WO2014032133A1

WO2014032133A1 - Concentrated sugar additive as high gloss agent for rubber surfaces

Info

Publication number: WO2014032133A1
Application number: PCT/BR2012/000326
Authority: WO
Inventors: Helio Haruo USHIJIMA; Ricardo Chagas da SILVA
Original assignee: Cargill Inc
Current assignee: Cargill Inc
Priority date: 2012-08-30
Filing date: 2012-08-30
Publication date: 2014-03-06
Anticipated expiration: 2015-02-28
Also published as: AR092394A1; BR112015004410A2

Description

CONCENTRATED SUGAR ADDITIVE AS HIGH GLOSS AGENT FOR RUBBER

SURFACES

FIELD OF THE INVENTION

The present invention generally concerns a concentrated sugar additive comprising (a) raffinate derived from citric acid recovery industry and (b) sugar- containing solution useful as high gloss agent for rubber surfaces, promoting shine effect with improved adherence and fast drying, while preventing cracking, browning and premature aging.

BACKGROUND OF THE INVENTION

Rubber surface has a tendency to dry and lose shine. Several factors influence this process, for instance time, weather and temperature. In addition to the undesirable aesthetic appearance, this process shortens the shelf life of the matter.

Consequently, numerous alternatives have been developed to promote finishing and protecting the rubber to avoid or minimize such a process.

Solutions containing water and inverted sugar, vegetable oils, silicone and glycerin to provide a shiny aspect to tires are commonly found in the prior art. Despite the considerable amount of disclosed alternatives, such solutions are not efficient enough due to low durability and costs.

In particular, although sugar solutions provide good appearance in rubber surfaces, one may observe disadvantages such as poor durability, attraction of insects, white powder marks, among others.

Thus, there remains a need in the art for an efficient and low cost solution useful for promoting shine in rubber surfaces, such as in flooring (carpets, floors, etc.), shoes, furniture, tool handles, rubber-coated articles, tires and other vehicle parts including boats, cars, motorcycles or bikes.

DESCRIPTION OF THE INVENTION

In order to overcome the prior art inconveniences, a specific concentrated sugar additive was developed to be used as high gloss agent for rubber surfaces, promoting a shiny effect with improved adherence and fast drying, while preventing cracking, browning and premature aging.

The additive according to the present invention comprises (a) raffinate and (b) sugar-containing solution.

According to the present invention the raffinate (a) is an aqueous solution effluent (for instance syrup or liquor) from fermentation processes (residuary or not) . Raffinate (a) is an aqueous solution comprising at least citric acid, inorganic matter (such as minerals) , proteic matter and sugar matter.

Typically, sugar matter includes carbohydrate selected from fructose, dextrose, maltose and/or polyol selected from arabitol, erythritol, or mixtures thereof. The inorganic matter is measured by analyzing ashes and typically includes nitrogen, phosphorus, potassium, calcium, magnesium, sulphur, iron, manganese, copper, zinc, boron, sodium or mixtures thereof.

In a particular embodiment, raffinate (a) may be a by-product derived from the citric acid recovery process, for instance as disclosed in the patent US 4,994,609, assigned to Cargill Inc. (1991), incorporated herein as reference. The contents of raffinate (a) ingredients depend on the performance of the recovery industry.

One advantage of this invention resides in the fact that a by-product without commercial application is used as raw material for the manufacture of a commercial product, also avoiding the cost with waste disposal treatment .

The sugar-containing solution (b) may be obtained from several sources, for instance corn, sugar cane, cassava, potato, wheat, rice, etc. In a particular embodiment such a solution may be syrup, i.e. a viscous liquid with sugar content. Such a component also includes enzymatic or acid conversion syrup, independently from the conversion grade.

Sugar, according to the present invention, is selected from carbohydrates or saccharides in general, including monosaccharides, disaccharides , oligosaccharides, polysaccharides, and mixtures thereof. For instance, the solution (b) comprises monosaccharide such as glucose (dextrose), fructose (levulose), galactose, xylose or ribose; disaccharides such as sucrose, maltose or lactose; oligosaccharides such as raffinose or stachyose; polysaccharides such as or starch, amylose, amylopectin, cellulose, chitin; hydrolysates (for instance inverted sugar), derivatives or mixtures thereof.

According to ' the present invention the sugar- containing solution (b) may be a viscous concentrated solution of sugar, in water or other liquids (for instance alcohols) . Such a solution may also include other ingredients such as coloring agents, flavors or thickening agents .

In a particular embodiment component (b) contains about 40% equivalent dextrose in relation to about 80% total solids. For instance, such an ingredient (b) is commercialized as Glucogill 40/82 by the Cargill group in Brazil.

The concentrated sugar additive useful as high gloss agent for rubber surfaces comprises: (a) from about 10 to about 90%, preferably about 80% raffinate from a citric acid recovery process, and

(b) from about 10 to about 90%, preferably about 20% glucose syrup.

As a second aspect, the present invention also concerns a process for manufacturing a high gloss agent for rubber substrates comprising the following steps of:

(i) evaporating of raffinate component (a) up to about 65% solids;

(ii) mixing sugar-containing solution (b) and evaporated raffinate until homogenization;

(iii) controlling the viscosity by addition of sugar-containing solution (b) if necessary, considering a minimum of about 500 and a maximum of about 1,500 cP (at 25°C) .

The resulting high gloss agent for rubber surfaces according to the present invention presents the following characteristics:

(a) % Brix (sugar parameter) from about 65 to about 70.

(b) Viscosity: minimum of about 500 and a maximum of about 1,500 cP (at 25°C) .

The % Brix is analyzed by a refractometer . The viscosity is measured by cooling the sample at 25 °C and 20 rpm in a Brookfield viscometer DV I.

Due to the characteristics of the high gloss agent according to the present invention, especially with respect to controlled concentrations of sugar, as well as physical characteristics (viscosity) , it is possible to obtain an improved ingredient able to act as shine promoting with improved adherence and fast drying, while preventing cracking, browning and premature aging.

It was found that the use of sugars alone (for instance glucose) as gloss agents is not possible , due to its cracking effect, i.e. a tendency to form white powder on the rubber surface, which may jeopardize the appearance. Contrary to what one would expect, the raffinate (a) is able to control such an undesired effect allowing the high gloss agent application for rubber substrates, i.e. due the formation of a film with improved shine and protective properties. Moreover, waste derived from citric acid industry is given use, providing a low-cost and environmentfriendly product.

The concentrated sugar additive according to the present invention may also comprise other ingredients well known in the art, such as fragrances, surfactants, biocides, pH adjusters, thickeners, etc.

According to the invention "rubber surfaces" includes natural and synthetic rubber, such carpets, floors, shoes, clothes furniture, coatings, articles, tools, tires and other vehicle parts including boats, cars, motorcycles or bikes. In a preferred embodiment the high gloss agent according to the present invention is useful for tires.

The present invention also concerns the use of the composition described above as shine promoting agent or a method to promote shine on rubber surfaces that comprises applying an effective amount of a shine agent as described above to a rubber surfaces.

The following examples are provided for illustration and are not intended as a limitation to the scope of the present invention, other than what is described in the attached claims.

EXAMPLES OBTAINING OF RAFFINATE

A raffinate sample was obtained from the citric acid recovery process disclosed in the patent US 4,994,609, assigned to Cargill Inc. (1991).

Such an ingredient was evaluated in order to identify organic and mineral contents.

One test was carried out to verify the mineral ingredients contained in the raffinate (a) . Therefore, ashes without organic elements (i.e. water, citric acid, raw protein and sugar not converted) were evaluated and the following composition was identified:

Table 1 - Raffinate characteristics: inorganic elements

(<1.0%)

Ingredient Amount

Nitrogen 0.58%

Phosphorus 0.12%

Potassium 35.0 ppm

Calcium 148.0 ppm

Magnesium 25.0 ppm

Sulphur 0.25 ppm

iron 1.0 ppm

manganese 3.0 ppm

copper 3.0 ppm

zinc 10.0 ppm

boron 110.0 ppm

sodium 900.0 ppm

cobalt - molybdenum - aluminum - chlorine - nickel - organic carbon - organic matter 19,50 %

pH 2.2

density 1.25 g/mL

C / N ratio 19/1

electric 340.0

condition S/cm Organic elements detected in the sample, as shown in table 2, include:

Table 2- Raffinate characteristics: organic elements

The analyzed sample also contains solids (15%) and trace ingredients (<100ppm) . C/N ratio = 19 and pH = 3. PREPARATION OF THE HIGH GLOSS AGENT

A sample of the high gloss agent was prepared by:

(a) evaporation of a raffinate stream according to a process disclosed in the patent US 4,994,609 up to 65% solids ;

(b) mixing 8 kg of the raffinate obtained in the step (a) with 2 kg of glucose syrup, commercialized as Glucogill 40/82, until complete homogenization.

The viscosity, pH and sugar content of the resulting mixture was then analyzed:

(a) % Brix (sugar parameter) from about 65 to about 70.

(b) Viscosity: about 1,000 cP (25°C) .

(c) pH: 2.0-3.5

APPLICATION TEST

The high gloss agent produced according to the previous examples was used in performance tests. Fragrance was added to the high gloss agent in order to mask any burnt odor.

Before application, the high gloss agent was diluted (1:1) in water. The obtained solution was applied on tires of two trucks (the first one new and the second a used one) . Both applications immediately resulted in excellent brightness and a touch dry.

Afterwards, the trucks ran a few miles in order to simulate a real situation of use. It was not observed any white powder formation over the time.

COMPARATIVE TEST WITH GLUCOSE ALONE

This test was carried out to compare the performance of individual ingredients and the high gloss agent according to the present invention.

_ _. The following samples were used:

1-Raffinate stream according to a process disclosed in the patent US 4,994,609, dried to up to 70% solids (diluted 1:1 in water),

2 - Glucose syrup commercialized as Glucogill 40/82 in water (diluted 1:1),

Results :

Sample 1: glossy film with some tackiness (Figure 1, right side of the tire); moderate brightness film after dry (Figure 2A) .

Sample 2: glossy film with some tackiness (Figure

1, left side of the tire) ; and loss of brightness with cracking deposits after dry (Figure 2B) ,

COMPARATIVE TEST WITH GLYCERIN

Two tires were used: new and used with almost 30,000 km.

For the present evaluation 20% glycerin in water was used and the following formulations:

Table 3 - tested formulations

Sample Glucose raffinate Glycerin

1 48.80% 51.10% 0.10%

2 21.96% 76.95% 1.10%

3 02.20% 79.98% 0.00%

4 49.26% 49.65% 1.09% Table 4 - tested formulations characteristics

Results :

Glycerin: moderately glossy film (Figure 3) ; and poor shine effect after dry (Figure 4) .

Sample 1: high gloss film (Figure 5, left side of the tire); and same high gloss with no cracking deposit after dry (Figure 6) ,

Sample 2: high gloss film (Figure 5, right side- of the tire) ; and same high gloss with no cracking deposit after dry (Figure 7),

Sample 3: high gloss film (Figure 8, left side of the tire) ; and same high gloss with no cracking deposit after dry and a very homogenous film (Figure 9) .

Sample 4: high gloss film (Figure 8, right side of the tire) ; and same high gloss with some spots in the surface after dry (Figure 10).

The information contained in the foregoing, as well as in the examples, allows a person skilled in the art to perform alternative embodiments of the invention not expressly described, but which perform the functions taught herein with the results revealed herein. Such equivalent embodiments are encompassed by the scope of the invention and are therefore covered by the claims presented further on .

Claims

1. HIGH GLOSS AGENT FOR RUBBER SURFACE comprising a mixture of (a) raffinate and (b) sugar-containing solution .

2. AGENT, according to claim 1, wherein raffinate (a) is a by-product derived from citric acid recovery process .

3. AGENT, according to one of claims 1 or 2, wherein raffinate (a) is an aqueous solution comprising at

-least -at least; citric acid, inorganic matter, proteic matter and sugar matter.

4. AGENT, according to claim 3, wherein sugar matter comprises carbohydrate selected from fructose, dextrose, maltose and/or polyol selected from arabitol, erythritol, or mixtures thereof.

5. AGENT, according to claim 3, wherein inorganic matter includes nitrogen, phosphorus, potassium, calcium, magnesium, sulfur, iron, manganese, copper, zinc, boron, sodium, or mixtures thereof.

6. AGENT,, according to one of claims 1 to 5, comprising from about 10 to about 90% raffinate.

7. AGENT, according to one of claims 1 to 6, comprising about 80% raffinate.

8. AGENT, according to claim 1, wherein sugar- containing solution (b) comprises monosaccharide, disaccharide, oligosaccharide, polysaccharide; or mixture thereof .

9. AGENT, according to one of claims 1 or 8, wherein sugar-containing solution (b) comprises glucose, fructose, galactose, xylose, ribose, sucrose, maltose, lactose, raffinose, stachyose, starch, amylose, amylopectin, cellulose, chitin, hydrolysates , derivatives or mixtures thereof.

10. AGENT, according to one of claims 1, 8 or 9, wherein sugar-containing solution (b) is Glucogill 40/82.

11. AGENT, according to one of claims 1 or 8 to

10, comprising from about 10 to about 90% sugar-containing solution (b) .

12. AGENT, according to one of claims 1 or 8 to

11, comprising about 20% sugar-containing solution (b) .

13. AGENT, according to one of claims 1 or 8 to

12, wherein the sugar-containing solution (b) contains about 40% eguivalent dextrose in relation to about 80% total solids.

14. AGENT, according to one of claims 1 or 8 to

13, wherein the sugar-containing solution (b) is derived from corn.

15. AGENT according to one of claims 1 to 14 presenting the following characteristics:

(a) % Brix from about 65 to about 70;

(b) viscosity of minimum of about 500 and a maximum of about 1,500 cP (at 25°C) .

16. PROCESS FOR MANUFACTURING THE AGENT according to one of claims 1 to 15 comprising the steps of:

(a) evaporation of raffinate component (a) up to about 65% solids;

(b) mixing sugar-containing solution (b) until complete homogenization

(c) controlling the viscosity by addition of glucose syrup component (b) if necessary, considering a minimum of about 500 and a maximum of about 1, 500 cP (at 25°C) .

17. USE OF THE AGENT according to one of claims 1 to 15 for promoting shine in rubber substrate.

18. METHOD FOR PROMOTING SHINE IN RUBBER SUBSTRATE comprising applying a shine amount of an agent according to one of claims 1 to 15.