JP5209343B2 - Thermoplastic elastomer product and production method thereof - Google Patents

Description

  The present invention relates to a thermoplastic elastomer product and a method for producing the same, and more particularly to a thermoplastic elastomer product used for hoses, tanks and the like of automobiles and the method for producing the same.

  Conventionally, products that require elastomeric properties (such as hoses) have been commercialized by using synthetic rubber and vulcanizing it. However, this vulcanization process requires a large amount of heat, and there are concerns about adverse environmental effects such as the generation of carbon dioxide. Moreover, since a large amount of carbon dioxide is generated during the synthesis of the synthetic rubber, there is a concern about the environmental load. On the other hand, since the resin material softens at a high temperature, there is an advantage that a vulcanization step is not required at the time of molding, but there is a problem that it is inferior to a rubber material in terms of flexibility and heat resistance. is there. Therefore, thermoplastic elastomers (a blend of rubber and resin) have been developed to achieve both rubber and resin properties. Since this thermoplastic elastomer exhibits elastomeric properties at room temperature (use temperature) and the resin melts and exhibits resin properties (thermoplasticity) at high temperatures, a vulcanization step is unnecessary. However, commercially available thermoplastic elastomers usually use petroleum rubber or resin material, and the problem of generating a large amount of carbon dioxide in the synthesis of raw materials has not been solved.

In recent years, an increase in greenhouse gases on a global scale and soaring crude oil prices have become very serious problems. In order to cope with these, resin derived from vegetable oil (for example, polylactic acid resin) is used in place of the petroleum resin. For example, there has been proposed a vibration damping thermoplastic resin composition obtained by kneading a vibration damping imparting agent composition comprising a base polymer such as acrylic rubber, a phenolic compound, and a filler in a thermoplastic resin matrix. (Patent Document 1). And this patent document 1 describes using the mixture of an acrylic rubber and a polylactic acid resin as said base polymer.
JP 2007-238867 A

  However, by simply blending acrylic rubber and polylactic acid resin, if the ratio of acrylic rubber increases, acrylic rubber with a higher ratio becomes a matrix (sea phase), and polylactic acid resin with a lower ratio becomes an island phase. The volume change rate with respect to the fuel (for example, FUEL C) is increased, and the fuel permeability resistance is inferior. In addition, there is a drawback that rubber elasticity is poor due to non-crosslinking. Thus, the thing of the said cited reference 1 has the difficulty that the use as a flexible elastomer is difficult and it is inferior to the elastomer characteristic at normal temperature.

  The present invention has been made in view of such circumstances, and an object thereof is to provide a thermoplastic elastomer product excellent in elastomer characteristics at room temperature and a method for producing the same.

To achieve the above object, the present invention contains (A) ~ (C) the following components, said component (A) in the thermoplastic elastomer products obtained by dynamic crosslinking the above component (C) The weight mixing ratio of the component (A) to the component (B) is in the range of component (A) / component (B) = 55/45 to 95/5, and is the minor component (B). A thermoplastic elastomer product in which the island phase of the component (A), which is the above-mentioned large amount of the crosslinked component, is dispersed in a sea phase composed of a melt of the components is a first gist.
(A) Acrylic rubber.
(B) polylactic acid.
(C) At least one crosslinking agent component selected from the group consisting of zinc dimethyldithiocarbamate, ferric dimethyldithiocarbamate, N-phenyl-N- (trichloromethyl-sulfenyl) benzenesulfonamide, and derivatives thereof.

Moreover, this invention contains the following (A)-(C) component, and the weight mixing ratio of the said (A) component and (B) component is (A) component / (B) component = 55/45. In the thermoplastic elastomer composition in the range of ˜95 / 5, by dynamically crosslinking the component (A) with the component (C), a sea phase comprising a melt of the component (B) which is the minor component The second gist is a method for producing a thermoplastic elastomer product in which the island phase of the component (A), which is a large amount of the crosslinked component, is dispersed therein.
(A) Acrylic rubber.
(B) polylactic acid.
(C) zinc dimethyldithiocarbamate, ferric di-methyl dithiocarbamate, N- phenyl -N- (trichloromethyl - sulfenyl) benzenesulfonamide and at least one cross-linking agent component thereof selected from the induction member or Ranaru group .

That is, the present inventors have made extensive studies in order to obtain a thermoplastic elastomer product having excellent elastomer characteristics at room temperature. In general, when a thermoplastic elastomer is obtained by blending rubber and resin, if the rubber and resin are simply blended, the structure of the sea-island phase depends on the addition ratio, so the higher the addition ratio, the sea phase (matrix) Thus, the lower addition ratio becomes the island phase (dispersed phase). Conventional thermoplastic elastomers have obtained resin characteristics (thermoplasticity) by using a resin as a sea phase by increasing the resin addition ratio. However, since the ratio of rubber is low, compared to the rubber alone Elastomer properties are inferior. Therefore, in order to improve the elastomer characteristics, it is necessary to increase the ratio of rubber. However, since the rubber becomes a sea phase, it becomes difficult to obtain resin characteristics (thermoplasticity). To solve this contradictory problem, the present inventors have found that preferred combinations of rubber and resin, the results of extensive studies for both the blend ratio and the like, acrylic rubber (A component), polylactic acid (B component) Recalling that acrylic rubber (component A) having a weight mixing ratio of (A component) / (B component) = 55/45 to 95/5 is crosslinked (dynamically crosslinked). did. According to this, contrary to the common general knowledge, the addition ratio is low Ipoh polylactic acid (B component) is dispersed sea phase (matrix), and the addition ratio is higher acrylic rubber (A component) as the island phase. Therefore, thermoplastic elastomeric products of the present invention, the polylactic acid component (B) with the resin properties (thermoplastic), it is possible to achieve both elastomeric properties by acrylic rubber (A component). The reason for this becomes mass acrylic rubber (A component) by crosslinking (dynamic crosslinking) surrounds to melt around the polylactic acid component (B) consists of a melt of polylactic acid (B component) This is probably because cross-linked acrylic rubber (component A) is dispersed as an island phase in the sea phase (matrix).

Thus, the thermoplastic elastomer products of the present invention, low Ipoh polylactic acid ratio becomes sea phase, since the high acrylic rubber having a ratio is dispersed as an island phase, the high proportion of acrylic rubber, room temperature (use (Temperature) sometimes gives excellent elastomeric properties (flexibility etc.). The thermoplastic elastomer products of the present invention, since the low Ipoh polylactic acid ratio is sea phase (matrix), which has an excellent thermoplastic, fuel (e.g., FUEL C) an increase in the volume change rate for the It is possible to suppress the fuel permeation resistance.

Further, according to the production method of the thermoplastic elastomer products of the present invention, an acrylic rubber, approached the polarity of the polylactic acid, with compatibility therebetween can be improved, since the acrylic rubber has a higher viscosity by dynamic crosslinking, the ratio High acrylic rubber can be dispersed as an island phase. Therefore, it becomes possible to control the morphology and physical properties of the thermoplastic elastomer.

Then, among the fat aliphatic polyester, in particular the polylactic acid has excellent fuel permeation resistance is also excellent in compatibility with the acrylic rubber. Moreover, since the polylactic acid is a biomass material made of corn (raw material), the thermoplastic elastomer product of the present invention using this is an environment-friendly product and can realize an environmentally sustainable society. It becomes like this.

  Next, embodiments of the present invention will be described in detail.

Thermoplastic elastomer products of the present invention contains the acrylic rubber (A component) and polylactic acid (B component), a product obtained by crosslinking the acrylic rubber (A component).

In the present invention, the weight mixing ratio of the acrylic rubber (A component) and polylactic acid (B component) is in the range of (A component) / (B component) = 55 / 45-95 / 5, the The island phase of the component (A), which is the above-mentioned large amount of crosslinked components, is dispersed in the sea phase composed of the melt of the component (B), which is a minor component, and these are the greatest features.

  Examples of the acrylic rubber (component A) include those obtained by polymerizing acrylic acid esters or those obtained by copolymerization (emulsion polymerization or the like) mainly based on acrylic acid esters. Examples of the acrylic ester include methyl acrylate, ethyl acrylate, butyl acrylate, hexyl acrylate, and the like. Examples of the copolymer component include methyl vinyl ketone, acrylic acid, acrylonitrile, butadiene, and butyl methacrylate. For vulcanization of the copolymer, for example, ethyltetramine, tetraethylenepentamine or the like is used. As the crosslinking site, those having an epoxy group are particularly preferred.

Then, in the aliphatic polyester Le used with the acrylic rubber (A component), also in the name or, fuel permeation resistance, because in terms of the environment, the polylactic acid (B component) is excellent, the present invention Then, polylactic acid is used .

  The polylactic acid is a material known as a polyester-based resin obtained by polymerizing lactic acid obtained by fermentation of corn starch or the like. Poly-D-lactic acid, poly-L-lactic acid, or a complex thereof Either can be used. The polylactic acid is excellent in fuel permeability and compatibility with acrylic rubber (component A). Moreover, since the polylactic acid is a biomass material made of corn (raw material), the thermoplastic elastomer product of the present invention using this is an environment-friendly product and can realize an environmentally sustainable society. It becomes like this.

Mixing weight ratio of the acrylic rubber (A component) and polylactic acid (B component), (A component) / (B component) = 55 / 45-95 / 5 in the range of, preferably (A component) / (B component) = 70/30 to 90/10. That is, if the mixing ratio of the acrylic rubber (component A) is less than the lower limit (component B exceeds the upper limit), the component B is very high in rigidity, so that the elastomer characteristics are inferior and the flexibility is inferior. If the mixing ratio of the acrylic rubber (component A) exceeds the upper limit (component B is lower than the lower limit), it does not have thermoplasticity and the fuel permeation resistance deteriorates.

Then, as the A and the crosslinking agent component to be used together with the B component (C component), mixed kneading torque increases, in that proceed more dynamic crosslinking, zinc dimethyl dithiocarbamate, ferric dimethyl dithiocarbamate, N-phenyl-N- (trichloromethyl-sulfenyl) benzenesulfonamide and its derivatives are used, preferably a combination thereof.

  In addition, in this invention, a crosslinking agent component (C component) is a meaning also including a crosslinking accelerator and another component other than a crosslinking agent.

  The amount of the cross-linking agent component (C component) is preferably in the range of 0.1 to 5 parts, particularly preferably 0. It is in the range of 5 to 2.5 parts. That is, if the amount of the cross-linking agent component (C component) is too small, the cross-linking density is lowered and the elastomer properties are deteriorated. Conversely, if the amount of the cross-linking agent component (C component) is too large, the cross-linking density This is because of a tendency to become too high and the flexibility is inferior.

  The thermoplastic elastomer composition used in the present invention requires, for example, an anti-aging agent, process oil, vegetable oil, plasticizer, carbon black, silica, calcium carbonate, clay, etc. in addition to the components A to C described above. Depending on the case, it may be blended appropriately. These may be used alone or in combination of two or more.

  Examples of the anti-aging agent include carbamate-based anti-aging agents, phenylenediamine-based anti-aging agents, phenol-based anti-aging agents, diphenylamine-based anti-aging agents, quinoline-based anti-aging agents, imidazole-based anti-aging agents, and waxes. can give. These may be used alone or in combination of two or more.

  The blending amount of the anti-aging agent is preferably in the range of 1 to 10 parts, particularly preferably in the range of 2 to 5 parts, with respect to 100 parts of the acrylic rubber (component A).

  Examples of the process oil include naphthenic oil, paraffinic oil, and aroma oil. These may be used alone or in combination of two or more.

  The blending amount of the process oil is preferably in the range of 1 to 50 parts, particularly preferably in the range of 3 to 30 parts with respect to 100 parts of the acrylic rubber (component A).

Next, the thermoplastic elastomer product of the present invention can be obtained, for example, as follows. That is, a kneader (mill, mixer, etc.), acrylic rubber (A component), polylactic acid (B component) [e.g., pellets of the polylactic acid] and was charged at a predetermined mixing ratio, the predetermined time period (usually 1 to 60 minutes, preferably about 30 minutes). Next, the crosslinking agent component (component C) is charged into the kneader at a predetermined blending ratio, and kneaded for a predetermined time (usually about 1 to 30 minutes, preferably about 5 minutes) for dynamic crosslinking. This makes it possible to port in the polylactic acid sea phase consisting of the melt of component (B) (matrix), to obtain a thermoplastic elastomer product, which island phases of crosslinked acrylic rubber (A component) is dispersed.

  In the present invention, dynamic crosslinking refers to crosslinking performed when the acrylic rubber (component A) in the thermoplastic elastomer composition is mixed and stirred in a kneader, and is distinguished from mold crosslinking performed using a normal mold. It is synonymous with what is generally called “dynamic crosslinking (dynamic vulcanization)”.

Temperature of the kneader is preferably adjusted to a temperature higher 1 to 70 ° C. than the melting point of the polylactic acid component (B), especially preferably greater 10 to 30 ° C. than the melting point of the polylactic acid component (B) Temperature. The melting point of the upper Kipo polylactic acid (B component) is usually about 140 to 170 ° C..

Thermoplastic elastomer products of the present invention, in the sea phase (matrix) comprising a melt of polylactic acid (B component), the island phase of the crosslinked acrylic rubber (A component) is dispersed. The sea-island structure can be observed at a magnification of about 1000 to 10,000 using, for example, a scanning probe microscope (SPM).

  The average diameter of the island phase is preferably in the range of 0.1 to 10 μm, particularly preferably in the range of 0.1 to 1.0 μm. The average diameter of the island phase can be measured by, for example, measurement with a scanning probe microscope (SPM) and image analysis.

  Next, examples will be described together with comparative examples. However, the present invention is not limited to these examples.

[Example 1]
In a kneading machine (laboplast mill) temperature-controlled at 200 ± 10 ° C., polylactic acid (manufactured by Unitika Ltd., Latemac TE-2000) pellets and acrylic rubber (manufactured by Nippon Zeon Co., Ltd., Nipol AR31) are described below. The mixture was added at the blending ratio shown in Table 1 and kneaded for 15 minutes. Next, zinc dimethyldithiocarbamate (ZnMDC) (PZ) (manufactured by Ouchi Shinsei Chemical Co., Ltd., Noxeller PZ) as a vulcanization accelerator and ferric dimethyldithiocarbamate (TTFE) (TTF) as a vulcanization accelerator Chemical Industries, Noxeller TTFE) and N-phenyl-N- (trichloromethylthio) benzenesulfonamide and its derivative (E / C) (Lanxess, Valcurrent E / C) as vulcanization accelerators are described below. A thermoplastic elastomer product was obtained by charging at a blending ratio shown in Table 1 and dynamically crosslinking for 5 minutes.

[Examples 2 to 5, Comparative Examples 2 to 4]
As shown in Table 1 and Table 2 below, a thermoplastic elastomer product was obtained according to Example 1 except that the amount of each component was changed.

[Comparative Example 1]
In a kneading machine (laboplast mill) temperature-controlled at 200 ± 10 ° C., polylactic acid (manufactured by Unitika Ltd., Latemac TE-2000) pellets and acrylic rubber (manufactured by Nippon Zeon Co., Ltd., Nipol AR31) are described below. The mixture was added at the blending ratio shown in Table 2 and kneaded for 15 minutes.

[Comparative Example 5]
In a kneading machine (laboplast mill) temperature-controlled at 200 ± 10 ° C., polylactic acid (manufactured by Unitika Ltd., Latemac TE-2000) pellets and acrylic rubber (manufactured by Nippon Zeon Co., Ltd., Nipol AR31) are described below. The mixture was added at the blending ratio shown in Table 2 and kneaded for 15 minutes. Next, an amine-based vulcanizing agent [ammonium benzoate] (manufactured by Ouchi Shinsei Chemical Industry Co., Ltd., Barnock AB-S) is added at a blending ratio shown in Table 1 to be dynamically cross-linked for 5 minutes. As a result, a thermoplastic elastomer product was obtained.

  Using the thermoplastic elastomer products of Examples and Comparative Examples thus obtained, each characteristic was evaluated according to the following criteria. The results are shown in Tables 1 and 2 above.

[Observation of sea-island structure]
About each obtained thermoplastic elastomer product, the sea-island structure was observed with the magnification of 10000 time using the scanning probe microscope (SPM) (Shimadzu production company make, SPM-9500J3).

[Elongation at break]
The elongation at break was measured according to JIS K 6251 using each of the thermoplastic elastomer products. In the evaluation of flexibility, a case where the elongation at break was 180% or more was evaluated as “◯”, a case where the elongation was 100% or more and less than 180% was evaluated as “Δ”, and a case where it was less than 100% was evaluated as “X”.

[Volume change rate]
Using each of the above thermoplastic elastomer products, the test piece (size: 20 mm × 25 mm, thickness: 2 mm) was immersed in FUEL C at room temperature (25 ° C.) for 24 hours. Then, the volume change rate was measured according to the method described in JIS K 6258.

  From the results in the above table, it was confirmed that all the examples had an increase in kneading torque and that dynamic crosslinking had progressed. As a result of morphological observation, as shown in FIG. 1, it was confirmed that crosslinked acrylic rubber was dispersed as island phase 2 in the sea phase (matrix) 1 made of a polylactic acid melt (see FIG. 1). . For this reason, all the products of the examples had large elongation at break, excellent flexibility (elastomer characteristics), small volume change rate, and excellent fuel permeation resistance.

  On the other hand, the product of Comparative Example 1 has a higher ratio of acrylic rubber than polylactic acid, and is not simply crosslinked and kneaded (dynamically crosslinked) as shown in FIG. The acrylic rubber having a high ratio became the sea phase (matrix) 3, and the polylactic acid having a low ratio was dispersed as the island phase 4. Moreover, since the acrylic rubber was not bridge | crosslinked, the comparative example 1 goods had small elongation at break, and the softness | flexibility (elastomer characteristic) was inferior.

  In Comparative Examples 2 and 3, an increase in kneading torque was observed, and it was confirmed that dynamic crosslinking was progressing. As a result of morphological observation, it was confirmed that a crosslinked acrylic rubber was present as an island phase, and a structure using polylactic acid as a matrix was obtained. However, since the ratio of polylactic acid is high and polylactic acid has high rigidity, flexibility (elastomer characteristics) is inferior.

  In Comparative Example 4 products, an increase in kneading torque was observed, and it was confirmed that dynamic crosslinking had progressed. However, since the ratio of polylactic acid to be a matrix (island phase) was too low, a sea-island structure was not formed. Therefore, it was difficult to mold without showing thermoplasticity, and the elongation at break and the rate of volume change could not be measured.

  Since the comparative example 5 product uses an amine-based cross-linking agent, polylactic acid deteriorates and a decrease in kneading torque is observed. Therefore, the sheet could not be produced, and the elongation at break and the volume change rate could not be measured.

  Since the thermoplastic elastomer product of the present invention has elastomer properties at room temperature, it can be used for products in which an elastomer is usually used. The thermoplastic elastomer product of the present invention is particularly suitable for hoses and tanks of automobiles and the like because of its excellent fuel permeation resistance. For example, anti-vibration rubber, rolls for electrophotographic equipment (OA), sound absorbing materials, cushions, etc. It can also be used for materials, automobile interior materials, and the like.

It is a schematic diagram which shows the sea-island structure of an Example product. It is a schematic diagram which shows the sea-island structure of comparative example 1 goods.

Explanation of symbols

1 Sea phase (polylactic acid)
2 Island phase (acrylic rubber)

Claims (6)

A thermoplastic elastomer product containing the following components (A) to ( C ) and dynamically crosslinking the component (A) with the component (C), the component (A) and the component (B) The weight mixing ratio of (A) component / (B) component is in the range of 55/45 to 95/5, and it is crosslinked in the sea phase composed of the melt of component (B), which is the above-mentioned minor component. A thermoplastic elastomer product characterized in that the island phase of component (A), which is a large component, is dispersed.
(A) Acrylic rubber.
(B) polylactic acid.
(C) At least one crosslinking agent component selected from the group consisting of zinc dimethyldithiocarbamate, ferric dimethyldithiocarbamate, N-phenyl-N- (trichloromethyl-sulfenyl) benzenesulfonamide, and derivatives thereof. The thermoplastic elastomer product according to claim 1 , wherein the amount of the crosslinking agent component ( C ) is in the range of 0.1 to 5 parts by weight per 100 parts by weight of the acrylic rubber (A) . The thermoplastic elastomer product according to claim 1 or 2, which is an automobile hose or an automobile tank. The following (A)-(C) component is contained, The weight mixing ratio of the said (A) component and (B) component is the range of (A) component / (B) component = 55 / 45-95 / 5. In the thermoplastic elastomer composition, the component (A) was dynamically crosslinked with the component (C) , thereby being crosslinked in the sea phase composed of the melt of the component (B), which is the minor component. A method for producing a thermoplastic elastomer product, comprising dispersing the island phase of the component (A), which is a large component.
(A) Acrylic rubber.
(B) polylactic acid.
(C) zinc dimethyldithiocarbamate, ferric di-methyl dithiocarbamate, N- phenyl -N- (trichloromethyl - sulfenyl) benzenesulfonamide and at least one cross-linking agent component thereof selected from the induction member or Ranaru group . The method for producing a thermoplastic elastomer product according to claim 4 , wherein the amount of the crosslinking agent component (C) is in the range of 0.1 to 5 parts by weight with respect to 100 parts by weight of the acrylic rubber (A). . The method for producing a thermoplastic elastomer product according to claim 4 or 5, which is a method for producing a thermoplastic elastomer product which is an automobile hose or an automobile tank.

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