KR102040268B1 - Anti-cutting and anti-chipping agent for rubber and preparation method thereof - Google Patents
Anti-cutting and anti-chipping agent for rubber and preparation method thereof Download PDFInfo
- Publication number
- KR102040268B1 KR102040268B1 KR1020150098558A KR20150098558A KR102040268B1 KR 102040268 B1 KR102040268 B1 KR 102040268B1 KR 1020150098558 A KR1020150098558 A KR 1020150098558A KR 20150098558 A KR20150098558 A KR 20150098558A KR 102040268 B1 KR102040268 B1 KR 102040268B1
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- South Korea
- Prior art keywords
- rubber
- cutting
- chipping
- rosin
- reaction
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L93/00—Compositions of natural resins; Compositions of derivatives thereof
- C08L93/04—Rosin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L21/00—Compositions of unspecified rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2380/00—Tyres
Abstract
It is an object of the present invention to provide a rubber molding and a method of manufacturing the rubber molding which is further enhanced in heat resistance and chemical resistance as compared with a conventional rubber molded product having enhanced heat resistance and chemical resistance. In order to achieve the above object, the rubber molding method of the present invention mixes 70 to 90% by weight of a perfluoro elastomer and 10 to 30% by weight of isophorone diisocyanate, and then compresses with a roller to form a compact. step; Charging the press into a mold and heating the mold to form a molded product; Mapping the molding to remove foreign substances; Heat-treating the molded article from which the foreign substances have been removed in an oven; And washing the molding heat treated in the oven.
Description
The present invention relates to a rubber cutting and chipping inhibitor and a method for producing the same, while improving the cutting and chipping resistance of the rubber product.
Cutting and Chipping prevention agent refers to a rubber additive that serves to extend the life of the rubber shortened by external impact and to improve the mechanical properties of the rubber. Rubber products break down and tear off due to external shocks.
The patterned protrusions of the tire are the ones where friction with the ground is most high during driving and are cracked or cut off like a knife. Especially for agricultural / industrial tires, this phenomenon occurs more seriously in the bad conditions of the ground such as gravel, sand, mud, and even rubber hoses are cracked due to frequent friction with the floor during use. In addition, cracking or tearing occurs due to friction with the outside.
In particular, tire makers regard cut and chipping inhibitors as essential additives to produce tires with excellent wear resistance that can withstand tire stress caused by road friction and road friction.
PHAs (polycyclic aromatic hydrocarbons) are organic compounds consisting of linear or dense structure of two or more benzene rings. They are found in crude oil, coal, coal tar, etc. and are produced as by-products in the manufacture of petrochemical products. This is a substance that occurs during incomplete combustion of. PHAs have been identified as 50 benzo (a) pyrene and other compounds with known toxicity, and 17 of them are known to be more harmful than others. The typical hazards of PHAs are genotoxicity and carcinogenicity. Known.
In Europe, tires are evaluated for harmful substances based on the Substances of Very High Concern (SVHC). Nearly 50 substances are regulated. Every year, the number of hazardous substances registered with SVHC is increasing, and regulations are tightening. In the case of tires, PAHs are designated as prohibited substances. Currently, the PHAs included in SVHC account for eight items, and the number of items is expected to increase gradually. For this reason, the presence of hazardous substances has become an essential item to be considered in developing tire rubber materials.
Indeed, the EU and the United States are tightening regulations on hazardous materials in Chinese tires. A bigger problem is the use of safety as a means of normal pressure. Korean companies that have entered China are also hit hard, and this movement is shifting to trade barriers to neighboring Japan and Korea.
Therefore, in the future, most rubber material products must be considered whether it is environmentally friendly or harmful to humans. Accordingly, there is an urgent need to develop an environment-friendly cutting and chipping & chipping inhibitor.
The present invention has been derived to solve the above problems, the mechanical properties of the rubber is maintained at the same level or higher than the existing excellent cutting and chipping resistance, and at the same time harmless to the human body and environmentally friendly cutting and chipping (Cut & Chipping) To provide an inhibitor.
The present invention relates to a cutting and chipping inhibitor for rubber, and more particularly to a cutting and chipping inhibitor for rubber including a rosin derivative, wherein the rosin derivative is a dibasic acid in rosin. And / or obtained by reacting by adding the anhydride thereof.
In addition, another aspect of the present invention relates to a method for producing a cutting and chipping inhibitor for rubber, the reaction preparation step of raising the temperature after the rosin is added to the reactor and the reaction by adding a dibasic acid and / or its anhydride to the reactor A reaction step to produce the product.
Cutting and chipping prevention agent for rubber according to the present invention is harmless to the human body by including rosin derivative which is environmentally harmful and does not contain PHAs which are carcinogenic substances and is environmentally friendly, when applied to rubber products, the same level as conventional rubber products While maintaining the above mechanical properties, cutting and chipping resistance has the effect of producing a much better rubber products.
As the inventive concept allows for various changes and numerous embodiments, particular embodiments will be illustrated in the drawings and described in detail in the written description. However, this is not intended to limit the present invention to specific embodiments, it should be understood to include all transformations, equivalents, and substitutes included in the spirit and scope of the present invention. In the following description of the present invention, if it is determined that the detailed description of the related known technology may obscure the gist of the present invention, the detailed description thereof will be omitted.
The terminology used herein is for the purpose of describing particular example embodiments only and is not intended to be limiting of the present invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In this application, the terms "comprise" or "have" are intended to indicate that there is a feature, number, step, operation, component, part, or combination thereof described in the specification, and one or more other features. It is to be understood that the present invention does not exclude the possibility of the presence or the addition of numbers, steps, operations, components, components, or a combination thereof.
Terms such as first and second may be used to describe various components, but the components should not be limited by the terms. The terms are used only for the purpose of distinguishing one component from another.
The present invention relates to a cutting and chipping inhibitor for rubber, and more particularly to a cutting and chipping inhibitor for rubber including a rosin derivative, wherein the rosin derivative is a dibasic acid in rosin. And / or obtained by reacting by adding the anhydride thereof.
In the present invention, the rosin derivative is produced by synthesizing a rosin (rosin), which is a natural resin obtained by distilling rosin, and an additive, and the rosin derivative is a synthetic reaction of rosin, dibasic acid, and / or anhydride thereof. Any product can be used as long as it is produced. Preferably, it may be a rosin derivative represented by the following chemical structure.
Chemical structure
In general, rosin is a natural compound extracted from pine, and is an unsaturated cyclo compound having one carboxyl group, and is mainly an emulsifier for producing ABS (Acrylonitrile Butadiene styrene Copolymer) resin and other point and adhesive ester resins, and rosin modification for ink. It is used as a raw material for resins and paper industry. Particularly, in the present invention, the rosin has a property of imparting a softening effect to rubber, thereby improving the flexibility of the rubber product, and the rosin derivative of the present invention derived from the rosin imparts viscosity and adhesive effect to rubber, Contributes to make up for the lack of cutting and chipping performance. In addition, the rosin derivative does not contain PHAs (polycyclic aromatic hydrocarbons), which are environmentally harmful substances and are carcinogenic, which are harmless to the human body, and thus the rubber cutting and chipping prevention agent of the present invention including the rosin derivative is harmless to the human body. It has an environmentally friendly advantage.
In the present invention, the additive reacting with the rosin is not particularly limited as long as it is a dibasic acid and / or its anhydride, but the human-friendly rubber cutting and cutting body having the desired cutting resistance chipping performance In order to synthesize the chipping inhibitor, it is preferable to use any one or more selected from the group consisting of oxalic acid, succinic acid, citric acid and anhydrides thereof, and to synthesize a rosin derivative having the best anti-cutting chipping performance. An additive that can minimize the loss of reactants at high temperatures during the reaction process is succinic anhydride.
In addition, the present invention relates to a rubber product comprising the above-mentioned rosin derivative and the anti-cutting and chipping agent for rubber, wherein the rubber product includes all or part of the rubber, such as rubber tires, rubber hoses, sneakers as a material Products are all inclusive concepts. Rubber products comprising the cutting and chipping inhibitors for rubber of the present invention as additives have improved cutting resistance and chipping resistance compared to existing products, while maintaining the same or higher mechanical properties than conventional rubber products, and at the same time environmentally harmful substances In addition, by using a cutting and chipping prevention agent containing a rosin derivative that does not contain PHAs, which is a carcinogen, is harmful to the human body and has an environmentally friendly effect.
In addition, another aspect of the present invention relates to a method for producing a cutting and chipping inhibitor for rubber, the reaction preparation step of raising the temperature after the rosin is added to the reactor and the reaction by adding a dibasic acid and / or its anhydride to the reactor A reaction step to produce the product.
In the preparation method according to the present invention, the reaction preparation step is a ring-opening reaction with the additive to be added after the first rosin in the reaction tank prior to reacting the rosin and the dibasic acid and / or anhydride thereof is an additive In order to increase the temperature, the temperature range for raising the temperature is not particularly limited, but it is preferable to increase the temperature to 160 ° C to 200 ° C, and most preferably to 180 ° C. This is a problem that rosin does not react well with rosin and dibasic acid and / or its anhydride when the temperature is raised to less than 160 ℃ after the addition of rosin in the reaction tank, the temperature is raised to a temperature above 200 ℃ This is because a considerable amount of dibasic acid and / or its anhydride vaporizes and disappears before the reaction is too high and a sufficient reaction occurs, and thus the desired reaction result cannot be obtained.
In the production method according to the present invention, the reaction step is a step of adding a dibasic acid and / or an anhydride thereof to the reaction tank, ring-opening reaction with a rosin already added to the elevated temperature treatment to produce a rosin derivative as a product, the two base It is preferable to add the acid and / or its anhydride to the reactor and then react with stirring for 3 to 5 hours. This is because if the reaction is performed for less than 3 hours after the addition of the additive in the reaction step, the reaction time is too short under the reaction conditions of the elevated temperature range, so that the synthesis reaction between the rosin and the dibasic acid and / or its anhydride as additives sufficiently occurs. In addition, some of the reactants remain in the unreacted state, resulting in a poor yield of rosin derivatives. On the contrary, when the reaction product is reacted for more than 5 hours, the reaction time is too long, and some of the already produced products are returned back to the reactants. This is because there is a problem that the production yield of rosin derivative is lowered .
In the reaction step, the synthesis reaction should be carried out in a state well maintained in a closed state (close) state, it is preferable that the stirring while maintaining the stirring speed 200 to 300rpm until the reaction process is completed.
In addition, the addition amount of the dibasic acid and / or its anhydride in the reaction step is not particularly limited, but is preferably 5 to 20 parts by weight relative to 100 parts by weight of rosin. If the amount of the dibasic acid and / or its anhydride is less than 5 parts by weight relative to 100 parts by weight of rosin, deterioration of physical properties is a problem, and the amount of the dibasic acid and / or its anhydride added is 20 parts by weight relative to 100 parts by weight of rosin. This is because when the part is exceeded, the viscosity of the product becomes excessively high, which causes a problem of remarkably deteriorating workability .
In addition, in the reaction step, it is preferable to use any one or more selected from the group consisting of oxalic acid, succinic acid, citric acid and anhydrides thereof as the dibasic acid and / or its anhydride. It is most preferable to use succinic anhydride in order to maximize chipping complementary performance and to minimize the loss of reactants at high temperatures during the synthesis reaction process.
Another aspect of the present invention relates to a cutting and chipping inhibitor for environmentally-friendly rubber produced by the above manufacturing method, and also to a rubber product comprising the cutting and chipping inhibitor for rubber produced by the above manufacturing method as an additive will be. Rubber products manufactured by using the cutting and chipping inhibitors for rubber produced by the above manufacturing method as additives have improved cutting resistance and chipping resistance compared to existing products while maintaining the same or higher mechanical properties than conventional rubber products. At the same time, by using a cutting and chipping prevention agent including a rosin derivative which is an environmentally harmful substance and does not contain PHAs which are carcinogenic substances, it is harmless to the human body and has an environmentally friendly effect.
Hereinafter will be described through examples to help understand the present invention. The following examples are only examples for describing the present invention, and the scope of the present invention is not limited thereto.
<Example>
Example 1 Cutting and Anti-Chipping Agent-1
50 g of rosin was added to the reactor and heated up to 180 ° C., and then 5 parts by weight of succinic anhydride was added to the reactor for 4 hours.
After 4 hours, the acid value of the product in the reaction vessel was measured, and a rosin derivative as a product was taken out to prepare a cutting and chipping inhibitor. As a result of measuring the acid value, the numerical value was about 220 mgKOH / g, and it was confirmed that there was almost no loss due to vaporization of succinic anhydride during the synthesis reaction at high temperature.
Example 2 Cutting and Anti-Chipping Agent-2
A cutting and chipping inhibitor was prepared in the same manner as in Example 1, except that 10 parts by weight of succinic anhydride was added to 100 parts by weight of rosin. As a result of measuring the acid value of the product, it showed a value of about 220 mgKOH / g, and it was confirmed that there was almost no loss due to vaporization of succinic anhydride during the synthesis reaction at high temperature.
Example 3: Cutting and Anti-Chipping-3
A cutting and chipping inhibitor was prepared in the same manner as in Example 1 except adding 15 parts by weight of succinic anhydride to 100 parts by weight of rosin. As a result of measuring the acid value of the product, it showed a value of about 220 mgKOH / g, and it was confirmed that there was almost no loss due to vaporization of succinic anhydride during the synthesis reaction at high temperature.
Examples 4-6: Rubber products containing the cutting and chipping inhibitors of Examples 1-3
Using the cutting and chipping inhibitors prepared in Examples 1 to 3 as an additive, the composition is shown in Table 1 below, put in a Banbury mixer, and blended at 140 ° C. to prepare an unvulcanized rubber compound (CMB). To the unvulcanized rubber compound, 0.8 wt% of sulfur and 0.7 wt% of a vulcanization accelerator (N-cyclohexyl-2-benzothiazol sulfonamide (CZ)) were added (FMB) and vulcanized at 160 ° C. for 25 minutes to provide rubber specimens (Examples 4 to 6). Was prepared.
Comparative Example: Existing Rubber Products
After using the cutting and chipping preventive agents prepared in Examples 1 to 3 as an additive, and blended in the composition shown in Table 1, put in a Banbury mixer and blended at 140 ℃ to prepare a unvulcanized rubber compound (CMB), 0.8 wt% of sulfur and 0.7 wt% of a vulcanization accelerator (CZ) were added to the unvulcanized rubber compound (FMB) and vulcanized at 160 ° C. for 25 minutes to prepare a rubber specimen (comparative example).
(Existing product)
CMB
Furtherance
Furtherance
In Table 1, the abbreviations or symbols of the alphabet are conventionally used by those skilled in the art to which the present invention belongs, and the components indicated by each are as follows.
NR: Natural Rubber
SBR: styrene-butadiene synthetic rubber (styrene-butadiene-rubber)
C / B: Carbon Black
P-90: Plasticizer
A-2 (RAE): Process oil
Experimental Example
For rubber specimens prepared in Examples 4 to 6 and Comparative Examples, hardness, modulus (100%, 300%), tensile strength, elongation and tear resistance (according to ASTM) Tear resistance) was measured, and the results are shown in Table 2 below.
Hardness
(ShoreA law)
burglar
(kg / cm 2 )
Elongation
(%)
Tear resistance
(Existing product)
According to Table 2, Examples 4 to 6, which are rubber specimens prepared according to an example of the present invention, have physical properties equivalent to or higher than those of the comparative example, which is an existing product, and more excellent cutting resistance and chipping resistance than the comparative example, which is an existing product. It can be confirmed that excellent.
As described above, those skilled in the art will understand that the present invention can be implemented in other specific forms without changing the technical spirit or essential features. The scope of the present invention is shown by the claims to be described later rather than the detailed description, and all changes or modifications derived from the meaning and scope of the claims and their equivalent concepts are included in the scope of the present invention. Should be.
Claims (13)
The rosin derivative is a rubber cutting and chipping inhibitor obtained by reacting rosin by adding 5 to 20 parts by weight of succinic anhydride to 100 parts by weight of rosin.
The reaction step of adding a succinic anhydride to 5 to 20 parts by weight relative to 100 parts by weight of rosin in the reaction tank and then reacting while stirring for 3 to 5 hours to produce a reaction product.
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| KR1020150098558A KR102040268B1 (en) | 2015-07-10 | 2015-07-10 | Anti-cutting and anti-chipping agent for rubber and preparation method thereof |
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| KR1020150098558A KR102040268B1 (en) | 2015-07-10 | 2015-07-10 | Anti-cutting and anti-chipping agent for rubber and preparation method thereof |
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| KR102040268B1 true KR102040268B1 (en) | 2019-11-04 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR100846359B1 (en) | 2007-04-27 | 2008-07-15 | 금호타이어 주식회사 | Rubber compound for tire improved wear and cut/chip property |
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| KR100583417B1 (en) * | 2004-08-16 | 2006-05-25 | 한국신발피혁연구소 | Shoe sole composition containing recycled rubber |
| KR101862723B1 (en) * | 2010-09-24 | 2018-05-30 | 아라까와 가가꾸 고교 가부시끼가이샤 | Rosin based flux for solder paste |
| EP2697322A4 (en) * | 2011-04-11 | 2015-08-05 | Arizona Chemical Co Llc | Rosin esters for non-wovens |
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| KR100846359B1 (en) | 2007-04-27 | 2008-07-15 | 금호타이어 주식회사 | Rubber compound for tire improved wear and cut/chip property |
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