• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    Composition of improved curable bicomponent silicone elastomer. The invention relates to a bicomponent silicone elastomer composition curable at high temperature and room temperature, where the silicone is polydimethylsiloxane of high consistency, consisting of two components, A and B, in a ratio substantially close to 1: 1, where The bicomponent silicone elastomer composition has a Mooney viscosity before curing comprised between 15 and 75 mPa s, and a Shore hardness after curing comprised between 10 and 80 Sh A. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2685266A1
    申请号:ES201700494
    申请日:2017-03-31
    公开日:2018-10-08
    发明作者:Xabier LARRAÑAGA GARMENDIA；Juan Antonio GARATE ALDAZ
    申请人:Siliconas Silam S A；Siliconas Silam SA；
    IPC主号:
    专利说明:

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    COMPOSITION OF BICOMPONENT SILICONE ELASTOMER
    CURABLE IMPROVED
    The present invention relates to a new two-component high consistency silicone elastomer composition, curable both at high temperature, at room temperature and by electromagnetic waves. It can be used for various purposes, either for the personalization of the form of products for domestic recreational use as a teacher such as modeling clay, as for the obtaining of industrial or artistic products such as molds for duplicating objects, for jewelry, arts & Crafts .
    Background of the invention
    In the state of the art, curable silicone compositions are known at room temperature to allow users to adapt or customize the shape of the final products.
    Thus, ES2389759 discloses a silicone composition curable at room temperature with ambient humidity within 24 hours, comprising polydimethylsiloxane, pyrogenic silica treated with silane, magnesium silicate, a hydrolysable silane crosslinker and an amount of a curing catalyst, preferably a compound of tin such as dibutyltin dilaurate. It is a composition of a surface curable product, so that under this cured surface, the composition is still moldable and the user can continue modeling the product. However, in order to avoid curing, the moldable product must be packaged in an airtight and vacuum container and, therefore, all product that has not been properly packaged is wasted.
    Patent CN101671482 describes a bicomponent silicone of room temperature curing for the manufacture of manual modeling toys. The bicomponent silicone is formed by a putty component and a catalyst component, where the ratio between both components is 1: 1, and the putty component comprises methyl vinyl silicone oil, a crosslinking agent for methyl vinyl silicone, an inhibitor, microspheres of low density, hydrogen sequestering agent, mold release agent, a plasticizer and a filling agent; and the catalyst component comprises silica gel, a compound
    coordination complex of methyl vinyl siloxane and platinum, low density microspheres, a
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    mold release agent, a plasticizer and a filling agent. The inhibitor is a low molecular weight liquid of the siloxane type. However, the material disclosed in CN101671482 does not contemplate high temperature cure.
    On the other hand, thermoplastic materials have also been described that require high temperatures for curing, by hot air or hot water, where the curing takes place by evaporation of the solvent. For example, US5431563 and US5536544 disclose compositions that require the use of heat to allow the materials used to be moldable and / or curable.
    WO201425078 discloses a clay composition for modeling, which is curable with hot air. The modeling clay composition is prepared by mixing together a base silicone in a gelled state that is formed by mixing siloxane, silicone, vinyl finished group, methyl vinyl, dimethyl, a plasticity regulator made of a silica-based powder material to regulate hardness, an oily anti-caking agent made of a polydimethylsiloxane material to prevent agglomerate, an antimicrobial agent, and a platinum curing agent.
    The existence of three types of technologies for curing or vulcanizing silicones is part of the general knowledge of a person skilled in the art: hot cross-linking, cross-linking at room temperature, or UV radiation curing. Hot crosslinking, in general, is carried out by peroxides that generate free radicals with a first stage of mold consolidation at approximately 125 ° C, followed by a second post-curing stage for the removal of peroxides, water and small molecules originated, or by means of polysiloxane oligomer hardeners with hydride side group + Pt catalyst, where the reaction takes place in approximately 10-20 seconds at 175-190 ° C and in which the speed can be regulated with the presence of inhibitors or retarders In the composition. Cross-linking at room temperature in general is carried out by means of a condensation mechanism that is initiated by water vapor. And finally, by curing by UV radiation, limited to pieces of small thickness but that does not need temperature, nor humidity of the environment.
    The problem, in view of the state of the art, is how to provide a silicone elastomer composition that possesses the double property of room temperature curing and high temperature curing, in which the room temperature curing time
    It is also long enough for a user to customize the
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    One-piece modeling, providing the versatility of curing a modeling product with improved properties that make it versatile for different applications.
    Description of the invention
    With the improved two-component silicone elastomer composition of the invention, the aforementioned drawbacks are resolved, presenting other advantages that will be described below.
    To overcome the drawbacks of the state of the art, a curable two-component silicone elastomer composition is provided at high temperature and room temperature, where the silicone is high consistency polydimethylsiloxane, which is characterized by the fact that said composition consists of two components, A and B, present in a ratio substantially close to 1: 1 and each comprise the following ingredients:
    - component A formed by 40-85% polydimethylsiloxane elastomer, pyrogenic silica and / or 10-30% precipitated silica reinforcing filler, methyl hydrogen hydrogen curing catalyst and 0.5-10% hydrogen trapping agents where the percentages are expressed in weight with respect to the weight of component A, with the proviso that the sum of all components does not exceed 100%, and
    - component B formed by 40-85% polydimethylsiloxane elastomer, reinforcing filler pyrogenic silica and / or 10-30% precipitated silica, platinum curing agent: 1-8% and pigments: up to 5%, where the percentages are expressed in weight with respect to the weight of component B, provided that the sum of all components does not exceed 100%,
    where the two-component silicone elastomer composition has a Mooney viscosity before curing between 15 and 75 mPa s, and a Shore hardness after curing between 10 and 80 Sh A.
    The silicone is high consistency polydimethylsiloxane.
    Advantageously, the bicomponent silicone elastomer composition of the invention has the triple functionality of curing at high temperature, at room temperature, and by
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    Electromagnetic radiation being the transformation of 100% of the composition to elastic phase, which makes it a very useful silicone elastomer composition with a wide spectrum of applications.
    Curing or vulcanizing is activated when the two components are combined in a proportion substantially equal to 1: 1 (50%). The curing or vulcanization mode has been defined so that it is neither too fast, nor too slow, thus allowing a user enough time to model the two-component silicone composition, after mixing the two components A and B.
    Advantageously, the modeling time by the user can be several hours, said time being able to be adjusted, the percentages of catalyst in component A and the percentages of platinum curing agent in component B being modified in the composition. of catalyst and higher percentage of curing agent less curing time after mixing the two components A and B of the inventive composition of the invention.
    The authors of the present invention have found that in order to obtain the inventive composition of the invention both components A and B must contain the same ingredients with the exception of the catalyst and the curing agent, the pigments being able to incorporate together the component carrying the catalyst or to the component that carries the platinum curing agent.
    Component B comprises pigments in order to provide final products, parts or objects of various colors.
    In a preferred embodiment, the inventive composition of the invention consists of two components, A and B, in a ratio substantially close to 1: 1 and each of them comprises the following ingredients: component A is formed by 50- polydimethylsiloxane elastomer 80%, reinforcing charge pyrogenic silica and / or precipitated silica 15-25%, methyl hydrogen hydrogen curing catalyst and hydrogen sequestering or sequestering agents 1-5%, where the percentages are expressed by weight with respect to the weight of component A, with the proviso that the sum of all components does not exceed 100%, and component B is formed by 50-80% polydimethylsiloxane elastomer, pyrogenic silica reinforcing filler and / or 15-25% precipitated silica, curing agent Platinum: 1-5% and
    pigments: up to 5%, where the percentages are expressed in weight with respect to the
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    weight of component B, with the proviso that the sum of all components does not exceed 100%.
    In the present invention, a ratio between components A and B substantially close to 1: 1 includes a ratio between 0.8: 1.2 and 1.2: 0.8, preferably between 0.9: 1.1 and 1.1: 0.9, more preferably 1: 1.
    Component A of the composition is transparent.
    Component B of the composition is colored by the presence of pigments, although it can also be transparent if no pigment is incorporated.
    Component A, component B, and the bicomponent composition A + B before curing, that is, in its plastic phase, have a Williams plasticity, measured according to ASTM D926, between 100 and 800 mm.
    Component A, component B, and the bicomponent composition A + B before curing, that is, in its plastic phase, have a Mooney viscosity, measured according to DIN 53523/23 ° C, between 15 and 75 mPa s.
    In one embodiment, the two-component silicone elastomer composition is modelable at room temperature over a period of 5 hours. Curing materializes within 24-48 hours, depending on the size of the piece.
    In another alternative embodiment, the two-component silicone elastomer composition is curable in hot air or by electromagnetic radiation. The temperature of a conventional oven is suitable for curing in hot air, the usual temperature range being between 150 and 300 ° C, and the use of a conventional domestic microwave for curing by electromagnetic radiation, the power being between 500 and 2000 W. In these embodiments, the higher the power, the shorter the cure time and the higher the temperature, the lower the cure time.
    In another aspect, the invention relates to a modelable product obtained with the inventive composition of the invention. Advantageously, said product withstands extreme temperatures, which include temperatures between -40 and + 250 ° C
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    In another aspect, the modeling product obtained after curing stands out for being inert. It has excellent resistance to weathering and atmospheric agents (ozone, UV, salinity, humidity, etc.), making it an ideal product for external use applications.
    In another aspect, also highlight its atoxicity. It is well known that silicones, due to their characteristics, are used to manufacture products for food contact, for pharmaceutical, medical applications ... Our product, due to its silicone composition, is also a non-toxic material. It complies with the requirements and regulations that apply to the toy sector (DIN EN-71 Standard), making it an ideal product for recreational and / or teaching use.
    The modeling product obtained after curing has Shore hardness between 10 and 80 Sh A. For the determination of hardness, DIN 53505-A / 23 ° C / on 6mm thick specimens has been used.
    The invention also relates to the use of the inventive composition of the invention to obtain a mold to duplicate a product. With the mold obtained figures can be reproduced with different types of materials such as plaster, ice, polymer clay, wax, soap, resin, among others. It is even valid for use with low melting metals such as lead, zamak or pewter usually used in jewelry. Therefore, the invention also provides a finished product, after curing, resistant to high temperatures, this property not depending on the curing technique, that is, if the modeled product has been cured at room temperature, high temperature or by waves electromagnetic
    Advantageously, the inventive composition of the invention has good adhesive properties to other materials, especially porous materials such as plaster, wood, clays, etc.
    The invention also relates to a process for obtaining a moldable product, in which the inventive composition of the invention is mixed and modeled under ambient conditions, having a modeling time of up to 5 hours, in which the curing materializes in 24-48 hours at room temperature, depending on the size of the piece and in hot air or electromagnetic radiation in a matter of minutes depending on the temperature and the power and size of the piece, respectively.
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    The 100% transformation to the elastic phase (curing) will depend on the size of the piece or object modeled. It can be done in a period of 24-48 hours at room temperature and in a matter of minutes in a microwave or oven with hot air.
    Advantageously, the bicomponent silicone elastomer composition of the invention has the versatility of facilitating the modeling of the product, the part or object, for a period of up to 5 hours, being able, if desired, to accelerate curing at the time the user You have finished modeling the part or object by using hot air in a conventional oven or by using electromagnetic radiation in a conventional microwave. Alternatively, the part or object cures at room temperature in a period between 24-48 hours
    The bicomponent silicone composition of the invention has the following advantages over existing products in the state of the art:
    With respect to plasticine: the inventive composition of the invention can be molded in the same way, and the resulting product is elastic and durable, unlike plasticine. The inventive composition has a greater range of colors, even transparent.
    If preferred, it is also possible to use the product without curing or vulcanization being activated, using only component B (and its color variants). In this way the product does not vulcanize and its use resembles conventional plasticine. But with the advantage that it stains less, it does not harden or dry out, like conventional plasticine.
    Regarding polymer clay drying at room temperature:
    • Easier to model, it does not collapse unlike polymeric clays drying at room temperature;
    • It has a wider range of colors, more vivid, with the possibility of obtaining the transparent color;
    • Expiration: the inventive composition of the invention has a longer expiration period, since in contact with the air it does not dry out;
    • The inventive composition of the invention after vulcanization has superior elastic properties;
    • The inventive composition of the invention is inert. Do not get rid of contact with the
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    water, unlike polymeric clays drying at room temperature.
    Regarding high temperature drying polymer clay:
    • The inventive composition of the invention after vulcanization is elastic, unlike air-dried polymer clay that is rigid (non-elastic).
    Regarding clay, plaster, porcelain:
    • The inventive composition of the invention after vulcanization is elastic, this type of materials is not.
    Regarding silicones bicomponetes to manufacture molds:
    • Bicomponent silicones to make molds have a very limited modeling time (they vulcanize very quickly) which does not allow to create figures. With the inventive composition of the invention figures can be created, in addition to being used to make molds;
    Brief description of the figures
    For a better understanding of how much has been exposed, some figures are attached in which, schematically and only by way of non-limiting example, a practical case of embodiment is represented.
    Figure 1 shows four photographs (a-d) of different custom created products obtained with the inventive composition of the invention.
    Figure 2 shows a mold obtained with the inventive composition of the invention with the product duplicated with this mold.
    Figure 3 shows a bicycle handlebar protector obtained with the inventive composition of the invention.
    Figure 4 shows a plaster object glued using the inventive composition of the invention.
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    Example 1: Preparation of the two component silicone elastomer composition Component A: 1 kg
    Silicone elastomer (polydimethylsiloxane): 80%
    Pyrogenic silica reinforcing load: 15%
    Curing catalyst methyl hydrogen and hydrogen scavenging agents: 5%
    Component B: 1,200 kg, divided into several colors:
    Red color: 200 grams
    Silicone elastomer (polydimethylsiloxane): 80%
    Pyrogenic silica reinforcing load: 15%
    Platinum curing agent: 4%
    Red Pigment: 1%
    Yellow color: 200 grams
    Silicone elastomer (polydimethylsiloxane): 80%
    Pyrogenic silica reinforcing load: 15%
    Platinum curing agent: 4%
    Yellow Pigment: 1%
    Blue color: 200 grams
    Silicone elastomer (polydimethylsiloxane): 80%
    Pyrogenic silica reinforcing load: 15%
    Platinum curing agent: 4%
    Blue Pigment: 1%
    Transparent color: 200 grams
    Silicone elastomer (polydimethylsiloxane): 80%
    Pyrogenic silica reinforcing load: 15%
    Platinum curing agent: 4%
    White color: 200 grams
    Silicone elastomer (polydimethylsiloxane): 80%
    Pyrogenic silica reinforcing load: 15%
    Platinum curing agent: 4%
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    White Pigment: 1%
    Black color: 200 grams
    Silicone elastomer (polydimethylsiloxane): 80%
    Pyrogenic silica reinforcing load: 15%
    Platinum curing agent: 4%
    Black Pigment: 1%
    Example 2: Shawn sheep figure making
    First, you work with the different colors available in component B. The base colors are combined and mixed, since with these base colors (yellow, red and blue) in addition to white, black and transparent you can achieve a wide range of colors. Mixing in different proportions the different colors that make up the pieces are obtained: yellow, green, orange, gray .... etc. Adding the white and / or black color adjusts the final hue of the colors obtained.
    We already have all the necessary colors of component B (with each color a sphere has been formed). Next, each sphere of each color of component B is mixed with the same amount of component A (1: 1), the latter of transparent color, until a uniform color is obtained. As a result, spheres twice the size of each color are obtained. The quantity ratio of component A and B to be mixed has to be approximately 1: 1 but it does not need to be exact. No exact measurement is needed on a scale. Mixing two spheres of a similar size (measured by eye) is enough.
    Using these spheres of each color (A + B) it is time to start modeling the figures (see Fig. 1).
    The silicone composition of the invention is easily modeled. It does not collapse, it does not stain, it does not smell. Colored silicones stick together, and can even be easily peeled off, which makes it easier to correct modeling errors.
    Once the figures are created, proceed to cure. In this case the curing of the figures occurred in a microwave oven, at a power of 800 W and the curing was performed in about 10 minutes.
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    Example 2: Development of bicycle handlebar protector
    Component B (Blue) + Component A (transparent): two portions of approximately the same size of each component are taken, and mixed with the hands. Once the mixture has been homogenized (blue color), it is modeled. Churros of similar diameter are modeled, and spirally placed on the handlebars of the bicycle. Once the entire handlebar is covered with silicone, the silicone is allowed to cure on the handlebar at room temperature. Within 24-36 hours the silicone is already cured (see Fig. 3).
    Example 3: Mold making with the silicone composition of the invention Component B (transparent) + component A (transparent): two portions of approximately the same size of each component are taken, and mixed with the hands. Once the mixture has been homogenized (transparent color), the figure to be copied is modeled and embedded. In this way the cavity is created, or negative in the silicone composition of the invention. In this case, the figure is a plastic crab. It is allowed to cure at room temperature. Within a period of 24 to 36 hours the silicone composition of the invention is already cured, and the plastic figure is removed. Once the plastic figure has been removed, the mold ready for use with an infinity of products (soaps, wax, polymer clay, etc ...) is created (see Fig. 2).
    Although reference has been made to a specific embodiment of the invention, it is apparent to one skilled in the art that the inventive composition of the described invention is susceptible to minor variations and modifications, and that all the mentioned details can be replaced by others technically equivalent, without departing from the scope of protection defined by the appended claims.
    权利要求:
    Claims (11)
    [1]
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    1. Composition of two-component silicone elastomer of high consistency curable at high temperature, at room temperature or by electromagnetic radiation, where the silicone is high consistency polydimethylsiloxane, characterized by the fact that said composition consisting of two components, A and B , present in a ratio substantially close to 1: 1 and each comprise the following ingredients:
    - component A formed by 40-85% polydimethylsiloxane elastomer, pyrogenic silica and / or 10-30% precipitated silica reinforcing filler, methyl hydrogen hydrogen curing catalyst and 0.5-10% hydrogen trapping agents where the percentages are expressed in weight with respect to the weight of component A, with the proviso that the sum of all components does not exceed 100%, and
    - component B formed by 40-85% polydimethylsiloxane elastomer, reinforcing filler pyrogenic silica and / or 10-30% precipitated silica, platinum curing agent: 1-8% and pigments: up to 5%, where the percentages are expressed in weight with respect to the weight of component B, provided that the sum of all components does not exceed 100%,
    where the two-component silicone elastomer composition has a Mooney viscosity before curing between 15 and 75 mPa s, and a Shore hardness after curing between 10 and 80 Sh A.
    [2]
    2. Composition according to claim 1, wherein component A is formed by 50-80% polydimethylsiloxane elastomer, pyrogenic silica reinforcing filler and / or 15-25% precipitated silica, methyl hydrogen hydrogen curing catalyst and hydrogen scavenging agents 1- 5% where the percentages are expressed by weight with respect to the weight of component A, with the proviso that the sum of all components does not exceed 100%, and component B is formed by 50-80% polydimethylsiloxane elastomer, load Pyrogenic silica reinforcer and / or precipitated silica 15-25%, platinum curing agent: 1-5% and pigments: up to 5%, where the percentages are expressed by weight with respect to the weight of component B, with the proviso that The sum of all components does not exceed 100%.
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    [3]
    3. Composition according to any of the preceding claims, wherein the ratio between the two components, A and B, is 0.8: 1.2 to 1.2: 0.8, preferably 1: 1.
    [4]
    4. Composition according to any of the preceding claims 1, wherein component A is transparent.
    [5]
    5. Composition according to any of the preceding claims, wherein the
    Component B is colored by the presence of pigments, but that is transparent without the presence of pigments.
    [6]
    6. Composition according to any of the preceding claims, wherein the
    Two-component silicone elastomer composition is modelable at room temperature over a period of up to 5 hours, and vulcanizes within 2448 hours, depending on the size of the piece.
    [7]
    7. Composition according to any of the preceding claims, wherein the
    Two component silicone elastomer composition is curable in hot air or electromagnetic radiation.
    [8]
    8. Model product obtained with a composition according to any of the
    previous claims.
    [9]
    9. Product according to claim 8 that withstands extreme temperatures, including temperatures between -40 and + 250 ° C.
    [10]
    10. Use of the composition according to any of the preceding claims to obtain a mold to duplicate a product.
    [11]
    11. Method for obtaining a moldable product, wherein the composition according to any one of claims 1 to 7 is mixed and modeled under ambient conditions, and can be modeled in a period of up to 5 hours that cures at room temperature over a period of time between 24-48 hours, depending on the size of the piece, and in hot air or electromagnetic radiation in minutes.
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    同族专利:
    公开号 | 公开日
    WO2018178451A1|2018-10-04|
    ES2685266B1|2019-05-10|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US5977243A|1995-12-05|1999-11-02|Wacker-Chemie Gmbh|Organosilicon compounds, processes for their preparation, and their use in crosslinkable organopolysiloxane compositions|
    US5919884A|1996-07-17|1999-07-06|Wacker-Chemie Gmbh|Liquid silicon rubber with low compression set|
    ES2241062T3|1996-12-19|2005-10-16|Dentsply International, Inc.|IMPROVED MATERIAL OF IMPROVED POLIVINILSILOXANO.|
    EP1152729A1|1999-02-18|2001-11-14|Kerr Corporation|Hydrophilically modified curable silicone impression material|
    法律状态:
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    优先权:
    申请号 | 申请日 | 专利标题
    ES201700494A|ES2685266B1|2017-03-31|2017-03-31|Composition of improved curable bicomponent silicone elastomer|ES201700494A| ES2685266B1|2017-03-31|2017-03-31|Composition of improved curable bicomponent silicone elastomer|
    PCT/ES2018/070228| WO2018178451A1|2017-03-31|2018-03-23|Two-part silicone elastomer composition for modelling|
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