JP5906576B2 - Silicone rubber-based curable composition, method for measuring silicone rubber-based curable composition, and method for producing silicone rubber-based curable composition - Google Patents

Description

  The present invention relates to a silicone rubber-based curable composition whose structure has been analyzed by synchrotron radiation X-ray scattering measurement.

  Silicone rubber is excellent in heat resistance, flame retardancy, chemical stability, weather resistance, radiation resistance, electrical properties, and the like, and thus is used for various applications in a wide range of fields. In particular, silicone rubber is physiologically inactive and has little reaction to body tissue when touched by a living body. Therefore, silicone rubber is also used as a material for medical instruments such as various medical catheters.

  A medical catheter is a tube that is inserted into a body cavity such as the thoracic cavity or abdominal cavity, a lumen such as the digestive tract or ureter, a blood vessel, etc. In addition to biocompatibility, scratch resistance (tear resistance), kink resistance (tensile strength), transparency, flexibility (tensile elongation), and the like are required. Specific uses of medical catheters include, for example, post-operative drainage tubes for drainage removal such as blood and pus, and postoperative procedures such as percutaneous endoscopic gastrostomy (PEG). For example, a tube for nutrient intake. Further, in order to produce ultrathin tube-like silicone rubber for catheters, the silicone rubber composition, which is a silicone rubber material, is required to have extrudability.

  In addition to silicone rubber, soft polyvinyl chloride and the like are generally used as medical catheter materials. Although silicone rubber is superior in terms of biocompatibility and flexibility as compared with polyvinyl chloride and the like, it is required to improve strength such as tear strength and tensile strength, particularly tear strength. If the tear strength is not sufficient, the catheter may be torn due to a wound with a needle or blade during the operation, or if the tensile strength is not sufficient, the catheter will bend and yield and block (kink), Distribution of the drug solution or the like to be injected in the catheter is delayed.

  Therefore, various methods have been proposed to increase the tear strength and tensile strength of silicone rubber (for example, Patent Documents 1 to 7). Specific methods for imparting high tearability to the silicone rubber include addition of inorganic fillers such as silica fine particles, and densification of the crosslink density (the areas of high and low crosslink density in the silicone rubber system). Distributed). It is considered that the improvement in tearability due to the densification of the crosslink density is due to the fact that the region having a high crosslink density acts as a resistance against tear stress.

For example, in Patent Document 1, an organopolysiloxane having a high viscosity and a low vinyl group content (raw rubber (A)) is mainly used, and an organopolysiloxane having a low viscosity and a high vinyl group content (silicone oil (B)). ), Vinyl group-containing organopolysiloxane copolymer (vinyl group-containing silicone resin (C)), organohydrogensiloxane (crosslinking agent (D)), platinum or platinum compound (curing catalyst (E)), and finely divided silica ( A curable silicone rubber composition containing a filler (F)) is disclosed.

  In addition, as an example of analyzing a polymer material by X-ray scattering measurement, there is an example in which small-angle X-ray scattering measurement of acrylic fiber is performed (Patent Document 8), but the silicone rubber composition is still sufficiently measured by X-ray scattering measurement. No structural analysis has been performed.

JP 7-331079 A Japanese Patent Laid-Open No. 7-228782 JP-A-7-258551 U.S. Pat. No. 3,884,866 US Pat. No. 4,539,357 US Pat. No. 4,061,609 US Patent 3,671,480 JP-A-11-81053

  However, the correlation between the aggregate structure of inorganic fillers such as silica fine particles in silicone rubber and the tensile strength and tear strength has not yet been clarified. An object of the present invention is to provide a silicone rubber-based curable composition from which a silicone rubber excellent in tensile strength and tear strength can be obtained.

Such an object is achieved by the present invention described in the following (1) to ( 5 ).
(1) A silicone rubber-based curable composition,
Aggregate size of the unstretched when inorganic fillers obtained from synchrotron radiation X-ray scattering measurement is 20-25 nm, the silicone rubber based curable composition is a vinyl group-containing linear organopolysiloxanes, and hexamethyl disilazane treated Silica beads,
The vinyl group-containing linear organopolysiloxane, a silicone rubber based curable composition characterized by Ru predetermined terminal vinyl groups polyorganosiloxane der.
(2) The silicone rubber curable composition according to (1), wherein the silicone rubber curable composition has a maximum value of an orientation coefficient during stretching determined from the synchrotron radiation X-ray scattering measurement of 0.25 to 0.35. object.
(3) The silicone rubber-based curable composition according to (1) or (2), wherein the silicone rubber-based curable composition is 40 N / m or more in terms of JIS K6252 vulcanized rubber and thermoplastic rubber-tear strength. Composition.
(4) Silicone which performs synchrotron radiation X-ray scattering measurement at the same time that the silicone rubber-based curable composition according to (2) is stretched to cut at a stretching speed of 1 to 20 mm / sec using a high-speed tensile tester. Method for measuring rubber-based curable composition .
(5) A method for producing a silicone rubber-based curable composition according to (1),
After reacting octamethylcyclotetrasiloxane with 2,4,6,8-tetramethyl 2,4,6,8-tetravinylcyclotetrasiloxane in the presence of potassium siliconate, 1,3-divinyl By adding tetramethyldisiloxane, the number average molecular weight (Mn) is 277,734, the weight average molecular weight (Mw) is 573,906, or the vinyl group content is 0.13 mol%. Obtaining a terminal vinyl group polyorganosiloxane,
Adding a silica bead treated with hexamethyldisilazane to the terminal vinyl group polyorganosiloxane, and a method for producing a silicone rubber-based curable composition.

The silicone rubber obtained by curing the silicone rubber-based curable composition of the present invention is excellent in tear strength. Therefore, the molded body using the silicone rubber-based curable composition of the present invention and the medical tube composed of the molded body have high mechanical strength such as tear strength. That is, according to the present invention, it is possible to provide a medical catheter made of silicone rubber having excellent scratch resistance.

  The silicone rubber-based curable composition of the present invention is a vinyl group-containing linear organopolysiloxane, a linear organohydrogenpolysiloxane, a silica filler surface-treated with a silane coupling agent having a trimethylsilyl group, It is characterized by containing.

  In order to improve the mechanical strength of silicone rubber, especially tensile strength, silica filler is often added to the silicone-based curable composition, and silica filler surface-treated with a specific silica coupling agent is added. Therefore, it can be expected that the tear strength can be greatly improved.

  The reason why the tear strength is improved is considered as follows. That is, by improving the dispersibility of the silica filler, the interface between the silica filler and the rubber matrix increases, and the number of rubber molecular chains affected by the silica filler increases. Thereby, the reinforcement effect by a silica filler increases and mechanical strength improves. The rubber molecular chain subjected to the action of the silica filler has a lower molecular mobility due to the interaction with the silica filler, and has a harder structure than a portion having a high molecular mobility. In the tearing behavior of silicone rubber, if a tearing stress is applied to a hard structure when an initial crack grows and propagates, it acts as a drag, resulting in an increase in tearing strength.

  Thus, the dispersibility of the silica filler is considered to have a great influence on the mechanical strength. Therefore, the dispersibility and mechanical properties of the silica filler are analyzed by analyzing the average agglomerated size of the silica filler by conducting a small-angle X-ray scattering measurement this time. As a result of investigating the correlation between the strengths, it was found that the mechanical strength, particularly the tear strength, greatly increased when the dispersibility of the silica filler was improved.

  For example, the silicone rubber-based curable composition of the present invention is heated (primary curing) at 140 to 180 ° C. for 5 to 15 minutes and then post-baked (secondary curing) at 200 ° C. for 4 hours. Can be obtained.

  A silicone rubber-based curable composition is obtained by pressing at 170 ° C. and 10 MPa for 10 minutes, forming into a 1 mm sheet, and primary curing, followed by heating at 200 ° C. for 4 hours and secondary curing. A crescent-type test piece of JIS K6252 (2001) is prepared using the sheet-like silicone rubber, and the tear strength of the crescent-type test piece of JIS K6252 (2001) is measured.

  A ring-shaped silicone rubber is produced by punching the sheet-shaped silicone rubber with a ring cutter having a center circumference of 50 mm and a width of 1 mm.

  The ring-shaped silicone rubber is stretched to cut at a stretching speed of 1 to 20 mm / sec using a high-speed tensile tester, and at the same time, a synchrotron radiation X-ray scattering measurement is performed. Here, the synchrotron radiation X-ray scattering measurement includes small-angle X-ray scattering and wide-angle X-ray scattering.

  First, small angle X-ray scattering is a method of obtaining structural information of a substance by measuring X-rays that are scattered by irradiating the substance with X-rays and having a small scattering angle. Yes, the size, shape, regularity, and dispersibility of the internal structure are evaluated. The smaller the scattering angle, the larger the size of the corresponding structure.

  In addition, wide angle X-ray scattering is a method for obtaining structural information of a substance by measuring X-rays that are scattered by irradiating the substance with X-rays and having a large scattering angle. Yes, structural information smaller than small-angle X-ray scattering can be obtained. In addition to being used for crystal structure analysis, information on the degree of orientation of the sample can also be obtained.

  Further, in order to examine the correlation between the aggregation / dispersion state of the silica filler and the mechanical strength in detail, not only the small-angle X-ray scattering measurement was performed in an unstretched state but also the small-angle X-ray scattering measurement was performed simultaneously with the stretching.

  Further, not only the aggregation / dispersion state of the silica filler, but also any form of the vinyl group-containing linear organopolysiloxane (A) and the linear organohydrogenpolysiloxane (B) constituting the silicone rubber, particularly during stretching In order to clarify whether or not, wide-angle X-ray scattering measurement was performed simultaneously with stretching.

The small-angle X-ray scattering measurement and the wide-angle X-ray scattering measurement can be measured with a commercially available general-purpose X-ray apparatus. For example, it can be performed using a nanoscale X-ray structure evaluation apparatus NANO-Viewer manufactured by Rigaku Corporation.
Moreover, in order to perform measurement simultaneously with high-speed stretching, measurement in an extremely short time is necessary. To that end, the structural analysis of the silicone rubber-based curable composition is performed by performing small-angle X-ray scattering measurement and wide-angle X-ray scattering measurement by synchrotron radiation X-ray at SPring-8 (Spring Eight), a large synchrotron radiation facility. Can do.

  SPring-8 is a large-scale synchrotron radiation facility in the city of Harima Science Park in Hyogo Prefecture that can generate the world's highest performance synchrotron radiation, which accelerates electrons to a speed almost equal to that of light. It is a thin and powerful electromagnetic wave that is generated when the traveling direction is bent by a magnet.

  Small-angle X-ray scattering measurement and wide-angle X-ray scattering measurement can be performed in a shorter time as the X-ray intensity is stronger. Since it has a brightness of 100 million times that of the line, sufficient strength can be obtained even in extremely short time measurements, so structural analysis during the stretching process is possible.

The measurement conditions of synchrotron radiation X-ray scattering are shown below.
The measurement conditions for small-angle X-ray scattering were a wavelength of 1.50 mm and a camera length of 6 m, and II + CCD (Image Intensifier + Charge Coupled Device) was used as a detector.
The measurement conditions for wide-angle X-ray scattering were a wavelength of 0.832 mm, a camera length of 200 mm, and an II + CCD (Image Intensifier + Charge Coupled Device) was used as the detector.

  As intensity correction of X-ray scattering measurement data, dark correction (removes noise caused by dark current), background correction (removes scattering caused by objects other than the measurement sample such as air), transmittance correction (transmittance between samples) Taking into account the difference between

  The aggregate size of the silica filler in the silicone rubber-based curable composition was analyzed using a particle size / hole size analysis software NANO-Solver manufactured by Rigaku Corporation.

  The aggregate size of the silica filler in the silicone rubber-based curable composition by the above analysis method is preferably 30 nm or less. More preferably, it is 25 nm or less, and most preferably 20 nm or less. When the silica filler is larger than 30 nm, it cannot be said that the dispersibility is good and the mechanical strength cannot be improved. Further, since the silica filler has a particle size of about 7 to 14 nm, the aggregate size of the silica filler does not become the particle size of 7 to 14 nm or less.

ここで、fは配向係数、Ｉは散乱強度、φは円周方向角度であり、添え字hklは結晶面のミラー指数をそれぞれ示す。 The degree of orientation is evaluated using the orientation coefficient. The orientation factor can be calculated from the results of two-dimensional wide-angle X-ray scattering measurements. It calculates using the following numerical formula 1.

Here, f is the orientation coefficient, I is the scattering intensity, φ is the angle in the circumferential direction, and the subscript hkl indicates the mirror index of the crystal plane.

  When the orientation coefficient is 1, the orientation is completely oriented in the stretching direction, when it is 0, the orientation is random, and when it is -0.5, the orientation is oriented in the direction perpendicular to the stretching direction.

  By improving the dispersibility of the silica filler, it is considered that the interface between the silica filler and the rubber matrix increases, and the rubber molecular chains affected by the silica filler increase. However, the rubber molecular chains are not easily oriented by stretching. It is possible.

  The maximum value of the orientation coefficient of the rubber molecular chain in the silicone rubber-based curable composition under stretching by the above analysis method is preferably 0.45 or less. More preferably, it is 0.35 or less, and most preferably is 0.3 or less. When the orientation coefficient exceeds 0.45, the dispersibility of the filler is poor, suggesting that the rubber molecular chains not acting with the filler are oriented.

  The above-mentioned orientation means that the rubber molecular chain in the silicone rubber-based curable composition forms a liquid crystal phase, an intermediate phase (meso phase) or an optically anisotropic phase by stretching.

  As described above, the silicone rubber obtained by curing the silicone rubber-based curable composition of the present invention exhibits excellent tensile strength and tear strength. Therefore, by using the silicone rubber-based curable composition of the present invention, a silicone rubber catheter having excellent scratch resistance and kink resistance can be obtained.

Hereinafter, although an example explains one form of a silicone rubber system curable composition of the present invention, the present invention is not limited to these examples.

The raw materials used in the examples and comparative examples are as follows.
(A): Vinyl group-containing linear organopolysiloxane, vinyl group content 0.13 mol%, synthesized by the following synthesis scheme.
(B): Linear organohydrogenpolysiloxane, “TC25D” manufactured by Momentive
(C1): Silica filler surface-treated with hexamethyldisilazane, “Aerosil RX300” manufactured by Nippon Aerosil, specific surface area 300 m ² / g, primary average particle size 7 nm, carbon content 3.5% by weight
(C2): Silica filler surface-treated with dimethyldichlorosilane, “Aerosil R974” manufactured by Nippon Aerosil, specific surface area 200 m ² / g, primary average particle size 12 nm
(D) Platinum: "TC-25A" manufactured by Momentive

[Synthesis of vinyl group-containing linear organopolysiloxane (A)]
A first vinyl group-containing linear organopolysiloxane (A) was synthesized according to the following chemical formula (1).
Specifically, 74.7 g (252 mmol) of octamethylcyclotetrasiloxane, 2,4,6,8-tetramethyl 2,4,6 was placed in a 300 mL separable flask having a cooling tube and a stirring blade that was purged with Ar gas. , 8-tetravinylcyclotetrasiloxane 0.086 g (0.25 mmol) and potassium siliconate 0.1 g were added, the temperature was raised, and the mixture was stirred at 120 ° C. for 30 minutes. An increase in viscosity was confirmed.
Thereafter, the temperature was raised to 155 ° C., and stirring was continued for 3 hours. After 3 hours, 0.1 g (0.6 mmol) of 1,3-divinyltetramethyldisiloxane was added, and the mixture was further stirred at 155 ° C. for 4 hours.
After 4 hours, the mixture was diluted with 250 mL of toluene and then washed with water three times. The washed organic layer was washed several times with 1.5 L of methanol, and purified by reprecipitation to separate the oligomer and polymer. The obtained polymer was dried under reduced pressure at 60 ° C. overnight to obtain a second vinyl group-containing linear organopolysiloxane (Mn = 277,734, Mw = 573,906, IV value (dl / g) = 0.89).

[Example 1]
(Preparation of silicone rubber-based curable composition)
(A1) To 100 parts by weight of the first vinyl group-containing linear organopolysiloxane, 70 parts by weight of (C1) silica filler was added and kneaded to prepare a master batch.
Subsequently, (D) 0.5 parts by weight of platinum was mixed and kneaded until uniform, then (B) 2.0 parts by weight of linear organohydrogenpolysiloxane was added and kneaded, and silicone rubber-based curability was added. A composition was prepared.
Table 1 shows the weight ratio of each raw material.

(Evaluation of silicone rubber-based curable composition)
<Tear strength and tear stroke>
The obtained silicone rubber-based curable composition was pressed at 170 ° C. and 10 MPa for 10 minutes, molded into a 1 mm sheet, and primary cured.
Subsequently, it was heated at 200 ° C. for 4 hours and secondarily cured.
Using the obtained sheet-like silicone rubber, a crescent-type test piece is prepared according to JIS K6252 (2001), and the tear strength of the crescent-type test piece and the test piece are cut according to JIS K6252 (2001). The elongation (stroke) of was measured. However, the thickness of the test piece was 1 mm. The results are shown in Table 1.

<Tensile strength and tensile elongation>
The obtained silicone rubber-based curable composition was pressed at 170 ° C. and 10 MPa for 10 minutes, molded into a 1 mm sheet, and primary cured.
Subsequently, it was heated at 200 ° C. for 4 hours and secondarily cured.
Using the obtained sheet-like silicone rubber, a dumbbell-shaped No. 3 test piece was prepared according to JIS K6251 (2004), and the tensile strength of the dumbbell-shaped No. 3 test piece according to JIS K6251 (2004) and The elongation (strain) at the time of cutting was measured. However, the thickness of the test piece was 1 mm. The results are shown in Table 1.

<Filler aggregation size>
Using the obtained sheet-shaped silicone rubber, a ring-shaped silicone rubber was prepared by punching with a ring cutter having a center circumference of 50 mm and a width of 1 mm.
The obtained ring-shaped silicone rubber was stretched at a stretching speed of 1 mm / sec using a high-speed tensile testing machine, and small-angle X-ray scattering measurement was performed at the synchrotron radiation facility SPring-8.
The measurement conditions for small-angle X-ray scattering were a wavelength of 1.50 mm and a camera length of 6 m, and II + CCD (Image Intensifier + Charge Coupled Device) was used as a detector. The X-ray irradiation time in one measurement was 50 milliseconds, and the measurement was performed once every 3 seconds.
In order to know the scattering intensity of the measurement sample accurately, as the intensity correction of the X-ray scattering measurement data, dark correction (to remove noise caused by dark current) and background correction (to remove scattering caused by things other than the measurement sample such as air) ) And transmittance correction (considering the difference in transmittance between samples).
From the X-ray scattering measurement data subjected to the above correction, the aggregate size of the silica filler was analyzed using a particle size / hole size analysis software NANO-Solver manufactured by Rigaku Corporation. The results are shown in Table 1.

ここで、fは配向係数、Ｉは散乱強度、φは円周方向角度であり、添え字hklは結晶面のミラー指数をそれぞれ示す。
<Maximum orientation coefficient>
The obtained ring-shaped silicone rubber was stretched at a stretching speed of 1 mm / sec using a high-speed tensile tester, and wide-angle X-ray scattering measurement was performed at the synchrotron radiation facility SPring-8.
The measurement conditions for wide-angle X-ray scattering were a wavelength of 0.832 mm, a camera length of 200 mm, and an II + CCD (Image Intensifier + Charge Coupled Device) was used as the detector. The X-ray irradiation time in one measurement was 70 msec, and the measurement was performed once every 3 seconds.
The result of the wide angle X-ray scattering measurement was also corrected for intensity in the same manner as the small angle X-ray scattering measurement, and then the orientation coefficient was calculated using the following formula. The orientation coefficient becomes the maximum value immediately before stretching, and this value is called the maximum orientation coefficient. The results of the maximum orientation coefficient are shown in Table 1.

Here, f is the orientation coefficient, I is the scattering intensity, φ is the angle in the circumferential direction, and the subscript hkl indicates the mirror index of the crystal plane.

（*1）：シリカフィラーの比表面積
（*2）：シリカフィラーの一次平均粒径
（*3）：未延伸時のフィラー凝集サイズ

(* 1): Specific surface area of silica filler (* 2): Primary average particle size of silica filler (* 3): Filler aggregation size when unstretched

[Comparative Example 1]
A silicone rubber-based curable composition was prepared in the same manner as in Example 1 except that (C2) silica filler was used instead of (C1) silica filler.
Moreover, the test piece produced using the obtained silicone rubber-type curable composition was evaluated similarly to Example 1. FIG. The results are shown in Table 1.

[result]
As shown in Table 1, the silicone rubber obtained by curing the silicone rubber-based curable composition of Example 1 using the silica filler (C1) treated with the trimethylsilyl group-containing silane coupling agent has a tear strength of 28 N / The tensile strength was 7.5 MPa or more, and the tear strength and tensile strength were excellent. In particular, the tear strength of the silicone rubber of Example 1 was significantly improved as compared with the silicone rubber of Comparative Example 1 using a silica filler (C2) that was not treated with a trimethylsilyl group-containing silane coupling agent. Moreover, also about the elongation at the time of a stroke and a cutting | disconnection, compared with the silicone rubber of the comparative example 1, the silicone rubber of Example 1 showed remarkable improvement, and it turned out that it shows high elongation even if it is highly filled with silica. .

From the results of X-ray scattering analysis, the silicone rubber obtained by curing the silicone rubber-based curable composition of Example 1 has a smaller filler aggregation size than the silicone rubber of Comparative Example 1, and the rubber molecular chains are less likely to be oriented during stretching. I understood it. It is presumed that the silicone rubber of Comparative Example 1 has better filler dispersibility than the silicone rubber of Example 1. The improvement in dispersibility represents an increase in the interface between the silica filler and the rubber matrix. As a result, it is considered that the reinforcing effect by the silica filler is increased.

Claims (5)

A silicone rubber-based curable composition comprising:
Aggregate size of the unstretched when inorganic fillers obtained from synchrotron radiation X-ray scattering measurement is 20-25 nm, the silicone rubber based curable composition is a vinyl group-containing linear organopolysiloxanes, and hexamethyl disilazane treated Silica beads,
The vinyl group-containing linear organopolysiloxane, a silicone rubber based curable composition characterized by Ru terminal vinyl groups polyorganosiloxane der represented by the following formula.

In the terminal vinyl group polyorganosiloxane represented by the above formula, m and n are a number average molecular weight (Mn) of 277,734 and a weight average molecular weight (Mw) of 573,906 of the vinyl group-containing linear organopolysiloxane. Or the vinyl group content of the vinyl group-containing linear organopolysiloxane is 0.13 mol%.   The silicone rubber-based curable composition according to claim 1, wherein the silicone rubber-based curable composition has a maximum value of an orientation coefficient at the time of stretching determined from the synchrotron radiation X-ray scattering measurement of 0.25 to 0.35.   3. The silicone rubber-based curable composition according to claim 1, wherein the silicone rubber-based curable composition is 40 N / m or more in terms of JIS K6252 vulcanized rubber and thermoplastic rubber-tear strength.   The silicone rubber-based curable composition according to claim 2, wherein the stretching is performed until the cutting is performed at a stretching speed of 1 to 20 mm / sec. Method for measuring the composition.   A method for producing the silicone rubber-based curable composition according to claim 1,
  After reacting octamethylcyclotetrasiloxane with 2,4,6,8-tetramethyl 2,4,6,8-tetravinylcyclotetrasiloxane in the presence of potassium siliconate, 1,3-divinyl By adding tetramethyldisiloxane, the number average molecular weight (Mn) is 277,734, the weight average molecular weight (Mw) is 573,906, or the vinyl group content is 0.13 mol%. Obtaining a terminal vinyl group polyorganosiloxane,
  Adding a silica bead treated with hexamethyldisilazane to the terminal vinyl group polyorganosiloxane, and a method for producing a silicone rubber-based curable composition.