JP2003506549A - Method for producing rubber silica masterbatch based on the use of polymer latex - Google Patents

Abstract

  (57) [Summary] The present invention relates to a filled polymer masterbatch based on a polymer derived from latex, and to a method for its production. In one embodiment of the invention, the invention relates to the hydrophobization of particles, in particular mineral particles which are hydrophilic and have surface hydroxyl groups, such as silica, silicates, clays, alumina, titanium dioxide and the like. However, the invention also relates to the treatment of non-mineral particles, ie carbon black. In another embodiment of the present invention, the present invention further relates to a filled polymer latex, especially a silica filled polymer latex. In another embodiment, the present invention relates to a silica-rubber masterbatch and a method for making the same.

Description

Detailed Description of the Invention

FIELD OF THE INVENTION The present invention relates to a filled polymer masterbatch based on a polymer derived from a latex and a process for its preparation.

In one embodiment, the invention relates to hydrophobicizing particles, in particular mineral particles that are hydrophilic and have surface hydroxyl groups, such as silica, silicates, clays, alumina, titanium dioxide and the like. . However, the invention also includes the treatment of non-mineral particles, ie carbon black. In another embodiment, the present invention further relates to a filled, especially silica-filled, polymer latex. Moreover, in another embodiment, the present invention relates to a silica-rubber masterbatch and a method for producing the same.

Background Art In recent years, especially since 1992, Groupe Michelin (GM)
In a patent (EP 0501227A1; Au-A-11177192), a fairly significant improvement in silica reinforced tires is made, in which the tread compound mixed with precipitated silica is based on conventional carbon black fillers. It has been disclosed to have several important performance advantages over the ones described above. The improvement is this “green tire (Green Tire) when compared to a conventional tire filled with carbon black.
Tire) ”, improvements in terms of (a) low rolling endurance, (b) good traction on snow, and (c) low noise generation are claimed.

Rubber for tires is often supplied by tire manufacturers for tire production in the form of masterbatches that allow rapid processing into rubber compounds.
These masterbatches may contain two or more elastomers, in which case they are typically hydrocarbon rubbers, extender oils and / or fillers. An example of a commercially available masterbatch is Buyer (
Bayer), available from Takuten ^(Taktene (R)) 1359, a solution polybutadiene / carbon black / oil masterbatch and DSM Kopurima, U. S. A variety of carbomixes available from A (DSM coplymer USA) (C
arbomix ^®) Emulsion Includes styrene butadiene copolymer / carbon black masterbatch grade.

Commercial fillers for these commercial masterbatches contain carbon black in particulate form. These particles are usually hydrophobic and therefore
Disperses easily in hydrophobic elastomers. In contrast, precipitated silica has a fairly hydrophilic surface, which creates considerable difficulty when the filler is dispersed in a hydrophobic rubber elastomer.

Traditionally, efforts have been made by Burke, for example in US Pat. No. 3,700,690, to make masterbatches from elastomeric dispersions and aqueous dispersions of silica. Burke sought to overcome the previously known difficulties of uniformly mixing fine silica particles into a masterbatch. In Burk's method, no elastomeric silica masterbatch was brought to the market, and no commercial product using Burk's technology was ever produced.

EP 0849320 discloses silica masterbatches based on emulsion polymers. However, the nature of the resulting masterbatch was not disclosed, and the disclosed general formula of the applied coupling agent contains many different chemical units, in which case it is described in the manner described. Exhibits a wide range of efficacy. The coupling agent used in this invention or its beneficial effect is not publicly available by this document.

WO 98/53004 discloses silica masterbatches based on various polymers containing rubber. The method of making a masterbatch described in WO 98/53004 is based on the use of polymer solutions.

DISCLOSURE OF THE INVENTION The object of the present invention is to prevent or mitigate at least one of the disadvantages in the prior art indicated above.

Another object of the present invention is to provide a novel masterbatch composition containing a fairly hydrophobic particulate material and a polymer derived from a latex.

Another object of the present invention is to provide a new process for making a masterbatch composition containing a latex-derived polymer and a highly hydrophobic particulate material.

Another object of the invention is to provide the use of the rubber mixture in the manufacture of the molded or extruded product of the invention.

[0013] Detailed Description of the Invention   These purposes are (1) Particles of formula I:

[0014]

[Chemical 9]

[Wherein at least one of R ¹ , R ² and R ³ is a hydroxyl group or a hydrolyzable group; R ⁴ is a divalent group that is hydrolysis resistant at a Si—R ⁴ bond; R ⁵ is hydrogen; C _1-40 alkyl; C _2-40 mono-, di- or tri-unsaturated alkenyl group; C ₆ -C ₄₀ aryl group; formula

[0016]

[Chemical 10]

A group of wherein x is an integer from 2 to 10 and R ¹³ and R ¹⁴ may be the same or different and are each hydrogen; C _1-18 alkyl; C _2-18 Mono-, di- or tri-unsaturated alkenyl; phenyl;

[0018]

[Chemical 11]

[0019] A group of b, in which b is an integer from 1 to 10; formula

[0020]

[Chemical 12]

The group c, in which c is an integer from 1 to 10 and R ²² and R ²³ may be the same or different and each represents hydrogen, a C _1-10 alkyl group or a C _2-10 alkenyl group. With the proviso that there is no double bond at the α-position to the nitrogen atom;

[0022]

[Chemical 13]

A group of R, wherein r is an integer from 1 to 6 and d is an integer from 1 to 4; R ⁶ may be any group shown for R ⁵ . Alternatively, R ⁵ and R ⁶ are taken together to form the formula

[0024]

[Chemical 14]

To form a divalent group of A, wherein A is selected from the group containing a —CHR group or a —NR group, where R is hydrogen or a C _1-40 alkyl group or C _2-40 alkenyl _group, C 6 _{-C 40} aryl group, an oxygen atom and a sulfur atom, and, t
And v independently of one another are 1, 2, 3, or 4, provided that the sum of t and v does not exceed 6] or a acid addition salt thereof or a quaternary ammonium salt thereof. And (2) particles having the formula II:

[0026]

[Chemical 15]

[Wherein, R ¹⁵ , R ¹⁶ and R ¹⁷ have the same meanings as R ¹ , R ² and R ³ and R ¹² is a C _8-10 alkyl group or a C _8-40 mono group. -, Di- or tri-unsaturated alkenyl groups, which may be substituted by one or more aryl groups, preferably phenyl groups,

[0028]

[Chemical 16]

A group of R ¹⁸ is a divalent group resistant to hydrolysis with a Si—R ¹⁸ bond,
R ¹⁹ is a C _1-40 alkyl group, a C _2-40 mono-, di- or tri-unsaturated alkenyl group, a substituted aromatic group such as a phenylene group — (C ₆ H ₄ ) —,
Biphenylene group _{- (C 6 H 4) -} (C 6 H 4) -, group _{(C 6 H 4) -O- (} C 6 H 4) - , or a naphthylene group _{- (C} 10 _{H 6) -} are selected from, At that time, the aromatic group unsubstituted _{or, C 1 to 20} alkyl or _{C 2 to 20} mono -, di- - or tri - may be substituted by unsaturated alkenyl group; ^{and, R 20} is ^{R 1 9} And R ¹⁹ and R ²⁰ do not have a tertiary carbon atom adjacent to the nitrogen atom, and at least one of R ¹⁹ and R ²⁰ is , Having a carbon chain of at least 8 carbon atoms in length, uninterrupted by any heteroatoms] or its acid addition salt or its fourth
Contacting with an ammonium salt, and (3) particles of steps (1) and (2) and one or more polymers,
This is accomplished by a method of making the composition that includes the step of mixing in the latex state.

In compound (I), preferably ^{two of} R ¹ , R ² and R ³ , most preferably R ¹ , R ² and R ³ are hydroxyl groups or hydrolyzable groups.

[0031]   Furthermore, preferably R¹, R^TwoAnd R^ThreeAll three groups of are easily hydrolyzed
It is solvable. Suitable group R¹Is a hydroxyl group and the formula OC_pH_{Two p} It contains +1 hydrolyzable groups, where p has a value of 1-10. Alkyl chain is acid
It may be interrupted by elementary atoms, for example of the formula CH_ThreeOCH_TwoO-, CH _Three OCH_TwoOCH_TwoO-, CH_Three(OCH_Two)_FourO-, CH_ThreeOCH_TwoCH_TwoO
-, C_TwoH₅OCH_TwoO-, C_TwoH₅OCH_TwoOCH_TwoO- or C_TwoH₅OC
H_TwoCH_TwoThis produces an O-group. Other suitable hydrolyzable groups are phenoxy, acetoxy.
Ci, chloro, bromo, iodo, ONa, OLi, OK or amino or monoa
Includes alkylamino or dialkylamino, where one or more alkyls
A kill group has 1 to 30 carbon atoms.

[0032]   R^TwoAnd R^ThreeIs R¹May have the same meaning as R, provided that R¹, R ^Two And R^ThreeAt least one of is chloro, bromo or iodo. Good
R is better¹, R^TwoAnd R^ThreeOnly one or two of the
ONa, OLi or OK.

Non-limiting examples of groups R ² and R ³ that are not hydrolytic groups include C _1-10 alkyl, C _2-10 mono- or di-unsaturated alkenyl, and phenyl.

In addition, as shown below, R ² and R ³ may each be a group —R ⁴ —NR ⁵ R ⁶ . More preferably, R ¹ , R ² and R ³ are all the same,
_{CH 3 O-, C 2 H 5} O- or _C 3 _H 8 is O-. Most preferably all are those _CH 3 is O-.

In the divalent group R ⁴ , for example, N—R ⁴ —Si is represented by the formula: N— (CH ₂ ) _p (O) _o (C ₆ H ₄ ) n (CH ₂ ) _m (CH═CH ) _K- Si
[Wherein k, m, n, o and p may be any arbitrary numbers]. The arrangement of the portion between N and Si is not particularly limited, except that N or O does not directly bond to Si. The value of k is 0 or 1, and the value of m is 0.
20, the value of n is 0, 1 or 2, the value of o is 0 or 1, and the value of p is 0 to 20, provided that k, m, n, o and p are Is at least 1 and does not exceed 20, so when o is 1, p is 1 or more and the sum of k, m and n is 1 Or more, in which case the Si atom is directly bonded to the carbon atom. No hydrolytic bond between the silicon and nitrogen atoms should be included. Preferably m is 3 and l, n, o and p are all 0, in which case R ⁴ is-
CH ₂ CH ₂ CH ₂ - is.

The group R ⁵ is preferably a C _8-20 monounsaturated alkenyl group, most preferably a C _16-18 monounsaturated alkenyl group. R ⁶ is preferably hydrogen.

Suitable compounds of formula I include, without limitation, 3-amino-propylmethyldiethoxysilane, N-2- (vinylbenzylamino) -ethyl-3-aminopropyl-trimethoxysilane, N- (2-Aminoethyl) -3-aminopropyltrimethoxysilane, trimethoxysilylpropyldiethylenetriamine, N-2
-(Aminoethyl) -3-aminopropyltris (2-ethylhexoxy) silane, 3-aminopropyldiisopropylethoxysilane, N- (6-aminohexyl) aminopropyltrimethoxysilane, 4-aminobutyltriethoxysilane, 4- Aminobutyldimethylmethoxysilane, triethoxysilylpropyl-
Diethylenetriamine, 3-aminopropyltris (methoxyethoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyl-tris (2-ethylhexoxy) ) Silane, 3-aminopropyldiisopropylethoxysilane, N- (6-
Aminohexyl) aminopropyltrimethoxysilane, 4-aminobutyltriethoxysilane, and (cyclohexylaminomethyl) -methyldiethoxysilane.

Preferred compounds of formula I are those in which R ⁵ is hydrogen and R ⁶ is the following mixed alkyl groups: soya alkyl, tall oil alkyl, stearyl, tallow alkyl, dihydrogen. Tallow alkyl, coco alkyl, rosin alkyl, and palmityl, where the alkyl group is considered to optionally contain unsaturation.

Preferably, at least one of R ⁴ , R ¹³ and R ¹⁴ has a chain of at least 8 carbon atoms, more preferably at least 10 carbon atoms, uninterrupted by any heteroatoms.

The compound of formula I may be used as the free base or alternatively in the form of its acid addition salt or its quaternary ammonium salt, ie:

[0041]

[Chemical 17]

[Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ have the meanings given above;
R ⁷ is hydrogen, a C _1-10 alkyl group or a C _2-40 mono-, di- or tri-
Selected from unsaturated alkenyl groups, and X is an anion]. In this case, X is suitably chlorine, bromine or sulphate, chlorine and bromine being preferred and R ⁷ being preferably hydrogen.

Non-limiting examples of suitable salts of compounds of formula I are N-oleyl-N-[(3-triethoxysilyl) propyl] ammonium chloride, N-3-aminopropylmethyldiethoxysilane hydrobromide, (Aminoethylamino-methyl) phenyltrimethoxysilane hydrochloride, N-[(3-trimethoxysilyl) propyl] -N-methyl, N-N-diallylammonium chloride, N-tetradecyl-N, N-dimethyl-N -[(3-Trimethoxysilyl) propyl] ammonium bromide, 3 [2-N-benzylaminoethyl-aminopropyl] trimethoxysilane hydrochloride, N-octadecyl-N, N-dimethyl-N-[(3
-Tri-methoxysilyl) propyl] ammonium bromide, N-[(trimethoxysilyl) propyl] -N-tri (n-butyl) ammonium chloride, N-
Octadecyl-N-[(3-triethoxy-silyl) propyl] ammonium chloride and N-2- (vinylbenzylamino) ethyl-3-aminopropyl-
It is trimethoxysilane hydrochloride.

[0044]   The sum of t and v is preferably 4.

Preferably R ¹⁸ is a C ₁ -C ₄₀ saturated or unsaturated group (eg alkenyl, aryl, cycloalkyl etc.).

The compounds of formula I are preferably used in the form of salts. The most preferred compound is N
-Oleyl-N-[(3-trimethoxysilyl) propyl] ammonium chloride.

It is stated above that in compounds of formula II the possible and preferred values for R ¹⁵ , R ¹⁶ and R ¹⁷ are the possible and preferred values for R ¹ , R ² and R ^3. As shown above.

When R ¹² is an amino group of the formula —R ¹⁸ —NR ¹⁹ R ²⁰ , preferred values for R ¹⁸ are, for example, those of the formula N—R ¹⁸ —Si are of the formula: N— (CH _{2) p (O) o (} C 6 H 4) n (CH 2) m (CH = CH) k -Si
[Wherein, k is 0 or 1, m is 0 to 20, n is 0, 1 or 2, o is 0 or 1, and p is 0 to 20, provided that , K, m, n,
The sum of o and p is at least 1, and does not exceed 20, and when o is 1, p is also 1 or more, and k
, M and n are one or more].

The arrangement of the portion between N and Si is not particularly limited, except that N or O does not directly bond to Si. There should be no hydrolyzable groups between the silicon and nitrogen atoms. Preferably k, n, o and p are all 0, m is 3 and in particular R ¹⁸ is —CH ₂ CH ₂ CH ₂ —.

[0050]   R¹²Is at least one primary amine nitrogen, secondary amine nitrogen or tertiary amine
It may be a portion containing nitrogen. In this case, R¹⁸Amino group that binds to
Is the formula NR¹⁹R²⁰Given by. R¹⁹Is H or C_1-40Al
Kill group or C_2-40It is a mono-, di- or tri-unsaturated alkenyl group.
Furthermore, R¹⁹Is C_1-20Alkyl-substituted or C_2-20Alkenyl substitution
Is an aromatic group. For example, an aromatic group is a phenylene group- (C₆H_Four) −
, Biphenylene group-(C₆H_Four)-(C₆H_Four)-, Group (C₆H_Four) -O- (C ₆ H_Four)-Or a naphthylene group- (C₁₀H₆)-. R²⁰Is
R¹⁹May be the same as one of the¹⁹And R²⁰At least
One is at least 8 carbon atoms long, uninterrupted by heteroatoms
Of continuous carbon chains.

As indicated above, when R ¹⁹ and R ²⁰ are other than hydrogen, the carbon atom bonded to the nitrogen atom is not a tertiary carbon atom. Preferably, the carbon atom bonded to the nitrogen atom, a primary carbon atom, i.e., -CH 2 _- is.

It is preferred that R ¹⁹ is a mono-unsaturated alkenyl group of 12 to 20 carbon atoms in length, and most preferably R ¹⁹ is a mono-unsaturated alkenyl group of 16 to 18 carbon atoms in length. It is an unsaturated alkenyl group. Furthermore, it is most preferred that R ²⁰ is H.

Alternatively, R ¹² may be a moiety containing a mineral acid salt or a quaternary ammonium salt of an amine. Therefore, the formula for R ¹² is the extended formula -R ¹⁸ -N.
May be described by ^{R 19 R 20 · R 21 X} , this ^time, -R 18 ^{-, R 1 9} and ^{R 20} are those shown above, ^{and, R 21} is H or _{C. 1 to 40} alkyl or _{C 2 to 40} mono -, di- - or tri - an unsaturated alkenyl group and, X is an anion, preferably Cl ^- is, however, HSO4 ^{- -} or Br or SO4 ^- may be .

However, at least one of R ¹⁹ and R ²⁰ must comprise a continuous carbon chain of at least 8 carbon atoms, uninterrupted by any heteroatoms. R ¹⁹ is a mono- or di-unsaturated alkyl group of 12 to 20 carbon atoms in length, and preferably R ¹⁹ is mono- or di-unsaturated of 16 to 18 carbon atoms in length. When it is a saturated alkenyl group, the use of amine salts is preferred. Most preferably, R ²⁰ is H, R ²¹ is H and X is chlorine.

A preferred hydrophobicizing agent of formula II is N-oleyl-N
-(3-trimethoxy-silyl) propylammonium chloride.

Steps (a) and (b) may be carried out simultaneously or sequentially. Process (
When a) and (b) are carried out continuously, it is preferable to carry out step (b) subsequent to step (a).

As will be apparent in the prior art, for example, Formula I and Formula II are the same compounds, for example, R ⁵ and R ¹⁹ are C _8-40 alkyl groups, or R ⁵ and R ¹⁹ _{May be a C8-40} mono-, di- or tri-unsaturated alkenyl group. Thus, when Formulas I and II are the same compound, the process of the invention is a single step (ie, the compound of Formula I and II is added in a single step) and a multi-step (ie, Formula I And compounds of II are assigned and added in two or more steps).

Preferably steps (1) and / or (2) are carried out in an aqueous solution, dispersion or slurry, so that the process product is an aqueous dispersion or slurry of hydrophobized mineral particles. is there.

In one preferred embodiment, the dispersion or slurry resulting from the process of the invention and containing the treated particles (preferably mineral particles, eg silica) is subsequently mixed with a polymer latex. Form a preblend, which in this case subsequently solidifies and is dried to form a silica-filled polymer masterbatch. Depending on the hydrophobicity of the silica filler, it is well dispersed in the polymer. This preferred embodiment results in the in situ manufacture of a masterbatch composition containing the polymer and the treated particles. By "in situ production" is meant that the treated particles are not first isolated but mixed into the masterbatch composition (ie separated from the dispersion or slurry and then dried). Be done).

In another embodiment, the pre-blend containing the polymer latex and the treated particles and optionally auxiliaries does not agglomerate, however, directly for the production of paints, dips or coated fabrics. used.

In another aspect, the invention provides a polymer masterbatch containing treated particles having aminohydrocarboxylic silane moieties attached to the particles, ie, hydrocarbon moieties containing both silicon and nitrogen. To do.

[0062]   Preferably, the aminohydrocarboxylic silane has the formula

[0063]

[Chemical 18]

[Wherein R ^a , R ^b and R ^c are the same or different and each is selected from —O— and —C _p H _2p —, optionally one or Substituted by more oxygen atoms, and p is an integer from 1 to 10; and R ¹² is a C _8-40 alkyl group; C _8-40 mono-, di- or tri-unsaturated Alkenyl group; formula

[0065]

[Chemical 19]

Or an acid addition salt thereof or a quaternary ammonium salt thereof, wherein R ⁴ is a divalent group resistant to hydrolysis by a Si—R ⁴ bond, and R ⁵ is hydrogen, C _1-40 -alkyl, _C2-40 mono-, di- or tri-unsaturated alkenyl; formula

[0067]

[Chemical 20]

A group of wherein Ar is a divalent aromatic group, w is an integer from 1 to 20, and R ⁶ is any group shown for R ^5. Provided that at least one of R ⁵ and R ⁶ has an uninterrupted carbon chain of at least 8 carbons in length].

In another aspect, the invention provides a polymer / filler containing treated filler particles having a contact angle with water of at least about 100 ° C. Preferably, the treated particles are at least about 110 °, more preferably about 115 ° to about 160 °.
°, more preferably about 120 ° to about 150 °, and most preferably about 120 ° to about 140 °.

The contact angle between the particles and water may be simply measured by the following method: (i) A double sided tape is attached to a probe (eg stirrup) and the tape is placed in a sample of granular material. (Ii) Excess powder is removed by gentle tapping and large powder clusters are removed by careful swabbing; (iii) Probes coated with particulate material; Using a conventional contact angle analyzer (e.g. Cahn Dynamic Contact Angle Analysis).
zer) Immerse in distilled water at a rate of 100 microns per second.

[0071]   By this method, the contact angle of particles can be measured in advance.

The particles used in steps (1) and (2) are preferably hydrophobic and are silicates, silica (particularly silica produced by carbon dioxide precipitation of sodium silicate), clay, dioxide. It may be a mineral material selected from the group consisting of titanium, alumina, calcium carbonate, zinc oxide and mixtures thereof.
Further, the particles may be particles of a non-mineral material, such as carbon black. Of course, a mixture of particulate materials may be used.

In a preferred embodiment, steps (1) and (2) may be carried out in an aqueous dispersion or slurry, and the concentration of the aqueous dispersion or slurry of silica particles in silica is 1 to 1. It may be 30% by weight, preferably 5 to 25% by weight.

The dry amorphous silica suitable for use according to the invention may have an average agglomerated particle size of 1 to 100 μ, preferably 10 to 50 μ and most preferably 0 to 25 μ. The 10% by volume of the agglomerated particles are preferably 5 μ or less or 50 μ or more in size.

Suitable amorphous dry silicas also include DIN (Deutsche Industrie Norm) 6
BET surface area measured according to 6131 50-450 m ^{2 /} g and DBP absorption measured according to DIN 53601 Silica 10
It has 150 to 450 g per 0 g and has a dry loss of 0 to 10% by weight, measured according to DIN ISO 787 / II.

The filter cake used may be of any known method, for example Ullmann's
Encyclopedia of Industrial Chemical VOL A23 No.6
42-643, VCH, 1993 (copyright) (Ulmann's Encycling
opedia of Industrial Chemical Vol A23 pages 642-643, VCH Publishers, 199
It may be produced by a known method as described in 3.). The filter cake preferably has a solids content of 5 to 30% by weight, most preferably 15 to 25% by weight and is redispersed in water according to the process of the invention and 5-2.
It has a silica concentration of 0% by weight, most preferably 8-12% by weight. It is preferred to use a filter cake.

If unfiltered slurries made by the known reaction of alkali metal silicates with mineral acids or carbon dioxide are used, the solids content of the unfiltered slurries is from 1 to 30% by weight, It is preferably 5 to 10% by mass of silica.

If an unfiltered slurry is used, the pre-addition of an additional emulsifier or stabilizer for the latex serves to prevent premature coagulation during the masterbatch process. Suitable materials include nonionic emulsifiers and phosphates, especially trisodium phosphate.

The slurry temperature is 0-100 ° C. when the method is carried out under atmospheric pressure,
And, when the operation is carried out in a pressure vessel, it may be 0 to 135 ° C. Most preferably, the process is carried out at atmospheric pressure, the preferred temperature being between 30 and
95 ° C., and most preferably 45 to 90 ° C.

Prior to the addition of silica particles to the compound of formula I, the dispersion or slurry has a pH of between 6 and
It may have a pH of 8, more preferably pH 6.8-7.2. If necessary, the pH may be adjusted by the addition of acids or alkalis such as mineral acids, alkali metal hydroxides, alkaline earth hydroxides, ammonium hydroxide and the like. These may be added as they are or in the form of an aqueous solution.

The amount of the compound of formula I may be 0.1 to 20% by weight of mineral particles in the slurry (dry basis), and preferably 0.25 to 10% by weight, and most preferably Alternatively, it may be 0.5 to 2 mass% of mineral particles.

Preferably, the amount of the compound of formula I used may, conversely, be modified by the size of the mineral particles. The compound may be added to the slurry in its normal state as a liquid or solid. However, it is preferred to add the compound as a liquid to facilitate dispersion. When the melting point of the compound is lower than 95 ° C., it is preferable to add it to the slurry in a molten state at a temperature of at least 5 ° C. higher than the melting point, provided that the temperature of the compound in the liquefied state is 100 It does not exceed 0 ° C and the compound does not decompose under these conditions. It is most preferable to use a solvent when the melting point is higher than 95 ° C.

Preferred solvents are water and alcohols having 1 to 5 carbons, most preferably alcohols having 1 to 3 carbons, which are methanol, ethanol, n-propanol. Or is isopropanol. When the compound of formula I is an alkoxysilane, most preferably, the alkoxy group of the solvent alcohol may be similar to the alkoxy group of an alkoxysilane. For example, when the compound of formula I is methoxysilane, the preferred solvent is methanol. The concentration of the compound in the solvent is 10 to 90% by mass, more preferably 25 to 75% by mass, and most preferably 50% by mass. Preferably, the solution has a lower limit of 0 ° C. and an upper limit of at least 10 ° C. below the boiling point of the solvent and 9
It can be manufactured at 5 ° C. and added to the slurry. The dispersion of the compound is
It is caused by mixing.

For the particular compound of formula I added, the equivalent balance (
It is preferred to measure EB). EB is used to determine whether to add a mineral acid or an alkali metal hydroxide, or a solution thereof. Equivalent equilibrium (EB) is (if ^{present) X,} R 1, ^{R 2} and the absolute value of the sum of the valency of the group ^{R 3,} and X (if ^present), groups R 1, ^{R 2} and ^{R 3} Contribution of (contribu
may be determined from the total size of the ionization), the mass added, and the molecular weight of the compound of formula I, which is derived by the formula: where X = Cl or X = Br. The group contribution of X in is -1 and thus results in a value of -1 when X is present. The group contributions for each R ¹ , R ² and R ³ are:
Generally, it is 0 in all groups except: The group is CH ₃ COO.
, Cl or Br is -1, or +1 when the group is an amine (including imine), ONa, OK or OLi. X, R ¹ ,
If the sum of the group contributions for R ² and R ³ is 0, no adjustment with mineral acid or alkali metal hydroxide (or its solution) is necessary. When the total value of the groups is a positive integer, adjustment with a mineral acid is desirable, and when it is a negative integer, adjustment with an alkali metal hydroxide is desirable.

For example, if R ¹ ═OCH ₃ , R ² ═CH ₃ , R ³ ═Cl and X = Br, then the sum of the group valencies (gv) is:

[0086]

[Equation 1]

The negative sign in front of the sum indicates that adjustment with alkali metal hydroxide is required. The equivalent number of alkalis required is given by the equilibrium equilibrium (EB)
In this case, this includes the absolute value of the sum of the base contributions (Σabs.) As scaling factors:

[0088]

[Equation 2]

In a further example, if the process according to the invention requires 600 g of a compound of formula I having a molecular weight of 350 g and normalizes to a total group value of −2, then EB is Is calculated as:

[0090]

[Equation 3]

Therefore, in this example 34.28 gram equivalents of alkali metal hydroxide may be added. Sodium hydroxide is the preferred alkali metal hydroxide. The mass of sodium hydroxide is as follows:

[0092]

[Equation 4]

A preferred technique according to the present invention is to add an alkali metal hydroxide or mineral acid in water to 1 to 25% by weight, more preferably 5 to 10% by weight before adding the solution to the slurry.
It is to dissolve to some extent at the concentration of.

Preferably, the amount of the hydrophobic compound of formula II to be added is generally 0.5 to 20% by weight of particles (preferably mineral particles, eg silica) added to the slurry (dry basis). ), And in other words, it is proportional to the particle size of the silica particles.

The compounds can be added to the slurries in the usual way as liquids or solids. However, to facilitate dispersion, the compound is preferably added as a liquid, if possible. If the melting point of the compound is below 95 ° C,
It is preferable to add this in a state of being melted in a slurry at a temperature at least 5 ° C. higher than the melting point, provided that the temperature of the compound in the liquefied state does not exceed 100 ° C. Does not decompose under conditions. It is most preferable to use a solvent when the melting point is higher than 95 ° C. A suitable solvent is one carbon atom.
Alcohols containing .about.5, and most preferably those containing 1 to 3 carbon atoms, in this case methanol, ethanol, n-propanol or isopropanol. Most preferably, when the compound of formula II is an alkoxysilane, the alkoxy group of the solvent alcohol is the same as the alkoxy group of the alkoxysilane. For example, when the compound of formula II is methoxysilane, the preferred solvent is methanol. The compound concentration in the solvent is 10
It is 90% by mass, preferably 25 to 75% by mass, and most preferably 50% by mass. Preferably, the solution has a lower limit of 0 ° C. and a boiling point of the solvent of at least 1.
It may be added at an upper limit below 0 ° C and 95 ° C and may be added to the slurry.

[0096]   After the addition of the added hydrophobic compound of formula II, if necessary, the equivalent
Balance (EB) with any mineral acid or alkali metal hydroxide (or solution of these)
Should be calculated to determine how much should be added. Equivalent equilibrium (EB)
Is X, R¹⁵, R¹⁶And R¹⁷Absolute value of the sum of the group values of and
It may be determined from the mass as well as the molecular weight of the compound, in which case this is
The contribution of the group of X when X = Cl or X = Br is -1.
Yes, and thus has a value of -1 if X is present. Each R¹⁵, R ¹⁶ And R¹⁷The group contributions with respect to are generally for all groups except
Is 0 for: the group is CH_ThreeWhen it is COO-, Cl- or Br-,
It is -1, or when the group is amine, ONa, OK or OLi.
+1 in the case. X, R¹⁵, R¹⁶And R¹⁷Sum of group contributions with respect to
Is 0 and is adjusted by mineral acid or alkali metal hydroxide (or a solution thereof).
No adjustment is necessary. Adjust with a mineral acid if the sum of the group values is a positive integer
Is preferable and is a negative integer, adjust with alkali hydroxide.
Is preferred.

For example, R ¹⁵ is OC ₂ H ₅ , R ¹⁶ is OCH ₃ , and R ¹⁷ is C
When H ₃ and X is Cl, the sum Σ of the group valences (gv) is as follows:

[0098]

[Equation 5]

The negative sign in front of the sum indicates that adjustment with alkali metal hydroxide is necessary. The equivalent number of alkalis required is indicated by the equilibrium equilibrium (EB), where this is the absolute value of the sum of the group contributions (Σabs) as a scaling factor.
Indicates.

[0100]

[Equation 6]

Following the examples, according to the method according to the invention, a compound of formula II having a molecular weight of 466 g
When 3450 g of the compound of No. 1 is converted and the total value of the groups is -1, E
B is calculated as follows:

[0102]

[Equation 7]

Therefore, in this example 7.4 g gram equivalent of alkali metal hydroxide is added. Sodium hydroxide is the preferred alkali metal hydroxide. The mass of sodium hydroxide added is as follows:

[0104]

[Equation 8]

A preferred technique according to the invention is to add 2 to 25% by weight and most preferably 2 to 10% by weight of alkali hydroxide or mineral acid in water before adding the solution to the slurry.
It dissolves to some extent at the concentration of.

It is known to vulcanize coupling agents and mix them with the rubber used in tires. Suitable coupling agents include those described in U.S. Pat. No. 4,704,414, EP 0670347A1 and German patent 4435311A1. Suitable coupling agents are bis [3- (triethoxysilyl) propyl] monosulfane, bis [3- (triethoxysilyl)
Propyl] disulfane, a bis [3- (triethoxysilyl) propyl] trisulfane and bis [3- (triethoxysilyl) propyl] mixtures tetrasulfane, in this case, this is a registered trademark Si69 ^(R) (Degussa AG) or Silquest ^(R ) A-1289 (sulfan average 3)
． 5) and Silquest ^(R ) A-1589 (CK-Witco
, Sulfane average 2.0). Another suitable coupling agent is CK-Wi under the trademark Silquest ^(R ) RC-2.
It is a proprietary silane available from tco.

Traditionally, a good balance between the coupling agent and the particles, eg silica,
It has proven difficult to achieve without scorch or premature curing. In accordance with the invention, when particles, in particular silica particles, have been treated to render them hydrophobic for use in the rubber to be subsequently vulcanized, coupling in the process of the invention It is possible to include a step of adding an agent, so that the coupling agent binds to the surface of the hydrophobized mineral particles and disperses the mineral particles in the rubber.

Therefore, in some preferred embodiments of the present invention, the coupling agent is more preferably added to the dispersion after addition to the compound of formula I, but before addition of the compound of formula II. It As indicated above, in some cases Formulas I and II may represent similar compounds. In this case, it is preferred to add the coupling agent between successive additions of the compounds of formula I and formula II.

The coupling agent may be added after any addition of mineral acid or alkali metal hydroxide, which is indicated by the EB calculation. Suitable preferred coupling agents are those described in WO-A-98 / 53004.

In the present invention, hydrophobic silica, either in aqueous suspension or in a slurry, is mixed with a polymer latex, for example an elastomer latex, to form a silica rubber masterbatch. The hydrophobized silica is coupled to a coupling agent, such as Si-69 ^(R) or Silquest ^(R) , as indicated above.
It is particularly preferred to treat with RC-2 before mixing with the latex.

Non-limiting examples of suitable latices include those obtained directly by emulsion polymerization of butadiene, styrene, isoprene, acrylonitrile, vinyl chloride, acrylic acid, methacrylic acid, acrylic acid esters or mixtures thereof. Particularly suitable are emulsion latexes of butadiene-co-styrene and butadiene-co-acrylonitrile. Other suitable latices include those artificially prepared from polymer solutions or dry polymers, which are hereby incorporated by reference only, eg US Pat. No. 4,177,177. It is disclosed on the page. A preferred artificial latex is prepared by first dissolving the polymer in a suitable solvent to form a cement, emulsifying the formed cement with a suitable amount of water and an emulsifier, stripping the solvent, and if preferred. Is produced by concentrating the final latex.

Suitable artificial latices that can be produced in this way, however, include without limitation latexes such as butyl rubber, polychloroprene rubber, solution styrene-butylene copolymers, solution polybutadiene and the like. In addition, suitable for the process are natural latexes, for example hevea brasiliens.
produced by is and parthenium species, in which case
They are commonly applied as natural rubber latex and guayule rubber, respectively. Suitable are modified natural rubbers, for example those from epoxidized natural rubber latex.

Most preferred are latexes of butadiene-styrene copolymers, butadiene-acrylonitrile copolymers and butadiene-acrylonitrile-styrene terpolymers. More preferably, it is a latex produced through emulsion polymerization. The latex may be used directly from the polymerization process, however, it is preferred to strip off any residual monomer and concentrate it before use.

Polybutadiene, butadiene styrene copolymer, isoprene styrene copolymer, butadiene isoprene styrene terpolymer, butadiene acrylonitrile copolymer, butadiene acrylonitrile styrene
The terpolymer may optionally include other polymerizable monomers containing functional groups such as amines, amides, carboxyls, esters, sulfonic acids or hydroxyls.

Optionally, the process oil and antioxidant may be added to the polymer latex prior to mixing with the treated silica slurry or after mixing the treated silica slurry and latex. .

The amount of latex is such that the final masterbatch contains 5 parts silica per 100 parts polymer.
To 250 parts, preferably 35 to 100 parts, and most preferably 60 to 80 parts.

The latex and optionally oil and antioxidant are mixed with the treated silica slurry to form a preblend.

The preblends are most preferably produced by agglomeration and subsequent drying, or simply by drying alone.

If agglomeration is used to produce the masterbatch, standard emulsified rubber latex flocculants or latex destabilizers, eg solutions of mineral acid salts in water, solutions of mineral acids in water. Is used alone or in combination with a flocculant to destabilize the preblend, which gives a masterbatch in the form of a moist powder. Aggregation may be performed as a batch process or a continuous process. These and other techniques are known to those skilled in the art as conventional latex agglomeration.
Alternatively, the preblend may be agglomerated by high shear, eg, passing through a small orifice at high flow rate. In all of the above cases,
The wet masterbatch powder (especially the agglomerates of the preblend) is then mixed with the agglomeration liquid
The "serum" is separated by sieving or other solid-liquid separation step. The agglomerated wet masterbatch powder is further processed by washing,
And / or dehydrated by pressing. Finally, it is dried by a conventional method such as a hot air oven, a microwave dryer or a fluidized bed dryer to obtain a dried masterbatch.

Furthermore, masterbatches are easily produced by means such as, for example, hot air spray drying, by means such as wiped-film evaporators or dry extruders, without the agglomeration step of drying the preblend. May be.

Preferably, the dry masterbatch is agglomerated with the polyblend, a solution of mineral acid and / or a salt of water in water, alone or in combination with a flocculant,
It is produced by separating the powder by sieving, washing the powder with water and then drying the wet powder with a hot air dryer.

However, another object of the present invention is a filled latex, which in the wet state is in particular a preblend itself. Preblends are, for example, as such or together with additional stabilizers, paints, dips, such as rubber gloves, dental dams, balloons and especially inner tubes, or coated fibers, carpet backing. And may be used for paper. Furthermore, the filled latices, alone or in combination with auxiliaries, are suitable as bases for building fillers.

Moldings or extrudates within the scope of the present invention include cable coatings, hoses, conductive belts, conveyor belts, roll covers, shoe soles, gaskets, braking elements and tires, in particular tire treads.

In order to produce said moldings or extrudates from the masterbatch according to the invention, other rubbers and rubber auxiliaries are used in combination with one or more reaction accelerators, antioxidants, heat stabilizers, light stabilizers. Stabilizers, antiozonants, processing aids, plasticizers, adhesives, blowing agents, dyes, pigments, waxes, extenders, organic acids, setting retarders, metal oxides and activators, such as It may be added together with ethanolamine, polyethylene glycol, hexanetriol, trimethylolpropane or sulfur-containing silyl ethers, which are known in the rubber industry. In addition, other fillers may also be added to the rubber mixture. In addition, hydrophobic and non-hydrophobic oxides and silicate fillers, rubber gels and / or carbon black may be used.

Carbon blacks which may be used for this purpose are known in the rubber industry and may be produced using lamp black, furnace black or channel black processes and have a BET area of 20 to 200 m. ^It may have ² / g. Examples include SAF, ISAF, HAF, FEF and GPF carbon black.

The rubber auxiliaries are used in amounts known in the prior art, in which case this is based in part on the specified application. These amounts are 0.1 to the total amount of rubber.
It may be up to 50% by mass.

Sulfur, sulfur donors or peroxides may be used as cross-linking agents in the production of the shaped or extruded products. Furthermore, the rubber mixtures indicated above preferably contain vulcanization accelerators. Examples of such promoters include mercaptobenzothiazole, guanidine, thiuram, dithiocarbamate, thiourea and thiocarbonate. In addition to sulfur or peroxide, the vulcanization accelerator is used in an amount of 0.1 to 10% by weight (optimum: 0.1 to 5% by weight), based on the total amount of rubber.

The materials indicated above are advantageously mixed in a masterbatch, in particular by simple mixing in a Banbury mixer or other type of internal mixer, mixing extruder, or open mill. . Single-step or multi-step mixing steps may be used.

The mixed compounds may then be loaded into shaped bodies or formed into the desired shape. Vulcanization may be carried out at a temperature of 100-200 ° C. (optimal: 130-180 ° C.), if necessary under a pressure of 10-200 bar.

Embodiments of the present invention are illustrated below, but in this case this does not limit the scope of the invention.

[0131] To produce the examples according to embodiments the present invention, precipitated silica grade ^{HiSil (R)} 23
3 (PPG Industries, USA), sulfur silane Si69® ⁽ Degussa AG, Germany) and N-oleyl-N- (trimethoxysilyl) propylammonium chloride were used according to WO98 / 53004.

[0132] Example 1 Kurinoru ^{(Krynol (R)) 1712 (} ESBR, Bayer AG) was used as the latex component. Spread the latex with aromatic oil 37.5 phr,
Barca Knox ^(Vulkanox (R)) was stabilized with 4020 0.5phr. Example 1
The rubber / silica masterbatch of is based on the following composition: ESBR (76.5% butadiene, 23.5% styrene) 100.0 phr aromatic oil 37.5 phr silica 80.0 phr Si69 6.4 phr N-oleyl-N-. (Trimethoxysilyl) propylammonium chloride 4
． 0 phr 1) Preparation of a hydrophobic silica suspension: To obtain a 20% silica suspension, 367.82 g of silica are completely demineralized water.
It was mixed with 1471.28 g. The silica suspension was heated to 50 ° C. with stirring. 13.79 g of N-oleyl-N- (trimethoxysilyl) propylammonium chloride are added in the molten state, followed by a 2% NaOH solution 13.
79 g was added. 29.38 g of Si69 was then added over 30 minutes. After the addition of Si69, the mixture was stirred for 30 minutes. The treated silica suspension was then heated to 80 ° C. and 16.60 g of N-oleyl-N- (trimethoxysilyl) propylammonium chloride in the molten state were added over 5 minutes. 12.87 g of 10% NaOH solution was then added over 5 minutes. The mixture was stirred during all the above steps. Finally, complete demineralized water was added and diluted in a 10% hydrophobized silica suspension.

2) Preparation of oil blended latex and preblend of hydrophobic silica: 431.03 g of 40% oil emulsion in water, 10% ESBR latex 45
Added to 97.7 g and stirred thoroughly. The oil-extended latex contained the following components: ESSR 459.77 g and aromatic oil 172.41 g The oil-extended latex and the hydrophobic silica suspension were mixed for 15 minutes to form a preblend.

3) Agglomeration of oil-extended latex and hydrophobic silica preblends: Agglomeration was carried out by adding 10% sulfuric acid at room temperature to a stirred mixture of oil-extended latex and hydrophobic silica until pH was 4.8. Carried out. The resulting masterbatch powder was homogeneous in appearance. These were isolated by sieving through a 0.5 mm sieve. Very small amounts of masterbatch particles in the resulting serum were removed by refiltering through a 100 μm filter cloth. The resulting slightly cloudy serum was further filtered through a 589 ³ Blue Ribbon ashless filter paper circle (589 ³ Blue Ribbon ashless filter).
filtered through a paper circle) to remove a small amount of suspended silica. The resulting serum was clear. Then the filter was dried. The difference in the mass of the dried filter before and after filtration corresponds to the amount of silica lost.
This recovered a total of 0.40% of the initial silica added, which means that the masterbatch contains a silica content of 99.60%. The resulting moist masterbatch was dried at 70 ° C. in a vacuum oven.

[0135] Example 2 Kuriren ^{(Krylene (R)) 1500 (} ESBR, Bayer AG) was used as a latex component. Extend the latex with 20 phr of aromatic oil, and
Stabilized with 0.5 phr Vulkanox 4020. The rubber / silica masterbatch is based on the following composition: ESSR (76.5% butadiene, 23.5% styrene) 100.0 phr aromatic oil 20.0 phr silica 80.0 phr Si69 6.4 phr N-oleyl-N- (tri. Methoxysilyl) propylammonium chloride 4
． 0 phr 1) Preparation of Hydrophobic Silica Suspension To obtain a 20% silica suspension, 400 g of silica are completely demineralised 160
Mixed with 0 g. The silica suspension was heated to 50 ° C with stirring. N-oleyl-N- (trimethoxysilyl) propylammonium chloride was added in the molten state, followed by the addition of 15.0 g of a 2% NaOH solution. Si69 3
1.95 g was then added over 30 minutes. After the addition of Si69, the mixture was stirred for 30 minutes. The treated silica suspension was then heated to 80 ° C. and 18.05 g of N-oleyl-N- (trimethoxysilyl) propylammonium chloride was added in the molten state over 5 minutes. 10% NaOH
14.0 g was then added over 5 minutes. The mixture was stirred during all the above steps. Finally, complete demineralized water was added and diluted to a 10% hydrophobic silica suspension.

2) Preparation of oil-extended latex and hydrophobic silica preblend: 250 g of 40% oil emulsion in water was added to 5000 g of 10% ESBR and stirred thoroughly. The oil-extended latex included: 500 g ESBR and 100 g aromatic oil Oil-extended latex and a hydrophobic silica suspension were mixed over 15 minutes to form a preblend.

3) Aggregation of Oil-Extended Latex and Hydrophobic Silica Preblends: Agglomeration was performed by adding 10% sulfuric acid to the stirred preblends at room temperature until a pH of 4.8. The resulting masterbatch powder was uniform in appearance. It was isolated by sieving through a 0.5 mm screen. Very small amounts of masterbatch particles in the resulting serum were removed by refiltering through a 100 μm filter cloth. 58 more of the slightly cloudy serum that results
9 ³ Blue Ribbon Ashless Filter Paper Circle (589 ³ Blue Ri
It was filtered through a bbon ashless filter paper circle) to remove a small amount of suspended silica. The resulting serum was clear.
The filter was then dried. The difference in the mass of the dried filter before and after filtration corresponds to the amount of silica lost. This recovered a total of 0.35% of the silica initially added, in this case 9
It is meant to contain a silica content of 9.65%. The resulting wet masterbatch is 7
Dried in a vacuum oven at 0 ° C.

[0138] Example 3 Perubunan ^{(Perbunan (R)) NT2895 (} NBR, Bayer AG) was used as a latex component. The rubber / silica masterbatch is based on the following composition: NBR (72% butadiene, 28% acrylonitrile) 100.0 phr silica 80.0 phr Si69 6.4 phr N-oleyl-N- (trimethoxysilyl) propylammonium chloride 4
． 0 phr 1) Preparation of a hydrophobic silica suspension: 22.22 g of silica are completely demineralized water to obtain a 20% silica suspension.
Mixed with 8.88 g. The silica suspension was heated to 50 ° C with stirring. N-oleyl-N- (trimethoxysilyl) propylammonium chloride 0.11
g was added in the molten state, followed by 0.83 g of a 2% NaOH solution. 1.78 g of Si69 was then added over 30 minutes. After the addition of Si69, the mixture was stirred for a further 30 minutes. The treated silica suspension was then heated to 80 ° C. and 1.00 g of N-oleyl-N- (trimethoxysilyl) propylammonium chloride was added in the molten state over 5 minutes. 0.78 g of 10% NaOH solution was then added over 5 minutes. The mixture was stirred during all the above steps. As a final step, complete demineralized water was added and diluted to a 10% hydrophobic silica suspension.

2) Preparation of oil-extended latex and hydrophobic silica preblend: 277.78 g of 10% NBR latex and hydrophobic silica suspension were mixed for 10 minutes with stirring to obtain a preblend.

3) Aggregation of preblend of latex and hydrophobic silica: 500 g of completely demineralized water were placed in a glass container equipped with a stirrer. pH to 1
Adjusted to 5 with% sulfuric acid. A preblend of latex and hydrophobic silica was then added slowly and the water was acidified with continued stirring. During this step, a pH around 5 was maintained by adding 10% sulfuric acid. Aggregation was performed at room temperature.
The mixture was then stirred for a further 10 minutes. The resulting masterbatch powder was uniform in appearance. It was isolated by sieving through a 0.5 mm sieve. 100 μm of very small amount of masterbatch particles in the resulting serum
It was removed by refiltering with a filter cloth. The resulting slightly turbid serum is further added to 589 ³ blue ribbon ashless filter paper circle (589 ³ B
lue Ribbon Ashless Filter Paper Circ
le) to remove a small amount of suspended silica. The resulting serum was clear. The filter was then dried. The difference in the mass of the dried filter before and after filtration corresponds to the amount of silica lost. This resulted in a total recovery of 0.08% of the silica initially added, which in this case means that the masterbatch contains a silica content of 99.22%. The resulting wet masterbatch was dried in a vacuum oven at 70 ° C.

Example 4 A butadiene-styrene-acrylonitrile terpolymer (NSBR) was used as the latex component. The rubber / silica masterbatch is based on the following composition: NSBR 100.0 phr (10% acrylonitrile, 28% styrene, 62.
% Butadiene) Silica 80.0 phr Si69 6.4 phr N-oleyloo N- (trimethoxysilyl) propylammonium chloride 4
． 0 phr 1) Preparation of a hydrophobic silica suspension: 22.22 g of silica are completely demineralized water to obtain a 20% silica suspension.
Mixed with 8.88 g. The silica suspension was heated to 50 ° C with stirring. N-oleyl-N- (trimethoxysilyl) propylammonium chloride 0.11
g in the molten state, followed by 0.83 g of a 2% NaOH solution. 1.78 g of Si69 was then added over 30 minutes. The treated silica suspension was then heated to 80 ° C. and 1.00 g of N-oleyl-N- (trimethoxysilyl) propylammonium chloride were added in the molten state over 5 minutes. Then 0.78 g of 10% NaOH solution was added over 5 minutes. The mixture was stirred during all the above steps. Finally, complete desalted water was added to make a 5% hydrophobic silica suspension.

2) Preparation of a Preblend of Latex and Hydrophobic Silica: 555.6 g of 5% NSBR latex and a suspension of hydrophobic silica were mixed for 10 minutes to form a preblend.

3) Aggregation of Latex and Hydrophobic Silica: The latex and hydrophobic silica preblend was charged into a glass vessel equipped with a stirrer. Sodium dissolved in demineralized water 10 p while stirring the mixture
hr was added slowly. The pH was adjusted to 5 with 10% sulfuric acid. Aggregation was performed at room temperature. The mixture was then stirred for a further 10 minutes. The resulting masterbatch powder was uniform in appearance. It was isolated by sieving through a 0.5 mm screen. 100 μm of extremely small amount of masterbatch in the resulting serum
It was removed by filtering through a filter cloth. A slightly turbid the serum 589 ³ Blue Ribbon ashless filter paper circle ⁽⁵⁸⁹ 3 Blue arising
Further filtration with a Ribbon Ashless filter paper circle) removed a small amount of suspended silica. The resulting serum was clear. The filter was then dried. The difference in mass of the dried filter before and after filtration corresponds to the lost mass of silica. This recovered a total of 0.61% of the silica initially added, which in this case means the masterbatch contains 99.39% silica. The resulting wet masterbatch was dried at 70 ° C in a vacuum oven.

Example 5 A butadiene-styrene-acrylonitrile terpolymer (NSBR) was used as the latex component. The rubber / silica masterbatch is based on the following composition: NSBR 100.0 phr (21% acrylonitrile, 21% styrene, 58.
% Butadiene) silica 80.0 phr Si69 6.4 phr N-oleyl-N- (trimethoxysilyl) propylammonium chloride 4
． 0 phr 1) Preparation of a hydrophobic silica suspension: 22.22 g of silica are added to 88.
Mixed with 88 g. The silica suspension was heated to 50 ° C with stirring. Next, N-
Oleyl-N- (trimethoxysilyl) propylammonium chloride 0.1
1 g was added in the molten state, followed by 0.83 g of a 2% NaOH solution. After that, 1.78 g of Si69 was added over 30 minutes. After the addition of Si69, the mixture was stirred for another 30 minutes. The treated silica suspension was heated to 80 ° C. and 1.00 g of N-oleyl-N- (trimethoxysilyl) propylammonium chloride was added in the molten state over 5 minutes. After that,
0.78 g of 10% NaOH solution was added over 5 minutes. The mixture was stirred during all the above steps. Finally, 333.3 g of fully desalted water was added to and diluted into a 5% hydrophobic silica suspension.

2) Preparation of Preblend of Latex and Hydrophobic Silica: A preblend was prepared by stirring 555.6 g of 5% NSBR latex and a suspension of hydrophobic silica for 10 minutes.

3) Agglomeration of preblend of latex and hydrophobic silica: The preblend of latex and hydrophobic silica was placed in a glass tube equipped with a stirrer. Thereafter, about 10 phr of sodium chloride dissolved in demineralized water was added to the stirred mixture. The pH was adjusted to 5 with 10% sulfuric acid. Aggregation was performed at room temperature. After that, the mixture was stirred for a further 10 minutes. The resulting masterbatch powder was uniform in appearance. It was isolated by sieving through a 0.5 mm screen. Very small amounts of masterbatch particles in the resulting serum were removed by refiltering through a 100 μm filter cloth. The resulting slightly turbid serum is further filtered through a 589 ³ Blue Ribbon ashless filter paper circle (589 ³ Blue Ribbon ashless filter pa).
filtered through a per circle to remove a small amount of suspended silica. The resulting serum was clear. The filter was then dried. The difference in mass of the dry filter before and after filtration corresponds to the amount of silica lost. by this,
In total, 0.04% of the initially added silica was recovered, which in this case is
It is meant that the masterbatch contains 99.96% silica. The resulting wet masterbatch was dried in a vacuum oven at 70 ° C.

[0147] To prepare the Comparative Example Comparative Example, the silica grade ^HiSil (R) 233 (PPG I
ndustries, USA) again.

Comparative examples are US Pat. No. 5,763,388 and European Patent No. 084.
Prepared according to 9320.

Example 6 Example 6 is described in US Pat. No. 5,763,388 and European Patent 0849.
It corresponds to Example 3 in the specification of No. 320.

Krylene ^(R ) 1500 latex (ESBR, Bayer AG)
Was used as a latex.

[0151] Rubber / silica masterbatch is based on the following composition: Kuriren ^{(Krylene (R)) 1500 (} 23.5% styrene, 76.5
% Corresponding to 6.0pbw respect butadiene) 100.0Phr fragrance oil 20.0phr HiSil ^(R) 233 silica 45.0phr sill Quest ^{(Silquest (R)) A-} 189 2.7phr ( silica) example, U.S. Patent No. 5763388 and European Patent No. 84932.
Manufactured according to specification No. 0.

Preparation of Modified Silica Slurry: Aqueous mercaptosilane solution was added to a container and Silquest ^(R ) A-189 (OSi Speciali).
ties) 30 g, isopropanol 15 g, glacial acetic acid 0.6 g and demineralized water 15 g. The cloudy mixture was stirred at room temperature at high speed until the mixture became clear (after about 20 minutes). After that, 15g of demineralized water
Was added to the mixture, in which case the mixture became cloudy again. Stirring was continued for about 15 minutes until the mixture was clear again.

[0153] 1l vessel silica aqueous slurry of ^{(HiSil (R)} 233) 337.5
It was charged with g and stirred. Silquest ^(R ) A-1
10.21 g of an aqueous solution of 89 were then added with continuous stirring, followed by the addition of 10% sodium hydroxide in order to adjust the pH to 7.8.

The stirred slurry was then heated to 77 ° C. The temperature was maintained at 77 ° C for 4 hours and then cooled to 60 ° C.

Blending of Modified Silica Slurry with Latex: The modified silica slurry was mixed with 9.50 g of antioxidant emulsion (containing 10 wt% Vulkanox 4020) Klelen stabilized.
ene ^(R) 1500 SBR latex 632 containing 23.7% by weight
． It was loaded into a stirred 21 liter container containing 91 g and extended with 75 g of an oil emulsion containing 40% by weight of aromatic oil. After adding the modified silica slurry, it was stirred for 10 minutes.

Agglomeration of the modified silica slurry / latex blend: A stirred 4 l vessel was charged with 750 g of water, followed by p using 1% sulfuric acid.
Adjusted to H4. The slurry latex blend was then added slowly over 30 minutes. The pH was maintained at 4 by the addition of 1% sulfuric acid. The resulting masterbatch powder was uniform in appearance. It was isolated by sieving through a 0.5 mm screen. Very small amounts of masterbatch particles in the resulting serum were removed by refiltering through a 100 μm filter cloth. The resulting slightly turbid serum was further filtered through a 589 ³ Blue Ribbon ashless filter paper circle (589 ³ Blue Ribbon ashless filter p).
filtered through aper circle to remove a small amount of suspended silica. The resulting serum was clear. The filter was then dried. The difference in the mass of the dry filter before and after filtration corresponds to the amount of silica lost. This recovered a total of 0.21% of initially added silica, which means that the masterbatch contains 99.79% silica. The resulting wet masterbatch was dried in a vacuum oven at 70 ° C.

[0157] Example 7   A large amount of silica was used in this example, as is suitable in tire threads.

[0158] Rubber / silica Custer batches based on the following composition: Kuriren ^{(Krylene (R)) 1500 (} 23.5% styrene, 76.5
% Butadiene) corresponding to 6.0pbw respect 100.0phr fragrance oil 20.0phr HiSil ^(R) 233 silica 80.0phr sill Quest ^{(Silquest (R)) A-} 189 4.8phr ( silica) Example, USA Patent No. 5763338 and European Patent No. 08493
It was carried out according to Example 3 in the specification of No. 20.

The resulting masterbatch powder was uniform in appearance. It was isolated by sieving through a 0.5 mm screen. In the resulting serum, very small amounts of masterbatch particles were removed by refiltering through a 100 μm filter cloth. The resulting slightly turbid serous fluid was further filtered with 589 ³ Blue Ribbon ashless filter paper circle (589 ³ Blue Ribbon ashless).
Filtered through filter paper circle) to remove a small amount of suspended silica. The resulting serum was clear. The filter was then dried. The difference in mass of the dry filter before and after filtration corresponds to the amount of silica lost. This recovered a total of 0.19% of the silica initially added, which means that the masterbatch contains a silica content of 99.81%. The resulting wet masterbatch was dried in a vacuum oven at 70 ° C.

[0160] Example 8 large amounts of sill Quest ^{(Silquest (R)) A-} 189, was used in the comparative example. The ratio of Silquest ^(R) A-189 to rubber is
Corresponds to the silane / rubber ratio used in Examples 1-5 herein.

[0161] Rubber / silica masterbatch in this comparative example is based on the following composition: Kuriren ^{(Krylene (R)) 1500 100.0phr} (23.5%
Styrene, 76.5% butadiene) Aromatic oil 20.0 phr HiSil ^(R) 233 Silica 80.0 phr Silquest ^(R ) A-189 10.4 phr (equivalent to 13 pbw for silica) Example Patent No. 5763388 and European Patent No. 08493
It was carried out according to Example 3 in the specification of No. 20.

The resulting masterbatch powder was uniform in appearance. It was isolated by sieving through a 0.5 mm screen. Very small amounts of masterbatch particles in the resulting serum were removed by refiltering through a 100 μm filter cloth. The resulting slightly turbid serum was further filtered through 589 ³ Blue Ribbon ashless filter paper circle (589 ³ Blue Ribbon ashless).
Filtered through filter paper circle) to remove a small amount of suspended silica. The resulting serum was clear, the filter was subsequently dried. The difference in the mass of the dry filter before and after filtration corresponds to the amount of silica lost. This resulted in a total recovery of 0.06% of the initially added silica, which means that the masterbatch contains a silica content of 99.94%. The resulting wet masterbatch was dried in a vacuum oven at 70 ° C.

[0163] Example 9 Kurinoru ^{(Krynol (R))} 1712 latex (ERBR, Baye
r AG) was used in Example 9.

[0164] Rubber / silica masterbatch is based on the following composition: Kurinoru ^{(Krynol (R)) 1712 (} 23.5% styrene, 76.5 percent
Butadiene) 100.0 phr Aromatic oil 37.5 phr Silquest ^(R) A-189 4.8 phr (equivalent to 6.0 pbw for silica) Examples are given in U.S. Pat. No. 5,763,388 and European Patent No. 08493
No. 20 Example 3 was carried out.

The resulting masterbatch powder was uniform in appearance. It was isolated by sieving through a 0.5 mm screen. A very small amount of the masterbatch in the resulting serum was removed by refiltering through a 100 μm filter cloth. The resulting slightly turbid serum was further filtered through a 589 ³ Blue Ribbon ashless filter paper circle (589 ³ Blue Ribbon ashless filter).
er paper circle) to remove a small amount of suspended silica. The resulting serum was clear. Then the filter was dried.
The difference in the mass of the dry filter before and after filtration corresponds to the amount of silica lost. This recovered a total of 0.25% of the initially added silica,
In this case, this means that the masterbatch contains a silica content of 99.75%. The resulting wet masterbatch was dried at 70 ° C in a vacuum oven.

Vulcanization Properties Vulcanization properties were measured from Examples 1 and 2 (according to the invention) and Comparative Examples 7, 8 and 9.

The following auxiliaries were added to the masterbatches of Examples 1 and 2 (according to the invention) and Comparative Examples 2, 3 and 4: ZnO RS ¹⁾ 3.0 phr Stearic acid 1.0 phr Antilux ( Antilux ^(R) 654 ²⁾ 1.0 phr vulcanox (Vulkanox ^(R) ) HS ³⁾ 1.5 phr vulcanox (Vulkanox ^(R ) 4020 ⁴⁾ 1.5 phr vulcanite (Vulkacit ^(R) ) CZ ⁵⁾ 1.4 phr Vulkasite ^(R) D ⁶⁾ 2.0 phr Sulfur 1.6 phr ¹⁾ ZnORS (Zinc oxide, Brueggemann) ²⁾ Antilux ^(R) 654 (antiozonant wax, Rhein C)
hemie) ³⁾ Vulkanox ^(R) HS (TMQ, 2,2,4-trimethyl-1,2-
Dihydroquinoline those were ^{polymerized, Bayer AG) 4) Vulkanox (} R) 4020 (6PPD, N- (1,3- dimethyl - butyl)-N'-phenyl -p- phenylene - diamine, Bayer ^{AG) 5)} Vulkacit ^(R) CZ (CBS, benzothiazyl-2-cyclohexyl-sulfenamide, Bayer AG) ⁶⁾ Vulkacit ^(R) D (DPG, diphenylguanidine, Bayer
AG) Vulcanization MDR (Moving Die Rheometer, Alpha Technologies, former Monsant
o) in 170 ° C. The following results were obtained:

[0168]

[Table 1]

The value of t10 is the time taken in minutes to achieve a 10% vulcanization.

The value of t90 is the time in minutes required for 90% vulcanization to be achieved.

Examples 1 and 2 and Comparative Examples 2, 3 and 4 have similar t10 values.

Examples 1 and 2 are much lower than Comparative Examples 2, 3 and 4 and therefore have good values of t90. Fast cure times are economically important. If desired, one of ordinary skill in the art may adjust the cure rate to suit normal conditions by reducing the accelerator content. Furthermore, such a reduction in accelerator content also renders the compound economically advantageous.

[Procedure amendment]

[Submission date] February 14, 2002 (2002.2.14)

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be amended] Claims

[Correction method] Change

[Contents of correction]

[Claims]

[Chemical 1] [Wherein at least one of R ¹ , R ² and R ³ is a hydroxyl group or a hydrolyzing group; R ⁴ is a divalent group resistant to hydrolysis by a Si—R ⁴ bond; R ⁵ Is hydrogen; C _1-40 alkyl; C _2-40 mono-, di- or tri-unsaturated alkenyl group; C _6-40 aryl group; formula

[Chemical 2] The group x, in which x is an integer from 2 to 10, R ¹³ and R ¹⁴ may be the same or different and each is hydrogen, C _1-18 alkyl, C _2-18 mono-,
A di- or tri-unsaturated alkenyl group, a phenyl group;

[Chemical 3] A group of b, where b is an integer from 1 to 10;

[Chemical 4] Groups, where, c is an integer of 1 to 10, ^{and, R 22} and ^{R 23} may be the same or different, each is _hydrogen, with _{C 1-10} alkyl group or _{C. 2 to 10} alkenyl groups Yes, provided there is no double bond at the α-position to the nitrogen atom;

[Chemical 5] A group of R, wherein r is an integer from 1 to 6 and d is an integer from 1 to 4; R ⁶ may be any group shown for R ^{5. 5} and R ⁶ together form the formula

[Chemical 6] A divalent group of A, wherein A is selected from the group —CHR or —NR,
In this case, R is hydrogen or C_1-40Alkyl group or C_2-40Alkenyl group, C _6-40 An aryl group, a hydrogen atom and a sulfur atom, and t and v are independent of each other.
, 1, 2, 3 or 4, provided that the sum of t and v cannot exceed 6.
Or a quaternary ammonium salt thereof, or
One (2) particles and formula II

[Chemical 7] [Wherein R ¹⁵ , R ¹⁶ and R ¹⁷ have the same meanings of R ¹ , R ² and R ³ ; and R ¹² is a C _8-40 alkyl group or a C _8-40 mono-, Selected from groups containing di- or tri-unsaturated alkenyl groups, where these are
May be interrupted by one or more aryl groups, preferably phenyl groups;

[Chemical 8] Base, then R¹⁸Is Si-R¹⁸It is a divalent group that is resistant to hydrolysis by bonding,
R¹⁹Is hydrogen, C_1-40Alkyl group, C_2-40Mono-, di- or tri-
Unsaturated alkenyl group, substituted aromatic group, for example, phenylene group- (C₆H _Four )-, Biphenylene group- (C₆H_Four)-(C₆H_Four)-, Group- (C₆H_Four) −
O- (C₆H_Four)-Or a naphthylene group- (C₁₀H₆) −, Where
The aromatic group is unsubstituted or C_1-20Alkyl or C₂₀Mono-, di- or tho
Optionally substituted by a unsaturated alkenyl group; R²⁰Is R¹⁹Can be any group with respect to R¹⁹And R²⁰Is
R has no tertiary carbon atom adjacent to the nitrogen atom, and R¹⁹And R^{Two 0} At least one of the carbon atoms is not interrupted by any heteroatom
Having at least 8 carbon chains] or an acid addition salt thereof or a fourth thereof
Contact with ammonium salt, (3) The particles of steps (1) and (2) and one or more polymer latte.
A composition to form a preblend to form a preblend.
Method of manufacturing things.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C09D 5/02 C09D 5/02 7/12 7/12 121/00 121/00 201/00 201/00 ( 81) Designated countries EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE), OA (BF, BJ, CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, KE, LS, MW, MZ, SD, SL, SZ, TZ, UG, ZW), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AE, AG, AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, BZ, CA, C H, CN, CR, CU, CZ, DE, DK, DM, DZ, EE, ES, FI, GB, GD, GE, GH, GM, HR, HU, ID, IL, IN, IS, JP, KE , KG, KP, KR, KZ, LC, LK, LR, LS, LT, LU, LV, MA, MD, MG, MK, MN, MW, MX, MZ, NO, NZ, PL, PT, RO, R U, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, TZ, UA, UG, US, UZ, VN, YU, ZA, ZW (72) Inventor Rolf Peter Germany Dormagen, Federal Republic of Germany Am Weissen Kreuz 9 (72) Inventor Arti Augusto Koskey Canada Canada Wilkes Port Earl No. 1 British Road 1876 F Term (Reference) 4F070 AA05 AA06 AA07 AA08 AC23 AC52 AC53 AE01 FB03 4F0 71 AA11 AA12 AA13 AB26 AC12 AC16 AE17 AE18 BC07 4J002 AC011 AC031 AC071 AC081 AC091 BC031 BD041 BG051 BN151 DJ016 FB096 FB146 GH01 GN01 4J038 CA011 CA021 CA081 CR021 CC041 CC021 CC041 CC051 CC041 CC051 CC041 CC051 CC041 CC051 CC041 CC051 CC041 CC051 CC041 CC051 CC041 CC051 CC041 CC051 CC041 CC051

Claims (19)

[Claims] 1. A method for producing a composition, comprising: (1) Particles of formula I     [Chemical 1] [In the formula, R¹, R^TwoAnd R^ThreeAt least one of the
A decomposable group; R^FourIs Si-R^FourA hydrolytically resistant divalent group at the bond; R⁵Is hydrogen; C_1-40Alkyl; C_2-40Mono-, di- or tri-unsaturated
Alkenyl group; C_6-40Aryl group; formula     [Chemical 2] A group of x, in which x is an integer from 2 to 10;^ThirteenAnd R¹⁴Are the same or
They may be different, respectively hydrogen, C_1-18Alkyl, C_2-18Mono-
A di- or tri-unsaturated alkenyl group, a phenyl group; formula     [Chemical 3] A group of b, in which b is an integer from 1 to 10; formula     [Chemical 4] A group of c, where c is an integer from 1 to 10 and R²²And R²³Are the same
Or they may be different, respectively hydrogen, C_1-10Alkyl group or C_{2 to 10} An alkenyl group, provided there is no double bond in the α-position to the nitrogen atom; formula     [Chemical 5] A group of r, in which r is an integer from 1 to 6 and d is an integer from 1 to 4; R⁶Is R⁵May be any of the groups indicated for or R⁵and
R⁶Together, the formula     [Chemical 6] A divalent group of A, wherein A is selected from the group —CHR or —NR,
In this case, R is hydrogen or C_1-40Alkyl group or C_2-40Alkenyl group, C _6-40 An aryl group, a hydrogen atom and a sulfur atom, and t and v are independent of each other.
, 1, 2, 3 or 4, provided that the sum of t and v cannot exceed 6.
Or a quaternary ammonium salt thereof, or
One (2) particles and formula II     [Chemical 7] [In the formula, R¹⁵, R¹⁶And R¹⁷Is R¹, R^TwoAnd R^ThreeThe same meaning of
Have; and R¹²Is C_8-40Alkyl group or C_8-40Mono, J
Or a group containing a tri-unsaturated alkenyl group, wherein these are
Interrupted by one or more aryl groups, preferably phenyl groups
May; expression     [Chemical 8] Base, then R¹⁸Is Si-R¹⁸It is a divalent group that is resistant to hydrolysis by bonding,
R¹⁹Is hydrogen, C_1-40Alkyl group, C_2-40Mono-, di- or tri-
Unsaturated alkenyl group, substituted aromatic group, for example, phenylene group- (C₆H _Four )-, Biphenylene group- (C₆H_Four)-(C₆H_Four)-, Group- (C₆H_Four) −
O- (C₆H_Four)-Or a naphthylene group- (C₁₀H₆) −, Where
The aromatic group is unsubstituted or C_1-20Alkyl or C₂₀Mono-, di- or tho
Optionally substituted by a unsaturated alkenyl group; R²⁰Is R¹⁹Can be any group with respect to R¹⁹And R²⁰Is
R has no tertiary carbon atom adjacent to the nitrogen atom, and R¹⁹And R^{Two 0} At least one of the carbon atoms is not interrupted by any heteroatom
Having at least 8 carbon chains] or an acid addition salt thereof or a fourth thereof
Contact with ammonium salt, (3) The particles of steps (1) and (2) and one or more polymer latte.
A composition to form a preblend to form a preblend.
Method of manufacturing things. 2. The method of claim 1, further comprising the steps of (4) agglomerating the preblend and (5) drying the resulting product to obtain a polymeric filler masterbatch. 3. The compound of formula (I) is in the dry state in an amount of 0.
The method according to claim 1 or 2, which is used in an amount of 1 to 20% by mass. 4. A compound of formula (II) in the dry state, based on the mass of the particles,
． The method according to claim 1 or 2, which is used in an amount of 1 to 20% by mass. 5. The method according to claim 1, wherein steps (1) and (2) are carried out simultaneously. 6. The method according to claim 1, wherein steps (1) and (2) are carried out continuously. 7. The compound of formula I and formula II is the same compound.
Or the method described in 2. 8. The method of claim 1, wherein step (1) comprises contacting an aqueous slurry of particles with a compound of formula I. 9. The method according to claim 1 or 2, wherein the particles are silica particles. 10. Coupling agent is 0 relative to the mass of dry particles used.
The method according to claim 1 or 2, which is added in an amount of -20% by weight. 11. The latex is polybutadiene or butadiene styrene.
One selected from the group consisting of copolymer, isoprene styrene copolymer, butadiene isoprene styrene copolymer, butadiene acrylonitrile copolymer, butadiene acrylonitrile styrene copolymer, natural rubber, polystyrene, polychloroprene, ABS, polyvinyl chloride, poly (acrylate) or mixtures thereof. 2. The method of claim 1, which is a latex of polymer or higher. 12. The method of claim 11, wherein the polymer contains functional groups. 13. A filled latex produced by the method of claim 1. 14. A masterbatch produced by the method of claim 2. 15. A molded or extruded product produced from the masterbatch according to claim 14. 16. The filled latex is used as a paint.
The filled latex according to 3. 17. Filled according to claim 13 in the manufacture of dips, dental dams, balloons, special inner tubes, condoms, rubber gloves, paints, coated fibers, coated papers, carpet backings or tire threads. Use of latex. 18. Use of the masterbatch according to claim 14 in the manufacture of tire threads. 19. The product of claim 15, wherein the product is a tire thread.