JPH04189881A - Surface-treating agent and surface-treating filler - Google Patents

Abstract

PURPOSE:To provide a surface-treating agent having excellent stability in aqueous system and composed of a reaction product of a tetraalkoxytitanium (or its hydrolytic polycondensation product), a specific organic acid and a chelating agent capable of forming a chelate ring with Ti atom. CONSTITUTION:The objective treating agent is composed of a reaction product of (A) a tetraalkoxytitanium and/or a hydrolytic polycondensation product (polymer) of tetraalkoxytitanium having an average condensation degree of <=6, (B) an organic acid composed of keto acids, acyloxycarboxylic acids and/or alkoxyacetic acids and (C) a chelating agent capable of forming a chelate ring with Ti atom. The agent contains 0.1-2.0mol of the organic acid group of the component B and >=0.5mol of an alkoxytitanium derivative having the chelating agent group of the component C based on 1 atom of Ti.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a surface treatment agent used for surface modification of a filler in a polymer matrix-filler composite system. The present invention relates to a surface treatment agent which can be used in an aqueous system and whose main component is an alkoxytitanium derivative having a specific organic group and a chelating agent group capable of forming a chelate ring with a Ti atom.

The present invention also relates to a surface-treated filler having a partial hydrolyzate of an alkoxy titanium derivative obtained by surface-treating the filler using the surface-treating agent.

The surface treatment agent of the present invention is used for surface modification of fillers used in polymer matrix IJ Fuchs-filler composite systems, particularly for improving the dispersibility of inorganic fillers in polymer matrices. This surface-treated filler is suitable as a treatment agent, and since it has excellent dispersibility in polymer matrix IJ socks, it can be suitably used in the production of polymer matrix-filler composite systems.

[Conventional technology]

Polymer polymers) IJ Fuchs-filler composite systems, such as fillers used in synthetic resin moldings, paints, inks, etc.
Surface treatments are generally applied to improve the physical properties, workability, etc. of composite systems.

Silane coupling agents, titanium coupling agents, zirconium coupling agents, and the like are known as surface treatment agents for these fillers.

The solvent system for a silane coupling agent made of an organic silane compound is generally water or a water-alcohol solution.
As the solvent system for the titanium coupling agent made of an alkoxytitanium derivative, an organic solvent is usually used.

It has been disclosed that, as aqueous-stable alkoxytitanium derivatives, reaction products of tetraalkoxytitanium and amino alcohols, such as isobroboxytitanium aminoethanolate and isopropoxytri(aminoethanolade), are used as esterification catalysts. (U.S. Patent 1)
13P No. 3074818). It has also been proposed that water-insoluble titanium coupling agents be stabilized by the combined use of amine compounds such as aqueous ammonia, triethylamine, dimethylaminoethanol, triethanolamine, and morpholine, and used in aqueous systems. (Refer to Japanese Patent Publication No. 112973/1983).

[Problem that the invention seeks to solve]

The surface treatment effect of filler with silane coupling agent is
Although it is excellent for silicic acid fillers such as glass peas, it has little effect on fillers other than silicic acid.

On the other hand, titanium coupling agents have excellent surface treatment effects on fillers other than silicic acid, such as calcium carbonate and titanium oxide, but they are generally extremely hydrolyzable and difficult to use in aqueous systems. and is usually used in organic solvents.

However, organic solvents not only pose a risk of fire and explosion, but also may cause poisoning when inhaled, and there is a need for a titanium coupling agent that can be used in water-based systems.

In the case of titanium coupling agents that are stabilized in an aqueous system by the combination of alkoxytitanium derivatives and amino compounds that are stable in an aqueous system cited above, the surface treatment effect of the filler is not sufficient, and in general, treatment of the filler in an aqueous system is not possible. Not known.

An object of the present invention is to provide a titanium-based surface treatment agent that can be used in an aqueous system and a surface treatment filler that has excellent dispersibility in a polymer matrix.

[Means for solving problems]

As a result of intensive research to achieve the above object, the present inventors have discovered that an alkoxytitanium derivative consisting of a reaction product of tetraalkoxytitanium, a specific organic acid, and a chelating agent capable of forming a chelate ring with a Ti atom has been discovered. The present invention was completed by discovering that a filler that is extremely stable against hydrolysis and that has been surface-treated in an aqueous system using this reaction product has excellent dispersibility in polymeric polymer IJ hooks. did.

The present invention provides (a) tetraalkoxytitanium and/or
or a hydrolyzed condensation product (polymer) of tetraalkoxytitanium with an average degree of condensation of 6 or less (ω) At least one member selected from the group consisting of keto acids, acyloxycarboxylic acids, and alkoxyacetic acids (c) Ti atoms and A chelating agent capable of forming a chelate ring, consisting of the reaction products of the above (a), (b) and (c), Ti: 0.1 to 20 mol per atom of the above (b)
This is a surface treatment agent characterized by containing an alkoxytitanium derivative having an organic acid group as described in the item (c) above and a chelating agent group as described in the item (c) in an amount of 0.5 mol or more per Ti atom. (First invention) It is also a surface-treated filler characterized by having a coating of a partial hydrolyzate of an alkoxy titanium derivative obtained by surface-treating the filler using the surface-treating agent. (Second shot 1
! I'l) In the present invention, the tetraalkoxytitanium described in item (a) above is represented by the following general formula (1) % formula % (1), in which 0R is an alkoxy group, preferably,
an alkoxy group having 1 to 6 carbon atoms, such as a methoxy group,
It is an organic titanium compound having one or more types of ethoxy group, n-propoxy group, 1-propoxy group, n-butoxy group, tert-butoxy group, 1 pentoxy group, 1 n-hexoxy group, etc.

Tetraisopropoxytitanium and tetra-n-butoxytitanium are more preferably used because of their treatment effects as surface treatment agents.

Further, the hydrolyzed condensation product (polymer) of tetraalkoxy titanium may be one or two of the above-mentioned tetraalkoxy titaniums.
It is a polymer having an average degree of condensation of 6 or less obtained by hydrolyzing more than one species using an equimolar amount of water or less in the presence of an acid or alkali catalyst, and condensation polymerization. Regarding the polymer structure, there are various theories such as chain-like, cyclic, network-like, etc., but any of these may be used.

The keto acids described in item (b) above have the following general formula (2)%
It is represented by the formula % (2), in which R1 is an alkyl group having 1 to 5 carbon atoms, R
2 is a carboxylic acid which is an alkylene group having 1 to 5 carbon atoms.

Examples of the keto acids represented by the general formula (2) include the following compounds.

CIl, COCH2C0 Kano, CH3C)12
COCI1. [:Do)ICH3COC2H,C0OH
,C3H,C0CH,C0D)IC,fl,COC,t
l, COO1i, C, LCOC3H6C[)OH
Acyloxycarboxylic acids are expressed by the following general formula (3)% formula% (
3) R'' in the formula is an alkyl group having 1 to 5 carbon atoms,
At least one type of carboxylic acid in which R4 is an alkylene group having 1 to 5 carbon atoms.

Examples of the acyloxycarboxylic acids represented by the general formula (3) include the following compounds.

CH3CO0CH,C0OH,C2H5000C,H,
C00HCH3COOC3H6[:OOH, CH3CO
0C3H6COOII[:3H7[:0OCH2COO
)1. C,H,CDDC2H,C00II
C2H5CODC, H8C0DH, C2H7CDOC5
H,,C[]OH alkoxyacetic acids have the following general formula (4
)% formula % (4) where R5 is an alkyl group having 1 to 5 carbon atoms,
At least one carboxylic acid in which R6 is a methylene group
It is a seed.

Examples of the carboxylic acids represented by the general formula (4) include the following compounds.

CH30CII, CDDH, C, LDCH2COOII
C3) 1,0CH2COO)1. C,
119 mouths [:) 12cOOHC6H, 0CI1. C0O
H Examples of the chelating agent that can form a chelate ring with the Ti atom described in item (c) above include the following and (poly)alkylene glycols.

[Hydroxycarboxylic acids] Glycolic acid, lactic acid, α-oxy-n-butyric acid.

α-oxyisovaleric acid, 2-ethyl-2-oxybutanoic acid, doroacrylic acid, β-oxynebutyric acid.

α-Oquine acrylic acid, tartronic acid, oxymethylmalonic acid, malic acid, oxyglutaric acid, citric acid, glyceric acid, tartaric acid, etc., [β-diketones] Acetylacetone, 3-phenylacetylacetone, etc., [α- or β - Keto acids and their lower alkyl esters 1 Acetoacetic acid, propionylbutyric acid, etc. and their methyl, ethyl esters 1 Isopropyl, n-butyl esters, etc. The surface treatment agent is NtE. Ti: per atom, at least one of the above organic acids: 0.1 to 2
0 mol or more of the above chelating agent are reacted to transesterify the alkoxy group of tetraalkoxy titanium or its polymer with the selected organic acid group and chelating agent group. The active ingredient is an alkoxytitanium derivative having 0.1 to 2.0 mol of an organic acid group and 0.5 mol or more of the chelating agent group per atom.

The alkoxytitanium derivative is prepared by adding predetermined amounts of tetraalkoxytitanium and/or its polymer in item (a), at least one of the organic acids in item g), and a chelating agent in the presence or absence of a solvent. The reaction mixture is easily synthesized by stirring and holding at a temperature of 40 to 80°C for 5 to 1 hour, and then removing by-product alcohol and reaction solvent under reduced pressure.

The surface treatment agent is a solution containing the alkoxytitanium derivative as an active ingredient. As the solvent, any solvent that can dissolve the alkoxytitanium derivative can be used without particular limitation, and water, lower alcohols, aqueous solutions of organic solvents, etc. are used, and water is more preferably used.

The filler to be surface treated is not particularly limited as long as it can be combined with the polymer matrix and improve the properties of the composite system.

Examples of these fillers include the following.

[filler] Calcium carbonate, kaolin, clay, mica.

Curc, calcium silicate, titanium oxide, magnanium carbonate, alumina 1 calcium sulfate, barium sulfate, silicate, theolite, aluminum oxide, aluminum hydroxide, magnesium hydroxide, glass fiber, titanate fiber.

The surface treatment of the filler with a surface treatment agent such as carbon fiber is performed by immersing the filler in an aqueous solution of the surface treatment agent and stirring, and adding 0.05 to 58 parts by weight of the alkoxy titanium derivative to 100 parts by weight of the filler.
This is preferably carried out by depositing 0.5 to 2 parts by weight to form a coating of the partial hydrolyzate of the alkoxy titanium derivative on the surface of the filler. In particular, heavy calcium carbonate, kaolin, clay, produced by wet grinding of natural products,
However, for talc and the like, pulverization and surface treatment can be performed simultaneously by adding the surface treatment agent to the water used during pulverization. In addition, in the case of light calcium carbonate produced by the reaction of milk of lime and carbon dioxide gas, magnesium hydroxide, aluminum hydroxide, etc. produced by synthetic methods, the surface treatment agent is added to the aqueous reaction solution or grinding medium. By adding , surface treatment can be performed during the manufacturing process.

The surface-treated filler of the present invention (second invention) is a filler coated with a hydrolyzate of an alkoxytitanium derivative obtained by surface treatment with the surface treatment agent.

In the present invention, it is preferable that the hydrolyzate of the alkoxy titanium derivative be coated to form a continuous film on the surface of the filler, but this is not particularly essential.

The surface-treated filler of the present invention can be blended into various polymer matrices, and can be made into a polymer matrix-filler composite. As a composite polymer matrix,
The following can be mentioned.

[Polymer matrix] Polyurethane, epoxy resin, polyamide, polyester, polycarbonate, polysulfone.

Polysulfide, polyphenylene oxide, polyethylene, polypropylene, polyvinyl chloride.

Examples include acrylic resin, especially polyurethane.

Suitable for Epoquine resin, polyamide, polyether polyol, etc.

[For production]

As mentioned above, the surface treatment agent of the present invention has a hydrolyzable alkoxy group as a substituent, a non-hydrolyzable ketone acid,
The main component is an alkoxytitanium derivative having at least one organic acid group selected from the group consisting of siloxycarboxylic acids and alkoxyacetic acids and a chelating agent group.

Although various proposals have been made regarding the chemical structure of this alkoxytitanium derivative, none are definitive, and its mechanism of action is also unclear.

In order for an alkoxy titanium derivative to act as a surface treatment agent for fillers, it must have a hydrolyzable group and a non-hydrolyzable substituent. At least one of the organic acid groups and a chelating agent group are selected as the functional groups.

As shown in Examples below, this alkoxytitanium derivative is extremely stable in an aqueous system, and its aqueous solution can be used to perform surface treatment on fillers. It is presumed that this stability in an aqueous system is developed by introducing into the substituent a chelating agent group capable of forming a chelate ring with at least one of the above-mentioned organic acid groups and a Ti atom.

In addition, the stability of alkoxytitanium derivatives in aqueous systems is expressed because they can form a chelate ring with a Ti atom by introducing at least one of the above-mentioned organic acid groups into a substituent, but other chelating agent groups By introducing these together, the stability against aqueous systems is further improved.

If the number of organic acid groups per Ti atom is too small, the stability in an aqueous system will be reduced and the surface treatment effect of the filler will also be reduced, and if it is too large, the surface treatment effect of the filler will also be reduced. The content of organic acid groups in the alkoxy titanium derivative is preferably in the range of 01 to 20 moles per 1 Ti atom.

Furthermore, if the number of chelating agent groups capable of forming a chelate ring with a Ti atom is too small, the effect of improving stability in aqueous systems will not be sufficiently exerted. The number of chelating agent groups that can form a chelate ring with a Ti atom is TI.

The amount is preferably 0.5 mol or more per 1 atom.

Furthermore, if the average degree of condensation of the tetraalkoxytitanium polymer, which is the raw material for the synthesis of alkoxytitanium derivatives, is excessive, the molecular weight of the obtained alkoxytitanium derivatives will be excessive, and the adhesion rate to the filler will decrease. surface treatment effect is reduced. Therefore, the average degree of condensation of the raw material tetraalkoxytitanium polymer is preferably 6 or less.

The surface-treated filler of the present invention is a filler coated with a partial hydrolyzate of an alkoxy titanium derivative obtained by surface treatment using the above-mentioned surface treatment agent.

Therefore, due to the presence of organic acid groups with good affinity for the polymeric polymer IJ Fuchs on the surface of the filler, the dispersibility of the polymeric polymer IJ Fuchs is extremely excellent, and the fluidity of the composite system is greatly improved. be done.

〔Example〕

The present invention will be explained in more detail with reference to Examples and Comparative Examples.

However, the scope of the present invention is not limited in any way by the following examples.

In addition, in the following examples, "parts" and "%" are based on weight unless otherwise specified.

(1) Synthesis of surface treatment agent (a) Sample T-1 Into a reaction flask equipped with a stirrer, a thermometer, a water-cooled condenser, and a heating device, 1 mol (2
84 parts) and 1 mole of levulinic acid (116 parts) with stirring.
part) was gradually added.

Then, 2 moles (200 parts) of acetylacetone (AcAc) were gradually added. The reaction progressed gradually and generated heat. 6
After aging the reaction by stirring and holding at 0°C for 1 hour, the by-produced isopropanol was distilled off under reduced pressure to obtain a pale yellow solid sample T.
-1: 420 parts were obtained.

The obtained T1 had a TlO2 analytical value of 11.38% (theoretical value 11.40%).

As a result of analyzing T-1 by infrared absorption spectroscopy (IR analysis), absorption based on the carboxy group of the raw material levulinic acid disappeared, and absorption based on the -CO group of coordinated AcAc was observed. From the above results, T-1 has one isopropoxy group of tetraisopropoxy titanium,
It was estimated that it was a crude product of an alkoxytitanium derivative transesterified with a puric acid group and further coordinated with 1 mole of AcAc.

(b) Sample T-2 Into the reaction flask used for the synthesis of sample T-1, 1 mole of tetraisopropoxytitanium polymer with an average degree of condensation of 4 (8
30 parts) and 1 mol (1 mol) of acetoxyacetic acid with stirring.
19 parts) were gradually added. Then, glycolic acid (G
A) 1 mol (76 parts) and 2 mol (200 parts) were gradually added to Ac8. The reaction progressed gradually and generated heat. 6
After aging the reaction by stirring and holding at 0°C for 1 hour, the by-produced isopropanol was distilled off under reduced pressure, and a light brown liquid sample T was obtained.
-2 was obtained.

(c) Sample T''3 In the synthesis of sample T-1, each raw material was mixed with 1 mol (340 parts) of tetrabutoxytitanium and 1 mol (90 parts) of methoxyacetic acid.
9) and 3-phenylacetylacetone (PhAc)
The reaction and post-treatment were carried out under the same conditions as in the synthesis of sample T-1, except that the amount was changed to 1 mol (176 parts), and an orange liquid sample T-3 was obtained.

The obtained T-3 was Tin with an analytical value of 9.92% (theoretical value 9.866%).

As a result of analyzing T-3 by infrared absorption spectroscopy (IR analysis), it was found that the absorption based on the -CO group of metquinacetic acid as a raw material disappeared, and the absorption based on the -C6H5 group of coordinated PhAC was observed. From the above results, T-1 is
It was estimated that this was a crude product of an alkoxytitanium derivative in which one butoxy group of tetrabutoxytitanium was transesterified with a methquinacetic acid group and further coordinated with 1 mole of PhAc.

(d) Sample T-4 In the synthesis of Sample T-2, each raw material was mixed with 1 mol (1,390 parts) of tetrabutoxytitanium polymer with an average degree of condensation of 6, 1 mol (133 parts) of ethanoyl acetic acid, and lactic acid (LA )
1 mol (90 parts) and methyl acetoacetate (AAMe>
The reaction and post-treatment were carried out under the same conditions as in the synthesis of sample T-2, except that the amount was changed to 2 mol (232 parts), to obtain pale yellow solid sample T-4.

(e) Sample T-5 In the synthesis of Sample 111.1, the reaction and post-treatment were carried out under the same conditions as the synthesis of Sample T-1, except that 1 mole (104 parts) of ethoxyacetic acid was used in place of 1 mole of levulinic acid. The treatment was carried out to obtain a brown solid sample T-5.

(f) Sample T-6 In the synthesis of sample T-2, each raw material was mixed with 1 mol of tetraisopropoxytitanium polymer (1,0
12 parts), 1 mol (130 parts) of oxohexanoic acid and 1 mol (150 parts) of tartaric acid (TA) were used, but the reaction and post-treatment were carried out under the same conditions as in the synthesis of sample T-2, resulting in an orange solid. Sample T-6 was obtained.

((a) Comparative sample C-1 21 mol (340 parts) of tetrabutoxychloride was charged into the reaction flask used for the synthesis of sample T-1, and 2 mol (298 parts) of triethanolamine was gradually added while stirring. The reaction proceeded gradually and generated heat. After the addition of triethanolamine was completed, the reaction was maintained at 60° C. with stirring for an additional hour to ripen the reaction.

Then, the by-produced n-butanol was distilled off under reduced pressure to obtain pale yellow liquid C-1.

The obtained C-1 had a molecular weight of 490 and a specific gravity of 1.051, and gradually turned yellow during storage.

Comparative Sample C-2 1 mol (284 parts) of tetraisopropoxytitanium was charged into the reaction flask used for the synthesis of sample HT-1, and 3 mol (348 parts) of levulinic acid was gradually added while stirring. The reaction progressed gradually and generated heat.

After the addition of levulinic acid was completed, the reaction was aged by maintaining stirring at 60° C. for an additional hour. Then, the by-produced tights property tool was distilled off under reduced pressure to obtain pale yellow liquid C-2.

The obtained C,2 had a molecular weight of 452 and a specific gravity of 1102, and gradually turned yellow during storage.

(2) Surface treatment of heavy calcium carbonate (a) Surface treatment of heavy calcium carbonate Samples T-1 to T-6 synthesized in the above item (1) and comparative samples C-1 to C-2. Two parts of each were dissolved in 98 parts of water to prepare an aqueous solution.

Add 100 parts of heavy calcium carbonate (trade name: Whiten SSB, manufactured by Shiraishi Kogyo ■) to each of 50 parts of the prepared aqueous solution.
After mixing thoroughly in a mortar, it was spread on a stainless steel vat and dried for 2 hours in a hot air dry lamp at 110°C to form a surface-treated heavy calcium carbonate coated with a partial hydrolyzate of an alkoxytitanium derivative. Samples F-1 to F-6 and comparative samples H-1 and H-2 were prepared.

In addition, surface treatment of heavy calcium carbonate was performed using the 2% isopropanol solution of sample T-1 under the same conditions as above, and the surface-treated heavy calcium carbonate sample F-7 was also heated at room temperature for 30 days. Surface treatment of heavy calcium carbonate was carried out under the same conditions as above using a 2% aqueous solution of sample T-1 stored in , to prepare surface-treated heavy calcium carbonate sample F-8.

) Thinning effect of polyether polyol-heavy calcium carbonate composite system Surface-treated inorganic filler sample F prepared in the above item (a)
1 to F-8 and each 1 of comparative samples H-1 and H-2
00 parts to polyether polyol (trade name: Dial
3,000 (manufactured by Mitsui Nisso Tsuretan ■) and kneaded for 30 minutes using an Ishikawa type mulch crusher to obtain a kneaded product.

For comparison, in addition to 75 parts of the above polyether polyol,
Add 1 part of sample T-1 prepared in the above section (1) and 100 parts of untreated heavy carbonate cal/rum, and add the same □-
A kneaded product was obtained by kneading under the following conditions.

Further, as a blank, 100 parts of the above-mentioned heavy carbonate without surface treatment was added to 75 parts of the above-mentioned polyether polyol, and the mixture was kneaded under the same conditions as above to obtain a kneaded product.

The viscosity of the obtained kneaded product at 25°C was measured using a rotary viscometer (Model BgR, manufactured by Tokyo Keikimari) with rotor No.
, 7.2 Or p m.

The viscosity measurement results are shown in Table 1.

Note that 1f-0 in the table below represents an untreated filler.

Table 1 As shown in Table 1, even in the system in which the surface treatment agent of the present invention was directly added to the polymer matrix-filler composite system (see Comparative Example No. 3), the blank (see Comparative Example No. 4) )
However, the system in which the filler of the present invention, which has been surface-treated in advance using an aqueous solution or an alcoholic solvent solution of a surface treatment agent, is added to a polymer matrix (example) shows a significant viscosity-reducing effect compared to (see Comparative Examples 1 and 2), an even greater viscosity-reducing effect can be obtained that is equal to or greater than the system using an alkoxytitanium compound modified with a known amino compound (see Comparative Examples 1 and 2).

(c) Acrylic emulsion - heavy calcium carbonate composite system Surface treatment agent prepared in the above item (1): Samples T-1, T
-2, T-6 and comparative samples: 1 g each of C-1 and C-2 were mixed with 200 g of the above-mentioned heavy calcium carbonate and acrylic emulsion (trade name: Almatex B-175).
, manufactured by Mitsui Toatsu) and kneaded for 30 minutes using an Ishikawa crusher to prepare a kneaded product.

In addition, for comparison, a kneaded material without the addition of a surface treatment agent was prepared (
-It is.

The viscosity of the prepared kneaded product was measured under the same conditions as in section (a) above.

The measurement results are shown in Table 2.

As shown in Table 2, the system to which the surface treatment agent was added has an extremely large viscosity-reducing effect.

(3) Surface treatment of magnesium hydroxide (a) Surface treatment of magnesium hydroxide (1) above
Samples T-1 to T-4 prepared in Section 1 and comparative sample C-1
and C-2 were dissolved in 120 parts of water to prepare an aqueous solution of each sample.

To each of the prepared aqueous solutions, 100 parts of magnesium hydroxide (trade name: Nikyowa Suimag F, manufactured by Kyowa Chemical Co., Ltd.) was added, stirred and mixed, spread in a vat, and heated to 110 parts in the atmosphere.
Surface-treated magnesium hydroxide samples 1-9 to F-12 and comparative sample H-3 having a coating of a partial hydrolyzate of an alkoxy titanium derivative, dried by keeping at a temperature of
and H-4 were prepared.

In addition, using the impropatol solution of sample T-1 with the same concentration as above, surface treatment with magnesium hydroxide (described above) was performed under the same conditions as above, and surface-treated magnesium hydroxide sample F-13 was obtained. In addition, using the aqueous solution of sample T-1 stored at room temperature for 30 days, surface treatment with magnesium hydroxide (described above) was performed under the same conditions as above to obtain surface-treated magnesium hydroxide sample F-14. Prepared.

(b) Thinning effect of dioctyl phthalate (DOP)-surface-treated magnesium hydroxide composite system Surface-treated magnesium hydroxide samples F-9 to F-14 prepared in the above (a) and comparative samples H-3 and H-
100 parts of each of 4 were added to 240 parts of DOP and kneaded for 30 minutes using an Ishikawa crusher to prepare a kneaded product.

In addition, for comparison, DOP: 240 parts and sample T-
1:1 part and untreated magnesium hydroxide (supra) 1
00 parts were added and kneaded under the same conditions as above to obtain a kneaded product. Further, as a blank, 100 parts of untreated magnesium hydroxide (described above) was added to 240 parts of DOP to obtain a kneaded product in the same manner as above.

The viscosity at 25° C. of each of the prepared kneaded products was measured in the same manner as in section (2) (b) above.

The viscosity measurement results are shown in Table 3.

It is excellent in Table 3, and the viscosity-reducing effect of the DOP-magnonium hydroxide composite system is large.

(4) Surface treatment silica (a) Surface treatment of silica Dissolve 1 part each of samples T-1 to T-4 and comparative samples C-1 and C-2 prepared in the above item (1) in 100 parts of water. and prepared aqueous solutions of each.

Silica (trade name: Crystally) C was added to the prepared aqueous solution.
After adding 100 parts of MC-1 (manufactured by Denshoku Co., Ltd.) and stirring for 10 minutes, it was filtered and dried at 110°C to obtain a surface-treated silica sample F- coated with a partial hydrolyzate of an alkoxy titanium derivative.
15 to F-18 and comparative samples mH-5 and H-6 were prepared.

In addition, the surface treatment of silica (described above) was carried out using the isopropanol solution of sample T-1 with the same concentration as above and under the same conditions as above, and the surface-treated silica sample F-19 was also heated at room temperature. Using the aqueous solution of sample T-1, which had been stored for 30 days, surface treatment of silica (described above) was performed under the same conditions as above to prepare surface-treated silica sample F-20.

et al.) Epoxy resin-silica system Surface-treated silica sample F-15 prepared in section (a) above
5 each of F-20 and comparative samples IfH-5 and H-6
0 parts and 100 parts of a bisphenol A type epoxy resin (trade name: Epicoat 828, manufactured by Yuka Shell Epoxy Co., Ltd.) were thoroughly mixed using a triple roll, and the viscosity of the resulting mixture at 25°C was measured.

Further, as a blank, 50 parts of the above-mentioned silica without surface treatment was added to 100 parts of the above-mentioned bisphenol A type epoxy resin and kneaded under the same conditions as above, and the viscosity of a kneaded product was also measured.

Next, 100 parts of the aforementioned bisphenol A type epoxy resin, 6 parts of a curing agent (trade name: YHP-201, manufactured by Shell Chemical ■), surface-treated silica samples F-15 to F-20, comparative sample H-5, and H-6 = 180 parts was kneaded in a pickling machine, and the curing conditions were 100°C x 16 hours and 120°C x 4
The crack resistance (1 cycle from -45° C. to 150° C. for 30 minutes) was tested for the cured product over time.

These results are shown in Table 4.

[5) Surface treated titanium oxide (a) Surface treatment of titanium oxide Samples T-1, T-2, T-5 prepared in the above item (1)
, T-6 and comparative samples C-1 and C-2 were dissolved in 100 parts of water to prepare respective aqueous solutions.

Titanium oxide (trade name: Taibake R-830, manufactured by Ishikata Sangyo ■) 1001 was added to each of the prepared aqueous solutions, stirred for 10 minutes, filtered, and dried at 110°C to coat the partial hydrolyzate of the alkoxytitanium derivative. Surface-treated titanium oxide samples F-21 to F-24 and comparative samples H-7 and H-8 were prepared.

In addition, surface treatment of titanium oxide (described above) was carried out using the isopropanol solution of sample T-1 with the same concentration as above and under the same conditions as above, and surface-treated titanium oxide sample F-25
, and the above sample stored at room temperature for 30 days: T-
Using the aqueous solution of No. 1, titanium oxide (described above) was surface-treated under the same conditions as above to prepare a surface-treated titanium oxide sample F-26.

et al.) Acrylic emulsion - titanium oxide system (a) above
Surface-treated titanium oxide samples F-21 to F-2 prepared in Sections
6 and comparative samples H-7 and H-8, 50 parts each, and a pycrylic resin solution (trade name: Acrydec A166,
(manufactured by Dainippon Ink) and mix well to form a paint.
The viscosity of the obtained paint at 25°C was measured.

In addition, as a blank, the aforementioned acrylic tree sushi solution 100
The titanium oxide 50 mentioned above which has not been subjected to surface treatment
The viscosity of the kneaded product was also measured by adding 50% of the mixture and kneading it under the same conditions as above.

Next, apply this paint to the steel plate JIS G3141,
It was baked at 120°C for 15 minutes and examined for gloss, pencil hardness, and adhesion. Note that adhesion was also measured after the test piece was immersed in water at 50° C. for 4 days.

These results are shown in Table 5.

(6) Surface treatment filler [VE (a) Surface treatment of talc One part each of samples T-3 to T-6 and comparative samples C, -1 and C-2 prepared in the above item (1) was dissolved in water. 100 parts of each to prepare an aqueous solution.

To the prepared aqueous solution, 100 parts of talc (Shiraishi Kogyo ■!) was added, stirred for 10 minutes, filtered and dried at 110°C to obtain surface-treated talc F-27~F coated with a partial hydrolyzate of an alkoxytitanium derivative. =30 and comparative sample H-9
and H-10 were prepared.

In addition, talc (described above) was surface-treated using an isopropanol solution of sample T-3 with the same concentration as above and under the same conditions as above, and the surface-treated talc sample F-31 was also heated at room temperature. Using the aqueous solution of sample T-3, which had been stored for 30 days, surface treatment of talc (described above) was performed under the same conditions as above to prepare surface-treated talc sample F-32.

(b) HDPE-talc system Surface-treated talc F-27 to F- prepared in section (a) above
32, H-9 and H-10 in 1 (DP
In addition to 75 parts of E (trade name: Hysex 1300J, Mitsui Petrochemicals@tm), 15 parts of the mixture was kneaded for 20 minutes using two rolls heated to 1°C, then cooled and pulverized.

The melt viscosity of the obtained pulverized product was measured using a melt indexer.

In addition, the obtained pulverized product was heat-pressed (180°C, 500°C).
kg/cat) for 5 minutes to prepare test specimens, and the tensile strength, flexural strength and flexural modulus were measured.

The bending strength was also measured after the test piece was immersed in water at 50°C.

These results are shown in Table 6.

-〇2 (7) Surface treated filler CVI] (a) Surface treatment of mica 1 part each of samples T-1 to 1 and 4 prepared in the above item (1) and comparative samples C-1 and C-2 were dissolved in 100 parts of water to prepare respective aqueous solutions.

Add 100 parts of mica (trade name: Sujirite Mica 325-3, manufactured by Kuraray ■) to each of the prepared aqueous solutions.
After stirring for a minute, it was filtered and dried at 110° C. to prepare surface-treated mica samples F-33 to F-36 and comparative samples H-11 and H-12 having a coating of a partial hydrolyzate of an alkoxytitanium derivative.

In addition, surface treatment of mica (described above) was carried out using the isopropanol solution of sample T-1 with the same concentration as above and under the same conditions as above, and the surface-treated mica sample F-37 was also heated at room temperature. Using the aqueous solution of sample T-1, which had been stored for 30 days, surface-treated mica (described above) was prepared under the same conditions as above to prepare surface-treated mica sample F-38.

ω) Volutylene terephthalate resin-mica system Surface-treated mica sample F-33 prepared in item (11) above
~15 parts each of F-38 and comparative samples H-11 and H-12 and polyethylene terephthalate resin (molecular weight 9
000) were kneaded for 15 minutes using two rolls heated to 260°C, then crushed and pulverized.

The obtained pulverized material was heat-pressed (260℃, 500kg/
CI+! ) for 5 minutes to prepare test pieces, and their tensile strength, bending strength and elongation were measured.

Regarding tensile strength and bending strength, the test piece was
Measurements were also made on samples immersed in water at ℃ for 4 days.

These results are shown in Table 7.

(8) Surface treated filler [■] (a) Surface treatment of wollastonite Samples T-1, T-2, T-4, T-5'J6 prepared in the above item (1)
and 1 part each of Comparative Samples C-1 and C-2 in 100% water.
to prepare respective aqueous solutions.

To each of the prepared aqueous solutions, 100 parts of wollastonite (trade name: calcium silicate NYAD-G, manufactured by Nagase Sangyo ■) was added, stirred for 10 minutes, filtered, and dried at 110°C to partially hydrolyze the alkoxytitanium derivative. Surface-treated wollastonite samples F-39 to F-42 and comparative samples H-13 and H-14 having a coating of the same material were prepared.

In addition, surface treatment of wollastonite (described above) was performed using the isopropanol solution of sample T-1 with the same concentration as above and under the same conditions as above, and surface-treated wollastonite sample F-43 was prepared. In addition, using the aqueous solution of sample T-1 stored at room temperature for 30 days, surface treatment of wollastonite (described above) was performed under the same conditions as above to prepare surface-treated wollastonite sample F-44. did.

) Nylon-wollastonite system 30 parts each of the surface-treated wollastonite samples F-39 to F-44 prepared in the above item (a) and comparative samples H-13 and H-14 were added to nylon 6 (polymerization degree 600)7
After kneading for 20 minutes using two rolls heated to 250°C, the mixture was cooled and pulverized.

The melt viscosity of the obtained pulverized product was measured using a melt indexer.

In addition, the obtained pulverized material was heated at a resin temperature of 240°C and an injection pressure of 12°C.
A test piece was prepared by injection molding at 00 kg/cat and a mold temperature of 80°C, and its tensile strength, bending strength, and bending modulus were measured.

Regarding tensile strength and bending strength, the test piece was
Measurements were also made on samples immersed in water at ℃ for 4 days.

These results are shown in Table 8.

〔Effect of the invention〕

As shown in the above examples, the surface treatment agent of the present invention has a large surface treatment effect on the filler, and a polymer matrix-filler using a filler that has been surface-treated in advance with this surface treatment agent. The composite system has an extremely excellent viscosity reducing effect.

In particular, when the surface-treated filler of the present invention treated in an aqueous system is kneaded into a polymer matrix, the viscosity-reducing effect of the composite system is extremely large, and the dispersibility in the polymer matrix is extremely excellent.

By using a surface-treated filler that has been surface-treated using the filler surface treatment agent of the present invention, it is possible to improve workability due to high loading of the filler into the polymer matrix and a decrease in the viscosity of the composite system. becomes.

Furthermore, the filler surface treatment agent of the present invention is extremely stable in an aqueous system, and is extremely safe because it does not require the use of an organic solvent unlike conventional titanium force coupling agents.

The present invention provides a surface treatment agent with excellent stability in an aqueous system and a polymeric multi-IJ surface treated with this surface treatment agent.
It provides a surface-treated filler with excellent Fuchs dispersibility, and its industrial significance is extremely large.

Claims (6)

[Claims] (1) (a) Tetraalkoxytitanium and/or a hydrolyzed condensation product (polymer) of tetraalkoxytitanium with an average degree of condensation of 6 or less (b) Selected from the group consisting of keto acids, acyloxycarboxylic acids, and alkoxyacetic acids (c) at least one chelating agent capable of forming a chelate ring with a Ti atom; consisting of the reaction products of the above (a), (b) and (c); Ti: 0.1 to 2.0% per atom; 0 mol of said (b)
and an alkoxy titanium derivative having the above (c) chelating agent group in an amount of 0.5 mol or more per Ti atom. (2) In claim (1), the keto acids described in (b) have the general formula: R^1COR^2COOH (where R^1 is an alkyl group having 1 to 5 carbon atoms, R^ 2 represents an alkylene group having 1 to 3 carbon atoms) A surface treatment agent that is at least one compound represented by (3) In claim (1), the acyloxycarboxylic acid according to item (b) has the general formula: R^3COOR^4C
OOH (here, R^3 is an alkyl group having 1 to 5 carbon atoms,
R^4 represents an alkylene group having 1 to 5 carbon atoms) A surface treatment agent that is at least one compound represented by (4) In claim (1), the alkoxyacetic acid described in (b) has the general formula: R^5OCH_2COOH
(Here, R^5 represents an alkyl group having 1 to 5 carbon atoms.) A surface treatment agent that is at least one compound represented by (5) In claim (1), T as described in (c)
The chelating agent that can form a chelate ring with the i atom is hydroxycarboxylic acids, β-diketones, α- or β-
A surface treatment agent that is at least one member selected from the group consisting of keto acids and their lower alkyl esters and (poly)alkylene glycols. (6) A surface treatment filling characterized by having a coating of a partial hydrolyzate of an alkoxy titanium derivative consisting of the reaction products of (a), (b) and (c) according to claim (1). agent