JP2012057107A - Rubber composition, vulcanized rubber, and tire - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a rubber composition which can reduce rolling resistance while improving on-ice performance and abrasion resistance of a tire.SOLUTION: The rubber composition is configured by blending a fine particle-containing fiber (B), a foaming agent (C), an organosilicon compound (D), and an inorganic filler (E) with a rubber component (A), wherein the fine particle-containing fiber (B) comprises a metal oxide, a metal carbonate, at least one fine particle chosen from the group consisting of clay mineral containing metals, and a hydrophilic resin. The organosilicon compound (D) is chosen from compounds expressed by a specific constitutional formula.

Description

  The present invention relates to a rubber composition, a vulcanized rubber obtained by vulcanizing the rubber composition, and a tire including the vulcanized rubber, and more particularly to rolling resistance while improving on-ice performance and wear resistance of the tire. The present invention relates to a rubber composition capable of reducing the above.

  Since the spike tire was regulated, various studies have been made particularly on the tread portion of the tire in order to improve the braking performance and drivability (performance on ice) of the tire on an icy and snowy road surface. For example, by mixing hollow fibers in a tread rubber of a tire, water on an icy and snowy road surface is eliminated at the hollow portion of the hollow fibers, and the performance on ice of the tire is improved. However, in this case, there is a problem that the hollow fiber cannot maintain a hollow shape due to pressure, rubber flow, temperature, and the like at the time of molding the tread rubber, and the on-ice performance of the tire cannot be sufficiently improved.

  In order to solve this problem, Japanese Patent Application Laid-Open No. 11-60770 (Patent Document 1) and Japanese Patent Application Laid-Open No. 2001-2832 (Patent Document 2) use a rubber composition containing a foam-containing fiber for a tread portion of a tire. A technique for improving the drainage performance of the tire and improving the on-ice performance of the tire by forming a micro drainage groove in the tread portion has been proposed. Moreover, in JP, 2001-233993, A (patent documents 3), in the tire which used the rubber composition containing particulates containing organic fiber for a tread part, by increasing content of particulates contained in organic fiber, In addition to the ability of the tread to remove the water film, it has been reported that the scratching effect is improved and the on-ice performance of the tire is further improved.

Japanese Patent Laid-Open No. 11-60770 JP 2001-2832 A JP 2001-233993 A

  However, in recent years, regarding the performance on the ice of a tire, there is a demand for a technique that is superior to the techniques described in Patent Documents 1 to 3. In addition, as described in Patent Document 3, in order to improve the performance on ice, when fine particles are contained in the organic fiber, if the amount of fine particles is increased, the performance on ice increases, but the content of the fine particles is limited. For example, in the fiber manufacturing process, the fine particles mixed in the resin may induce fiber cutting at the spinning / stretching stage where the resin is stretched at a high temperature, so that the content of the fine particles is excessively increased. There is a problem that the production of the fiber becomes extremely difficult.

  On the other hand, by using a rubber composition containing a foaming agent-containing fiber for the tread portion of the tire and forming a micro drainage groove in the tread portion, the drainage performance of the tire can be improved and the performance on ice can be improved. However, in this case, since the micro drainage grooves formed in the tread portion scratch the road surface, there is a problem that the wear resistance of the tire when driving on a dry road surface in fine weather is reduced, or the rolling resistance of the tire is increased. was there.

  Accordingly, an object of the present invention is to provide a rubber composition capable of solving the above-mentioned problems of the prior art and reducing rolling resistance while improving the performance on ice and wear resistance of a tire. Another object of the present invention is to provide a vulcanized rubber obtained by vulcanizing such a rubber composition, and a tire provided with the vulcanized rubber in a tread portion.

  As a result of intensive investigations to achieve the above object, the present inventor has found that the rubber component contains fine particles containing specific fine particles and a hydrophilic resin, a foaming agent, a specific organosilicon compound, and an inorganic filler. It has been found that by applying a rubber composition containing the above to the tread portion of a tire, the rolling resistance can be reduced while improving the on-ice performance and wear resistance of the tire, and the present invention has been completed.

［式中、Ａ¹は、下記一般式(II)又は式(III)：

で表わされ、
式(I)及び式(II)中のＲ¹、Ｒ²及びＲ³は、少なくとも一つが下記一般式(IV)又は式(V)：

（式中、Ｍは−Ｏ−又は−ＣＨ₂−で、Ｘ及びＹはそれぞれ独立して−Ｏ−、−ＮＲ⁸−又は−ＣＨ₂−で、Ｒ⁶は−ＯＲ⁸、−ＮＲ⁸Ｒ⁹又は−Ｒ⁸で、Ｒ⁷は−ＮＲ⁸Ｒ⁹、−ＮＲ⁸−ＮＲ⁸Ｒ⁹又は−Ｎ＝ＮＲ⁸で、但し、Ｒ⁸は−Ｃ_nＨ_2n+1であり、Ｒ⁹は−Ｃ_qＨ_2q+1であり、ｌ及びｍはそれぞれ独立して０〜１０であり、ｎ及びｑはそれぞれ独立して１１〜２０である）で表わされ、その他が−Ｍ−Ｃ_rＨ_2r+1（ここで、Ｍは上記と同義であり、ｒは０〜２０である）或いは−（Ｍ−Ｃ_lＨ_2l）_yＣ_sＨ_2s+1（ここで、Ｍ及びｌは上記と同義であり、ｙ及びｓはそれぞれ独立して１〜２０である）で表わされ、但し、Ｒ¹、Ｒ²及びＲ³の一つ以上はＭが−Ｏ−であり、
Ｒ⁴は下記一般式(VI)又は式(VII)：

（式中、Ｍ、Ｘ、Ｙ、Ｒ⁶、ｌ及びｍは上記と同義であり、Ｒ¹⁰は−ＮＲ⁸−、−ＮＲ⁸−ＮＲ⁸−又は−Ｎ＝Ｎ−で、但し、Ｒ⁸は上記と同義である）或いは−Ｚ−Ｃ_lＨ_2l−（ここでＺは−Ｏ−、−ＮＲ⁸−又は−ＣＨ₂−で、但し、Ｒ⁸は上記と同義であり、ｌは上記と同義である）で表され、
式(III)中のＲ⁵は上記一般式(IV)又は式(V)或いは−Ｃ_lＨ_2l−Ｒ¹¹（ここで、Ｒ¹¹は−ＮＲ⁸Ｒ⁹、−ＮＲ⁸−ＮＲ⁸Ｒ⁹、−Ｎ＝ＮＲ⁸又は−Ｚ−Ｃ_mＨ_2m+1であり、但し、Ｒ⁸、Ｒ⁹、Ｚ、ｌ及びｍは上記と同義である）で表わされ、
ｘは１〜１０である］で表わされる化合物、及び下記一般式(VIII)：

［式中、Ａ²は、下記一般式(IX)又は式(III)：

で表わされ、
式(VIII)及び式(IX)中のＷは−ＮＲ⁸−、−Ｏ−又は−ＣＲ⁸Ｒ¹⁵−（ここで、Ｒ¹⁵は−Ｒ⁹又は−Ｃ_mＨ_2m−Ｒ⁷であり、但し、Ｒ⁷は−ＮＲ⁸Ｒ⁹、−ＮＲ⁸−ＮＲ⁸Ｒ⁹又は−Ｎ＝ＮＲ⁸であり、Ｒ⁸は−Ｃ_nＨ_2n+1で、Ｒ⁹は−Ｃ_qＨ_2q+1で、ｍは０〜１０であり、ｎ及びｑはそれぞれ独立して１１〜２０である）で表わされ、
Ｒ¹²及びＲ¹³はそれぞれ独立して−Ｍ−Ｃ_lＨ_2l−（ここで、Ｍは−Ｏ−又は−ＣＨ₂−で、ｌは０〜１０である）で表わされ、
Ｒ¹⁴は−Ｍ−Ｃ_rＨ_2r+1又は−Ｍ−Ｃ_rＨ_2r−Ｒ¹¹（ここで、Ｍは上記と同義であり、Ｒ¹¹は−ＮＲ⁸Ｒ⁹、−ＮＲ⁸−ＮＲ⁸Ｒ⁹、−Ｎ＝ＮＲ⁸又は−Ｚ−Ｃ_mＨ_2m+1であり、但し、Ｚは−Ｏ−、−ＮＲ⁸−又は−ＣＨ₂−で、Ｒ⁸、Ｒ⁹及びｍは上記と同義であり、ｒは０〜２０である）或いは−（Ｍ−Ｃ_lＨ_2l）_yＣ_sＨ_2s+1（ここで、Ｍ及びｌは上記と同義であり、ｙ及びｓはそれぞれ独立して１〜２０である）で表わされ、但し、Ｒ¹²、Ｒ¹³及びＲ¹⁴の一つ以上はＭが−Ｏ−であり、
Ｒ⁴は下記一般式(VI)又は式(VII)：

（式中、Ｍ、ｌ及びｍは上記と同義であり、Ｘ及びＹはそれぞれ独立して−Ｏ−、−ＮＲ⁸−又は−ＣＨ₂−で、Ｒ⁶は−ＯＲ⁸、−ＮＲ⁸Ｒ⁹又は−Ｒ⁸で、Ｒ¹⁰は−ＮＲ⁸−、−ＮＲ⁸−ＮＲ⁸−又は−Ｎ＝Ｎ−であり、但し、Ｒ⁸及びＲ⁹は上記と同義である）或いは−Ｚ−Ｃ_lＨ_2l−（ここで、Ｚは−Ｏ−、−ＮＲ⁸−又は−ＣＨ₂−で、但し、Ｒ⁸は上記と同義であり、ｌは上記と同義である）で表され、
式(III)中のＲ⁵は下記一般式(IV)又は式(V)：

（式中、Ｍ、Ｘ、Ｙ、Ｒ⁶、Ｒ⁷、ｌ及びｍは上記と同義である）或いは−Ｃ_lＨ_2l−Ｒ¹¹（ここで、Ｒ¹¹は−ＮＲ⁸Ｒ⁹、−ＮＲ⁸−ＮＲ⁸Ｒ⁹、−Ｎ＝ＮＲ⁸又は−Ｚ−Ｃ_mＨ_2m+1であり、但し、Ｒ⁸、Ｒ⁹、Ｚ、ｌ及びｍは上記と同義である）で表わされ、
ｘは１〜１０である］で表わされる化合物からなる群から選択される少なくとも一種である
ことを特徴とする。ここで、親水性樹脂は、水との接触角が９０°以下である。 That is, the rubber composition of the present invention is
・ For rubber component (A)
-Fine particle-containing fiber (B),
・ Foaming agent (C),
・ Contains an organosilicon compound (D) and an inorganic filler (E),
The fine particle-containing fiber (B) comprises at least one kind of fine particles selected from the group consisting of a metal oxide, a metal carbonate, and a clay mineral containing a metal, and a hydrophilic resin;
The organosilicon compound (D) has the following general formula (I):

[Wherein A ¹ represents the following general formula (II) or formula (III):

Represented by
At least one of R ¹ , R ² and R ³ in formula (I) and formula (II) is the following general formula (IV) or formula (V):

(In the formula, M is —O— or —CH ₂ —, X and Y are independently —O—, —NR ⁸ — or —CH ₂ —, and R ⁶ is —OR ⁸ , —NR ⁸ R. ⁹ or -R ⁸ , R ⁷ is -NR ⁸ R ⁹ , -NR ⁸ -NR ⁸ R ⁹ or -N = NR ⁸ , provided that R ⁸ is -C _n H _{2n + 1} , R ⁹ is -C _q is H _{2q + 1,} l and m are 0 independently, n and q are represented by each independently a 11-20), others -M-C _r H _{2r + 1} (where M is as defined above and r is 0 to 20) or − (M−C ₁ H _2l ) _y C _s H _{2s + 1} (where M and l are the same as above) And y and s are each independently 1 to 20), provided that at ^{least one} of R ¹ , R ² and R ³ is M is —O—,
R ⁴ represents the following general formula (VI) or formula (VII):

(In the formula, M, X, Y, R ⁶ , l and m are as defined above, and R ¹⁰ is —NR ⁸ —, —NR ⁸ —NR ⁸ — or —N═N—, wherein R ⁸ Is as defined above, or —Z—C ₁ H _2l — (wherein Z is —O—, —NR ⁸ — or —CH ₂ —, wherein R ⁸ is as defined above, and l is as defined above. Is synonymous with
R ⁵ in formula (III) is the above general formula (IV), formula (V), or —C ₁ H _2l —R ¹¹ (where R ¹¹ is —NR ⁸ R ⁹ , —NR ⁸ —NR ⁸ R ^9). a -N = NR ⁸ or _{-Z-C m H 2m + 1} , ^{where, R 8, R 9, Z} , l and m are represented by the same meaning as above),
x is 1 to 10], and the following general formula (VIII):

[In the formula, A ² represents the following general formula (IX) or formula (III):

Represented by
W in formula (VIII) and formula (IX) is —NR ⁸ —, —O— or —CR ⁸ R ¹⁵ — (wherein R ¹⁵ is —R ⁹ or —C _m H _2m —R ⁷ ; However, R ⁷ is -NR ⁸ R ^9, a -NR ⁸ -NR ⁸ R ⁹ or -N = NR ^8, R ⁸ is _{-C n H 2n + 1, R} 9 is -C _q H _{2q + 1} M is 0 to 10, and n and q are each independently 11 to 20).
R ¹² and R ¹³ are each independently represented by —M—C ₁ H _{2 1} — (wherein M is —O— or —CH ₂ —, and 1 is 0 to 10),
R ¹⁴ represents —M—C _r H _{2r + 1} or —M—C _r H _2r —R ¹¹ (where M is as defined above, and R ¹¹ represents —NR ⁸ R ⁹ , —NR ⁸ —NR ^8. R ⁹ , —N═NR ⁸ or —Z—C _m H _{2m + 1} , wherein Z is —O—, —NR ⁸ — or —CH ₂ —, and R ⁸ , R ⁹ and m are as described above. are synonymous, r is 0 to 20) or _{- (M-C l H 2l} ) y C s H 2s + 1 ( where, M and l are as defined above, y and s are each independently Wherein at least one of R ¹² , R ¹³ and R ¹⁴ is M is —O—,
R ⁴ represents the following general formula (VI) or formula (VII):

Wherein M, l and m are as defined above, X and Y are each independently —O—, —NR ⁸ — or —CH ₂ —, and R ⁶ is —OR ⁸ , —NR ⁸ R ⁹ or -R ^8, R ¹⁰ is ^{-NR 8 -, - NR 8 -NR} 8 - or -N = a N-, provided that, R ⁸ and R ⁹ are as defined above) or -Z-C _l H _2l — (wherein Z is —O—, —NR ⁸ — or —CH ₂ —, wherein R ⁸ is as defined above, and l is as defined above),
R ⁵ in the formula (III) is the following general formula (IV) or formula (V):

(Wherein, M, X, Y, R ⁶ , R ⁷ , l and m are as defined above) or —C ₁ H _2l —R ¹¹ (where R ¹¹ is —NR ⁸ R ⁹ , —NR ^8— NR ⁸ R ⁹ , —N═NR ⁸ or —Z—C _m H _{2m + 1} , where R ⁸ , R ⁹ , Z, l and m are as defined above.
x is 1 to 10], which is at least one selected from the group consisting of compounds represented by: Here, the hydrophilic resin has a contact angle with water of 90 ° or less.

  In a preferred example of the rubber composition of the present invention, the hydrophilic resin is a resin containing at least one functional group selected from the group consisting of a carboxyl group, a hydroxyl group, an ester group, an ether group and a carbonyl group. In this case, the water collecting effect of long bubbles is high.

  In the rubber composition of the present invention, the metal oxide is preferably titanium oxide or aluminum oxide, more preferably at least one of ceramics and zeolite (aluminosilicate). In the rubber composition of the present invention, calcium carbonate is preferable as the metal carbonate, and montmorillonite is preferable as the clay mineral containing the metal. In these cases, the adhesiveness with the hydrophilic resin can be improved.

  In another preferable example of the rubber composition of the present invention, the fine particle-containing fiber (B) contains 0.5 to 200 parts by mass of the fine particles with respect to 100 parts by mass of the hydrophilic resin. In this case, the effect of scratching long bubbles is high.

  In another preferable example of the rubber composition of the present invention, the content of the fine particle-containing fiber (B) is 0.5 to 30 parts by mass with respect to 100 parts by mass of the rubber component (A). In this case, it is possible to reliably improve the water collection to the elongated bubbles.

  In the rubber composition of the present invention, the fine particles preferably have a particle size of 0.1 to 500 μm. In this case, the ease of manufacturing the fine particle-containing fiber is high.

  In the rubber composition of the present invention, the fine particle-containing fiber (B) preferably has an average diameter of 1 to 100 μm and an average length of 0.1 to 20 mm. In this case, the elongated bubbles can function reliably as micro drainage grooves.

  In the rubber composition of the present invention, the hydrophilic resin preferably has a melting point or a softening point lower than the maximum vulcanization temperature.

  In the organosilicon compound (D) blended in the rubber composition of the present invention, the M is preferably —O—.

When the organosilicon compound (D) blended in the rubber composition of the present invention is represented by the above general formula (I),
At least one of R ¹ , R ² and R ³ is represented by —O—C ₁ H _{2 1} —R ⁷ (where R ⁷ and 1 are as defined above), and the others are —O—C. _l H _{2l + 1} (where l is as defined above),
R ⁴ is represented by —C ₁ H _2l — (wherein l is as defined above),
The R ⁵ is preferably represented by —C ₁ H _2l —R ¹¹ (where R ¹¹ and l are as defined above).

When the organosilicon compound (D) blended in the rubber composition of the present invention is represented by the above general formula (I),
At least one of R ¹ , R ² and R ³ is represented by —O—C ₁ H _{2 1} —NR ⁸ R ⁹ (where R ⁸ , R ⁹ and 1 are as defined above),
More preferably, R ⁵ is represented by —C _l H _{2l + 1} (where l is as defined above).

When the organosilicon compound (D) blended in the rubber composition of the present invention is represented by the above general formula (VIII),
W is represented by —NR ⁸ — (wherein R ⁸ is as defined above),
R ¹² and R ¹³ are each independently represented by —O—C ₁ H _2l — (wherein l is as defined above),
R ¹⁴ is —O—C ₁ H _2l —R ¹¹ (where R ¹¹ and l are as defined above) or —C _r H _{2r + 1} (where r is as defined above). Represented,
R ⁴ is represented by —C ₁ H _2l — (wherein l is as defined above),
The R ⁵ is preferably represented by —C ₁ H _{2 1} —CH ₂ —C _m H _{2m + 1} (wherein l and m are as defined above).

When the organosilicon compound (D) blended in the rubber composition of the present invention is represented by the above general formula (VIII),
W is represented by —O— or —CR ⁸ R ⁹ — (wherein R ⁸ and R ⁹ are as defined above),
R ¹² and R ¹³ are each independently represented by —O—C ₁ H _2l — (wherein l is as defined above),
R ¹⁴ is represented by —O—C ₁ H _{2 1} —NR ⁸ R ⁹ (wherein R ⁸ , R ⁹ and l are as defined above),
R ⁴ is represented by —C ₁ H _2l — (wherein l is as defined above),
It is also preferable that R ⁵ is represented by —C ₁ H _2l —CH ₂ —C _m H _{2m + 1} (wherein l and m are as defined above).

The rubber composition of the present invention is formed by blending 5 to 140 parts by mass of the inorganic filler (E) with respect to 100 parts by mass of the rubber component (A).
It is preferable that 1-20 mass% of the compounding quantity of the said inorganic filler (E) is included for the said organosilicon compound (D).

In another preferred embodiment of the rubber composition of the present invention, the inorganic filler (E) is silica or aluminum hydroxide. Here, the silica preferably has a BET surface area of 40 to 350 m ² / g.

  The vulcanized rubber of the present invention is obtained by vulcanizing the above rubber composition, and has a long bubble. Here, the vulcanized rubber of the present invention preferably has a foaming rate of 3 to 50%.

  Furthermore, the tire of the present invention is characterized by using the above vulcanized rubber in the tread portion. Here, in the tire of the present invention, it is preferable that the elongated bubbles are oriented in the tire circumferential direction.

  According to the present invention, fine particle-containing fibers composed of specific fine particles and a hydrophilic resin, a foaming agent, a specific organosilicon compound, and an inorganic filler are blended to improve the on-ice performance and wear resistance of the tire. On the other hand, it is possible to provide a rubber composition capable of reducing rolling resistance. Further, a vulcanized rubber having elongated cells obtained by vulcanizing such a rubber composition, a tire having the vulcanized rubber in a tread portion, and having excellent on-ice performance, wear resistance, and low fuel consumption Can be provided. In addition, since the fine particle-containing fiber blended in the rubber composition of the present invention contains a hydrophilic resin, the water collecting effect of long air bubbles acting as micro drainage grooves is high, and the on-ice performance of the tire is greatly improved. Can do.

It is sectional drawing of an example of the vulcanized rubber of this invention. It is sectional drawing of an example of the tire of this invention.

<Rubber composition>
The present invention is described in detail below. The rubber composition of the present invention comprises a rubber component (A) and a fine particle-containing fiber (B), a foaming agent (C), an organosilicon compound (D), and an inorganic filler (E). The fine particle-containing fiber (B) comprises at least one kind of fine particles selected from the group consisting of metal oxides, metal carbonates, and metal-containing clay minerals, and a hydrophilic resin, and the organosilicon compound (D ) Is at least one selected from the group consisting of the compound represented by the general formula (I) and the compound represented by the general formula (VIII).

  As described above, it is known that the performance on ice of a tire is improved by using a rubber composition containing fine particle-containing fibers. However, the fine particles may cut the fibers during production. Here, the present inventor has examined the fine particle-containing fiber in detail, and found that when a fine particle containing a metal is added to a hydrophilic resin, the fiber can be easily produced by the adhesive action between the resin and the fine particle. It was. Therefore, the rubber composition of the present invention in which the fine-particle-containing fiber (B) and the foaming agent (C), which are highly manufacturable, are blended, reliably imparts a scratching effect to the elongated bubbles formed after vulcanization. This can improve the on-ice performance of the tire. Further, the vulcanized rubber obtained by vulcanizing such a rubber composition is generally composed of a rubber component (A) having hydrophobicity and long cells covered with a hydrophilic resin. The water on the road surface can be efficiently collected into long bubbles covered with a hydrophilic resin, and can be reliably drained by the micro drainage grooves. Therefore, the on-ice performance of the tire can be greatly improved by applying the rubber composition of the present invention to the tread portion.

  In addition, as described above, when the rubber composition containing the foaming agent-containing fiber is used for the tread portion of the tire and the micro drainage groove is formed in the tread portion, the micro drainage groove scratches the road surface. Wear resistance is reduced or rolling resistance is increased, but by adding the specific organosilicon compound (D) to the rubber composition, the rolling resistance of the tire is reduced and the wear resistance is improved. Can do. The organosilicon compound (D) contains nitrogen-containing functional groups such as an amino group, an imino group, a substituted amino group, and a substituted imino group that have a high affinity with the surface of the inorganic filler (E) such as silica. The unshared electron pair of atoms can participate in the reaction between the organosilicon compound (D) and the inorganic filler (E), and the speed of the coupling reaction is high. Therefore, by adding the organosilicon compound (D) to the inorganic filler-containing rubber composition, the coupling efficiency is improved. As a result, the hysteresis loss of the rubber composition is greatly reduced, and the wear resistance is improved. Can be greatly improved. Moreover, since the said organosilicon compound (D) has high addition efficiency, the high effect is acquired even if it is a small quantity, and it contributes also to the reduction of a mixing | blending cost.

<< Rubber component (A) >>
The rubber component (A) of the rubber composition of the present invention is not particularly limited. In addition to natural rubber (NR), polyisoprene rubber (IR), styrene-butadiene copolymer rubber (SBR), polybutadiene rubber (BR) ), Ethylene-propylene-diene rubber (EPDM), chloroprene rubber (CR), halogenated butyl rubber, acrylonitrile-butadiene rubber (NBR), etc., natural rubber and / or diene synthetic rubber Preferably it consists of. These rubber components (A) may be used alone or in a blend of two or more.

<< Fine particle-containing fiber (B) >>
The fine particle-containing fiber (B) used in the rubber composition of the present invention comprises at least one kind of fine particles selected from the group consisting of metal oxide, metal carbonate and metal-containing clay mineral, and a hydrophilic resin. Cost. By blending the fine particle-containing fiber (B) with the rubber composition of the present invention, the long bubbles can be covered with a hydrophilic resin. In addition, by mixing fibers in the rubber composition, long bubbles functioning as micro drainage grooves are formed, and long bubbles are not formed only by directly blending the resin.

  In the rubber composition of the present invention, examples of the hydrophilic resin constituting the fine particle-containing fiber (B) include resins containing functional groups such as a carboxyl group, a hydroxyl group, an ester group, an ether group, and a carbonyl group. As the hydrophilic resin, a resin containing a hydroxyl group or a carboxyl group is particularly preferable. The hydrophilic resin is preferably an ionomer.

  In the rubber composition of the present invention, the hydrophilic resin constituting the fine particle-containing fiber (B) has a melting point or a softening point that is the highest temperature that the rubber composition reaches when the rubber composition is vulcanized, that is, the highest vulcanization temperature. It is preferable that the temperature is lower than the temperature. When the fine particle-containing fiber (B) is blended in the rubber composition containing the foaming agent (C), the hydrophilic resin constituting the fine particle-containing fiber (B) is melted or softened during vulcanization, The gas generated from the foaming agent (C) during vulcanization in the rubber matrix tends to stay inside the melted or softened hydrophilic resin constituting the fiber, compared to the rubber matrix in which the vulcanization reaction has proceeded. is there. Here, if the melting point or softening point of the hydrophilic resin is less than the maximum vulcanization temperature, the resin quickly melts or softens during the vulcanization of the rubber composition, and long cells are efficiently formed. Can do. On the other hand, if the melting point or softening point of the hydrophilic resin is too close to the maximum vulcanization temperature, the hydrophilic resin does not melt immediately (including softening) at the initial stage of vulcanization, and the hydrophilic resin melts at the end of vulcanization. To do. At the end of vulcanization, the gas generated from the foaming agent (C) is dispersed or taken into the vulcanized rubber matrix, and a sufficient amount of gas is not retained in the molten resin.

  The upper limit of the melting point or softening point of the hydrophilic resin is preferably selected in consideration of the above points, and is generally preferably 10 ° C. or lower than the maximum vulcanization temperature of the rubber composition, More preferably, it is 20 ° C. or lower. The industrial vulcanization temperature of the rubber composition is generally about 190 ° C. at the maximum. For example, when the maximum vulcanization temperature is set to 190 ° C., the melting point of the hydrophilic resin or The softening point is usually selected within a range of 190 ° C. or less, preferably 180 ° C. or less, and more preferably 170 ° C. or less.

  In the rubber composition of the present invention, the fine particles constituting the fine particle-containing fiber (B) exhibit an adhesive action with the hydrophilic resin. Examples of the fine particles include fine particles of metal oxides such as titanium oxide (titania) and aluminum oxide (alumina), fine particles of metal carbonates such as calcium carbonate, fine particles of clay minerals such as montmorillonite, and the like. Among these, fine particles of clay mineral are particularly preferable because of the presence of metal ions. These fine particles may be used individually by 1 type, and may use 2 or more types together. The metal oxide may be used as ceramics or zeolite (aluminosilicate).

  In the rubber composition of the present invention, the fine particles constituting the fine particle-containing fiber (B) preferably have a particle size of 0.1 to 500 μm from the viewpoint of ease of production. If the particle size is less than 0.1 μm, the scratching effect on the snowy and snowy road surface cannot be sufficiently obtained. On the other hand, if the particle size exceeds 500 μm, the yarn is cut during fiber production (melt spinning). It becomes difficult.

  In the rubber composition of the present invention, the fine particle-containing fiber (B) preferably contains 0.5 to 200 parts by mass of fine particles, preferably 1 to 100 parts by mass with respect to 100 parts by mass of the hydrophilic resin. Further preferred. When the content of the fine particles is less than 0.5 parts by mass, a sufficient scratching effect on the snowy and snowy road surface cannot be obtained. On the other hand, when the content exceeds 200 parts by mass, the spinning operability is poor and thread breakage may occur. .

  In the rubber composition of the present invention, the content of the fine particle-containing fiber (B) is preferably 0.5 to 30 parts by mass with respect to 100 parts by mass of the rubber component (A). If the content of the fine particle-containing fiber (B) is less than 0.5 parts by mass, the volume ratio of the elongated voids in the vulcanized rubber is small, so there is a risk that sufficient performance on ice may not be obtained, When it exceeds 30 parts by mass, the dispersibility of the fine particle-containing fiber (B) in the rubber composition is lowered, and the processability of the rubber composition may be lowered.

  The fine particle-containing fiber (B) used in the rubber composition of the present invention preferably has an average diameter of 1 to 100 μm, and more preferably 10 to 100 μm. In this case, the long air bubbles covered with the hydrophilic resin constituting the fiber can function efficiently as a micro drainage groove. Further, if the average diameter of the fine particle-containing fiber (B) is less than 1 μm, there is a possibility that spinning from the hydrophilic resin and the fine particle may not be possible, while if it exceeds 100 μm, the weight of the fine particle-containing fiber (B) increases. There exists a possibility that the compounding part number in a rubber composition may become high too much.

  The fine particle-containing fiber (B) used in the rubber composition of the present invention preferably has an average length of 0.1 to 20 mm, more preferably 0.5 to 20 mm, and 1 to 10 mm. Even more preferred. In this case, the long air bubbles covered with the hydrophilic resin constituting the fiber can function efficiently as a micro drainage groove. In addition, when the average length of the fine particle-containing fiber (B) is less than 0.1 mm, it is difficult to form long bubbles. On the other hand, when the average length of the fine particle-containing fiber (B) exceeds 20 mm, the hardness of the fiber becomes too high to be sufficiently kneaded, and the sipe of the tread is usually about 20 mm. Even if the average length exceeds 20 mm, it is difficult to improve the performance on ice.

  The fine particle-containing fiber (B) used in the rubber composition of the present invention can be produced by a conventional method, and examples of the method for producing the fiber include a melt spinning method, a gel spinning method, and a solution spinning method. For example, in the melt spinning method, after the raw material resin is heated and melted in an extruder, fine particles are dispersed, and then a bundle of fibers extruded from a spinning nozzle is stretched in a spinning cylinder and cooled by an air stream to be solidified. Then, the fine particle-containing fiber (B) can be produced by applying an oil agent, collecting them together, and winding them up. On the other hand, in the solution spinning method, fine particles are dispersed in a polymer solution in which a raw material resin is dissolved, and this is extruded from a spinning nozzle, and fiber removal is performed to remove the solvent, thereby producing a fiber.

<< Foaming agent (C) >>
Examples of the foaming agent (C) used in the rubber composition of the present invention include azodicarbonamide (ADCA), dinitrosopentamethylenetetramine (DPT), dinitrosopentastyrenetetramine, benzenesulfonylhydrazide derivatives, p, p′-oxybis. Benzenesulfonyl hydrazide (OBSH), ammonium bicarbonate generating carbon dioxide, sodium bicarbonate, ammonium carbonate, nitrososulfonylazo compound generating nitrogen, N, N'-dimethyl-N, N'-dinitrosophthalamide, toluene Examples thereof include sulfonyl hydrazide, p-toluenesulfonyl semicarbazide, p, p′-oxybisbenzenesulfonyl semicarbazide and the like. Among these foaming agents (C), azodicarbonamide (ADCA) and dinitrosopentamethylenetetramine (DPT) are preferable from the viewpoint of production processability, and azodicarbonamide (ADCA) is particularly preferable. These foaming agents may be used individually by 1 type, and may use 2 or more types together. Moreover, the compounding quantity of this foaming agent (C) is although it does not specifically limit, The range of 0.1-10 mass parts is preferable with respect to 100 mass parts of said rubber components (A).

  The foaming agent (C) is preferably used in combination with urea, zinc stearate, zinc benzenesulfinate, zinc white or the like as a foaming aid. These may be used individually by 1 type and may use 2 or more types together. By using a foaming aid in combination, the foaming reaction can be promoted to increase the degree of completion of the reaction, and unnecessary deterioration can be suppressed over time.

<< Organic silicon compound (D) >>
The organosilicon compound (D) used in the rubber composition of the present invention is selected from the group consisting of the compound represented by the general formula (I) and the compound represented by the general formula (VIII). The organosilicon compound (D) may be used alone or in combination of two or more. Moreover, it is preferable that this organosilicon compound (D) has 1-6 silicon-oxygen bonds (Si-O). When the organosilicon compound (D) has 1 to 6 silicon-oxygen bonds (Si—O), the reactivity with the inorganic filler (E) such as silica is high, and the coupling efficiency is further improved.

<<< Compound of Formula (I) >>>
In the general formula (I), A ¹ is represented by the general formula (II) or the formula (III), and x is 1 to 10. Here, x is preferably in the range of 2-4.

In the above formulas (I) and (II), at least one of R ¹ , R ² and R ³ is represented by the above general formula (IV) or formula (V), and the others are -M-C _r H _{2r + 1} (where M is —O— or —CH ₂ — and r is 0 to 20) or — (M−C ₁ H _2l ) _y C _s H _{2s + 1} (where M is − O— or —CH ₂ —, 1 is 0-10, and y and s are each independently 1-20. Provided that M is —O— in one or more of R ¹ , R ² and R ³ . Incidentally, -C _r H _{2r + 1,} since r is 0 to 20, hydrogen or an alkyl group having 1 to 20 carbon atoms. Here, as the alkyl group having 1 to 20 carbon atoms, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, Examples include a pentadecyl group, a hexadecyl group, a heptadecyl group, a stearyl group, and the like. The alkyl group may be linear or branched. Moreover, since l is 0 to 10, -C _l H _2l -is a single bond or an alkylene group having 1 to 10 carbon atoms. Here, examples of the alkylene group having 1 to 10 carbon atoms include a methylene group, an ethylene group, a trimethylene group, and a propylene group, and the alkylene group may be linear or branched. Further, -C _s H _{2s + 1,} since s is 1 to 20, an alkyl group having 1 to 20 carbon atoms. Here, as the alkyl group having 1 to 20 carbon atoms, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, Examples include a pentadecyl group, a hexadecyl group, a heptadecyl group, a stearyl group, and the like. The alkyl group may be linear or branched. Further, y is a number of repetitions of the (M-C _l H _2l) units is 1-20. In addition, it is preferable that M in the (M-C ₁ H _2l ) unit is —O— (oxygen).

In the above formulas (IV) and (V), M is —O— or —CH ₂ —, and 1 is 0 to 10. In the above formula (IV), m is 0-10.

In the above formula (IV), X and Y are each independently —O—, —NR ⁸ — or —CH ₂ —. Wherein, R ⁸ is -C _n H _{2n + 1, n} is 11 to 20. Note that -C _n H _{2n + 1} is an alkyl group having 11 to 20 carbon atoms because n is 11 to 20. Here, examples of the alkyl group having 11 to 20 carbon atoms include a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, a stearyl group, and the alkyl group may be linear or branched. It may be in the shape.

In the above formula (IV), R ⁶ is —OR ⁸ , —NR ⁸ R ⁹ or —R ⁸ . Wherein, R ⁸ is _{-C n H 2n + 1, R} 9 is -C _q H _{2q + 1,} n and q are 11-20 independently. Note that the -C _n H _{2n + 1,} are as described above, -C _q H _{2q + 1,} since q is 11 to 20, an alkyl group having 11 to 20 carbon atoms. Here, examples of the alkyl group having 11 to 20 carbon atoms include a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, a stearyl group, and the alkyl group may be linear or branched. It may be in the shape.

In the above formula (V), R ⁷ is —NR ⁸ R ⁹ , —NR ⁸ —NR ⁸ R ^9, or —N═NR ⁸ . Wherein, R ⁸ is _{-C n H 2n + 1, R} 9 is -C _q H _{2q + 1,} n and q are 11-20 independently. Note that the -C _n H _{2n + 1} and -C _q H _{2q + 1,} is as described above.

In the above formulas (I) and (II), R ⁴ is represented by the above general formula (VI) or formula (VII), or —Z—C ₁ H _2l —, particularly —C ₁ H _2l. - is preferably represented by, where, Z is -O -, - NR ⁸ - or -CH ₂ -, l is 0. In addition, since l is 0 to 10, —C ₁ H _2l — is a single bond or an alkylene group having 1 to 10 carbon atoms. Here, examples of the alkylene group having 1 to 10 carbon atoms include a methylene group, an ethylene group, a trimethylene group, and a propylene group, and the alkylene group may be linear or branched. Also, R ⁸ is -C _n H _{2n + 1, n} is 11 to 20. Note that -C _n H _{2n + 1} is as described above.

In the above formulas (VI) and (VII), M is —O— or —CH ₂ —, and l and m are 0-10. —C ₁ H _2l — in the formulas (VI) and (VII) is as described above. Further, -C _m H _2m in formula (VI) and (VII) - Since m is 0-10, a single bond or an alkylene group having 1 to 10 carbon atoms. Here, examples of the alkylene group having 1 to 10 carbon atoms include a methylene group, an ethylene group, a trimethylene group, and a propylene group, and the alkylene group may be linear or branched. In the above formula (VI), X and Y are each independently —O—, —NR ⁸ — or —CH ₂ —, and R ⁶ is —OR ⁸ , —NR ⁸ R ⁹ or —R ⁸ . is there. R ⁸ and R ⁹ are as described above. Further, in the above formula (VII), R ¹⁰ is —NR ⁸ —, —NR ⁸ —NR ⁸ —, or —N═N—, wherein R ⁸ is —C _n H _{2n + 1} , the -C _n H _{2n + 1,} as described above.

R ⁵ in the above formula (III) is represented by the above general formula (IV) or (V), or —C ₁ H _2l —R ¹¹ , and in particular —C ₁ H _2l —CH ₂ —. it is preferably represented by C _m H _{2m + 1,} where, R ^{11 is, -NR 8 R 9, -NR 8} -NR 8 R 9, -N = NR 8 or -Z-C _m H _{2m + 1} Provided that R ⁸ , R ⁹ , Z, l and m are as defined above. Incidentally, -C _l H _2l - for and -C _l H _{2l + 1} is are as described above. Further, -C _m H _{2m + 1,} since m is 0-10, is hydrogen or an alkyl group having 1 to 10 carbon atoms, wherein the alkyl group having 1 to 10 carbon atoms, a methyl group, Examples thereof include an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and a decyl group. The alkyl group may be linear or branched.

In the compound of the above formula (I), M is preferably —O— (oxygen). In this case, M is -CH ₂ - are highly reactive with an inorganic filler such as silica as compared to compounds wherein.

In the compound of the above formula (I), at least one of R ¹ , R ² and R ³ is represented by —O—C ₁ H _2l —R ⁷ , and the other is —O—C ₁ H _{2l +.} is preferably represented by _1, the R ⁴ is -C _l H _2l - is preferably represented by the above R ⁵ is preferably represented by -C _l H _2l -R ^11.

Further, in the compound of the above formula (I), it is more preferable that at least one of R ¹ , R ² and R ³ is represented by —O—C ₁ H _{2 1} —NR ⁸ R ⁹ , and R ⁴ is — It is preferably represented by C ₁ H _2l- , and the R ⁵ is more preferably represented by -C ₁ H _{2l + 1} .

<<< Compound of Formula (VIII) >>>
In the general formula (VIII), A ² is represented by the general formula (IX) or the formula (III), and x is 1 to 10. Here, x is preferably in the range of 2-4.

In the above formulas (VIII) and (IX), W is represented by —NR ⁸ —, —O— or —CR ⁸ R ¹⁵ —, wherein R ¹⁵ is —R ⁹ or —C _m H _2m —. R ⁷ wherein R ⁷ is —NR ⁸ R ⁹ , —NR ⁸ —NR ⁸ R ⁹ or —N═NR ⁸ , R ⁸ is —C _n H _{2n + 1} , and R ⁹ is —C _{In qH2q + 1} , m is 0-10, and n and q are each independently 11-20. Incidentally, -C _m H _2m -, since m is 0-10, a single bond or an alkylene group having 1 to 10 carbon atoms. Here, examples of the alkylene group having 1 to 10 carbon atoms include a methylene group, an ethylene group, a trimethylene group, and a propylene group, and the alkylene group may be linear or branched. Moreover, -C _n H _{2n + 1} and -C _q H _{2q + 1,} since n and q are 11 to 20, an alkyl group having 11 to 20 carbon atoms. Here, examples of the alkyl group having 11 to 20 carbon atoms include a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, a stearyl group, and the alkyl group may be linear or branched. It may be in the shape.

In the above formulas (VIII) and (IX), R ¹² and R ¹³ are each independently represented by —M—C ₁ H _{2 1} —, and R ¹⁴ is —M—C _r H _{2r + 1} or —M— C _r H _2r —R ¹¹ or — (M—C ₁ H _{2 l} ) _y C _s H _{2s + 1} , where M is —O— or —CH ₂ —, and R ¹¹ is —NR ⁸ R ⁹ , —NR ⁸ —NR ⁸ R ⁹ , —N═NR ⁸ or —Z—C _m H _{2m + 1} , where Z is —O—, —NR ⁸ — or —CH ₂ —, R ⁸ is —C _n H _{2n + 1} , R ⁹ is —C _q H _{2q + 1} , l and m are each independently 0 to 10, r is 0 to 20, y and s are Each is independently 1-20, and n and q are each independently 11-20. However, in one or more of R ¹² , R ¹³ and R ¹⁴ , M is —O—. In addition, since l is 0 to 10, —C ₁ H _2l — is a single bond or an alkylene group having 1 to 10 carbon atoms. Here, the alkylene group having 1 to 10 carbon atoms includes a methylene group, Examples thereof include an ethylene group, a trimethylene group, and a propylene group. The alkylene group may be linear or branched. Further, -C _m H _{2m + 1,} since m is 0-10, is hydrogen or an alkyl group having 1 to 10 carbon atoms, wherein the alkyl group having 1 to 10 carbon atoms, a methyl group, Examples thereof include an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and a decyl group. The alkyl group may be linear or branched. -C _r H _{2r + 1} is hydrogen or an alkyl group having 1 to 20 carbon atoms because r is 0 to 20, where the alkyl group having 1 to 20 carbon atoms is a methyl group, Ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, stearyl group, etc. The alkyl group may be linear or branched. Note that the -C _n H _{2n + 1} and -C _q H _{2q + 1,} is as described above. -C _r H _2r -is hydrogen or an alkylene group having 1 to 20 carbon atoms because r is 0 to 20, and examples of the alkylene group having 1 to 20 carbon atoms include a methylene group, an ethylene group, and trimethylene. Group, propylene group, tetramethylene group, hexamethylene group, octamethylene group, decamethylene group, dodecamethylene group, tetradecamethylene group, hexadecamethylene group, octadecamethylene group, etc., and the alkylene group is linear Or branched. Further, -C _s H _{2s + 1,} since s is 1 to 20, an alkyl group having 1 to 20 carbon atoms, wherein the alkyl group having 1 to 20 carbon atoms, a methyl group, an ethyl group Propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, stearyl group, etc., the alkyl group May be linear or branched. Further, y is a number of repetitions of the (M-C _l H _2l) units is 1-20. In addition, it is preferable that M in the (M-C ₁ H _2l ) unit is —O— (oxygen).

In the above formulas (VIII) and (IX), R ⁴ is represented by the above general formula (VI) or formula (VII), or —Z—C ₁ H _2l —, particularly —C ₁ H _2l — Wherein Z is —O—, —NR ⁸ — or —CH ₂ —, wherein R ⁸ is —C _n H _{2n + 1} and l is 0-10. Yes, n is 11-20. In addition, -C ₁ H _2l -and -C _n H _{2n + 1} are as described above.

In the above formulas (VI) and (VII), M is —O— or —CH ₂ —, and l and m are 0-10. In the above formula (VI), X and Y are each independently —O—, —NR ⁸ — or —CH ₂ —, and R ⁶ is —OR ⁸ , —NR ⁸ R ⁹ or —R ⁸ . Yes, where R ⁸ is —C _n H _{2n + 1} and R ⁹ is —C _q H _{2q + 1} . Further, in the above formula (VII), R ¹⁰ is —NR ⁸ —, —NR ⁸ —NR ⁸ —, or —N═N—, where R ⁸ is —C _n H _{2n + 1} . Note that the -C _n H _{2n + 1} and -C _q H _{2q + 1,} is as described above.

R ⁵ in the above formula (III) is represented by the above general formula (IV) or (V), or —C ₁ H _2l —R ¹¹ , particularly —C ₁ H _{2l + 1} —CH ₂ -C _m H _{2m + 1} , wherein R ¹¹ is —NR ⁸ R ⁹ , —NR ⁸ —NR ⁸ R ⁹ , —N═NR ⁸ or —Z—C _m H _{2m. +1} , provided that R ⁸ , R ⁹ , Z, l and m are as defined above. In addition, -C _l H _2l- is as described above, and -C _m H _{2m + 1} is hydrogen or an alkyl group having 1 to 10 carbon atoms because m is 0 to 10. Here, examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and a decyl group. It may be linear or branched.

In the compound of the above formula (VIII), M is preferably —O— (oxygen). In this case, M is -CH ₂ - are highly reactive with an inorganic filler such as silica as compared to compounds wherein.

When W is represented by —NR ⁸ —, R ¹² and R ¹³ are preferably each independently represented by —O—C ₁ H _2l —, and R ¹⁴ is represented by —O—C ₁ H. is preferably represented by _2l -R ¹¹ or -C _r H _{2r + 1,} the R ⁴ is -C _l H _2l - is preferably represented by the above R ⁵ is -C _l H _2l -CH ₂ -C It is preferably represented by _m H _{2m + 1} .

On the other hand, when the W is represented by —O— or —CR ⁸ R ⁹ —, the R ¹² and R ¹³ are preferably each independently represented by —O—C ₁ H _2l —, and the R ¹⁴ is It is preferably represented by —O—C ₁ H _2l —NR ⁸ R ⁹ , R ⁴ is preferably represented by —C ₁ H _2l —, and R ⁵ is represented by —C ₁ H _2l —CH ₂ —C. It is preferably represented by _m H _{2m + 1} .

<<< Method for Synthesizing Organosilicon Compound (D) >>>
The organosilicon compound (D) is represented by, for example, the above general formula (I), R ¹ , R ² and R ³ are represented by —M—C ₁ H _{2l + 1} , and R ¹ , R ² And in which at least one of M in R ³ is —O—, N-lauryldiethanolamine, N-myristyldiethanolamine, N-palmityldiethanolamine, N-stearyldiethanolamine, N-aralkyldiethanolamine, didodecylethanol Amine, ditetradecylethanolamine, dihexadecylethanolamine, dioctadecylethanolamine, amine compounds such as diicosylethanolamine are added, and acids such as p-toluenesulfonic acid and hydrochloric acid, and titanium tetra-n- A titanium alkoxide such as butoxide is added and heated, and one or more of R ¹ , R ² and R ³ are represented by formula (IV) or formula (V). Or by substituting R ¹ and R ² with a divalent nitrogen-containing group represented by —R ¹² —W—R ¹³ —.

<<< Specific Example of Organosilicon Compound (D) >>>
Specifically, as the organosilicon compound (D), 3-octanoylthio-propyl (ethoxy) 1,3-dioxa-6-dodecylaza-2-silacyclooctane, 3-octanoylthio-propyl (ethoxy) 1,3- Dioxa-6-tridecylaza-2-silacyclooctane, 3-octanoylthio-propyl (ethoxy) 1,3-dioxa-6-tetradecylaza-2-silacyclooctane, 3-octanoylthio-propyl (ethoxy) 1,3- Dioxa-6-pentadecylaza-2-silacyclooctane, 3-octanoylthio-propyl (ethoxy) 1,3-dioxa-6-hexadecylaza-2-silacyclooctane, 3-octanoylthio-propyl (ethoxy) 1,3-dioxa- 6-Heptadecylaza-2-silacyclooctane, 3-octanoylthio-propyl (ethoxy) 1,3-dioxa- -Octadecylaza-2-silacyclooctane, 3-octanoylthio-propyl (ethoxy) 1,3-dioxa-6-nonadecylaza-2-silacyclooctane, 3-octanoylthio-propyl (ethoxy) 1,3-dioxa-6- Eicosylaza-2-silacyclooctane, 3-octanoylthio-propyl (methyl) 1,3-dioxa-6-dodecylaza-2-silacyclooctane, 3-octanoylthio-propyl (methyl) 1,3-dioxa-6-pentadecylaza- 2-Silacyclooctane, 3-octanoylthio-propyl (methyl) 1,3-dioxa-6-octadecylaza-2-silacyclooctane, 3-octanoylthio-propyl (decanoxy) 1,3-dioxa-6-dodecylaza-2 -Silacyclooctane, 3-octanoylthio-propyl (decanoxy) 1,3-dioxa-6-pentadecyl Aza-2-silacyclooctane, 3-octanoylthio-propyl (decanoxy) 1,3-dioxa-6-octadecylaza-2-silacyclooctane, 3-octanoylthio-propyl (dodecanoxy) 1,3-dioxa-6-dodecylaza -2-Silacyclooctane, 3-octanoylthio-propyl (dodecanoxy) 1,3-dioxa-6-pentadecylaza-2-silacyclooctane, 3-octanoylthio-propyl (dodecanoxy) 1,3-dioxa-6-octadecylaza- 2-Silacyclooctane, 3-octanoylthio-propyl (octadecanoxy) 1,3-dioxa-6-dodecylaza-2-silacyclooctane, 3-octanoylthio-propyl (octadecanoxy) 1,3-dioxa-6-pentadecylaza-2- Silacyclooctane, 3-octanoylthio-propyl (octadecanoxy ) 1,3-Dioxa-6-octadecylaza-2-silacyclooctane, 3-octanoylthio-propyl (2- (butoxyethoxy) ethoxy) 1,3-dioxa-6-dodecylaza-2-silacyclooctane, 3- Octanoylthio-propyl (2- (butoxyethoxy) ethoxy) 1,3-dioxa-6-pentadecylaza-2-silacyclooctane, 3-octanoylthio-propyl (2- (butoxyethoxy) ethoxy) 1,3-dioxa-6- Octadecylaza-2-silacyclooctane, 3-octanoylthio-propyl (ethyl) 1,3-dioxa-6-dodecylaza-2-silacyclooctane, 3-octanoylthio-propyl (ethyl) 1,3-dioxa-6-pentadecylaza -2-Silacyclooctane, 3-octanoylthio-propyl (ethyl) 1,3-dioxa-6-octadecylaza-2-si Cyclooctane,
3-ethanoylthio-propyl (ethoxy) 1,3-dioxa-6-dodecylaza-2-silacyclooctane, 3-ethanoylthio-propyl (ethoxy) 1,3-dioxa-6-pentadecylaza-2-silacyclooctane, 3- Ethanoylthio-propyl (ethoxy) 1,3-dioxa-6-octadecylaza-2-silacyclooctane, 3-ethanoylthio-propyl (methyl) 1,3-dioxa-6-dodecylaza-2-silacyclooctane, 3-ethanoylthio -Propyl (methyl) 1,3-dioxa-6-pentadecylaza-2-silacyclooctane, 3-ethanoylthio-propyl (methyl) 1,3-dioxa-6-octadecylaza-2-silacyclooctane, 3-ethanoylthio- Propyl (decanoxy) 1,3-dioxa-6-dodecylaza-2-silacyclooctane, 3-ethanoylthio-propyl Canoxy) 1,3-dioxa-6-pentadecylaza-2-silacyclooctane, 3-ethanoylthio-propyl (decanoxy) 1,3-dioxa-6-octadecylaza-2-silacyclooctane, 3-ethanoylthio-propyl (dodecanoxy) ) 1,3-Dioxa-6-dodecylaza-2-silacyclooctane, 3-ethanoylthio-propyl (dodecanoxy) 1,3-dioxa-6-pentadecylaza-2-silacyclooctane, 3-ethanoylthio-propyl (dodecanoxy) 1 1,3-dioxa-6-octadecylaza-2-silacyclooctane, 3-ethanoylthio-propyl (octadecanoxy) 1,3-dioxa-6-dodecylaza-2-silacyclooctane, 3-ethanoylthio-propyl (octadecanoxy) 1, 3-Dioxa-6-pentadecylaza-2-silacyclooctane, 3-ethanoylthio- Lopyl (octadecanoxy) 1,3-dioxa-6-octadecylaza-2-silacyclooctane, 3-ethanoylthio-propyl (2- (butoxyethoxy) ethoxy) 1,3-dioxa-6-dodecylaza-2-silacyclooctane 3-Ethanoylthio-propyl (2- (butoxyethoxy) ethoxy) 1,3-dioxa-6-pentadecylaza-2-silacyclooctane, 3-ethanoylthio-propyl (2- (butoxyethoxy) ethoxy) 1,3-dioxa -6-octadecylaza-2-silacyclooctane, 3-ethanoylthio-propyl (ethyl) 1,3-dioxa-6-dodecylaza-2-silacyclooctane, 3-ethanoylthio-propyl (ethyl) 1,3-dioxa- 6-Pentadecylaza-2-silacyclooctane, 3-ethanoylthio-propyl (ethyl) 1,3-dioxa-6-octade Ruaza -2 silacyclooctane,
3-Pentanoylthio-propyl (ethoxy) 1,3-dioxa-6-dodecylaza-2-silacyclooctane, 3-pentanoylthio-propyl (ethoxy) 1,3-dioxa-6-pentadecylaza-2-silacyclo Octane, 3-pentanoylthio-propyl (ethoxy) 1,3-dioxa-6-octadecylaza-2-silacyclooctane, 3-pentanoylthio-propyl (methyl) 1,3-dioxa-6-dodecylaza-2 -Silacyclooctane, 3-pentanoylthio-propyl (methyl) 1,3-dioxa-6-pentadecylaza-2-silacyclooctane, 3-pentanoylthio-propyl (methyl) 1,3-dioxa-6-octadecyl Aza-2-silacyclooctane, 3-pentanoylthio-propyl (decanoxy) 1,3-dioxa-6-dodecylaza-2-silacyclooctane, 3-pentanoyl O-propyl (decanoxy) 1,3-dioxa-6-pentadecylaza-2-silacyclooctane, 3-pentanoylthio-propyl (decanoxy) 1,3-dioxa-6-octadecylaza-2-silacyclooctane, 3 -Pentanoylthio-propyl (dodecanoxy) 1,3-dioxa-6-dodecylaza-2-silacyclooctane, 3-pentanoylthio-propyl (dodecanoxy) 1,3-dioxa-6-pentadecylaza-2-silacyclooctane 3,3-pentanoylthio-propyl (dodecanoxy) 1,3-dioxa-6-octadecylaza-2-silacyclooctane, 3-pentanoylthio-propyl (octadecanoxy) 1,3-dioxa-6-dodecylaza-2- Silacyclooctane, 3-pentanoylthio-propyl (octadecanoxy) 1,3-dioxa-6-pentadecylaza-2-silacyclo Kutan, 3-pentanoylthio-propyl (octadecanoxy) 1,3-dioxa-6-octadecylaza-2-silacyclooctane, 3-pentanoylthio-propyl (2- (butoxyethoxy) ethoxy) 1,3-dioxa -6-dodecylaza-2-silacyclooctane, 3-pentanoylthio-propyl (2- (butoxyethoxy) ethoxy) 1,3-dioxa-6-pentadecylaza-2-silacyclooctane, 3-pentanoylthio-propyl (2- (Butoxyethoxy) ethoxy) 1,3-dioxa-6-octadecylaza-2-silacyclooctane, 3-pentanoylthio-propyl (ethyl) 1,3-dioxa-6-dodecylaza-2-silacyclo Octane, 3-pentanoylthio-propyl (ethyl) 1,3-dioxa-6-pentadecylaza-2-silacyclooctane, 3-pentanoylthiopropyl Lopyr (ethyl) 1,3-dioxa-6-octadecylaza-2-silacyclooctane,
3-dodecanoylthio-propyl (ethoxy) 1,3-dioxa-6-dodecylaza-2-silacyclooctane, 3-dodecanoylthio-propyl (ethoxy) 1,3-dioxa-6-pentadecylaza-2-silacyclooctane, 3- Dodecanoylthio-propyl (ethoxy) 1,3-dioxa-6-octadecylaza-2-silacyclooctane, 3-dodecanoylthio-propyl (methyl) 1,3-dioxa-6-dodecylaza-2-silacyclooctane, 3-dodecanoylthio -Propyl (methyl) 1,3-dioxa-6-pentadecylaza-2-silacyclooctane, 3-dodecanoylthio-propyl (methyl) 1,3-dioxa-6-octadecylaza-2-silacyclooctane, 3-dodecanoylthio- Propyl (decanoxy) 1,3-dioxa-6-dodecylaza-2-silacyclooctane, 3-dodecanoyl O-propyl (decanoxy) 1,3-dioxa-6-pentadecylaza-2-silacyclooctane, 3-dodecanoylthio-propyl (decanoxy) 1,3-dioxa-6-octadecylaza-2-silacyclooctane, 3-dodecanoylthio -Propyl (dodecanoxy) 1,3-dioxa-6-dodecylaza-2-silacyclooctane, 3-dodecanoylthio-propyl (dodecanoxy) 1,3-dioxa-6-pentadecylaza-2-silacyclooctane, 3-dodecanoylthio-propyl (Dodecanoxy) 1,3-dioxa-6-octadecylaza-2-silacyclooctane, 3-dodecanoylthio-propyl (octadecanoxy) 1,3-dioxa-6-dodecylaza-2-silacyclooctane, 3-dodecanoylthio-propyl Octadecanoxy) 1,3-dioxa-6-pentadecylaza-2-silacyclo Kutan, 3-dodecanoylthio-propyl (octadecanoxy) 1,3-dioxa-6-octadecylaza-2-silacyclooctane, 3-dodecanoylthio-propyl (2- (butoxyethoxy) ethoxy) 1,3-dioxa-6-dodecylaza -2-Silacyclooctane, 3-dodecanoylthio-propyl (2- (butoxyethoxy) ethoxy) 1,3-dioxa-6-pentadecylaza-2-silacyclooctane, 3-dodecanoylthio-propyl (2- (butoxyethoxy) ethoxy) ) 1,3-Dioxa-6-octadecylaza-2-silacyclooctane, 3-dodecanoylthio-propyl (ethyl) 1,3-dioxa-6-dodecylaza-2-silacyclooctane, 3-dodecanoylthio-propyl (ethyl) 1,3-dioxa-6-pentadecylaza-2-silacyclooctane, 3-dodecanoylthiop Lopyr (ethyl) 1,3-dioxa-6-octadecylaza-2-silacyclooctane,
3-hexadecanoylthio-propyl (ethoxy) 1,3-dioxa-6-dodecylaza-2-silacyclooctane, 3-hexadecanoylthio-propyl (ethoxy) 1,3-dioxa-6-pentadecylaza-2- Silacyclooctane, 3-hexadecanoylthio-propyl (ethoxy) 1,3-dioxa-6-octadecylaza-2-silacyclooctane, 3-hexadecanoylthio-propyl (methyl) 1,3-dioxa-6 -Dodecylaza-2-silacyclooctane, 3-hexadecanoylthio-propyl (methyl) 1,3-dioxa-6-pentadecylaza-2-silacyclooctane, 3-hexadecanoylthio-propyl (methyl) 1,3 -Dioxa-6-octadecylaza-2-silacyclooctane, 3-hexadecanoylthio-propyl (decanoxy) 1,3-dioxa-6-dodecylaza-2-silacy Looctane, 3-hexadecanoylthio-propyl (decanoxy) 1,3-dioxa-6-pentadecylaza-2-silacyclooctane, 3-hexadecanoylthio-propyl (decanoxy) 1,3-dioxa-6-octadecylaza -2-Silacyclooctane, 3-hexadecanoylthio-propyl (dodecanoxy) 1,3-dioxa-6-dodecylaza-2-silacyclooctane, 3-hexadecanoylthio-propyl (dodecanoxy) 1,3-dioxa -6-pentadecylaza-2-silacyclooctane, 3-hexadecanoylthio-propyl (dodecanoxy) 1,3-dioxa-6-octadecylaza-2-silacyclooctane, 3-hexadecanoylthio-propyl (octadecanoxy) 1,3-dioxa-6-dodecylaza-2-silacyclooctane, 3-hexadecanoylthio-propyl (octade Noxy) 1,3-dioxa-6-pentadecylaza-2-silacyclooctane, 3-hexadecanoylthio-propyl (octadecanoxy) 1,3-dioxa-6-octadecylaza-2-silacyclooctane, 3-hexadeca Noylthio-propyl (2- (butoxyethoxy) ethoxy) 1,3-dioxa-6-dodecylaza-2-silacyclooctane, 3-hexadecanoylthio-propyl (2- (butoxyethoxy) ethoxy) 1,3- Dioxa-6-pentadecylaza-2-silacyclooctane, 3-hexadecanoylthio-propyl (2- (butoxyethoxy) ethoxy) 1,3-dioxa-6-octadecylaza-2-silacyclooctane, 3-hexadeca Noylthio-propyl (ethyl) 1,3-dioxa-6-dodecylaza-2-silacyclooctane, 3-hexadecanoylthio-propyl (ethyl) ) 1,3-dioxa-6-Pentadeshiruaza 2-silacyclooctane, 3-hexadecanol Neu thio - propyl (ethyl) 1,3-dioxa-6-octadecyl-aza-2-silacyclooctane,
3-octanoylthio-propyl (didodecylmethylaminoethoxy) monoethoxysilane, 3-octanoylthio-propyl (dipentadecylmethylaminoethoxy) monoethoxysilane, 3-octanoylthio-propyl (dihexadecylmethylaminoethoxy) monoethoxysilane, 3-octanoylthio-propyl (dioctadecylmethylaminoethoxy) monoethoxysilane, 3-octanoylthio-propyl (diecosylmethylaminoethoxy) monoethoxysilane, 3-octanoylthio-propyl (monododecylmethylaminoethoxy) diethoxysilane, 3 -Octanoylthio-propyl (monopentadecylmethylaminoethoxy) diethoxysilane, 3-octanoylthio-propyl (monohexadecylmethylaminoethoxy) diethoxysilane Lan, 3-octanoylthio-propyl (monooctadecylmethylaminoethoxy) diethoxysilane, 3-octanoylthio-propyl (monoeicosylmethylaminoethoxy) diethoxysilane, 3-octanoylthio-propyl (dididodecylaminoethoxy) monoethoxysilane, 3-octanoylthio-propyl (didipentadecylaminoethoxy) monoethoxysilane, 3-octanoylthio-propyl (didihexadecylaminoethoxy) monoethoxysilane, 3-octanoylthio-propyl (didioctadecylaminoethoxy) monoethoxysilane, 3-octanoylthio -Propyl (didiecosylaminoethoxy) monoethoxysilane, 3-octanoylthio-propyl (didodecylmethylaminoethoxy) monomethylsilane, 3-octano Ruthio-propyl (dipentadecylmethylaminoethoxy) monomethylsilane, 3-octanoylthio-propyl (dihexadecylmethylaminoethoxy) monomethylsilane, 3-octanoylthio-propyl (dioctadecylmethylaminoethoxy) monomethylsilane, 3-octanoylthio-propyl (Dieicosylmethylaminoethoxy) monomethylsilane, 3-octanoylthio-propyl (monododecylmethylaminoethoxy) dimethylsilane, 3-octanoylthio-propyl (monopentadecylmethylaminoethoxy) dimethylsilane, 3-octanoylthio-propyl (monohexa Decylmethylaminoethoxy) dimethylsilane, 3-octanoylthio-propyl (monooctadecylmethylaminoethoxy) dimethylsilane, 3-octanoylthio -Propyl (monoeicosylmethylaminoethoxy) dimethylsilane, 3-octanoylthio-propyl (dididodecylaminoethoxy) monomethylsilane, 3-octanoylthio-propyl (didipentadecylaminoethoxy) monomethylsilane, 3-octanoylthio-propyl (didihexa) Decylaminoethoxy) monomethylsilane, 3-octanoylthio-propyl (didioctadecylaminoethoxy) monomethylsilane, 3-octanoylthio-propyl (didiecosylaminoethoxy) monomethylsilane,
3-octanoylthio-propyl (didodecylmethylaminoethoxy) monodecanoxysilane, 3-octanoylthio-propyl (dipentadecylmethylaminoethoxy) monodecanoxysilane, 3-octanoylthio-propyl (dihexadecylmethylaminoethoxy) Monodecanoxysilane, 3-octanoylthio-propyl (dioctadecylmethylaminoethoxy) monodecanoxysilane, 3-octanoylthio-propyl (diecosylmethylaminoethoxy) monodecanoxysilane, 3-octanoylthio-propyl (mono Dodecylmethylaminoethoxy) didecanoxysilane, 3-octanoylthio-propyl (monopentadecylmethylaminoethoxy) didecanoxysilane, 3-octanoylthio-propyl (monohexadecylmethylaminoethoxy) ) Didecanoxysilane, 3-octanoylthio-propyl (monooctadecylmethylaminoethoxy) didecanoxysilane, 3-octanoylthio-propyl (monoeicosylmethylaminoethoxy) didecanoxysilane, 3-octanoylthio-propyl (dididodecylamino) Ethoxy) monodecanoxysilane, 3-octanoylthio-propyl (didipentadecylaminoethoxy) monodecanoxysilane, 3-octanoylthio-propyl (didihexadecylaminoethoxy) monodecanoxysilane, 3-octanoylthio-propyl ( Didioctadecylaminoethoxy) monodecanoxysilane, 3-octanoylthio-propyl (didiecosylaminoethoxy) monodecanoxysilane, 3-octanoylthio-propyl (didodecylmethylaminoethoxy) Monododecanoxysilane, 3-octanoylthio-propyl (dipentadecylmethylaminoethoxy) monododecanoxysilane, 3-octanoylthio-propyl (dihexadecylmethylaminoethoxy) monododecanoxysilane, 3-octanoylthio-propyl ( Dioctadecylmethylaminoethoxy) monododecanoxysilane, 3-octanoylthio-propyl (dieicosylmethylaminoethoxy) monododecanoxysilane, 3-octanoylthio-propyl (monododecylmethylaminoethoxy) didodecanoxysilane, 3 -Octanoylthio-propyl (monopentadecylmethylaminoethoxy) didodecanoxysilane, 3-octanoylthio-propyl (monohexadecylmethylaminoethoxy) didodecanoxysilane, 3-octanoylthio-pro Pill (monooctadecylmethylaminoethoxy) didodecanoxysilane, 3-octanoylthio-propyl (monoeicosylmethylaminoethoxy) didodecanoxysilane, 3-octanoylthio-propyl (didododecylaminoethoxy) monododecanoxysilane, 3-octanoylthio-propyl (didipentadecylaminoethoxy) monododecanoxysilane, 3-octanoylthio-propyl (didihexadecylaminoethoxy) monododecanoxysilane, 3-octanoylthio-propyl (didioctadecylaminoethoxy) monododecano Xysilane, 3-octanoylthio-propyl (diediecosylaminoethoxy) monododecanoxysilane,
3-octanoylthio-propyl (didodecylmethylaminoethoxy) mono (2- (butoxyethoxy) ethoxy) silane, 3-octanoylthio-propyl (dipentadecylmethylaminoethoxy) mono (2- (butoxyethoxy) ethoxy) silane, 3 -Octanoylthio-propyl (dihexadecylmethylaminoethoxy) mono (2- (butoxyethoxy) ethoxy) silane, 3-octanoylthio-propyl (dioctadecylmethylaminoethoxy) mono (2- (butoxyethoxy) ethoxy) silane, 3- Octanoylthio-propyl (dieicosylmethylaminoethoxy) mono (2- (butoxyethoxy) ethoxy) silane, 3-octanoylthio-propyl (monododecylmethylaminoethoxy) di (2- (butoxyethoxy) ethoxy) silane, 3-o Octanoylthio-propyl (monopentadecylmethylaminoethoxy) di (2- (butoxyethoxy) ethoxy) silane, 3-octanoylthio-propyl (monohexadecylmethylaminoethoxy) di (2- (butoxyethoxy) ethoxy) silane, 3- Octanoylthio-propyl (monooctadecylmethylaminoethoxy) di (2- (butoxyethoxy) ethoxy) silane, 3-octanoylthio-propyl (monoeicosylmethylaminoethoxy) di (2- (butoxyethoxy) ethoxy) silane, 3-octanoylthio -Propyl (dididodecylaminoethoxy) mono (2- (butoxyethoxy) ethoxy) silane, 3-octanoylthio-propyl (didipentadecylaminoethoxy) mono (2- (butoxyethoxy) ethoxy) silane, 3-octanoy Thio-propyl (didihexadecylaminoethoxy) mono (2- (butoxyethoxy) ethoxy) silane, 3-octanoylthio-propyl (didioctadecylaminoethoxy) mono (2- (butoxyethoxy) ethoxy) silane, 3-octanoylthio-propyl (Didiecosylaminoethoxy) mono (2- (butoxyethoxy) ethoxy) silane,
3-dodecanoylthio-propyl (didodecylmethylaminoethoxy) monoethoxysilane, 3-dodecanoylthio-propyl (dipentadecylmethylaminoethoxy) monoethoxysilane, 3-dodecanoylthio-propyl (dihexadecylmethylaminoethoxy) monoethoxysilane, 3-dodecanoylthio-propyl (dioctadecylmethylaminoethoxy) monoethoxysilane, 3-dodecanoylthio-propyl (diecosylmethylaminoethoxy) monoethoxysilane, 3-dodecanoylthio-propyl (monododecylmethylaminoethoxy) diethoxysilane, 3 -Dodecanoylthio-propyl (monopentadecylmethylaminoethoxy) diethoxysilane, 3-dodecanoylthio-propyl (monohexadecylmethylaminoethoxy) diethoxysilane Lan, 3-dodecanoylthio-propyl (monooctadecylmethylaminoethoxy) diethoxysilane, 3-dodecanoylthio-propyl (monoeicosylmethylaminoethoxy) diethoxysilane, 3-dodecanoylthio-propyl (dididodecylaminoethoxy) monoethoxysilane, 3-dodecanoylthio-propyl (didipentadecylaminoethoxy) monoethoxysilane, 3-dodecanoylthio-propyl (didihexadecylaminoethoxy) monoethoxysilane, 3-dodecanoylthio-propyl (didioctadecylaminoethoxy) monoethoxysilane, 3-dodecanoylthio -Propyl (didiecosylaminoethoxy) monoethoxysilane, 3-dodecanoylthio-propyl (didodecylmethylaminoethoxy) monomethylsilane, 3-dodecano Ruthio-propyl (dipentadecylmethylaminoethoxy) monomethylsilane, 3-dodecanoylthio-propyl (dihexadecylmethylaminoethoxy) monomethylsilane, 3-dodecanoylthio-propyl (dioctadecylmethylaminoethoxy) monomethylsilane, 3-dodecanoylthio-propyl (Dieicosylmethylaminoethoxy) monomethylsilane, 3-dodecanoylthio-propyl (monododecylmethylaminoethoxy) dimethylsilane, 3-dodecanoylthio-propyl (monopentadecylmethylaminoethoxy) dimethylsilane, 3-dodecanoylthio-propyl (monohexa) Decylmethylaminoethoxy) dimethylsilane, 3-dodecanoylthio-propyl (monooctadecylmethylaminoethoxy) dimethylsilane, 3-dodecanoyl -Propyl (monoeicosylmethylaminoethoxy) dimethylsilane, 3-dodecanoylthio-propyl (dididodecylaminoethoxy) monomethylsilane, 3-dodecanoylthio-propyl (didipentadecylaminoethoxy) monomethylsilane, 3-dodecanoylthio-propyl (didihexa) Decylaminoethoxy) monomethylsilane, 3-dodecanoylthio-propyl (didioctadecylaminoethoxy) monomethylsilane, 3-dodecanoylthio-propyl (didiecosylaminoethoxy) monomethylsilane,
3-dodecanoylthio-propyl (didodecylmethylaminoethoxy) monodecanoxysilane, 3-dodecanoylthio-propyl (dipentadecylmethylaminoethoxy) monodecanoxysilane, 3-dodecanoylthio-propyl (dihexadecylmethylaminoethoxy) Monodecanoxysilane, 3-dodecanoylthio-propyl (dioctadecylmethylaminoethoxy) monodecanoxysilane, 3-dodecanoylthio-propyl (diecosylmethylaminoethoxy) monodecanoxysilane, 3-dodecanoylthio-propyl (mono Dodecylmethylaminoethoxy) didecanoxysilane, 3-dodecanoylthio-propyl (monopentadecylmethylaminoethoxy) didecanoxysilane, 3-dodecanoylthio-propyl (monohexadecylmethylaminoethoxy) ) Didecanoxysilane, 3-dodecanoylthio-propyl (monooctadecylmethylaminoethoxy) didecanoxysilane, 3-dodecanoylthio-propyl (monoeicosylmethylaminoethoxy) didecanoxysilane, 3-dodecanoylthio-propyl (dididodecylamino) Ethoxy) monodecanoxysilane, 3-dodecanoylthio-propyl (didipentadecylaminoethoxy) monodecanoxysilane, 3-dodecanoylthio-propyl (didihexadecylaminoethoxy) monodecanoxysilane, 3-dodecanoylthio-propyl Didioctadecylaminoethoxy) monodecanoxysilane, 3-dodecanoylthio-propyl (didiecosylaminoethoxy) monodecanoxysilane,
3-dodecanoylthio-propyl (didodecylmethylaminoethoxy) mono (2- (butoxyethoxy) ethoxy) silane, 3-dodecanoylthio-propyl (dipentadecylmethylaminoethoxy) mono (2- (butoxyethoxy) ethoxy) silane, 3 -Dodecanoylthio-propyl (dihexadecylmethylaminoethoxy) mono (2- (butoxyethoxy) ethoxy) silane, 3-dodecanoylthio-propyl (dioctadecylmethylaminoethoxy) mono (2- (butoxyethoxy) ethoxy) silane, 3- Dodecanoylthio-propyl (dieicosylmethylaminoethoxy) mono (2- (butoxyethoxy) ethoxy) silane, 3-dodecanoylthio-propyl (monododecylmethylaminoethoxy) di (2- (butoxyethoxy) ethoxy) silane, 3-do Decanoylthio-propyl (monopentadecylmethylaminoethoxy) di (2- (butoxyethoxy) ethoxy) silane, 3-dodecanoylthio-propyl (monohexadecylmethylaminoethoxy) di (2- (butoxyethoxy) ethoxy) silane, 3- Dodecanoylthio-propyl (monooctadecylmethylaminoethoxy) di (2- (butoxyethoxy) ethoxy) silane, 3-dodecanoylthio-propyl (monoeicosylmethylaminoethoxy) di (2- (butoxyethoxy) ethoxy) silane, 3-dodecanoylthio -Propyl (dididodecylaminoethoxy) mono (2- (butoxyethoxy) ethoxy) silane, 3-dodecanoylthio-propyl (didipentadecylaminoethoxy) mono (2- (butoxyethoxy) ethoxy) silane, 3-dodecanoic Thio-propyl (didihexadecylaminoethoxy) mono (2- (butoxyethoxy) ethoxy) silane, 3-dodecanoylthio-propyl (didioctadecylaminoethoxy) mono (2- (butoxyethoxy) ethoxy) silane, 3-dodecanoylthio-propyl (Didiecosylaminoethoxy) mono (2- (butoxyethoxy) ethoxy) silane,
3-hexadecanoylthio-propyl (didodecylmethylaminoethoxy) monoethoxysilane, 3-hexadecanoylthio-propyl (dipentadecylmethylaminoethoxy) monoethoxysilane, 3-hexadecanoylthio-propyl (dihexa) Decylmethylaminoethoxy) monoethoxysilane, 3-hexadecanoylthio-propyl (dioctadecylmethylaminoethoxy) monoethoxysilane, 3-hexadecanoylthio-propyl (diecosylmethylaminoethoxy) monoethoxysilane, 3- Hexadecanoylthio-propyl (monododecylmethylaminoethoxy) diethoxysilane, 3-hexadecanoylthio-propyl (monopentadecylmethylaminoethoxy) diethoxysilane, 3-hexadecanoylthio-propyl (monohexadecylme Tylaminoethoxy) diethoxysilane, 3-hexadecanoylthio-propyl (monooctadecylmethylaminoethoxy) diethoxysilane, 3-hexadecanoylthio-propyl (monoeicosylmethylaminoethoxy) diethoxysilane, 3-hexa Decanoylthio-propyl (dididodecylaminoethoxy) monoethoxysilane, 3-hexadecanoylthio-propyl (didipentadecylaminoethoxy) monoethoxysilane, 3-hexadecanoylthio-propyl (didihexadecylaminoethoxy) mono Ethoxysilane, 3-hexadecanoylthio-propyl (didioctadecylaminoethoxy) monoethoxysilane, 3-hexadecanoylthio-propyl (didiecosylaminoethoxy) monoethoxysilane, 3-hexadecanoylthio-propyl (Didodecylmethylaminoethoxy) monomethylsilane, 3-hexadecanoylthio-propyl (dipentadecylmethylaminoethoxy) monomethylsilane, 3-hexadecanoylthio-propyl (dihexadecylmethylaminoethoxy) monomethylsilane, 3- Hexadecanoylthio-propyl (dioctadecylmethylaminoethoxy) monomethylsilane, 3-hexadecanoylthio-propyl (diecosylmethylaminoethoxy) monomethylsilane, 3-hexadecanoylthio-propyl (monododecylmethylaminoethoxy) Dimethylsilane, 3-hexadecanoylthio-propyl (monopentadecylmethylaminoethoxy) dimethylsilane, 3-hexadecanoylthio-propyl (monohexadecylmethylaminoethoxy) dimethylsilane, 3-hexa Canoylthio-propyl (monooctadecylmethylaminoethoxy) dimethylsilane, 3-hexadecanoylthio-propyl (monoeicosylmethylaminoethoxy) dimethylsilane, 3-hexadecanoylthio-propyl (dididodecylaminoethoxy) monomethylsilane, 3 -Hexadecanoylthio-propyl (didipentadecylaminoethoxy) monomethylsilane, 3-hexadecanoylthio-propyl (didihexadecylaminoethoxy) monomethylsilane, 3-hexadecanoylthio-propyl (didioctadecylaminoethoxy) monomethyl Silane, 3-hexadecanoylthio-propyl (diediecosylaminoethoxy) monomethylsilane,
3-hexadecanoylthio-propyl (didodecylmethylaminoethoxy) monodecanoxysilane, 3-hexadecanoylthio-propyl (dipentadecylmethylaminoethoxy) monodecanoxysilane, 3-hexadecanoylthio- Propyl (dihexadecylmethylaminoethoxy) monodecanoxysilane, 3-hexadecanoylthio-propyl (dioctadecylmethylaminoethoxy) monodecanoxysilane, 3-hexadecanoylthio-propyl (diecosylmethylamino) Ethoxy) monodecanoxysilane, 3-hexadecanoylthio-propyl (monododecylmethylaminoethoxy) didecanoxysilane, 3-hexadecanoylthio-propyl (monopentadecylmethylaminoethoxy) didecanoxysilane, 3 -Hexadecanoylthio-propyl (mono Hexadecylmethylaminoethoxy) didecanoxysilane, 3-hexadecanoylthio-propyl (monooctadecylmethylaminoethoxy) didecanoxysilane, 3-hexadecanoylthio-propyl (monoeicosylmethylaminoethoxy) didecanoxy Silane, 3-hexadecanoylthio-propyl (dididodecylaminoethoxy) monodecanoxysilane, 3-hexadecanoylthio-propyl (didipentadecylaminoethoxy) monodecanoxysilane, 3-hexadecanoylthio- Propyl (didihexadecylaminoethoxy) monodecanoxysilane, 3-hexadecanoylthio-propyl (didioctadecylaminoethoxy) monodecanoxysilane, 3-hexadecanoylthio-propyl (didiecosylaminoethoxy) mono Decanoxysilane,
3-hexadecanoylthio-propyl (didodecylmethylaminoethoxy) mono (2- (butoxyethoxy) ethoxy) silane, 3-hexadecanoylthio-propyl (dipentadecylmethylaminoethoxy) mono (2- (butoxyethoxy) ) Ethoxy) silane, 3-hexadecanoylthio-propyl (dihexadecylmethylaminoethoxy) mono (2- (butoxyethoxy) ethoxy) silane, 3-hexadecanoylthio-propyl (dioctadecylmethylaminoethoxy) mono ( 2- (Butoxyethoxy) ethoxy) silane, 3-hexadecanoylthio-propyl (diecosylmethylaminoethoxy) mono (2- (butoxyethoxy) ethoxy) silane, 3-hexadecanoylthio-propyl (monododecylmethyl) Aminoethoxy) di (2- (butoxyethoxy Ethoxy) silane, 3-hexadecanoylthio-propyl (monopentadecylmethylaminoethoxy) di (2- (butoxyethoxy) ethoxy) silane, 3-hexadecanoylthio-propyl (monohexadecylmethylaminoethoxy) di ( 2- (Butoxyethoxy) ethoxy) silane, 3-hexadecanoylthio-propyl (monooctadecylmethylaminoethoxy) di (2- (butoxyethoxy) ethoxy) silane, 3-hexadecanoylthio-propyl (monoeicosylmethyl) Aminoethoxy) di (2- (butoxyethoxy) ethoxy) silane, 3-hexadecanoylthio-propyl (dididodecylaminoethoxy) mono (2- (butoxyethoxy) ethoxy) silane, 3-hexadecanoylthio-propyl ( Didipentadecylaminoethoxy) mono (2- ( Toxiethoxy) ethoxy) silane, 3-hexadecanoylthio-propyl (didihexadecylaminoethoxy) mono (2- (butoxyethoxy) ethoxy) silane, 3-hexadecanoylthio-propyl (didioctadecylaminoethoxy) mono ( 2- (butoxyethoxy) ethoxy) silane, 3-hexadecanoylthio-propyl (didiecosylaminoethoxy) mono (2- (butoxyethoxy) ethoxy) silane,
Bis (3- (ethoxy) 1,3-dioxa-6-dodecylaza-2-silacyclooctyl-propyl) disulfide, bis (3- (ethoxy) 1,3-dioxa-6-tridecylaza-2-silacyclooctyl- Propyl) disulfide, bis (3- (ethoxy) 1,3-dioxa-6-tetradecylaza-2-silacyclooctylpropyl) disulfide, bis (3- (ethoxy) 1,3-dioxa-6-pentadecylaza- 2-Silacyclooctyl-propyl) disulfide, bis (3- (ethoxy) 1,3-dioxa-6-hexadecylaza-2-silacyclooctyl-propyl) disulfide, bis (3- (ethoxy) 1,3-dioxa- 6-octadecylaza-2-silacyclooctyl-propyl) disulfide, bis (3- (ethoxy) 1,3-dioxa-6-nonadecylaza-2-silacyclooctyl-propyl Ropyl) disulfide, bis (3- (ethoxy) 1,3-dioxa-6-eicosylaza-2-silacyclooctyl-propyl) disulfide, bis (3- (ethoxy) 1,3-dioxa-6-dodecylaza-2- Silacyclooctyl-propyl) tetrasulfide, bis (3- (ethoxy) 1,3-dioxa-6-tridecylaza-2-silacyclooctyl-propyl) tetrasulfide, bis (3- (ethoxy) 1,3-dioxa- 6-tetradecylaza-2-silacyclooctyl-propyl) tetrasulfide, bis (3- (ethoxy) 1,3-dioxa-6-pentadecylaza-2-silacyclooctyl-propyl) tetrasulfide, bis (3- ( Ethoxy) 1,3-dioxa-6-hexadecylaza-2-silacyclooctyl-propyl) tetrasulfide, bis (3- (ethoxy) 1,3-dioxa-6 -Octadecylaza-2-silacyclooctyl-propyl) tetrasulfide, bis (3- (ethoxy) 1,3-dioxa-6-nonadecylaza-2-silacyclooctyl-propyl) tetrasulfide, bis (3- (ethoxy) 1,3-dioxa-6-eicosylaza-2-silacyclooctyl-propyl) tetrasulfide, bis (3- (methyl) 1,3-dioxa-6-dodecylaza-2-silacyclooctyl-propyl) disulfide, bis ( 3- (Methyl) 1,3-dioxa-6-tridecylaza-2-silacyclooctyl-propyl) disulfide, bis (3- (methyl) 1,3-dioxa-6-tetradecylaza-2-silacyclooctyl- Propyl) disulfide, bis (3- (methyl) 1,3-dioxa-6-pentadecylaza-2-silacyclooctyl-propyl) disulfide, bis (3- (me 1) 1,3-dioxa-6-hexadecylaza-2-silacyclooctyl-propyl) disulfide, bis (3- (methyl) 1,3-dioxa-6-octadecylaza-2-silacyclooctyl-propyl) disulfide, Bis (3- (methyl) 1,3-dioxa-6-nonadecylaza-2-silacyclooctyl-propyl) disulfide, bis (3- (methyl) 1,3-dioxa-6-eicosylaza-2-silacyclooctyl- Propyl) disulfide, bis (3- (methyl) 1,3-dioxa-6-dodecylaza-2-silacyclooctyl-propyl) tetrasulfide, bis (3- (methyl) 1,3-dioxa-6-tridecylaza-2 -Silacyclooctyl-propyl) tetrasulfide, bis (3- (methyl) 1,3-dioxa-6-tetradecylaza-2-silacyclooctyl-propyl) tetrasulfi Bis (3- (methyl) 1,3-dioxa-6-pentadecylaza-2-silacyclooctyl-propyl) tetrasulfide, bis (3- (methyl) 1,3-dioxa-6-hexadecylaza-2-silacyclo Octyl-propyl) tetrasulfide, bis (3- (methyl) 1,3-dioxa-6-octadecylaza-2-silacyclooctyl-propyl) tetrasulfide, bis (3- (methyl) 1,3-dioxa-6 -Nonadecylaza-2-silacyclooctyl-propyl) tetrasulfide, bis (3- (methyl) 1,3-dioxa-6-eicosylaza-2-silacyclooctyl-propyl) tetrasulfide,
Bis (3- (ethoxy) 1,3-dioxa-6-dodecylaza-2-silacyclooctyl-propyl) trisulfide, bis (3- (ethoxy) 1,3-dioxa-6-hexadecylaza-2-silacyclooctyl -Propyl) trisulfide, bis (3- (ethoxy) 1,3-dioxa-6-octadecylaza-2-silacyclooctyl-propyl) trisulfide, bis (3- (methyl) 1,3-dioxa-6- Dodecylaza-2-silacyclooctyl-propyl) trisulfide, bis (3- (methyl) 1,3-dioxa-6-hexadecylaza-2-silacyclooctyl-propyl) trisulfide, bis (3- (methyl) 1, 3-Dioxa-6-octadecylaza-2-silacyclooctyl-propyl) trisulfide, bis (3- (butoxy) 1,3-dioxa-6-dodecylaza-2-silacyclooctyl- Ropyl) trisulfide, bis (3- (butoxy) 1,3-dioxa-6-hexadecylaza-2-silacyclooctyl-propyl) trisulfide, bis (3- (butoxy) 1,3-dioxa-6-octadecylaza -2-Silacyclooctyl-propyl) trisulfide, bis (3- (ethyl) 1,3-dioxa-6-dodecylaza-2-silacyclooctyl-propyl) trisulfide, bis (3- (ethyl) 1,3 -Dioxa-6-hexadecylaza-2-silacyclooctyl-propyl) trisulfide, bis (3- (ethyl) 1,3-dioxa-6-octadecylaza-2-silacyclooctyl-propyl) trisulfide, bis (3 -(Decanoxy) 1,3-dioxa-6-dodecylaza-2-silacyclooctyl-propyl) trisulfide, bis (3- (decanoxy) 1,3-dioxa-6-hexa Silaza-2-silacyclooctyl-propyl) trisulfide, bis (3- (decanoxy) 1,3-dioxa-6-octadecylaza-2-silacyclooctyl-propyl) trisulfide, bis (3- (dodecanoxy) 1 , 3-Dioxa-6-dodecylaza-2-silacyclooctyl-propyl) trisulfide, bis (3- (dodecanoxy) 1,3-dioxa-6-hexadecylaza-2-silacyclooctyl-propyl) trisulfide, bis ( 3- (dodecanoxy) 1,3-dioxa-6-octadecylaza-2-silacyclooctyl-propyl) trisulfide, bis (3- (2- (butoxyethoxy) ethoxy) 1,3-dioxa-6-dodecylaza- 2-Silacyclooctyl-propyl) trisulfide, bis (3- (2- (butoxyethoxy) ethoxy) 1,3-dioxa-6-hexadecyla The-2-silacyclooctyl-propyl) trisulfide, bis (3- (2- (butoxyethoxy) ethoxy) 1,3-dioxa-6-octadecylaza-2-silacyclooctyl-propyl) trisulfide, bis ( 3- (decyl) 1,3-dioxa-6-dodecylaza-2-silacyclooctyl-propyl) trisulfide, bis (3- (decyl) 1,3-dioxa-6-hexadecylaza-2-silacyclooctyl-propyl ) Trisulfide, bis (3- (decyl) 1,3-dioxa-6-octadecylaza-2-silacyclooctyl-propyl) trisulfide, bis (3- (dodecyl) 1,3-dioxa-6-dodecylaza- 2-silacyclooctyl-propyl) trisulfide, bis (3- (dodecyl) 1,3-dioxa-6-hexadecylaza-2-silacyclooctyl-propyl) trisulfide, Bis (3- (dodecyl) 1,3-dioxa-6-octadecylaza-2-silacyclooctyl-propyl) trisulfide, bis (3- (octadecyl) 1,3-dioxa-6-dodecylaza-2-silacyclo Octyl-propyl) trisulfide, bis (3- (octadecyl) 1,3-dioxa-6-hexadecylaza-2-silacyclooctyl-propyl) trisulfide, bis (3- (octadecyl) 1,3-dioxa-6- Octadecylaza-2-silacyclooctyl-propyl) trisulfide,
Bis (3- (butoxy) 1,3-dioxa-6-dodecylaza-2-silacyclooctyl-propyl) tetrasulfide, bis (3- (butoxy) 1,3-dioxa-6-hexadecylaza-2-silacyclooctyl -Propyl) tetrasulfide, bis (3- (butoxy) 1,3-dioxa-6-octadecylaza-2-silacyclooctyl-propyl) tetrasulfide, bis (3- (ethyl) 1,3-dioxa-6- Dodecylaza-2-silacyclooctyl-propyl) tetrasulfide, bis (3- (ethyl) 1,3-dioxa-6-hexadecylaza-2-silacyclooctyl-propyl) tetrasulfide, bis (3- (ethyl) 1, 3-Dioxa-6-octadecylaza-2-silacyclooctyl-propyl) tetrasulfide, bis (3- (decanoxy) 1,3-dioxa-6-dodecylaza-2-silacy Crooctyl-propyl) tetrasulfide, bis (3- (decanoxy) 1,3-dioxa-6-hexadecylaza-2-silacyclooctyl-propyl) tetrasulfide, bis (3- (decanoxy) 1,3-dioxa-6 -Octadecylaza-2-silacyclooctyl-propyl) tetrasulfide, bis (3- (dodecanoxy) 1,3-dioxa-6-dodecylaza-2-silacyclooctyl-propyl) tetrasulfide, bis (3- (dodecanoxy) 1,3-dioxa-6-hexadecylaza-2-silacyclooctyl-propyl) tetrasulfide, bis (3- (dodecanoxy) 1,3-dioxa-6-octadecylaza-2-silacyclooctyl-propyl) tetrasulfide, Bis (3- (2- (butoxyethoxy) ethoxy) 1,3-dioxa-6-dodecylaza-2-silacyclooctyl-propyl Pyr) tetrasulfide, bis (3- (2- (butoxyethoxy) ethoxy) 1,3-dioxa-6-hexadecylaza-2-silacyclooctyl-propyl) tetrasulfide, bis (3- (2- (butoxyethoxy)) Ethoxy) 1,3-dioxa-6-octadecylaza-2-silacyclooctyl-propyl) tetrasulfide, bis (3- (decyl) 1,3-dioxa-6-dodecylaza-2-silacyclooctyl-propyl) tetra Sulfide, bis (3- (decyl) 1,3-dioxa-6-hexadecylaza-2-silacyclooctyl-propyl) tetrasulfide, bis (3- (decyl) 1,3-dioxa-6-octadecylaza-2- Silacyclooctyl-propyl) tetrasulfide, bis (3- (dodecyl) 1,3-dioxa-6-dodecylaza-2-silacyclooctyl-propyl) tetras Fido, bis (3- (dodecyl) 1,3-dioxa-6-hexadecylaza-2-silacyclooctyl-propyl) tetrasulfide, bis (3- (dodecyl) 1,3-dioxa-6-octadecylaza-2- Silacyclooctyl-propyl) tetrasulfide, bis (3- (octadecyl) 1,3-dioxa-6-dodecylaza-2-silacyclooctyl-propyl) tetrasulfide, bis (3- (octadecyl) 1,3-dioxa- 6-hexadecylaza-2-silacyclooctyl-propyl) tetrasulfide, bis (3- (octadecyl) 1,3-dioxa-6-octadecylaza-2-silacyclooctyl-propyl) tetrasulfide, bis (3- (ethyl ) 1,3-Dioxa-6-dodecylaza-2-silacyclooctyl-propyl) disulfide, bis (3- (ethyl) 1,3-dioxa-6-he) Sadecylaza-2-silacyclooctyl-propyl) disulfide, bis (3- (ethyl) 1,3-dioxa-6-octadecylaza-2-silacyclooctyl-propyl) disulfide, bis (3- (decanoxy) 1,3 -Dioxa-6-dodecylaza-2-silacyclooctyl-propyl) disulfide, bis (3- (decanoxy) 1,3-dioxa-6-hexadecylaza-2-silacyclooctyl-propyl) disulfide, bis (3- (decanoxy) ) 1,3-dioxa-6-octadecylaza-2-silacyclooctyl-propyl) disulfide, bis (3- (dodecanoxy) 1,3-dioxa-6-dodecylaza-2-silacyclooctyl-propyl) disulfide, bis (3- (dodecanoxy) 1,3-dioxa-6-hexadecylaza-2-silacyclooctyl-propyl) disulfide, bis ( 3- (dodecanoxy) 1,3-dioxa-6-octadecylaza-2-silacyclooctyl-propyl) disulfide,
Bis (3- (2- (butoxyethoxy) 1,3-dioxa-6-dodecylaza-2-silacyclooctyl-propyl) disulfide, bis (3- (2- (butoxyethoxy) 1,3-dioxa-6- Hexadecylaza-2-silacyclooctyl-propyl) disulfide, bis (3- (2- (butoxyethoxy) 1,3-dioxa-6-octadecylaza-2-silacyclooctyl-propyl) disulfide, bis (3- (decyl) ) 1,3-dioxa-6-dodecylaza-2-silacyclooctyl-propyl) disulfide, bis (3- (decyl) 1,3-dioxa-6-hexadecylaza-2-silacyclooctyl-propyl) disulfide, bis ( 3- (decyl) 1,3-dioxa-6-octadecylaza-2-silacyclooctyl-propyl) disulfide, bis (3- (dodecyl) 1,3-dioxa-6-dodecyl The-2-silacyclooctyl-propyl) disulfide, bis (3- (dodecyl) 1,3-dioxa-6-hexadecylaza-2-silacyclooctyl-propyl) disulfide, bis (3- (dodecyl) 1,3- Dioxa-6-octadecylaza-2-silacyclooctyl-propyl) disulfide, bis (3- (octadecyl) 1,3-dioxa-6-dodecylaza-2-silacyclooctyl-propyl) disulfide, bis (3- (octadecyl) ) 1,3-Dioxa-6-hexadecylaza-2-silacyclooctyl-propyl) disulfide, bis (3- (octadecyl) 1,3-dioxa-6-octadecylaza-2-silacyclooctyl-propyl) disulfide, bis (3- (Ethoxy) (dididodecylaminoethoxy) silylpropyl) disulfide, bis (3- (ethoxy) (diditride Silaminoethoxy) silylpropyl) disulfide, bis (3- (ethoxy) (diditetradecylaminoethoxy) silylpropyl) disulfide, bis (3- (ethoxy) (didipentadecylaminoethoxy) silylpropyl) disulfide, bis (3 -(Ethoxy) (didihexadecylaminoethoxy) silylpropyl) disulfide, bis (3- (ethoxy) (didioctadecylaminoethoxy) silylpropyl) disulfide,
Bis (3- (ethoxy) (di (methyl) (dodecyl) aminoethoxy) silylpropyl) disulfide, bis (3- (ethoxy) (di (methyl) (tridecyl) aminoethoxy) silylpropyl) disulfide, bis (3- (Ethoxy) (dimonomethylmonotetradecylaminoethoxy) silylpropyl) disulfide, bis (3- (ethoxy) (di (methyl) (pentadecyl) aminoethoxy) silylpropyl) disulfide, bis (3- (ethoxy) (di ( Methyl) (hexadecyl) aminoethoxy) silylpropyl) disulfide, bis (3- (ethoxy) (di (methyl) (octadecyl) aminoethoxy) silylpropyl) disulfide, bis (3- (ethoxy) (di (ethyl) (dodecyl)) ) Aminoethoxy) silylpropyl) disulfide, Bis (3- (ethoxy) (di (ethyl) (tridecyl) aminoethoxy) silylpropyl) disulfide, bis (3- (ethoxy) (di (ethyl) (tetradecyl) aminoethoxy) silylpropyl) disulfide, bis (3- (Ethoxy) (di (ethyl) (pentadecyl) aminoethoxy) silylpropyl) disulfide, bis (3- (ethoxy) (di (ethyl) (hexadecyl) aminoethoxy) silylpropyl) disulfide, bis (3- (ethoxy) ( Di (ethyl) (octadecyl) aminoethoxy) silylpropyl) disulfide, bis (3- (diethoxy) (didodecylaminoethoxy) silylpropyl) disulfide, bis (3- (diethoxy) (ditridecylaminoethoxy) silylpropyl) disulfide , Bis (3- (diethoxy (Ditetradecylaminoethoxy) silylpropyl) disulfide, bis (3- (diethoxy) (dipentadecylaminoethoxy) silylpropyl) disulfide, bis (3- (diethoxy) (dihexadecylaminoethoxy) silylpropyl) disulfide, Bis (3- (diethoxy) (dioctadecylaminoethoxy) silylpropyl) disulfide,
Bis (3- (methyl) (dididodecylaminoethoxy) silylpropyl) disulfide, bis (3- (methyl) (diditridecylaminoethoxy) silylpropyl) disulfide, bis (3- (methyl) (diditetradecylaminoethoxy) ) Silylpropyl) disulfide, bis (3- (methyl) (didipentadecylaminoethoxy) silylpropyl) disulfide, bis (3- (methyl) (didihexadecylaminoethoxy) silylpropyl) disulfide, bis (3- (methyl ) (Didioctadecylaminoethoxy) silylpropyl) disulfide, bis (3- (decanoxy) (dididodecylaminoethoxy) silylpropyl) disulfide, bis (3- (decanoxy) (diditridecylaminoethoxy) silylpropyl) disulfide, bis (3- Decanoxy) (diditetradecylaminoethoxy) silylpropyl) disulfide, bis (3- (decanoxy) (didipentadecylaminoethoxy) silylpropyl) disulfide, bis (3- (decanoxy) (didihexadecylaminoethoxy) silylpropyl) Disulfide, bis (3- (decanoxy) (didioctadecylaminoethoxy) silylpropyl) disulfide, bis (3- (dodecanoxy) (dididodecylaminoethoxy) silylpropyl) disulfide, bis (3- (dodecanoxy) (diditridecylamino) Ethoxy) silylpropyl) disulfide, bis (3- (dodecanoxy) (diditetradecylaminoethoxy) silylpropyl) disulfide, bis (3- (dodecanoxy) (didipentadecylaminoethoxy) silylpro Disulfide, bis (3- (dodecanoxy) (didihexadecylaminoethoxy) silylpropyl) disulfide, bis (3- (dodecanoxy) (didioctadecylaminoethoxy) silylpropyl) disulfide, bis (3- (2- (butoxy Ethoxy) (dididodecylaminoethoxy) silylpropyl) disulfide, bis (3- (2- (butoxyethoxy) (diditridecylaminoethoxy) silylpropyl) disulfide, bis (3- (2- (butoxyethoxy)) (diditetra Decylaminoethoxy) silylpropyl) disulfide, bis (3- (2- (butoxyethoxy) (didipentadecylaminoethoxy) silylpropyl) disulfide, bis (3- (2- (butoxyethoxy) (didihexadecylaminoethoxy)) Silylpropyl) di Rufido, bis (3- (2- (butoxyethoxy) (Gigi octadecyl amino ethoxy) silyl propyl) disulfide, and the like.

  The compounding amount of the organosilicon compound (D) is preferably in the range of 1 to 20% by mass with respect to the compounding amount of the inorganic filler (E) described later. When the content of the organosilicon compound (D) is less than 1% by mass of the blending amount of the inorganic filler (E), the effect of reducing the hysteresis loss of the rubber composition and the effect of improving the wear resistance are insufficient. On the other hand, if it exceeds 20% by mass, the effect is saturated.

<< Inorganic filler (E) >>
Examples of the inorganic filler (E) used in the rubber composition of the present invention include silica, aluminum hydroxide, alumina, clay, calcium carbonate, etc. Among these, silica and aluminum hydroxide are preferable from the viewpoint of reinforcing properties. Silica is preferred and particularly preferred. When the inorganic filler (E) is silica, the organosilicon compound (D) has a functional group having a high affinity for the silanol group on the silica surface and / or a functional group having a high affinity for the silicon atom (Si). For this reason, the coupling efficiency is greatly improved, the hysteresis loss of the rubber composition is reduced, and the effect of improving the wear resistance becomes more remarkable. The silica is not particularly limited, and wet silica (hydrous silicic acid), dry silica (anhydrous silicic acid) and the like can be used. Are preferably used.

The silica preferably has a BET surface area of 40 to 350 m ² / g. When the BET surface area of silica is 40 m ² / g or less, the particle size of the silica is too large and wear resistance is greatly reduced. When the BET surface area of silica is 350 m ² / g or more, the silica Since the particle diameter of the particles is too small, the hysteresis loss is greatly increased.

  The blending amount of the inorganic filler (E) is preferably in the range of 5 to 140 parts by mass with respect to 100 parts by mass of the rubber component (A). If the blending amount of the inorganic filler (E) is less than 5 parts by mass with respect to 100 parts by mass of the rubber component (A), the effect of reducing the hysteresis is insufficient, whereas if it exceeds 140 parts by mass, the workability is increased. This is because of the remarkable deterioration.

<< Method for Producing Rubber Composition >>
The rubber composition of the present invention comprises the rubber component (A), a fine particle-containing fiber (B), a foaming agent (C), an organosilicon compound (D), an inorganic filler (E), a foaming aid, Additives commonly used in the industry, such as other fillers such as carbon black, softeners, stearic acid, anti-aging agents, zinc white, vulcanization accelerators, vulcanizing agents, etc. It can be produced by appropriately selecting and blending within the range not to be kneaded, kneading, heating, extruding and the like.

<Vulcanized rubber>
Next, the vulcanized rubber of the present invention will be described in detail with reference to the drawings. FIG. 1 is a cross-sectional view of an example of a vulcanized rubber according to the present invention. The vulcanized rubber of the present invention can be obtained by vulcanizing the above rubber composition. As shown in FIG. 1, the vulcanized rubber 1 of the present invention has long cells 2, and The bubble 2 is surrounded by the coating 3, and the coating 3 surrounding the elongated bubble 2 is composed of the hydrophilic resin 3a and the fine particles 3b constituting the fine particle-containing fiber. Here, while the scratch effect on the snowy and snowy road surface is enhanced by the fine particles 3b constituting the coating 3, water on the snowy and snowy road surface is efficiently collected by the hydrophilic resin 3a and acts as a micro drainage groove 2 By draining, the on-ice performance of the tire can be greatly improved.

  The elongated bubbles 2 shown in FIG. 1 are oriented in a certain direction, but as a method for aligning the orientation of the elongated bubbles, fine particle-containing fibers dispersed in the unvulcanized rubber composition are fixed. What is necessary is just to arrange in a direction, for example, the method of extruding the rubber composition containing microparticles | fine-particles containing fiber using the extruder which a flow-path cross-sectional area reduces toward an exit is mentioned.

  The foaming rate (Vs) of the vulcanized rubber of the present invention is preferably 3 to 50%, more preferably 3 to 40%, and still more preferably 5 to 35%. If the foaming rate is less than 3%, the volume of long bubbles capable of removing water on the snowy and snowy road surface is too small, and the drainage performance may be deteriorated. The number of tires is too large, and the durability of the tire decreases. In addition, the said foaming rate (Vs) is a total foaming rate of a long bubble and the bubble formed without staying inside the hydrophilic resin which comprised the microparticle containing fiber.

The foaming rate (Vs) (%) is expressed by the following formula (X):
Vs = (ρ ₀ / ρ ₁ −1) × 100 (X)
[Wherein, ρ ₁ is the density (g / cm ³ ) of the vulcanized rubber, and ρ ₀ is the density of the solid phase part (g / cm ³ ) in the vulcanized rubber].

<Tire>
Next, the tire of the present invention will be described in detail with reference to the drawings. FIG. 2 is a cross-sectional view of an example of the tire of the present invention. The tire shown in FIG. 2 has a pair of left and right bead portions 4 and a pair of sidewall portions 5, and a tread portion 6 connected to both sidewall portions 5, and extends in a toroidal shape between the pair of bead portions 4. Then, a carcass 7 that reinforces each of these parts 4, 5, and 6 and a belt 8 that is disposed on the outer side in the tire radial direction of the crown part of the carcass 7 are provided. Here, the tire of the present invention is characterized in that the vulcanized rubber described above is applied to the tread portion 6. In the tire according to the present invention, by providing the vulcanized rubber in the tread portion 6, long bubbles are formed at least in the ground contact portion, and excellent performance on ice can be exhibited. In addition, since the rubber composition used for the vulcanized rubber has a small hysteresis loss, the tread portion 6 has low heat generation properties, and the rolling resistance of the tire can be reduced. Furthermore, since the vulcanized rubber produced from the rubber composition has high wear resistance, the wear resistance of the tread portion 6 can be greatly improved.

  The carcass 7 of the tire shown in FIG. 2 is composed of a single carcass ply, and a main body portion extending in a toroid shape between a pair of bead cores 9 embedded in the bead portion 4, and each bead core. 9, and the folded portion wound radially outward from the inner side to the outer side in the tire width direction. In the tire of the present invention, the number of plies and the structure of the carcass 7 are not limited thereto. .

  Further, the belt 8 of the tire shown in FIG. 2 is composed of two belt layers, and each belt layer is usually a rubberized layer of cords, preferably steel, extending obliquely with respect to the tire equatorial plane. The belt 8 is composed of a rubberized layer of cords, and two belt layers are laminated so that the cords constituting the belt layers intersect with each other across the tire equator plane. Although the belt 8 in the figure is composed of two belt layers, the number of belt layers constituting the belt 8 in the tire of the present invention is not limited to this.

  Further, in the tire of the present invention, an unvulcanized tread rubber is formed using the rubber composition, and a raw tire provided with the unvulcanized tread rubber in a tread portion is formed according to a conventional method. By vulcanization, long air bubbles covered with the hydrophilic resin constituting the fine particle-containing fiber can be formed in the tread portion.

  Furthermore, in the tire of the present invention, it is preferable that the long bubbles are oriented in the tire circumferential direction from the viewpoint of improving drainage. In this case, an unvulcanized tread rubber is formed using the rubber composition obtained by the above-described method and in which fibers are arranged in a certain direction, and the orientation direction of the fibers in the unvulcanized tread rubber is the tire circumferential direction. The unvulcanized tread rubber may be disposed so as to coincide with the above to form a green tire. In the pneumatic tire of the present invention, as the gas filled in the tire, normal or air with a changed oxygen partial pressure, or an inert gas such as nitrogen can be used.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.

<Production example of fine particle-containing fiber>
Using the hydrophilic resin and fine particles having the formulation shown in Table 1, fine particle-containing fibers were produced according to a normal melt spinning method. In addition, the average diameter and average length of this fiber were measured by the following method. The results are shown in Table 1.

(1) Average diameter and average length The obtained fine particle-containing fibers were randomly selected at 20 locations, the diameter (μm) and length (mm) were measured using an optical microscope, and the average value was obtained.

* 1 Polyethylene, manufactured by Nippon Polyethylene Co., Ltd., “HDPE”, contact angle with water = 120 °
* 2 “High Milan 1557” manufactured by Mitsui DuPont Polychemical Co., Ltd., a resin containing a carboxyl group derived from methacrylic acid as a functional group, contact angle with water = 73 °
* 3 Compounding amount of fine particles with respect to 100 parts by mass of resin (parts by mass)
* 4 Could not be fiberized

  From Table 1, it can be seen that when polyethylene is used as the resin (fiber A, fiber G), the fiber cannot be formed as the content of fine particles increases. On the other hand, when the ionomer resin which is a hydrophilic resin is used (fibers B to F), it can be seen that even if the content of the fine particles is increased, the fine particle-containing fibers can be produced.

<Production Example 1 of Organosilicon Compound>
In a 1 L four-necked eggplant flask, 23.8 g of 3-mercaptopropyltriethoxysilane and 11.1 g of triethylamine were dissolved in 300 mL of toluene under a nitrogen atmosphere. To this solution, 16.2 g of octanoic chloride was added dropwise over 30 minutes and stirred for 2 hours. Thereafter, the precipitate was separated by filtration and the solvent was removed by a rotary evaporator at 20 hPa / 40 ° C. to obtain 34.8 g of 3-octanoylthio-propyltriethoxysilane.

で表わされる３-オクタノイルチオ-プロピル（エトキシ）１,３-ジオキサ-６-メチルアザ-２-シラシクロオクタン［有機ケイ素化合物（Ｄ−１）］35.1 gを得た。生成物の¹Ｈ−ＮＭＲでの分析結果を以下に示す。
¹Ｈ−ＮＭＲ（CDCl₃, 700 MHz, δ; ppm）= 3.8(m;6H), 2.8(t;2H), 2.5(m;6H), 2.4(m;3H), 1.6(m;4H), 1.2(m;11H), 0.8(t;3H), 0.7(t;2H) Subsequently, 34.8 g of 3-octanoylthio-propyltriethoxysilane, 11.4 g of N-methyldiethanolamine and 0.05 g of titanium tetra-n-butoxide were dissolved in 200 mL of xylene in a 500 mL four-necked eggplant flask. The temperature was raised to 150 ° C. and stirred for 6 hours. Thereafter, the solvent was removed by a rotary evaporator at 20 hPa / 40 ° C., and then the remaining volatile components were removed by a rotary pump (10 Pa) and a cold trap (dry ice + ethanol).

35.1 g of 3-octanoylthio-propyl (ethoxy) 1,3-dioxa-6-methylaza-2-silacyclooctane [organosilicon compound (D-1)] represented by the formula: The results of ¹ H-NMR analysis of the product are shown below.
¹ H-NMR (CDCl ₃ , 700 MHz, δ; ppm) = 3.8 (m; 6H), 2.8 (t; 2H), 2.5 (m; 6H), 2.4 (m; 3H), 1.6 (m; 4H) , 1.2 (m; 11H), 0.8 (t; 3H), 0.7 (t; 2H)

<Production Example 2 of organosilicon compound>
To a 200 mL four-necked eggplant flask, 18.0 g of manganese dioxide was added to 23.8 g of 3-mercaptopropyltriethoxysilane under a nitrogen atmosphere. The temperature was raised to 110 ° C. and stirred for 4 hours. Thereafter, the precipitate is filtered off, and the low boiling point remaining at 10 Pa / 150 ° C. is removed using a rotary pump and a cold trap (dry ice + ethanol), and bis (3-triethoxysilyl-propyl) is removed. 20.0 g of disulfide was obtained.

で表わされるビス（３-（エトキシ）１,３-ジオキサ-６-メチルアザ-２-シラシクロオクチル-プロピル）ジスルフィド［有機ケイ素化合物（Ｄ−２）］22.0 gを得た。生成物の¹Ｈ−ＮＭＲでの分析結果を以下に示す。
¹Ｈ−ＮＭＲ（CDCl₃, 700 MHz, δ; ppm）= 3.8(m;12H), 2.7(t;4H), 2.5(m;8H), 2.4(m;6H), 1.8(m;4H), 1.2(m;6H), 0.7(t;4H) Subsequently, 20.0 g of bis (3-triethoxysilyl-propyl) disulfide, 10.2 g of N-methyldiethanolamine, and 0.05 g of titanium tetra-n-butoxide were added to 200 mL of xylene in a 500 mL four-necked eggplant flask. Dissolved. The temperature was raised to 150 ° C. and stirred for 6 hours. Thereafter, the solvent was removed by a rotary evaporator at 20 hPa / 40 ° C., and then the remaining volatile components were removed by a rotary pump (10 Pa) and a cold trap (dry ice + ethanol).

22.0 g of bis (3- (ethoxy) 1,3-dioxa-6-methylaza-2-silacyclooctyl-propyl) disulfide [organosilicon compound (D-2)] represented by the formula: The results of ¹ H-NMR analysis of the product are shown below.
¹ H-NMR (CDCl ₃ , 700 MHz, δ; ppm) = 3.8 (m; 12H), 2.7 (t; 4H), 2.5 (m; 8H), 2.4 (m; 6H), 1.8 (m; 4H) , 1.2 (m; 6H), 0.7 (t; 4H)

で表わされる３-オクタノイルチオ-プロピル（エトキシ）１,３-ジオキサ-６-ドデシルアザ-２-シラシクロオクタン［有機ケイ素化合物（Ｄ−３）］43.1 gを得た。生成物の¹Ｈ−ＮＭＲでの分析結果を以下に示す。
¹Ｈ−ＮＭＲ（CDCl₃, 700 MHz, δ; ppm）= 3.8(m;6H), 2.8(t;2H), 2.5(m;6H), 2.4(t;2H), 1.6(m;4H), 1.4(m;2H), 1.3(m;18H), 1.2(m;11H), 0.9(t;3H), 0.8(t;3H), 0.7(t;2H) <Production Example 3 of organosilicon compound>
In a 500 mL four-necked eggplant flask, 34.8 g of 3-octanoylthio-propyltriethoxysilane, 26.1 g of N-lauryldiethanolamine, and 0.05 g of titanium tetra-n-butoxide were dissolved in 200 mL of xylene under a nitrogen atmosphere. The temperature was raised to 150 ° C. and stirred for 2 hours. Thereafter, the solvent was removed by a rotary evaporator at 20 hPa / 40 ° C., and then the remaining volatile components were removed by a rotary pump (10 Pa) and a cold trap (dry ice + ethanol).

43.1 g of 3-octanoylthio-propyl (ethoxy) 1,3-dioxa-6-dodecylaza-2-silacyclooctane [organosilicon compound (D-3)] represented by the formula: The results of ¹ H-NMR analysis of the product are shown below.
¹ H-NMR (CDCl ₃ , 700 MHz, δ; ppm) = 3.8 (m; 6H), 2.8 (t; 2H), 2.5 (m; 6H), 2.4 (t; 2H), 1.6 (m; 4H) , 1.4 (m; 2H), 1.3 (m; 18H), 1.2 (m; 11H), 0.9 (t; 3H), 0.8 (t; 3H), 0.7 (t; 2H)

<Production Example 4 of organosilicon compound>
In a 1 L four-necked eggplant flask, 18.0 g of 3-mercaptopropyldimethoxymethylsilane and 11.1 g of triethylamine were dissolved in 300 mL of toluene under a nitrogen atmosphere. To this solution, 16.2 g of octanoic chloride was added dropwise over 30 minutes and stirred for 2 hours. Thereafter, the precipitate was separated by filtration and the solvent was removed by a rotary evaporator at 20 hPa / 40 ° C. to obtain 29.0 g of 3-octanoylthio-propyldimethoxymethylsilane.

で表わされる３-オクタノイルチオ-プロピル（メチル）１,３-ジオキサ-６-ラウリルアザ-２-シラシクロオクタン［有機ケイ素化合物（Ｄ−４）］30.0 gを得た。生成物の¹Ｈ−ＮＭＲでの分析結果を以下に示す。
¹Ｈ−ＮＭＲ（CDCl₃, 700 MHz, δ; ppm）= 3.8(m;4H), 2.8(t;2H), 2.5(m;6H), 2.4(m;3H), 1.6(m;4H), 1.2(m;11H), 0.7(t;2H), 0.1(s;3H) Subsequently, 29.0 g of 3-octanoylthio-propyldimethoxymethylsilane, 11.4 g of N-lauryldiethanolamine, and 0.05 g of titanium tetra-n-butoxide were dissolved in 200 mL of xylene in a 500 mL four-necked eggplant flask. The temperature was raised to 150 ° C. and stirred for 2 hours. Thereafter, the solvent was removed by a rotary evaporator at 20 hPa / 40 ° C., and then the remaining volatile components were removed by a rotary pump (10 Pa) and a cold trap (dry ice + ethanol).

30.0 g of 3-octanoylthio-propyl (methyl) 1,3-dioxa-6-laurylaza-2-silacyclooctane [organosilicon compound (D-4)] represented by the formula: The results of ¹ H-NMR analysis of the product are shown below.
¹ H-NMR (CDCl ₃ , 700 MHz, δ; ppm) = 3.8 (m; 4H), 2.8 (t; 2H), 2.5 (m; 6H), 2.4 (m; 3H), 1.6 (m; 4H) , 1.2 (m; 11H), 0.7 (t; 2H), 0.1 (s; 3H)

<Production Example 5 of organosilicon compound>
In a 1 L four-necked eggplant flask, 23.8 g of 3-mercaptopropyltriethoxysilane and 11.1 g of triethylamine were dissolved in 300 mL of toluene under a nitrogen atmosphere. To this solution, 21.8 g of dodecanoic acid chloride was added dropwise over 30 minutes and stirred for 2 hours. Thereafter, the precipitate was separated by filtration and the solvent was removed by a rotary evaporator at 20 hPa / 40 ° C. to obtain 39.9 g of 3-dodecanoylthio-propyltriethoxysilane.

で表わされる３-ドデカノイルチオ-プロピル（エトキシ）１,３-ジオキサ-６-ドデシルアザ-２-シラシクロオクタン［有機ケイ素化合物（Ｄ−５）］54.1 gを得た。生成物の¹Ｈ−ＮＭＲでの分析結果を以下に示す。
¹Ｈ−ＮＭＲ（CDCl₃, 700 MHz, δ; ppm）= 3.8(m;6H), 2.8(t;2H), 2.5(m;6H), 2.4(t;2H), 1.6(m;4H), 1.4(m;2H), 1.3(m;18H), 1.2(m;19H), 0.9(t;3H), 0.8(t;3H), 0.7(t;2H) Subsequently, 39.9 g of 3-dodecanoylthio-propyltriethoxysilane, 26.0 g of N-lauryldiethanolamine, and 0.05 g of titanium tetra-n-butoxide were dissolved in 200 mL of xylene in a 500 mL four-necked eggplant flask. The temperature was raised to 150 ° C. and stirred for 6 hours. Thereafter, the solvent was removed by a rotary evaporator at 20 hPa / 40 ° C., and then the remaining volatile components were removed by a rotary pump (10 Pa) and a cold trap (dry ice + ethanol).

Thus, 54.1 g of 3-dodecanoylthio-propyl (ethoxy) 1,3-dioxa-6-dodecylaza-2-silacyclooctane [organosilicon compound (D-5)] represented by the formula: The results of ¹ H-NMR analysis of the product are shown below.
¹ H-NMR (CDCl ₃ , 700 MHz, δ; ppm) = 3.8 (m; 6H), 2.8 (t; 2H), 2.5 (m; 6H), 2.4 (t; 2H), 1.6 (m; 4H) , 1.4 (m; 2H), 1.3 (m; 18H), 1.2 (m; 19H), 0.9 (t; 3H), 0.8 (t; 3H), 0.7 (t; 2H)

で表わされる３-ドデカノイルチオ-プロピル（エトキシ）１,３-ジオキサ-６-オクタデシルアザ-２-シラシクロオクタン［有機ケイ素化合物（Ｄ−６）］62.0 gを得た。生成物の¹Ｈ−ＮＭＲでの分析結果を以下に示す。
¹Ｈ−ＮＭＲ（CDCl₃, 700 MHz, δ; ppm）= 3.8(m;6H), 2.8(t;2H), 2.5(m;6H), 2.4(t;2H), 1.6(m;4H), 1.4(m;2H), 1.3(m;30H), 1.2(m;19H), 0.9(t;3H), 0.8(t;3H), 0.7(t;2H) <Production Example 6 of organosilicon compound>
In a 500 mL four-necked eggplant flask, 39.9 g of 3-dodecanoylthio-propyltriethoxysilane, 34.0 g of N-stearyldiethanolamine, and 0.05 g of titanium tetra-n-butoxide were dissolved in 200 mL of xylene under a nitrogen atmosphere. The temperature was raised to 150 ° C. and stirred for 6 hours. Thereafter, the solvent was removed by a rotary evaporator at 20 hPa / 40 ° C., and then the remaining volatile components were removed by a rotary pump (10 Pa) and a cold trap (dry ice + ethanol).

62.0 g of 3-dodecanoylthio-propyl (ethoxy) 1,3-dioxa-6-octadecylaza-2-silacyclooctane [organosilicon compound (D-6)] represented by the formula: The results of ¹ H-NMR analysis of the product are shown below.
¹ H-NMR (CDCl ₃ , 700 MHz, δ; ppm) = 3.8 (m; 6H), 2.8 (t; 2H), 2.5 (m; 6H), 2.4 (t; 2H), 1.6 (m; 4H) , 1.4 (m; 2H), 1.3 (m; 30H), 1.2 (m; 19H), 0.9 (t; 3H), 0.8 (t; 3H), 0.7 (t; 2H)

で表わされるビス（３-（エトキシ）１,３-ジオキサ-６-ドデシルアザ-２-シラシクロオクチル-プロピル）ジスルフィド［有機ケイ素化合物（Ｄ−７）］34.0 gを得た。生成物の¹Ｈ−ＮＭＲでの分析結果を以下に示す。
¹Ｈ−ＮＭＲ（CDCl₃, 700 MHz, δ; ppm）= 3.8(m;12H), 2.7(t;4H), 2.5(m;8H), 2.4(m;4H), 1.8(m;4H), 1.4(m;4H), 1.3(m;18H), 1.2(m;6H), 0.9(t;6H), 0.7(t;4H) <Production Example 7 of Organosilicon Compound>
In a 500 mL four-necked eggplant flask, 20.0 g of bis (3-triethoxysilyl-propyl) disulfide, 23.4 g of N-lauryldiethanolamine, and 0.05 g of titanium tetra-n-butoxide were dissolved in 200 mL of xylene under a nitrogen atmosphere. The temperature was raised to 150 ° C. and stirred for 6 hours. Thereafter, the solvent was removed by a rotary evaporator at 20 hPa / 40 ° C., and then the remaining volatile components were removed by a rotary pump (10 Pa) and a cold trap (dry ice + ethanol).

34.0 g of bis (3- (ethoxy) 1,3-dioxa-6-dodecylaza-2-silacyclooctyl-propyl) disulfide [organosilicon compound (D-7)] represented by the formula: The results of ¹ H-NMR analysis of the product are shown below.
¹ H-NMR (CDCl ₃ , 700 MHz, δ; ppm) = 3.8 (m; 12H), 2.7 (t; 4H), 2.5 (m; 8H), 2.4 (m; 4H), 1.8 (m; 4H) , 1.4 (m; 4H), 1.3 (m; 18H), 1.2 (m; 6H), 0.9 (t; 6H), 0.7 (t; 4H)

<Production Example 8 of organosilicon compound>
In a 500 mL four-necked eggplant flask, 12.2 g of 2-aminoethanol and 59.2 g of 1-iodododecane were dissolved in 200 mL of tetrahydrofuran under a nitrogen atmosphere. The temperature was raised to 60 ° C. and stirred for 24 hours. Subsequently, 44.9 g of triethylamine was added dropwise and stirred for 24 hours. Thereafter, the solvent was removed with a rotary evaporator at 20 hPa / 40 ° C., and then the remaining volatile components were removed with a rotary pump (10 Pa) and a cold trap (dry ice + ethanol) to give didodecylethanolamine 75.0 g was obtained.

で表わされるビス（３-（ジジドデシルアミノエトキシ）エトキシシリル-プロピル）ジスルフィド［有機ケイ素化合物（Ｄ−８）］170.0 gを得た。生成物の¹Ｈ−ＮＭＲでの分析結果を以下に示す。
¹Ｈ−ＮＭＲ（CDCl₃, 700 MHz, δ; ppm）= 3.8(m;12H), 2.7(t;4H), 2.5(m;8H), 2.4(m;16H), 1.8(m;4H), 1.4(m;16H), 1.3(m;72H), 1.2(m;6H), 0.9(t;24H), 0.7(t;4H) In a 500 mL four-necked eggplant flask, 23.7 g of bis (3-triethoxysilyl-propyl) disulfide, 168.8 g of didodecylethanolamine, and 0.05 g of titanium tetra-n-butoxide were dissolved in 200 mL of xylene under a nitrogen atmosphere. The temperature was raised to 150 ° C. and stirred for 6 hours. Thereafter, the solvent was removed by a rotary evaporator at 20 hPa / 40 ° C., and then the remaining volatile components were removed by a rotary pump (10 Pa) and a cold trap (dry ice + ethanol).

170.0 g of bis (3- (dididodecylaminoethoxy) ethoxysilyl-propyl) disulfide [organosilicon compound (D-8)] represented by the formula: The results of ¹ H-NMR analysis of the product are shown below.
¹ H-NMR (CDCl ₃ , 700 MHz, δ; ppm) = 3.8 (m; 12H), 2.7 (t; 4H), 2.5 (m; 8H), 2.4 (m; 16H), 1.8 (m; 4H) , 1.4 (m; 16H), 1.3 (m; 72H), 1.2 (m; 6H), 0.9 (t; 24H), 0.7 (t; 4H)

で表わされる３-オクタノイルチオ-プロピル（ジジドデシルアミノエトキシ）エトキシシラン［有機ケイ素化合物（Ｄ−９）］85.0 gを得た。生成物の¹Ｈ−ＮＭＲでの分析結果を以下に示す。
¹Ｈ−ＮＭＲ（CDCl₃, 700 MHz, δ; ppm）= 3.8(m;6H), 2.8(t;2H), 2.5(m;6H), 2.4(m;8H), 1.6(m;4H), 1.4(m;8H), 1.3(m;36H), 1.2(m;11H), 0.9(t;12H), 0.7(t;2H) <Production Example 9 of organosilicon compound>
In a 500 mL four-necked eggplant flask, 36.2 g of 3-octanoylthio-propyltriethoxysilane, 79.4 g of didodecylethanolamine, and 0.05 g of titanium tetra-n-butoxide were dissolved in 200 mL of xylene in a nitrogen atmosphere. The temperature was raised to 150 ° C. and stirred for 6 hours. Thereafter, the solvent was removed by a rotary evaporator at 20 hPa / 40 ° C., and then the remaining volatile components were removed by a rotary pump (10 Pa) and a cold trap (dry ice + ethanol).

Thus, 85.0 g of 3-octanoylthio-propyl (dididodecylaminoethoxy) ethoxysilane [organosilicon compound (D-9)] represented by the formula: The results of ¹ H-NMR analysis of the product are shown below.
¹ H-NMR (CDCl ₃ , 700 MHz, δ; ppm) = 3.8 (m; 6H), 2.8 (t; 2H), 2.5 (m; 6H), 2.4 (m; 8H), 1.6 (m; 4H) , 1.4 (m; 8H), 1.3 (m; 36H), 1.2 (m; 11H), 0.9 (t; 12H), 0.7 (t; 2H)

<Manufacture example 10 of an organosilicon compound>
In a 500 mL four-necked eggplant flask, 23.8 g of 3-mercapto-propyltriethoxysilane, 27.3 g of N-lauryldiethanolamine, and 0.05 g of titanium tetra-n-butoxide were dissolved in 200 mL of xylene under a nitrogen atmosphere. The temperature was raised to 150 ° C. and stirred for 6 hours. Subsequently, 16.2 g of 2- (2-butoxyethoxy) ethanol was added dropwise and stirred for 2 hours. Thereafter, the solvent is removed by a rotary evaporator at 20 hPa / 40 ° C., and then the remaining volatile components are removed by a rotary pump (10 Pa) and a cold trap (dry ice + ethanol) to obtain 53.5 g of an organosilicon compound. Got.

で表わされる３-オクタノイルチオ-プロピル（２-（２-ブトキシエトキシ）エトキシ）１,３-ジオキサ-６-ドデシルアザ-２-シラシクロオクタン［有機ケイ素化合物（Ｄ−１０）］63.5 gを得た。生成物の¹Ｈ−ＮＭＲでの分析結果を以下に示す。
¹Ｈ−ＮＭＲ（CDCl₃, 700 MHz, δ; ppm）= 3.8(m;6H), 3.5(m;8H), 2.8(t;2H), 2.5(m;6H), 2.4(t;2H), 1.6(m;4H), 1.5(m;2H), 1.4(m;2H), 1.3(m;20H), 1.2(m;8H), 0.9(t;6H), 0.8(t;3H), 0.7(t;2H) In a 1 L four-necked eggplant flask, 53.5 g of an organosilicon compound and 11.1 g of triethylamine obtained in a nitrogen atmosphere were dissolved in 300 mL of toluene. To this solution, 16.2 g of octanoic chloride was added dropwise over 30 minutes and stirred for 2 hours. Thereafter, the precipitate was filtered off and the solvent was removed by a rotary evaporator at 20 hPa / 40 ° C., and the following chemical formula:

Thus, 63.5 g of 3-octanoylthio-propyl (2- (2-butoxyethoxy) ethoxy) 1,3-dioxa-6-dodecylaza-2-silacyclooctane [organosilicon compound (D-10)] represented by the formula: The results of ¹ H-NMR analysis of the product are shown below.
¹ H-NMR (CDCl ₃ , 700 MHz, δ; ppm) = 3.8 (m; 6H), 3.5 (m; 8H), 2.8 (t; 2H), 2.5 (m; 6H), 2.4 (t; 2H) , 1.6 (m; 4H), 1.5 (m; 2H), 1.4 (m; 2H), 1.3 (m; 20H), 1.2 (m; 8H), 0.9 (t; 6H), 0.8 (t; 3H), 0.7 (t; 2H)

で表わされるビス（３-（２-（２-ブトキシエトキシ）エトキシ）１,３-ジオキサ-６-ドデシルアザ-２-シラシクロオクチル-プロピル）ジスルフィド［有機ケイ素化合物（Ｄ−１１）］50.0 gを得た。生成物の¹Ｈ−ＮＭＲでの分析結果を以下に示す。
¹Ｈ−ＮＭＲ（CDCl₃, 700 MHz, δ; ppm）= 3.8(m;12H), 3.5(m;16H), 2.7(t;4H), 2.5(m;8H), 2.4(m;4H), 1.8(m;4H), 1.5(m;4H), 1.4(m;4H), 1.3(m;40H), 0.9(t;12H), 0.7(t;4H) <Production Example 11 of Organosilicon Compound>
In a 500 mL four-necked eggplant flask, 23.7 g of bis (3-triethoxysilyl-propyl) disulfide, 27.3 g of N-lauryldiethanolamine, and 0.05 g of titanium tetra-n-butoxide were dissolved in 200 mL of xylene under a nitrogen atmosphere. The temperature was raised to 150 ° C. and stirred for 6 hours. Subsequently, 16.2 g of 2- (2-butoxyethoxy) ethanol was added dropwise and stirred for 2 hours. Thereafter, the solvent was removed by a rotary evaporator at 20 hPa / 40 ° C., and then the remaining volatile components were removed by a rotary pump (10 Pa) and a cold trap (dry ice + ethanol).

50.0 g of bis (3- (2- (2-butoxyethoxy) ethoxy) 1,3-dioxa-6-dodecylaza-2-silacyclooctyl-propyl) disulfide [organosilicon compound (D-11)] Obtained. The results of ¹ H-NMR analysis of the product are shown below.
¹ H-NMR (CDCl ₃ , 700 MHz, δ; ppm) = 3.8 (m; 12H), 3.5 (m; 16H), 2.7 (t; 4H), 2.5 (m; 8H), 2.4 (m; 4H) , 1.8 (m; 4H), 1.5 (m; 4H), 1.4 (m; 4H), 1.3 (m; 40H), 0.9 (t; 12H), 0.7 (t; 4H)

<Production Example 12 of organosilicon compound>
In a 500 mL four-necked eggplant flask, 23.8 g of 3-mercapto-propyltriethoxysilane, 27.3 g of N-lauryldiethanolamine, and 0.05 g of titanium tetra-n-butoxide were dissolved in 200 mL of xylene under a nitrogen atmosphere. The temperature was raised to 150 ° C. and stirred for 6 hours. Subsequently, 15.8 g of decyl alcohol was added dropwise and stirred for 2 hours. Thereafter, the solvent was removed by a rotary evaporator at 20 hPa / 40 ° C., and then the remaining volatile components were removed by a rotary pump (10 Pa) and a cold trap (dry ice + ethanol) to obtain 53.1 g of an organosilicon compound. Got.

で表わされる３-オクタノイルチオ-プロピル（デカノキシ）１,３-ジオキサ-６-ドデシルアザ-２-シラシクロオクタン［有機ケイ素化合物（Ｄ−１２）］60.7 gを得た。生成物の¹Ｈ−ＮＭＲでの分析結果を以下に示す。
¹Ｈ−ＮＭＲ（CDCl₃, 700 MHz, δ; ppm）= 3.8(m;6H), 2.8(t;2H), 2.5(m;6H), 2.4(m;2H), 1.6(m;4H), 1.5(m;2H), 1.4(m;2H), 1.3(m;40H), 0.9(t;6H), 0.8(t;3H), 0.7(t;2H) In a 1 L four-necked eggplant flask, 53.1 g of the organosilicon compound and 11.1 g of triethylamine obtained in a nitrogen atmosphere were dissolved in 300 mL of toluene. To this solution, 16.2 g of octanoic chloride was added dropwise over 30 minutes and stirred for 2 hours. Thereafter, the precipitate was filtered off and the solvent was removed by a rotary evaporator at 20 hPa / 40 ° C., and the following chemical formula:

60.7 g of 3-octanoylthio-propyl (decanoxy) 1,3-dioxa-6-dodecylaza-2-silacyclooctane [organosilicon compound (D-12)] represented by the formula: The results of ¹ H-NMR analysis of the product are shown below.
¹ H-NMR (CDCl ₃ , 700 MHz, δ; ppm) = 3.8 (m; 6H), 2.8 (t; 2H), 2.5 (m; 6H), 2.4 (m; 2H), 1.6 (m; 4H) , 1.5 (m; 2H), 1.4 (m; 2H), 1.3 (m; 40H), 0.9 (t; 6H), 0.8 (t; 3H), 0.7 (t; 2H)

<Preparation and evaluation of rubber composition>
The fibers A to F are used as fine particle-containing fibers, and the organosilicon compounds (D-1) to (D-12) or bis (3-triethoxysilylpropyl) disulfide (silane compound A) are used as the organosilicon compounds. Or the rubber composition of the mixing | blending prescription according to Table 2 was knead | mixed and prepared with the Banbury mixer using 3-octanoyl thio- propyl triethoxysilane (silane compound B). Next, the vulcanization physical property of the obtained rubber composition was measured by the following method. The results are shown in Tables 3-9.

(2) Dynamic viscoelasticity Using a spectrometer (dynamic viscoelasticity measuring tester) manufactured by Ueshima Seisakusho, tan δ of vulcanized rubber was measured at a frequency of 52 Hz, initial strain of 10%, measurement temperature of 60 ° C. and dynamic strain of 1% Then, the value of tan δ of Comparative Example 1 was taken as 100 and displayed as an index. The smaller the index value, the lower the tan δ, indicating that the rubber composition is less exothermic.

(3) Abrasion resistance test In accordance with JIS K 6264-2: 2005, a test was performed using a Lambone-type abrasion tester under conditions of room temperature and a slip ratio of 25%. As an index. The larger the index value, the smaller the wear amount and the better the wear resistance.

<Production and evaluation of tire>
According to the formulation shown in Table 2, a rubber composition in which the compounded fine particle-containing fibers are arranged in a certain direction was prepared. A tread rubber was produced using the rubber composition, and a raw tire was produced by arranging the tread rubber so that the fine particle-containing fibers in the rubber composition were oriented in the tire circumferential direction. Next, the obtained raw tire was vulcanized to produce a radial tire for passenger cars of size 185 / 70R13. The maximum vulcanization temperature during vulcanization of each rubber composition was 200 ° C. For the obtained tire, the foaming rate of the vulcanized rubber forming the tread portion was calculated by the above formula (X), the performance on ice was evaluated by the following method, and the foaming form was confirmed by the following method. The results are shown in Tables 3-9.

(4) Performance on ice A passenger car with a tire with a 20% wear rate on the tread runs on a flat surface on ice, brakes at a speed of 20 km / h, locks the tire, and stops. The braking distance was measured. The reciprocal of the braking distance of the tire of Comparative Example 1 is shown as an index with 100 as the inverse. The larger the index value, the better the braking performance on ice. The wear rate of the tread portion was calculated by the following formula.
Wear rate (%) = (1−groove depth after wear / groove depth when new) × 100

(5) Foamed form A vulcanized rubber piece was cut out from the tread center portion of the obtained tire, and this sample was observed with a scanning electron microscope (SEM). In any of the tires, long bubbles covered with the resin constituting the fiber could be confirmed.

* 5 “BR01” manufactured by JSR Corporation, cis-1,4-polybutadiene * 6 “Carbon N220” manufactured by Asahi Carbon Corporation
* 7 Made by Nippon Silica Kogyo Co., Ltd., “Nipsil-VN3”, BET specific surface area = 220 m ² / g
* 8 Fibers A to F produced by the above method, types and blending amounts of fibers used are shown in Tables 3 to 9 * 9 Organosilicon compounds (D-1) to (D-12) synthesized by the above method Alternatively, bis (3-triethoxysilylpropyl) disulfide (silane compound A) or 3-octanoylthio-propyltriethoxysilane (silane compound B), the types and amounts of the organosilicon compounds used are shown in Tables 3 to 9 * 10 Ouchi Shinsei Chemical Industry Co., Ltd., “NOCRACK 6C”
* 11 Dibenzothiazyl disulfide * 12 N-cyclohexyl-2-benzothiazolyl-sulfenamide * 13 Azodicarbonamide * 14 Zinc benzenesulfinate * 15 Urea: Stearic acid = 85:15 (mass ratio) ) Mixture of

  From Tables 3-9, it replaces with the conventional silane coupling agent (silane compound A, silane compound B), and mix | blends the organosilicon compound (D) represented by Formula (I) or Formula (VIII), rubber | gum It can be seen that the tan δ of the composition can be greatly reduced, that is, the hysteresis loss can be greatly reduced, and the heat resistance can be greatly improved while the heat generation is reduced.

  Moreover, from Tables 5-9, the rubber composition of the comparative example containing an organosilicon compound (C-1 to C-2) and the rubber composition of the Example containing an organosilicon compound (C-3 to C-12). From the comparison, the rubber composition of the organic silicon compound having 11 to 20 carbon atoms in the alkyl group bonded to nitrogen is more than the organic silicon compound having 10 or less carbon atoms in the alkyl group bonded to nitrogen. It can be seen that the effect of improving the low exothermic property and wear resistance is great.

  Furthermore, as is clear from Tables 3 to 9, the rubber compositions of Examples 1 to 50, in which the fine particle-containing fiber (B) according to the present invention is blended, have fine particle-containing fibers composed of a combination of ordinary resin and fine particles. Compared to the blended rubber compositions of Comparative Examples 1 to 14, the on-ice performance of the tire can be greatly improved.

DESCRIPTION OF SYMBOLS 1 Vulcanized rubber 2 Elongated bubble 3 Coating 3a Hydrophilic resin 3b Fine particle 4 Bead part 5 Side wall part 6 Tread part 7 Carcass 8 Belt 9 Bead core

Claims (23)

For rubber component (A), fine particle-containing fiber (B), foaming agent (C), organosilicon compound (D) and inorganic filler (E) are blended,
The fine particle-containing fiber (B) is composed of at least one fine particle selected from the group consisting of a metal oxide, a metal carbonate, and a clay mineral containing a metal, and a hydrophilic resin,
The organosilicon compound (D) is represented by the following general formula (I):

[Wherein A ¹ represents the following general formula (II) or formula (III):

Represented by
At least one of R ¹ , R ² and R ³ in formula (I) and formula (II) is the following general formula (IV) or formula (V):

(In the formula, M is —O— or —CH ₂ —, X and Y are independently —O—, —NR ⁸ — or —CH ₂ —, and R ⁶ is —OR ⁸ , —NR ⁸ R. ⁹ or -R ⁸ , R ⁷ is -NR ⁸ R ⁹ , -NR ⁸ -NR ⁸ R ⁹ or -N = NR ⁸ , provided that R ⁸ is -C _n H _{2n + 1} , R ⁹ is -C _q is H _{2q + 1,} l and m are 0 independently, n and q are represented by each independently a 11-20), others -M-C _r H _{2r + 1} (where M is as defined above and r is 0 to 20) or − (M−C ₁ H _2l ) _y C _s H _{2s + 1} (where M and l are the same as above) And y and s are each independently 1 to 20), provided that at ^{least one} of R ¹ , R ² and R ³ is M is —O—,
R ⁴ represents the following general formula (VI) or formula (VII):

(In the formula, M, X, Y, R ⁶ , l and m are as defined above, and R ¹⁰ is —NR ⁸ —, —NR ⁸ —NR ⁸ — or —N═N—, wherein R ⁸ Is as defined above, or —Z—C ₁ H _2l — (wherein Z is —O—, —NR ⁸ — or —CH ₂ —, wherein R ⁸ is as defined above, and l is as defined above. Is synonymous with
R ⁵ in formula (III) is the above general formula (IV), formula (V), or —C ₁ H _2l —R ¹¹ (where R ¹¹ is —NR ⁸ R ⁹ , —NR ⁸ —NR ⁸ R ^9). a -N = NR ⁸ or _{-Z-C m H 2m + 1} , ^{where, R 8, R 9, Z} , l and m are represented by the same meaning as above),
x is 1 to 10], and the following general formula (VIII):

[In the formula, A ² represents the following general formula (IX) or formula (III):

Represented by
W in formula (VIII) and formula (IX) is —NR ⁸ —, —O— or —CR ⁸ R ¹⁵ — (wherein R ¹⁵ is —R ⁹ or —C _m H _2m —R ⁷ ; However, R ⁷ is -NR ⁸ R ^9, a -NR ⁸ -NR ⁸ R ⁹ or -N = NR ^8, R ⁸ is _{-C n H 2n + 1, R} 9 is -C _q H _{2q + 1} M is 0 to 10, and n and q are each independently 11 to 20).
R ¹² and R ¹³ are each independently represented by —M—C ₁ H _{2 1} — (wherein M is —O— or —CH ₂ —, and 1 is 0 to 10),
R ¹⁴ represents —M—C _r H _{2r + 1} or —M—C _r H _2r —R ¹¹ (where M is as defined above, and R ¹¹ represents —NR ⁸ R ⁹ , —NR ⁸ —NR ^8. R ⁹ , —N═NR ⁸ or —Z—C _m H _{2m + 1} , wherein Z is —O—, —NR ⁸ — or —CH ₂ —, and R ⁸ , R ⁹ and m are as described above. are synonymous, r is 0 to 20) or _{- (M-C l H 2l} ) y C s H 2s + 1 ( where, M and l are as defined above, y and s are each independently Wherein at least one of R ¹² , R ¹³ and R ¹⁴ is M is —O—,
R ⁴ represents the following general formula (VI) or formula (VII):

Wherein M, l and m are as defined above, X and Y are each independently —O—, —NR ⁸ — or —CH ₂ —, and R ⁶ is —OR ⁸ , —NR ⁸ R ⁹ or -R ^8, R ¹⁰ is ^{-NR 8 -, - NR 8 -NR} 8 - or -N = a N-, provided that, R ⁸ and R ⁹ are as defined above) or -Z-C _l H _2l — (wherein Z is —O—, —NR ⁸ — or —CH ₂ —, wherein R ⁸ is as defined above, and l is as defined above),
R ⁵ in the formula (III) is the following general formula (IV) or formula (V):

(Wherein, M, X, Y, R ⁶ , R ⁷ , l and m are as defined above) or —C ₁ H _2l —R ¹¹ (where R ¹¹ is —NR ⁸ R ⁹ , —NR ^8— NR ⁸ R ⁹ , —N═NR ⁸ or —Z—C _m H _{2m + 1} , where R ⁸ , R ⁹ , Z, l and m are as defined above.
x is 1 to 10.] A rubber composition characterized by being at least one selected from the group consisting of compounds represented by:   The rubber composition according to claim 1, wherein the hydrophilic resin is a resin containing at least one functional group selected from the group consisting of a carboxyl group, a hydroxyl group, an ester group, an ether group, and a carbonyl group.   The rubber composition according to claim 1, wherein the metal oxide is at least one of titanium oxide and aluminum oxide.   The rubber composition according to claim 1 or 3, wherein the metal oxide is at least one of ceramics and zeolite.   The rubber composition according to claim 1, wherein the metal carbonate is calcium carbonate.   The rubber composition according to claim 1, wherein the metal-containing clay mineral is montmorillonite.   The rubber composition according to claim 1, wherein the fine particle-containing fiber (B) contains 0.5 to 200 parts by mass of the fine particles with respect to 100 parts by mass of the hydrophilic resin.   2. The rubber composition according to claim 1, wherein the content of the fine particle-containing fiber (B) is 0.5 to 30 parts by mass with respect to 100 parts by mass of the rubber component (A).   The rubber composition according to claim 1, wherein the fine particles have a particle size of 0.1 to 500 μm.   The rubber composition according to claim 1, wherein the fine particle-containing fiber (B) has an average diameter of 1 to 100 μm and an average length of 0.1 to 20 mm.   The rubber composition according to claim 1, wherein the hydrophilic resin has a melting point or a softening point lower than a maximum vulcanization temperature.   The rubber composition according to claim 1, wherein in the organosilicon compound (D), the M is —O—. The organosilicon compound (D) is represented by the general formula (I),
At least one of R ¹ , R ² and R ³ is represented by —O—C ₁ H _{2 1} —R ⁷ (where R ⁷ and 1 are as defined above), and the others are —O—C. _l H _{2l + 1} (where l is as defined above),
R ⁴ is represented by —C ₁ H _2l — (wherein l is as defined above),
The rubber composition according to claim 1, wherein R ⁵ is represented by —C ₁ H _2l —R ¹¹ (wherein R ¹¹ and l are as defined above). The organosilicon compound (D) is represented by the general formula (I),
At least one of R ¹ , R ² and R ³ is represented by —O—C ₁ H _{2 1} —NR ⁸ R ⁹ (where R ⁸ , R ⁹ and 1 are as defined above),
2. The rubber composition according to claim 1, wherein R ⁵ is represented by —C ₁ H _{2l + 1} (wherein l is as defined above). The organosilicon compound (D) is represented by the general formula (VIII),
W is represented by —NR ⁸ — (wherein R ⁸ is as defined above),
R ¹² and R ¹³ are each independently represented by —O—C ₁ H _2l — (wherein l is as defined above),
R ¹⁴ is —O—C ₁ H _2l —R ¹¹ (where R ¹¹ and l are as defined above) or —C _r H _{2r + 1} (where r is as defined above). Represented,
R ⁴ is represented by —C ₁ H _2l — (wherein l is as defined above),
_2. The rubber composition according to claim 1, wherein R ⁵ is represented by —C ₁ H _{2 1} —CH ₂ —C _m H _{2m + 1} (wherein l and m are as defined above). . The organosilicon compound (D) is represented by the general formula (VIII),
W is represented by —O— or —CR ⁸ R ⁹ — (wherein R ⁸ and R ⁹ are as defined above),
R ¹² and R ¹³ are each independently represented by —O—C ₁ H _2l — (wherein l is as defined above),
R ¹⁴ is represented by —O—C ₁ H _{2 1} —NR ⁸ R ⁹ (wherein R ⁸ , R ⁹ and l are as defined above),
R ⁴ is represented by —C ₁ H _2l — (wherein l is as defined above),
_2. The rubber composition according to claim 1, wherein R ⁵ is represented by —C ₁ H _{2 1} —CH ₂ —C _m H _{2m + 1} (wherein l and m are as defined above). . The inorganic filler (E) is blended in an amount of 5 to 140 parts by mass with respect to 100 parts by mass of the rubber component (A).
2. The rubber composition according to claim 1, wherein the organosilicon compound (D) is contained in an amount of 1 to 20% by mass based on the amount of the inorganic filler (E).   The rubber composition according to claim 1, wherein the inorganic filler (E) is silica or aluminum hydroxide. The rubber composition according to claim 18, wherein the silica has a BET surface area of 40 to 350 m ² / g.   A vulcanized rubber having elongated cells obtained by vulcanizing the rubber composition according to claim 1.   The vulcanized rubber according to claim 20, wherein the foaming rate is 3 to 50%.   A tire using the vulcanized rubber according to claim 20 or 21 in a tread portion.   The tire according to claim 22, wherein the elongated bubbles are oriented in the tire circumferential direction.

Images