JP2002060547A - Rubber composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a rubber composition that has an improved appearance without deterioration by ozone. SOLUTION: The objective rubber composition comprises (A) natural rubber and/or diene synthetic rubber, (B) a wax rubber antioxidant, (C) a higher alcohol with the DSC melting peak temperature of 60-105 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a comb composition, and more particularly, to a comb composition having improved appearance of a comb surface.

[0002]

2. Description of the Related Art Conventionally, it has been known to incorporate a wax in order to prevent cracking of a corn product due to air or sunlight. When the wax is mixed with the comb, the wax oozes on the surface to form a thin film, and this thin film blocks the contact between the comb and the oxygen or oxygen, thereby preventing the deterioration of the comb. However, these remarkable anti-aging agents of fluorinated glass often have a problem that crystals precipitated on the surface of the comb composition are whitened to impair the appearance of the product, and the effect of preventing precipitation is reduced by precipitation. In view of the sustainability of the anti-aging effect, it is desirable to suppress the blooming as much as possible. In order to improve this phenomenon, a wax-based antioxidant having 16-41 carbon atoms and a wide distribution of carbon atoms (US Pat. No. 3,423,348) or a linear hydrocarbon having 26-29 carbon atoms is used. A wax-based antioxidant containing 25-70% of a linear hydrocarbon having a carbon number of 34-40 and 30-75% (Japanese Patent Publication No. 54-25062); a carbon of a non-linear hydrocarbon having a carbon number of 29-39; The ratio to the linear hydrocarbon having 28 to 36 carbon atoms is 20 to 55%, and the total amount of the non-linear hydrocarbon having 29 to 39 carbon atoms and the linear hydrocarbon having 28 to 36 carbon atoms is 30.
-65%, the total amount of linear and non-linear hydrocarbons having 20-25 carbon atoms is 7-30%, the linear hydrocarbons having 38-53 carbon atoms and the non-linear hydrocarbons having 42-51 carbon atoms. The total amount of linear hydrocarbons is 15-35%, and the total amount of linear hydrocarbons having 32-46 carbon atoms and non-linear hydrocarbons having 38-46 carbon atoms is 6%.
0% or less of a wax-based antioxidant (JP-A-11-246)
706).

[0003] It has been well known that blending of a hydrocarbon-based high melting point wax such as microcrystalline wax, Fischer trophy wax, low molecular weight polyethylene, etc. prevents blooming.
Incorporation of these waxes not only significantly lowers the performance of static oxidation, but also has insufficient anti-flaming properties. Accordingly, a wax-based antioxidant in which the proportion of linear hydrocarbons having 58 or more carbon atoms is 1% or less and the proportion of linear hydrocarbons having 48 to 57 carbon atoms is 3 to 30% (JP-A-5-43744). As described above, proposals have been made to prevent blooming without lowering static anti-osmosis performance, but the blooming performance is not always satisfactory.

[0004]

SUMMARY OF THE INVENTION The present invention relates to a comb composition which is not satisfactory in the prior art and has a good appearance on the surface of the comb and can maintain its performance for a long time.

[0005]

SUMMARY OF THE INVENTION In view of such circumstances, the present inventors have studied waxes having more excellent anti-flaming properties than conventional high melting point hydrocarbon waxes such as microcrystalline wax and low molecular weight polyethylene wax. As a result of the repetition, it was found that higher alcohols having a specific DSC melting peak temperature were extremely effective, and furthermore, the reduction of the ozone resistance due to the blending of these waxes was small. Thus, it has been found that by using the above higher alcohol in combination with a wax-based antioxidant, a comb composition having excellent appearance and weather resistance, particularly excellent ozone resistance, can be obtained. That is, the present invention provides a natural comb and / or
Alternatively, the present invention provides a rubber composition comprising a synthetic rubber (A), an antioxidant (B), and a higher alcohol (C) having a DSC peak temperature of 70 to 105 ° C.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The comb composition of the present invention is characterized by using a wax-based anti-aging agent and a higher alcohol having a specific DSC melting peak temperature in combination, and is excellent in ozone resistance and wax-based aging. It is a composition having a good surface appearance and a good comb appearance with a small amount of inhibitory agent.

[0007] The composition of the present invention requires a natural comb and / or a diene synthetic comb (A), a wax antioxidant (B), and a higher alcohol (C) having a DSC melting peak temperature of 60-105 ° C. As a component, it preferably contains a filler, a vulcanizing agent, a vulcanization accelerator, a vulcanization aid, an antioxidant, a processing aid, a softener and the like.

[0008] As the synthetic resin used in the present invention, styrene-phthalic acid (SB)
R), phthalic acid (BR), acrylonitrile-phthalic acid (NBR), isophenyl (IR), chlorophenyl (CR) and the like. The natural components and the synthetic resins based on silicone as the components of the components may be used alone or in combination of two or more.

[0009] The wax-based antioxidant (B) used in the present invention is a commonly used paraffin wax,
Microcrystalline wax or a mixture thereof, and the type and combination of paraffin wax and microcrystalline wax are selected according to the temperature range in which the composition is used. It should be noted that there is no problem even if these waxes are blended with Fischer-Trops wax, low molecular weight polyethylene, etc. for the purpose of preventing blooming. The compounding amount of (B) is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight, per 100 parts by weight of the natural comb and / or the diene-based synthetic comb (A). Exceeding 10 parts by weight causes inconveniences such as poor appearance due to severe blooming, and less than 0.1 part by weight is undesirable because the ozone resistance decreases.

Higher alcohol (C) used in the present invention
Use a higher alcohol having a DSC melting peak temperature of 60 to 105 ° C, preferably 80 to 100 ° C. DSC
If the melting peak temperature is less than 60 ° C., the effect of preventing the blooming is insufficient, and if it exceeds 105 ° C., the effect of preventing the blooming is small and the anti-osmosis performance is significantly reduced. Higher alcohols having such properties can be produced by various methods, and those obtained by any of the methods can be used without particular limitation. For example, higher alcohols and olefins obtained by reduction or saponification of conventionally known natural fats and oils, higher alcohols synthesized from petrochemical products such as paraffin by the oxo method, the sun contact method, the Alfol method, or the like, or these higher alcohols can be used. Alcohol is distilled under reduced pressure,
It can be obtained by appropriately combining a solvent deoiling method and the like. For example, examples of commercially available products include Unilin ^™ 350, 425, 550, and 700 manufactured by Petrolite, and Valacol 5070 manufactured by Nippon Seiro Co., Ltd.

The mixing ratio of the higher alcohol (C) and the wax-based antioxidant (B) is such that the higher alcohol (C) is a natural comb and / or a diene-based synthetic comb (A) 10
0.1 to 10 parts by weight, preferably 0.1 to 10 parts by weight, based on 0 parts by weight.
When 5 to 5 parts by weight is contained, (B): (C) = 10
It is preferred to have a weight ratio of 0: 1 to 1: 1.
When the ratio of (B) :( C) is lower than 100: 1, the effect of preventing higher alcohol (C) from exhibiting full bloom is not exhibited, and when the ratio is higher than 1: 1, the resistance to ozone is remarkably reduced.

In the composition of the present invention, in addition to the above essential components, a filler, a vulcanizing agent, a vulcanization accelerator, a vulcanization aid, an antioxidant, a processing aid, as long as the object of the present invention is not impaired. Additives such as agents and softeners can be appropriately compounded. Examples of the filler used in the present invention include calcium carbonate, barium sulfate, talc, clay, titanium oxide, carbon black, white carbon, and silica.

Examples of the vulcanizing agent and vulcanization accelerator used in the present invention include sulfur, organic sulfur-containing compounds such as tetramethylthiuramite sulfite (TMTD), tetraethylthiuramite sulfite (TETD), and dipentamethylene thiuram sulfite (DPTT). And organic peroxides such as succinyl peroxy oxide.

The antioxidants used in the present invention include:
N-isofluoro-N'-phenyl-p-phenylenediamine, N-octyl-N'-phenyl-p-phenylenediamine, N, N'-diallyl-p-phenylenediamine, N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine,
N, N'-di (1,4-dimethylmethylpentyl) -p
P-phenylenediamines such as -phenylenediamine; 6-ethoxy-2,2,4-trimethyl-1-2
And ketone-amine reaction products such as dihydroquinoline.

The vulcanizing method and vulcanizing conditions of the composition of the present invention may be those according to the usual methods and conditions, for example, pressure vulcanization and steam vulcanization at 140 to 190 ° C. for 10 to 90 minutes. It may be vulcanized by a method such as vulcanization or hot water vulcanization.

[0016]

Next, the present invention will be described in more detail with reference to Examples, Comparative Examples and Conventional Examples, but the present invention is not limited to these Examples.

The numerical values described in Examples, Comparative Examples and Conventional Examples were measured by the following methods.

Comb appearance test (room test):
Vulcanized sheet (size 145 x 145 x 2 mm) at temperature 3
It was hung in a constant temperature drying oven at 0 and 40 ° C., left for 50 days, taken out, and the wax that had been formed on the surface of the comb sheet was scraped off with a cutter knife and the weight was measured. The smaller the weight, the better the appearance.

Ozone resistance test (according to JIS K6301): A sheet after vulcanization was punched out with a punch-shaped No. 1 sample, and an Oswenometer OMS-1V manufactured by Ska Tester Co., Ltd. was used to obtain an ozone concentration of 100 ppm.
The test was conducted under the conditions of a temperature of 40 and 50 ° C. and an elongation of 30 to 70%. The state of crack generation of the test piece was evaluated using the maximum elongation at which no crack was formed as a critical strain. The higher the numerical value, the better the ozone resistance.

DSC melting peak temperature measurement: 5 to 10 mg of a sample wax was weighed and measured at a rate of 5 ° C./min from −30 ° C. to 150 ° C. with a differential scanning calorimeter (DSC-220, manufactured by Seiko Instruments Inc.). And the melting peak temperature was determined from the melting curve at that time.

Examples 1 to 7, Comparative Examples 1 and 2, Conventional Example 1,
( 2 ) A DSC melting peak temperature of 49.1 to 105.7 was obtained by vacuum distillation of Unilin ^TM alcohol (manufactured by Hetrolite Co., Ltd., trade name "Unilin ^TM 425, 700").
Each fraction at ° C was obtained.

Comb compositions shown in Tables 1 and 2 below were prepared, and the above-mentioned Unilin ^™ alcohol fraction and a commercially available higher alcohol wax (trade name “Haracol 5070”, manufactured by Nippon Seiwa Co., Ltd.) were prepared. Was added in an amount of 0.4 phr. Incidentally, UNILIN ^TM alcohol fraction obtained free formulation as a conventional example 1, microcrystalline wax instead of UNILIN ^TM alcohol fractionation products and Pas Rakoru 5070 in the conventional example 2 (Nippon Seiro Co., Ltd., trade name "Hi −
Mic-1080 ") was added in an amount of 0.4 phr, and Example 1
-6 have DSC melting peak temperatures of 69.8-98.9.
UNILIN ^{T M} alcohol fractionation of ° C., c ° in Example 7 Rakoru 5070 (DSC melting heat ° over peak temperature 86.2
° C) and Comparative Examples 1 and 2 had a DSC melting peak temperature of 4
A 9.1, 105.7 ° C. Unilin ^™ alcohol fraction was blended. This was vulcanized under the conditions of a vulcanization temperature of 160 ° C. and a vulcanization time of 20 minutes to prepare a predetermined comb composition test piece. Tables 3 and 4 show the results of the appearance test and the oxidation resistance test of the comb.

The judgment in Table 3 is made based on the following criteria. ◎: The amount of bloom was reduced by 30% or more as compared with the compound without Unilin ^TM alcohol fraction (Conventional Example 1) ○: The amount of bloom was 10% or more 30 compared to Conventional Example 1
%: Less than 10% decrease in the amount of bloom compared to Conventional Example 1 ×: Increase in the amount of bloom compared to Conventional Example 1

The determination in Table 4 is made based on the following criteria. ：: Decrease in critical strain is 5% or less as compared with the compound containing no uniline ^TM alcohol fraction (Conventional Example 1) Δ: Decrease in critical strain is 10% compared to Conventional Example 1 ×: Compared with Conventional Example 1 15% or more decrease in critical strain

Examples 8 to 10 and Comparative Examples 3 and 4 Uniline ^TM alcohol fraction (DSC melting peak temperature of 88.5 ° C.) was added to the comb compositions shown in Tables 1 and 2 in an amount of 0.01 to 4 phr. . In Examples 8 to 10, 0.02 to 2 phr of Uniline ^TM alcohol fraction was used.
Comparative Example 3 contained 0.01 phr, and Comparative Example 4 contained 4 phr. This was vulcanized under the conditions of a vulcanization temperature of 160 ° C. and a vulcanization time of 20 minutes to prepare a predetermined comb composition test piece.
Tables 5 and 6 show the results of the appearance test and the oxidation resistance test of the comb.

[0026]

[Table 1]

[0027]

[Table 2]

[0028]

[Table 3]

[0029]

[Table 4]

[0030]

[Table 5]

[0031]

[Table 6]

The following can be understood from the results of Tables 3 and 4. As in Comparative Examples 1 and 2, when the DSC melting peak temperature of the Unilin ^TM alcohol fraction is lower than the specified value, the effect of preventing the blooming is small. Conversely, when the temperature is higher than the specified value, the effect of preventing the blooming is small, and the anti-soaking performance is low. Is significantly reduced. On the other hand, when the DSC melting peak temperature is within the specified range as in Examples 1 to 7, the effect of preventing blooming is large, and the decrease in the anti-osmosis performance is small. Further, according to Conventional Example 2 and Examples 1 to 7, higher alcohols having a DSC melting peak temperature within the specified range are more effective in preventing fluorinated wax than microcrystalline wax conventionally used for the purpose of preventing fluorinated wax. Is large.

The following can be understood from the results of Tables 5 and 6. As in Comparative Examples 3 and 4, the blending amount of the Unilin ^™ alcohol fraction was 0.01 phr (wax-based antioxidant: Unilin ^™ alcohol fraction = 200:
In the case of 1), the effect of preventing flamming is small, and conversely, the compounding amount is 4 phr (wax-based antioxidant: Uniline
^TM alcohol fraction = 1: 2) has a sufficient effect of preventing blooming, but significantly lowers the anti-oxidation performance. On the other hand, Examples 8 to 10 (wax-based anti-aging agent: Uniline ^TM alcohol fraction = 100:
In the case of (1: 1: 1), there is also an effect of preventing blooming, and a decrease in the anti-osmosis performance is small.

[0034]

According to the present invention, by using a wax-based antioxidant in combination with a higher alcohol having a specific DSC melting peak temperature, the appearance is improved without lowering the ozone resistance of the comb composition. The resulting comb composition can be obtained.

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Claims (2)

[Claims] 1. A composition comprising a natural comb and / or a diene synthetic comb (A), a wax antioxidant (B), and a higher alcohol (C) having a DSC melting peak temperature of 60-105 ° C. 2. The amount of (B) is 0.1 to 10 parts by weight based on 100 parts by weight of (A), and the weight ratio of (B) to (C) is 100: 1 to 1: 1. The comb composition according to claim 1.