JPS6042437A - Surface-coated inorganic filler - Google Patents

Abstract

PURPOSE:An inorganic filler excellent in dispersibility in a high-molecular matrix, prepared by surface-coating an inorganic substance with a reaction product between a specified silane soupling agent and an organic compound of a MW of 80-5,000. CONSTITUTION:Use is made of at least one silane coupling agent selected from the group consisting of amino group-containing silane coupling agents (e.g., formula I ), isocyanato group-containing silane coupling agents (e.g, formula II), mercapto group-containing silane coupling agents (e.g., formula III), and chloro group-containing silane coupling agents (e.g., formula IV). Namely, an inorganic filler (A) (e.g., white carbon or talc), is mixed with about 0.3-15wt%, based on component A, above silane coupling agent (B), and an organic compound (C), MW of 80-5,000, having a functional group reactive with the employed coupling agent (preferably, in an amount <= the stoichiometric amount in relation to component B) to effect the surface coating, by bonding, of the inorganic filler with the reaction product between components B and C.

Description

[Detailed description of the invention] Regarding the S-free fee.

It is expected that the physical properties of articles containing fillers will be improved, such as improved abrasion resistance.

Inorganic fillers can be modified by surface treatment, which can improve the tensile strength and abrasion resistance of articles containing such inorganic fillers, or increase their affinity with plastics, making them more suitable for plastics. Favorable effects such as a reduction in the mixing time with

Therefore, the use of such surface-modified inorganic fillers brings about favorable effects such as simplifying the molding process and equipment for molded products containing inorganic fillers, and reducing power energy and thermal energy. Surface modification technology is a very important technology from an industrial standpoint.

The surface modification method that is widely used today is to adsorb a surfactant onto the surface of an inorganic filler. Improvements may be seen in the wettability of the inorganic filler, the processability of the molded product containing the inorganic filler, the strength and abrasion resistance of the molded product, the fluidity of the inorganic filler itself, and the like.

Recently, attempts have also been made to modify the surface of an inorganic filler by reacting with or adsorbing a silane coupling agent or a titanium coupling agent to the surface of the inorganic filler.

However, even when surface-modified inorganic fillers are made using these surfactants, silane coupling agents, titanium coupling agents, etc., many improvements still remain.

That is, in the case of inorganic fillers treated with surfactants,
If sufficient wettability and dispersibility of IJ Lux cannot be obtained, the adhesive strength between the polymer matrix and the filler may decrease, resulting in a decrease in various physical properties such as strength of the product. For example, coatings containing inorganic fillers treated with surfactants generally have poor aqueous properties, making such coatings unusable outdoors or in humid areas.

Furthermore, molded products containing these inorganic fillers often have deteriorated tensile strength, bending strength, and abrasion resistance.

On the other hand, inorganic fillers treated with a silane coupling agent or a titanium coupling agent generally have improved wettability and dispersibility with a polymer matrix, but the effects are insufficient. In addition, although the strength of plastic molded products containing such inorganic fillers is generally improved compared to when untreated fillers are used, the degree of improvement is small and cannot be said to be satisfactory. Recognizing the above-mentioned current situation regarding
After numerous experiments and studies on inorganic fillers whose surfaces are coated with a compound, we found that a reaction product between a certain type of silane coupling agent and a compound that has a functional group that can react with the coupling agent. The inorganic filler whose surface is coated with
Coatings and plastic moldings manufactured using such fillers have improved physical properties such as strength and abrasion resistance, and coatings and plastic moldings manufactured using surface-coated conductive inorganic fillers have improved physical properties such as strength and abrasion resistance. The inventors have completed the present invention by discovering that the material becomes a more uniform conductor and also increases the electrical conductivity.

That is, the present invention provides a group consisting of (1) a silane coupling agent having an amine group, a 7-run coupling agent having an isocyanate group, a silane coupling agent having a mercapto group, and a silane coupling agent having a chloro group. A reaction product of one or more carefully selected silane coupling agents and an organic compound having a molecular weight of 80 to 5,000 and having a functional group that can react with the silane coupling agent of (I). Silane coupling agents that can be used in the present invention include H2N02H, NHO, H681(00□H5)3 as silane coupling agents having amino groups. +
・H,,N02H1lNHO,H65i(OH,)(O
CR, )2°H2No, H65i (002)! ,),
.

H,, N-CΣ5i (OCR mountain The following compounds can be exemplified.

As a silane coupling agent having an isocyanate group, 0ON-(OH2)6-NHoON)1(O)1. ,)
,81(OOH,),.

OR.

Oh.

0ON06H12NH0ONHO,,H,WHO,H6
5i (OCR5), .

0ON06H1□NucoNna2n, Ngo, n6s
t (on town) 2゜OH.

0(!N06H1□NHO□H,N-0,H,,5i(
00□H1).

0H20120H The following compounds can be exemplified.

Further, examples of the silane coupling agent having a mercapto group include H80, H65i (OCR,).

aso, n6st (o○2H5)! l'aso, u6
Examples include compounds such as s1(on, )(OOH,)2, and examples of silane coupling agents having a chloro group include 0, #O, H681(001,), and the like.

070, H681 (002H,),.

□ The organic compound with a molecular weight of 80 to 5000 that can be used in the present invention is a functional compound that can react with the silane coupling agent. It is necessary to have a group, and such compounds include many -Nu2. Compounds selected from the group of compounds having a functional group such as -NH- are preferred.

Examples of compounds having 10OOH include saturated or unsaturated fatty acids such as lauric acid, halistic acid, stearic acid, behenic acid, and oleic acid, and aliphatic oxyacids such as hydroxystearic acid, hydroxybalmitic acid, and ricinoleic acid. , maleic acid-itacon rljts, octadecenylsuccinic acid, dodecenylsuccinic acid, and other dicarboxylic acids.

Examples of the compound having 0 -OR include acid anhydrides such as phtadecenylsuccinic anhydride, dodecenylsuccinic anhydride, dodecylsuccinic anhydride, maleic anhydride, phthalic anhydride, and trimellitic anhydride. , aliphatic alcohols such as octyl alcohol, decyl alcohol, laurel alcohol, myristyl alcohol, cetyl alcohol, and stearyl alcohol, alkylene oxide adducts of these aliphatic alcohols, and alkylene oxide adducts of higher fatty acids having 8 to 50 carbon atoms. , hydroxyalkyl methacrylate-containing polymers, butyral resins, and polyols such as butanediol, glycerin, trimethylolpropane, pentaeryth IJ)/l/, etc. Compounds having 0-IJH2 include 1, for example, hexylamine. , primary amines such as laurylamine, fullkylenediamines such as pentamethylenecyazine and hexamethylenediamine, polyalyalenebolyamines such as diethylenetriamine, triethylenetetramine, and 2-methylenepentamine, 1-aminopentane-5- Examples include alkanolamines such as ol, N-(2-oxyethyl)ethylenediamine, and the like.

-MH--containing compounds include dipropylamine,
Examples include secondary amines such as didecylamine and didecylamine, and cyclic polymethyleneimines such as hexylimine, octyl imine, and decyl imine.

In the present invention, all inorganic fillers that are widely used today can be used, and these inorganic fillers include white carbon, calcium carbonate, alumina, glass for FRP, asbestos, talc,
Kaolin, bentonite, sericite, saponified tin, antimony oxide, iron with oxidized surface layer, nickel, chromium,
Examples include copper and alloys thereof.

The method for obtaining the surface-coated inorganic filler of the present invention is not particularly limited, as long as the desired coating layer is formed on the surface of the inorganic filler, and the following method may be exemplified.

b) First, the inorganic filler (1) is treated with the silane coupling agent (ii) of the above (I), and then the compound (iiD) of the above (I) having a functional group that can react with the silane coupling agent is treated. How to handle it.

(1) A method in which (ii) is first reacted with 6-layer to obtain a reaction product, and then (1) is treated with the reaction product.

c') (+), (A method of processing the inside by mixing iD and (iii) at once.

In carrying out each of the above methods, a wet method (for example, dispersing the inorganic filler in a reaction solvent) or a dry method (for example, dispersing the above (11) or GiD as an inorganic filler without using a reaction solvent) ) can be selected as appropriate. .

Examples of reaction solvents that can be used in the present invention include inert organic solvents such as benzene, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.

The amount of the silane coupling agent (1) used in the present invention depends on the surface area of the inorganic filler, but is generally about 0.3 to 15% by weight based on the inorganic filler. Moreover, the above (IF) which can react with a silane coupling agent
It is preferable that the amount of the compound used is such that, from a stoichiometric perspective, they do not remain as unreacted substances.

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to examples, but the present invention is not limited to these examples. All parts in the examples represent parts by weight.

Example 1 It is an amino group-containing silane coupling agent.

a2No2u,uuc,I(6st(ooH,), 0
．． 20 parts of toluene solution containing 7 parts of white carbon (
The mixture was mixed with 10 parts of Nippon Aerosil Co., Ltd. (≠130) and stirred at 110°C for 2 hours. Next, a mixture of 10 parts of toluene and 1.2 F of octadecenylsuccinic anhydride was added thereto, and the mixture was stirred at 85° C. for 2 hours. Thereafter, the white carbon was washed with a large amount of toluene/methyl ethyl ketone mixed solvent (mixed weight ratio 1:1) and dried to obtain surface-coated white carbon.Next, 100 parts of the surface-coated white carbon and 1000 parts of butyl rubber were rolled. A sheet was prepared by kneading and pressing, and its tensile strength and abrasion resistance were examined. These results are shown in Table-1.

1 Example 2 Surface-coated white carbon was obtained in the same manner as in Example 1 except that 1 part of lauric acid was used instead of octadecenylsuccinic anhydride used in Example 1, and 100 parts of the surface-coated white carbon was obtained. and 1,000 parts of butyl rubber were kneaded in a roll, pressed to make a sheet, and the tensile strength and abrasion resistance of this sheet were examined. These results are shown in Table-1.

Example 3 Instead of the amino group-containing silane coupling agent used in Example 1, an isocyanate group-containing silane coupling agent oaN-(a′H2)6NuaoNH(a[(2
).

Surface-coated white carbon was obtained in the same manner as in Example 1, using 0.7 parts of 51 (oou, ), and 1 part of dihexylamine instead of the octadecenyl succinic anhydride used in Example 1. Then, 100 parts of the surface-coated white carbon and 1000 parts of butyl rubber were kneaded with a roll and pressed to form a sheet, and the tensile strength and abrasion resistance of the sheet were examined.

These results are shown in Table-1.

Example 4 In addition to the amino group-containing silane coupling agent used in Example 1, C, a chlorine-containing 7-run coupling agent, was added.
Using 0.7 parts of 1#O, H65i (OOH, ), 1.5 parts of 1-stearylpropylene diamine was used in place of the same octadecenyl succinic anhydride used in Example 1. Other than that, surface-coated white carbon was obtained in the same manner as in Example 1, and the surface-coated white carbon 1
00 parts and 1000 parts of butyl rubber were kneaded in a roll, pressed to form a sheet, and the tensile strength and abrasion resistance of this sheet was examined. These results are shown in Table 1. Comparative Example 1 100 parts of the white carbon used in Example 1 was mixed with 100 parts of butyl rubber without any treatment.
0 part was kneaded with a roll and pressed to make a sheet, and its tensile strength and abrasion resistance were examined. These results are shown in Table 1.
Shown below.

Comparative Example 2 100 parts of white carbon whose surface was hydrophobically treated (4R972 from Nippon Aerosil Co., Ltd.) and 1000 parts of butyl rubber
The mixture was kneaded with a roll to make a pressed sheet, and its tensile strength and abrasion resistance were examined.

These results are shown in Table-1.

Table-1 Note) Abrasion resistance was examined using the ASTM-P59a method.

The abrasion resistance results are shown as relative values when the abrasion loss value of the sheet of Example 1 is set as 100. The larger the relative value, the greater the amount of wear loss, which means that the wear resistance is poorer.

Example 5 1! Add 100 ml of surface oxidized nickel powder to 4 solo flasks.
part, isocyanate group-containing 7-run coupling agent 0ON-(OH2)6NHOONH(CH2), 5l(
OOH, ), o, y parts, toluene 300 parts, and butyral resin (denka butyral≠2000-L) 2
The mixture was stirred at 90°C for 2 hours. Thereafter, the nickel powder was washed with a large amount of methyl ethyl ketone and dried to obtain a surface-coated nickel powder.

Further, surface-coated nickel powder was obtained by the method described above using two parts of DENKA BUTYRAL+3000-2 and DENKA BUTYRAL-$5000-K instead of the above-mentioned butyral resin +2000-L.

Using these three types of surface-coated nickel powders, three types of melamine alkyd paints were prepared to form coating films.

On the other hand, untreated surface oxidized nickel powder and dodecylamine acetate (acetamine 24 from Kako Soap Co., Ltd.) were used as a dispersant.
A melamine alkyd paint was similarly prepared using P) to form a coating film.

As described above, when the conductivity was measured for a total of four types of coating films, it was found that the coating film containing the surface-coated nickel powder of the present invention has 15 to 70 times more conductivity than the coating film containing untreated nickel powder. I understand.

Example 6 0ONO-NHOONH03H6S, which is an incyanate group-containing silane coupling agent, was placed in 1!4 Lof flasks.
1 (oC2H5) 30.5 parts, lauryl methacrylate (ML)/hydroxyethyl methacrylate (HIMA) copolymer of molecule 'J11600 (copolymerization molar ratio M
2 parts of L/HFIMA=80720) and 400 parts of toluene were added, and the mixture was stirred at 70°C for 6 hours.

Next, 100 parts of particulate talc was added to this system, and 110 parts of fine talc was added.
After stirring at ℃ for 3 hours, the talc powder was mixed with a large amount of toluene/methyl ethyl ketone mixed solvent (mixed weight ratio 1:1).
The surface-coated talc powder was obtained by washing and drying.

Next, 140 parts of the surface coating Merck and 20 parts of PVC paste were added.
0 parts were mixed and stirred until uniform, and the viscosity at 25°C was measured. The results are shown in Table-2.

Example 7 ML/BEMA with a molecular weight of 1600 used in Example 6
Copolymer (copolymerization molar ratio MTJ/HBM = 80/20
) instead of ML/i older HA copolymer with a molecular weight of 700 (ratio to copolymerization % M L /HBMA = 80/20)
A surface-coated talc powder was obtained in the same manner as in Example 6, except that 2 parts of PVC was used, and the talc powder was mixed with vinyl chloride paste, and its viscosity was measured at 25°C.

The results are shown in Table 2IC.

Example 8 ML/HF with a molecular weight of 1600 used in Example 6! M.A.
Copolymer (copolymerization molar ratio M L /H1!iMA=8
0 /20), M L / with a molecular weight of 5600
HEMA copolymer (copolymerization molar ratio M: [J/HIMA=
Surface-coated Merck powder was obtained in the same manner as in Example 6, except that 2 parts of 80/20) were used, mixed with PVC paste, and its viscosity was measured at 25°C.The results are shown in Table-
Shown in 2.

Comparative Example 5 ML/HEIMA copolymer with a molecular weight of 1600 used in Example 6 (copolymerization molar ratio ML/HIttMA=80/20
), ML/HIMA copolymer with a molecular weight of 8300 (copolymerization molar ratio ML/H1i!MA=80720
) Surface-coated Merck powder was obtained in the same manner as in Example 6, except that 2 parts were used, mixed with PVC paste, and 25 parts
The viscosity was measured at °C. The results are shown in Table-2.

Comparative Example 4 140 parts of the talc powder used in Example 6 without any surface treatment, 200 parts of the PVC paste used in Example 6,
and ethylene oxide of stearic acid 1 as a dispersant.
6.8 parts of the 2 molar adduct were mixed, stirred until homogeneous and the viscosity was measured at 25°C. The results are shown in Table 2. As is clear from Table 2, the PVC paste containing the inorganic filler of the present invention has high fluidity, and the processability of the PVC paste is improved.

Table-2 *) Using a Brookfield viscometer It was measured. The unit is centiboise. Ru.

Applicant's agent Kaoru Furutani

Claims (1)

[Claims] 1(I) A group consisting of a silane coupling agent having an amine group, a silane coupling agent having an inquanate group, a silane coupling agent having a mercapto group, and a silane coupling agent having a chloro group. Selected 1
The surface is coated with a reaction product of a species or two or more silane coupling agents and (π) an organic compound with a molecular weight of 80 to 50% having a functional group that can react with the silane coupling agent of (1) above. Inorganic filler. 2 The organic compound having a molecular weight of 80 to 5,000 and having a functional group capable of reacting with the sila/coupling agent of (I) above is one or more selected from the group consisting of the following (a) to (e). The surface-coated inorganic filler according to claim 1, which is a compound. (a) Compound having 1000H in the molecule (b) Compound 1 having -a-C- in the molecule /＼♂0ゞ0 (c) Compound having -OR in the molecule (d) Compound having - in the molecule Compound (e) with 'kJH2 -Nu in the molecule
a compound with