JP2012067201A - Phenol-based biomass resin composition and rubber composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a rubber composition that has a high hardness and a high storage elastic modulus and can lessen dependence on fossil fuels in the composition to thereby exhibit a high inhibiting effect on increase of carbon dioxide.SOLUTION: The phenol-based biomass resin composition comprises a phenol-based biomass resin obtained by crosslinking, with an aldehyde, phenol compounds comprising a natural phenol (A) derived from a non-edible part of a plant and a phenol (B) derived from fossil fuels with a mass ratio (A)/(B) within the range of 10/90 to 40/60, and a silane coupling agent. The rubber composition comprises a rubber, the phenol-based biomass resin composition, a curing agent and a filler.

Description

  The present invention relates to a phenol-based biomass resin composition and a rubber composition using the same, and more specifically, has an effect of improving the hardness and high storage elastic modulus of rubber, and preventing global warming accompanying an increase in biomass ratio. The present invention relates to an effective phenol-based biomass resin composition, and more particularly to a rubber composition for a pneumatic tire using the same.

  Conventionally, to increase the hardness of rubber for tires and to increase the storage elastic modulus, the amount of carbon black is increased, the type of carbon black is changed, and sulfur is blended. At the same time, phenol-formaldehyde resin and paratertiary butylphenol-formaldehyde Alkylphenol-formaldehyde resins such as resins and paraoctylphenol-formaldehyde resins have been blended (see, for example, Non-Patent Document 1).

  On the other hand, in recent years, in order to prevent global warming, carbon neutrals that do not increase the total amount of carbon dioxide in the atmosphere by reducing the amount of carbon dioxide emitted during incineration of used products and by using raw materials derived from biomass. The idea of Carbon neutral is a plant that absorbs and immobilizes carbon dioxide by photosynthesis during its growth process, so the amount of carbon dioxide generated from disposal and incineration is offset by the amount of carbon dioxide absorbed by photosynthesis, and carbon dioxide in the atmosphere. Is not to increase. For this reason, in various industrial products, the ratio of materials that use raw materials derived from fossil fuels is reduced, and the ratio of materials that use raw materials derived from non-fossil fuels, including so-called biomass materials that use plant-derived components as raw materials instead. Development of environmentally conscious materials with a high carbon dioxide emission suppression effect has been actively promoted.

  These development trends are no exception in the tire industry, and development is progressing to increase the ratio of materials using non-fossil fuel-derived raw materials. For example, in environmentally friendly tires (eco-tyres) with a high carbon dioxide emission suppression effect, natural rubber is used to replace the synthetic rubber component in the tire composition, or carbon black used in ordinary tires is replaced with natural inorganic fillers. The content ratio of the non-fossil fuel-derived material in the entire tire is increased by substituting the tire composition with a biomass material or a natural inorganic material, such as a method to do so.

"Handbook" editorial office "Handbook rubber and plastic compounding chemical latest edition" Rubber Digest Co., Ltd. March 30, 1989 p. 466-467

However, at present, in general rubber compositions for tires and environmentally conscious tires, phenolic resins and alkylphenol resins blended for the purpose of improving hardness and increasing storage elastic modulus, anti-aging agents, vulcanization accelerators, etc. are fossil. It is in a situation where materials derived from fuel must be used. The amount of phenolic resin in the tire rubber composition is small for the entire tire, but the production of tires worldwide is very large, so carbon dioxide derived from fossil fuels generated from the compounded phenolic resin during tire incineration. The amount is also enormous.
An object of the present invention is to provide a rubber composition having functions of high hardness and high storage elastic modulus and suppressing increase in the total amount of carbon dioxide.

The present invention has the following configuration.
[1] The mass ratio (A) / (B) of natural phenols (A) derived from non-edible parts of plants and phenols (B) derived from fossil fuels is in the range of 10/90 to 40/60. A phenolic biomass resin composition comprising a phenolic biomass resin obtained by crosslinking phenols with aldehydes and a silane coupling agent.
[2] The phenol-based biomass resin composition according to [1], wherein the natural phenol (A) derived from the non-edible part of the plant is at least one of cashew nut shell liquid, cardanol, and urushiol.
[3] The phenol-based biomass resin composition according to [1] or [2], wherein the concentration of metal element in the natural phenols (A) derived from the non-edible part of the plant is less than 100 ppm.
[4] A rubber composition comprising a rubber, the phenol-based biomass resin composition according to any one of [1] to [3], a curing agent, and a filler.
[5] The rubber composition according to [4], wherein the curing agent is hexamethylenetetramine.

  The rubber composition of the present invention has functions of high hardness and high storage elastic modulus, and can reduce dependence on fossil fuel in the composition. Furthermore, since the raw material used is a non-edible part of the plant, there is no trade-off with food.

<Phenolic biomass resin composition>
In the phenol-based biomass resin composition of the present invention, the mass ratio (A) / (B) of natural phenols (A) derived from non-edible parts of plants and phenols (B) derived from fossil fuels is 10/90. It contains phenolic biomass resin obtained by crosslinking phenols in the range of ˜40 / 60 with aldehydes, and a silane coupling agent.

First, the phenolic biomass resin contained in the phenolic biomass resin composition of the present invention will be described. The phenol-based biomass resin has a mass ratio (A) / (B) of natural phenols (A) derived from non-edible parts of plants and phenols (B) derived from fossil fuels in the range of 10/90 to 40/60. These are phenols crosslinked with aldehydes.
Examples of natural phenols (A) derived from non-edible parts of plants include cashew nut shell oil, cardanol and urushiol. These may be used individually by 1 type and may be used in combination of 2 or more type. In general, natural phenols derived from non-edible parts of plants often contain metal elements such as potassium, sodium, calcium, magnesium, iron, manganese, etc., but if these components increase, phenols and aldehydes This hinders the reaction, prevents high molecular weight during resin synthesis, reduces the reinforcing effect of the rubber composition, and does not increase the hardness. In order not to inhibit the reaction between phenols and aldehydes, the metal element concentration of natural phenols (A) derived from non-edible parts of plants is preferably less than 100 ppm.
The phenols derived from fossil fuels (B) are not particularly limited, but include phenol, resorcin, cresol, xylenol, propylphenol, butylphenol, octylphenol, phenylphenol, bisphenol A, bisphenol F, etc. May be used in combination, or two or more may be used in combination. Among these, phenol, cresol, and bisphenol A are preferable from the viewpoints of economic efficiency, improved hardness of the tire composition, and higher storage elastic modulus.
In the mass ratio of the natural phenols (A) and the fossil fuel-derived phenols (B), if the component (A) is 10% by mass or more, the plant-derived rate in the phenol-based biomass resin is increased, and the environment is harmonized. The contribution effect to sex is improved. Moreover, if (B) component is 60 mass% or more, the hardness and storage elastic modulus of a rubber composition will become favorable.

  Although it does not specifically limit as aldehydes made to react with phenol, Formaldehyde, paraformaldehyde, trioxane, acetaldehyde, propionaldehyde, glyoxal, benzaldehyde, salicylaldehyde, etc. are mentioned, These may be used individually by 1 type. And two or more kinds may be used in combination. Among these, formaldehyde and paraformaldehyde are preferable from the viewpoint of economy and reactivity with phenols.

  A phenol-based biomass resin can be obtained as a novolak-type phenol resin or a resol-type phenol resin by subjecting the above phenols and aldehydes to a conventional phenol resin production method in the presence of an acidic catalyst or in the presence of a basic catalyst. it can.

Next, the silane coupling agent contained in the phenol biomass resin composition will be described. The silane coupling agent is not particularly limited, but vinyltrimethoxysilane, vinyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-aminopropyltriethoxysilane, N- 2- (aminoethyl) -3-aminopropyltrimethoxysilane and the like may be mentioned, and these may be used alone or in combination of two or more.
Moreover, 0.01-10 mass parts is preferable with respect to 100 mass parts of phenol-type biomass resins, and, as for the quantity of the silane coupling agent contained in a phenol-type biomass resin composition, 0.1-5 mass parts is more preferable. If it is 0.01 mass part or more of silane coupling agents with respect to 100 mass parts of phenol type biomass resin, the reinforcement effect of rubber will become large by improving the adhesiveness of resin and a filler, and if it is 10 mass parts or less. , Economically superior.

  The phenol-based biomass resin composition may contain a phenol resin using only phenols derived from fossil fuel as raw materials (hereinafter referred to as “fossil fuel raw material phenol resin”). The fossil fuel raw material phenol resin is not particularly limited, and examples thereof include phenol-formaldehyde resin, para-tertiary butyl phenol-formaldehyde resin, para-octyl phenol-formaldehyde resin, cresol-formaldehyde resin, phenol-para tertiary butyl phenol-formaldehyde resin, etc. May contain 1 type independently, and may contain it in combination of 2 or more type. The content of the fossil fuel raw material phenol resin in the phenolic biomass resin composition is not particularly limited, but the mass ratio of the phenolic biomass resin and the fossil fuel raw material phenol resin is in the range of 5/95 to 100/0. 30/70 to 100/0 is preferable. If the mass ratio of the phenol-based biomass resin is 5/95 or more, the plant-derived rate in the phenol-based biomass resin composition is increased, and the contribution effect to environmental harmony is improved.

<Rubber composition>
The rubber composition of the present invention contains rubber, a phenol-based biomass resin composition, a curing agent and a filler.
The rubber used in the rubber composition of the present invention is not particularly limited, but besides natural rubber (NB), butadiene rubber (BR), isoprene rubber (IR), butyl rubber (IIR), styrene-butadiene rubber (SBR), Synthetic diene rubbers such as acrylonitrile-butadiene rubber (NBR) may be used, and these may be used alone or in combination of two or more. Among these, it is preferable to use natural rubber in order to improve the plant-derived rate in the rubber composition or the tire used therefor and to enhance environmental harmony.

  Although the compounding ratio of the rubber | gum used for the rubber composition of this invention and phenol-type biomass resin is not specifically limited, It is 1-50 mass parts of phenol resins with respect to 100 mass parts of rubber | gum, More preferably, it is 1-30 mass parts. When phenol resin is 1-50 mass parts with respect to 100 mass parts of rubber | gum, the hardness improvement with respect to a rubber composition and high storage elastic modulus improvement will become favorable.

  The curing agent used in the rubber composition of the present invention is not particularly limited, and examples include hexamethylenetetramine, hexamethoxymethylmelamine, paraformaldehyde, glyoxal, etc. Among them, hexamethylenetetramine is economical and compatible with rubber. From the viewpoint of stability after production of the rubber composition, it is preferable.

  The filler used in the rubber composition of the present invention is not particularly limited, and examples thereof include carbon black, silica, calcium carbonate, magnesium carbonate, alumina, magnesium oxide, aluminum hydroxide, magnesium hydroxide, talc, clay and mica. Of these, carbon black and silica are preferred from the viewpoint of imparting hardness to the rubber composition.

  In addition to this, the rubber composition of the present invention is usually used in the rubber industry, such as a reinforcing agent such as carbon black, a vulcanizing agent such as sulfur, a vulcanization accelerator, an anti-aging agent, a plasticizer, various oils, and waxes. You may contain the compounding agent used.

  The rubber composition of the present invention can be produced by a general method, for example, by kneading a reinforcing agent or a compounding agent used as necessary in addition to the phenol resin and the rubber component with a Banbury mixer, a roll, a kneader or the like. it can.

  The rubber composition of the present invention has functions of high hardness and high storage elastic modulus, and can reduce dependence on fossil fuel in the composition, so that it can be used for tire applications.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated more concretely, this invention is not limited at all by these Examples.

[Synthesis Example 1]
A 3 L four-necked flask equipped with a stirrer, a condenser, and a thermometer was charged with 300 g of cardanol having a metal element concentration of 68 ppm, 1081 g of phenol, 645 g of 50% formalin, and 27.6 g of oxalic acid, and refluxed for 6 hours. This was heated up to 200 ° C. by dehydration and reflux, concentrated under reduced pressure at 0.093 MPa for 1 hour, added with 5 g of a silane coupling agent (KBE-903 manufactured by Shin-Etsu Chemical Co., Ltd.) at 140 ° C., taken out, and phenolic biomass 1436 g of resin composition a was obtained.

[Synthesis Example 2]
A 2 L four-necked flask equipped with a stirrer, a condenser, and a thermometer was charged with 158 g of urushiol having a metal element concentration of 55 ppm, 1296 g of phenol, 450 g of 50% formalin, and 28.9 g of oxalic acid, and refluxed for 6 hours. This was heated to 200 ° C. by dehydration and reflux, concentrated under reduced pressure at 0.093 MPa for 1 hour, added with 2 g of a silane coupling agent (KBE-903 manufactured by Shin-Etsu Chemical Co., Ltd.) at 140 ° C., taken out, and phenolic biomass. 1428 g of resin composition b was obtained.

[Synthesis Example 3]
A 2 L four-necked flask equipped with a stirrer, a condenser, and a thermometer was charged with 300 g of cashew nut shell oil having a metal element concentration of 3480 ppm, 630 g of phenol, 277 g of 50% formalin, and 19.2 g of oxalic acid, and refluxed for 6 hours. This was heated up to 200 ° C. by dehydration and reflux, concentrated under reduced pressure at 0.093 MPa for 1 hour, added with 5 g of a silane coupling agent (KBE-903 manufactured by Shin-Etsu Chemical Co., Ltd.) at 140 ° C., taken out, and phenolic biomass 1000 g of resin composition c was obtained.

[Comparative Synthesis Example 1]
A 2 L four-necked flask equipped with a stirrer, a condenser, and a thermometer was charged with 158 g of urushiol having a metal element concentration of 55 ppm, 1296 g of phenol, 450 g of 50% formalin, and 28.9 g of oxalic acid, and refluxed for 6 hours. This was heated up to 200 ° C. by dehydration and reflux, then concentrated under reduced pressure at 0.093 MPa for 1 hour, taken out, and 1428 g of phenol-based biomass resin was obtained.

(Measurement of metal element concentration)
Metal element concentrations of natural phenols derived from non-edible parts of plants used in Synthesis Examples 1 to 3 and Comparative Synthesis Example 1 were measured with an inductively coupled plasma emission spectrometer SPS4000 manufactured by SSI Nanotechnology.

The softening points of the phenolic biomass resin compositions obtained in Synthesis Examples 1 to 3 and the phenolic biomass resin obtained in Comparative Synthesis Example 1 were measured by the following method, and the plant-derived rate was calculated by the following method. The results are shown in Table 1.
[Softening point]
It measured according to JIS K6910.
[Plant-derived rate in phenolic biomass resin composition]
Plant-derived ratio in phenol-based biomass resin composition = (natural phenols derived from non-edible parts of plants) / (phenol-based biomass resin composition yield mass) × 100
However, the phenol-based biomass resin of Comparative Synthesis Example 1 was calculated by the following method.
Plant-derived ratio in phenol-based biomass resin = (natural phenols derived from non-edible parts of plants) / (phenol-based biomass resin yield mass) × 100

(Manufacture of rubber composition)
Various compounding materials used in Examples and Comparative Examples will be described collectively below.
Natural rubber (NR): RSS No. 3 Fossil fuel raw material phenol resin: PS-6200 (phenol-formaldehyde resin, plant-derived rate 0%, manufactured by Gunei Chemical Industry Co., Ltd.)
Carbon black: HAF (Mitsubishi Chemical Corporation)
Wax: Sunnock (Ouchi Shinko Chemical Co., Ltd.)
Oil: Diana Process AH40 (made by Idemitsu Kosan Co., Ltd.)
Anti-aging agent: NOCRACK 6C (manufactured by Ouchi Shinko Chemical Co., Ltd.)
Stearic acid: Sakura stearate (manufactured by NOF Corporation)
Sulfur: Sulfur (manufactured by Tsurumi Chemical Co., Ltd.)
Zinc flower: Zinc oxide (manufactured by Sakai Chemical Co., Ltd.)
Curing agent: Hexamethylenetetramine (Mitsubishi Gas Chemical Co., Ltd.)
Vulcanization accelerator: Noxeller NS-P (Ouchi Shinko Chemical Co., Ltd.)

[Example 1]
100 g of natural rubber, 10 g of phenol-based biomass resin composition a, 60 g of carbon black, 2 g of wax, 4 g of oil, 2 g of anti-aging agent, 4 g of stearic acid, and 5 g of zinc white were kneaded in a pressure kneader at 150 ° C. for 5 minutes. To this, 2.5 g of sulfur, 5 g of a curing agent, and a vulcanization accelerator were added and kneaded with a biaxial roll at 80 ° C. for 2 minutes to obtain a sheet-like unvulcanized rubber composition.

[Example 2]
An unvulcanized rubber composition was obtained in the same manner as in Example 1 except that 10 g of the phenolic biomass resin composition b was used instead of 10 g of the phenolic biomass resin composition a.

[Example 3]
An unvulcanized rubber composition was obtained in the same manner as in Example 1 except that 10 g of the phenol-based biomass resin composition c was used instead of 10 g of the phenol-based biomass resin composition a.

[Comparative Example 1]
An unvulcanized rubber composition was obtained in the same manner as in Example 1 except that 10 g of phenol-based biomass resin was used instead of 10 g of phenol-based biomass resin composition a.

[Comparative Example 2]
An unvulcanized rubber composition was obtained in the same manner as in Example 1 except that 10 g of the fossil fuel raw material phenol resin was used instead of 10 g of the phenol-based biomass resin composition a.

  About the unvulcanized rubber composition obtained in Examples 1-3 and Comparative Examples 1-2, the plant origin rate was computed according to the following formula, respectively. The results are shown in Table 2.

[Plant-derived rate in rubber composition]
Plant-derived rate in rubber composition (%) = [(phenolic biomass resin composition usage) × (plant-derived rate in phenolic biomass resin composition) × 0.01 + (natural rubber usage)] / ( Total amount of all ingredients used) x 100
However, the rubber composition of Comparative Example 1 was calculated by the following method.
Plant-derived ratio in rubber composition = [(phenolic biomass resin usage) × (plant-derived ratio in phenolic biomass resin) × 0.01 + (natural rubber usage)] / (total amount of all components used) × 100
Plant-derived components are obtained by photosynthesis using carbon dioxide in the atmosphere. For this reason, it is considered that the increase in carbon dioxide is not affected by the above-mentioned idea of carbon neutral. Therefore, the higher the value of the plant-derived rate, the more the increase in carbon dioxide in the atmosphere can be suppressed, and the global warming prevention effect becomes higher.

  For the unvulcanized rubber compositions obtained in Examples 1 to 3 and Comparative Examples 1 to 2, test samples were prepared by press vulcanization at 150 ° C. for 30 minutes using a 150 mm × 150 mm × 2 mm mold, respectively. The hardness, breaking strength, and storage elastic modulus were measured by the following methods. The measurement results are shown in Table 2.

[Hardness]
According to JIS K6253, hardness (Shore A) was measured using a TECLOCK type A durometer GS-719G. The higher the hardness (Shore A) value, the better and better the hardness.

[Breaking strength]
In accordance with JIS K6251, the breaking strength of the test piece having a dumbbell shape No. 3 was measured with a strograph V10-C manufactured by Toyo Seiki. The higher the breaking strength value, the better the tensile strength.

[Storage modulus]
The storage elastic modulus was measured at a temperature of 40 ° C. and a frequency of 10 Hz using SMS NanoTechnology DMS110. The higher the storage modulus value, the better the rigidity.

From the results shown in Table 2, Examples 1 to 3 showed that the plant-derived rate of the rubber composition was 0.6 to 1.6% higher than that of Comparative Example 2. Although the difference in the plant-derived rate as a rubber composition is small, as described above, since the tire production volume in the world is very large, the effect of suppressing the increase in the total amount of carbon dioxide is large. Moreover, since Examples 1-3 are high in storage elastic modulus and hardness compared with the comparative example 2, when such a rubber composition is used as a tire, it becomes a tire excellent in steering stability. In particular, Examples 1 and 2 in which the metal element concentration of the natural phenols derived from the non-edible part of the plant used as a raw material of the blended phenol resin composition is less than 100 ppm are harder than Example 3 of 100 ppm or more. The breaking strength and storage elastic modulus were high.
In Comparative Example 1 in which no silane coupling agent was blended, the hardness, breaking strength, and storage elastic modulus were lower than in Example 2. Therefore, when the rubber composition of Comparative Example 1 is a tire, the effect on steering stability is reduced.

Claims (5)

  Phenols having a mass ratio (A) / (B) of natural phenols (A) derived from non-edible parts of plants and phenols (B) derived from fossil fuels in the range of 10/90 to 40/60 A phenolic biomass resin composition comprising a phenolic biomass resin crosslinked with an aldehyde and a silane coupling agent.   The phenol-based biomass resin composition according to claim 1, wherein the natural phenols (A) derived from the non-edible part of the plant is at least one of cashew nut shell liquid, cardanol, and urushiol.   The phenol-based biomass resin composition according to claim 1 or 2, wherein the concentration of metal element in the natural phenols (A) derived from the non-edible part of the plant is less than 100 ppm.   A rubber composition comprising rubber, the phenol-based biomass resin composition according to any one of claims 1 to 3, a curing agent, and a filler.   The rubber composition according to claim 4, wherein the curing agent is hexamethylenetetramine.