Use of mixture for light calcium carbonate 1ooVAff
i (phf) and the mixing ratio in the mixture (by
vt) are shown in Table 10. As a reference example, untreated light calcium carbonate was used. With 75 parts of these fillers? 100 parts of soprene rubber, 5 parts of zinc oxide, 2*iS stearic acid, 2 parts of sulfur, 1 part of vulcanization accelerator and DPGα2
Table 1 shows the results of kneading 5 parts and comparing the lh properties of vulcanized rubber.
0. It was shown to. Example 10-1 is the same as Comparative Example 10-2 and Reference Example 10-
Compared to 3, the modulus is significantly improved by 300%. Table 10

Claims (1)

[Claims] 1. i: H% jp, J The surface of the oxide particles is expressed by the general formula % 0y2RI. All Xs do not have to be the same, and the above 6
It may be a mixture of 76, 2 va g, *. however,
At least one or more is 0% ((C)(s) t S
10) It must be t R'. R' is an aqueous or monovalent hydrocarbon group having a carbon number of 5 or less σ). l is 1
~100. a is 1-20. ) An inorganic oxide particle composition formed by treating with a mixture of an organopolysiloxane compound and an organic silane compound. 2. Claim 1, wherein the inorganic oxide particles are alkaline earth metal carbonate, sulfate, or sulfite particles.
Compositions as described in Section.