Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
  • C08L71/02—Polyalkylene oxides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
• • 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
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
  • C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups

Definitions

• the present invention relates to a silicone oil
• composition a gelation time adjusting additive, and a method for designing a silicone oil and a silicone oil composition, and more specifically, a silicone oil or a silicone oil composition in which a gelation time has been efficiently adjusted so as to promote or prevent gelation under a high temperature condition without a restriction on the silicone oil, and a method for designing the same.
• a silicone oil which is generally a colorless
• a silicone oil exhibits excellent properties in terms of electrical characteristics, mold release properties, water repellency, defoaming properties, lubricity, and the like, and is widely used in the field of, for example, electrical, mechanical, and chemical industries.
• a silicone oil has a technical advantage in that a viscosity varies less with temperature when a use environment is at a high temperature or a low temperature.
• the temperature of the silicone oil reaches a high temperature of 160 to 300°C, the silicone oil becomes thickened and gelatinized.
• a gelation time can be adjusted in order to manipulate this gelation in both directions of promotion and prevention from the standpoint of a function required for the silicone oil.
• Patent Literature 1 is focused on prevention of gelation at a high temperature when a silicone oil is used for a fiber
• a filament is coated with a silicone oil agent excellent in heat resistance in order to prevent fusion between single fibers at the time of the flameproofing treatment performed at about 160 to 300°C.
• Patent Literature 1 further describes the following matters. It becomes possible to improve penetration of an amino-modified silicone into a fiber and prevent gelation thereof by simultaneously using the amino-modified silicone, a surfactant, and a compound having a primary amino group and an oxyalkylene group.
• the compound having a primary amino group and an oxyalkylene group used as a characteristic component causes a reduction in the amount of silicones over time. This impairs a function originally performed by the amino-modified silicone oil agent over time.
• the compound having a primary amino group and an oxyalkylene group prevents gelation only in the presence of a surfactant, and thus a surfactant is required even in an application that does not need emulsification. This increases the number of components in a silicone oil agent, sometimes causing inconsistency in the quality of a silicone oil agent and an increase in the production cost of an oil agent.
• Patent Literature 2 discloses a fiber bundle to which a silicone oil is attached.
• Patent Literature 2 discloses that thermal fusion between fibers caused by a thermal decomposition residue at a high temperature is prevented by lowering a ratio of a non-silicone oil agent as exemplified by a surfactant relative to a silicone oil agent.
• the disclosure is not directly focused on gelation, much less on a gelation time, of an oil agent at a high temperature.
• Patent Literature 3 discloses an emulsion composition that restricts the viscosity of a
• Patent Literature 3 is not directly focused on a gelation time at a high temperature.
• Patent Literature 3 a polyoxyethylene alkyl ether exhibiting an emulsifying function exerts other effects according to applications, and no reference is made to whether a polyoxyethylene alkyl ether has any effect on a gelation time at a high temperature.
• Patent Literature 1 W02018/003347
• Patent Literature 2 Japanese Patent Application Laid- Open No. 2016-199824
• Patent Literature 3 Japanese Patent No. 6017109
• a problem of the present invention relates to a silicone oil composition, a gelation time adjusting additive, and a method for designing a silicone oil and a silicone oil composition, and an object thereof is to provide to a silicone oil composition in which a gelation time has been adjusted so as to promote or prevent gelation under a high temperature condition without a restriction on a silicone oil, or a gelation time adjusting additive for the silicone oil
• a gelation time can be adjusted according to the addition molar number of the polyoxyalkylene unit in the gelation time adjusting additive simultaneously used with a silicone oil and this adjustment can be performed after preferentially determining a structural factor important for expressing a function of the silicone oil, thereby completing the present invention.
• composition provided by the present invention is a composition provided by the present invention
• silicone oil composition including a silicone oil defined by the following chemical formula (1) and a gelation time adjusting additive defined by the following chemical formula (2), and the silicone oil composition is characterized in that the addition molar number of the silicone oil composition
• polyoxyalkylene unit in the gelation time adjusting additive has been adjusted according to the silicone oil and a required gelation time of the silicone oil at a predetermined heating temperature .
• the required gelation time refers to a gelation time at a temperature to which the silicone oil or the
• R 7 is a monovalent to trivalent saturated or unsaturated hydrocarbon functional group having 3 to 60 carbon atoms
• R 8 is a divalent hydrocarbon group having 2 to 4 carbon atoms
• r is an integer from 3 to 200
• s is an integer from 1 to 3.
• polyoxyalkylene unit thereof has been adjusted according to the silicone oil and a required gelation time of the silicone oil at a predetermined heating temperature.
• the method for designing a silicone oil composition of the present invention is a method for designing a silicone oil composition in which a gelation time has been adjusted, characterized by including the steps of:
• a silicone oil composition capable of promoting and preventing gelation at high temperature without a restriction on a silicone oil, or a gelation time adjusting additive therefor, by adjusting the gelation time of the silicone oil by the addition molar number of the polyoxyalkylene unit of the gelation time adjusting additive under a required gelation time at a predetermined heating temperature of the silicone oil depending on the application of the silicone oil,
• silicone oil is a reactive or non reactive silicone oil.
• the method for designing a silicone oil in which a gelation time has been adjusted including the steps of:
• This method can preferentially determine a structural factor important for expressing a function of a silicone oil at a high temperature without a restriction on the silicone oil, and effectively adjust the gelation time to promote or suppress gelation.
• R 1 to R 6 are the same as or different from each other and are each any one selected from the group consisting of a saturated or unsaturated monovalent hydrocarbon functional group, a hydroxyl group, a nitrogen- containing group, a sulfur-containing group, and a hydrogen atom, and p and q are each an integer greater than or equal to
• R 7 is a monovalent to trivalent saturated or unsaturated hydrocarbon functional group having 3 to 60 carbon atoms
• R 8 is a divalent
• the present invention relates to a silicone oil composition in which a gelation time has been adjusted, and a gelation time adjusting additive, and a method for designing a silicone oil and a silicone oil composition.
• a silicone oil composition in which a gelation time has been adjusted, and a gelation time adjusting additive, and a method for designing a silicone oil and a silicone oil composition.
• R 11 to R 12 are each a hydrogen atom or a saturated hydrocarbon group having 1 to 10 carbon atoms and being linear, branched, or cyclic, and t is an integer of 0 or 1, but is preferably 1 from the viewpoint of the production of the composition.
• Examples of the functional group satisfying this condition may include -CH 2 -CH 2 -CH 2 -NH (CH 3 ) , -CH 2 -CH 2 -CH 2 -N (CH 3 ) 2 , -CH 2 -CH 2 -NH- CH 2 -CH 2 -NH 2 , -CH 2 -CH 2 -CH 2 -NH (CH 3 ) , -CH 2 -CH 2 -CH 2 -NH-CH 2 -CH 2 -NH 2 , - CH 2 -CH 2 -CH 2 -NH-CH 2 -CH 2 -N (CH 3 ) 2 , -CH 2 -CH 2 -CH 2 -NH-CH 2 -CH 2 -NH (CH 2 CH 3 ) , -CH 2 -CH 2 -CH 2 -NH-CH 2 -CH 2 -NH (CH 2 CH 3 ) , -CH 2 -CH 2 -CH 2 -NH-CH 2 -CH 2 -
• the gelation time adjusting additive in the present invention serves to adjust the gelation time of a silicone oil in the composition of the present invention.
• the structural formula is represented by the aforementioned chemical formula (2) .
• R 7 is a monovalent to trivalent saturated or unsaturated hydrocarbon functional group having 3 to 60 carbon atoms, which may have a branched structure therein or an ester bond, an ether bond, or a hydroxyl group. Specific examples thereof may include an alkoxy group such as a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a
• R 8 is a divalent hydrocarbon group and examples thereof may include an alkylene group having 2 to 4 carbon atoms such as an ethylene group and a propylene group.
• p is an integer of 3 to 200
• q is an integer of 1 to 3.
• the compound satisfying the aforementioned chemical formula (2) may be mentioned various organic compounds containing polyoxyalkylene units, and examples thereof may include a polyoxyalkylene adduct of an aliphatic alcohol such as a polyoxyethylene dodecyl ether, a fatty acid ester of a polyoxyalkylene such as a polyoxyethylene oleate, and a
• polyoxyethylene (hydrogenated) castor oil polyoxyethylene (hydrogenated) castor oil.
• silicone oil in which a gelation time has been adjusted characterized by including the steps of:
• the method for designing a silicone oil composition containing the silicone oil defined by the above-described chemical formula (1) and the gelation time adjusting additive defined by the above-described chemical formula (2) is a method for designing a silicone oil composition in which a gelation time has been adjusted, characterized by including the steps of:
• each of the above steps may be performed in any order.
• considering a silicone oil and a silicone oil composition each of the above steps may be performed in any order.
• the most preferable designing method may be exemplified as follows.
• the type of a silicone oil is preferably selected according to a required heating
• a specific heating temperature is determined within the above-described temperature range and a required gelation time of a silicone oil is further determined. After determining these, a
• silicone oil to be used is determined.
• a silicone oil having an amino-modified group is specified as the type of a silicone oil to be used.
• a shift is preferably made to a step of obtaining an approximate formula.
• an approximate formula is derived using three factors, namely, an amino equivalent, a viscosity at the normal temperature, and a both-terminal reactive functional group ratio of the silicone oil, as variables.
• G, A, B, and C represent a gelation time, an amino equivalent, a viscosity at the normal
• a is a proportional constant determined by a measurement value of G.
• Exponents a, b, and c and the proportional constant a are required for performing fitting so as to calculate the measured gelation time, and they are real numbers determined by a temperature to which the silicone oil is exposed and satisfy a > 0, b > 0, c > 0, and a > 0.
• the above-described formula (1) is characterized by being an approximate formula which is derived on the basis of the following phenomenon related to the gelation time and the structural factors.
• b, c and the proportional constant a in the above-described formula (1) may vary between a silicone oil with an amino-modified group and a silicone oil without an amino-modified group even at the same predetermined heating temperature.
• the silicone oils By measuring the gelation time of various silicone oils placed at a high temperature within the above-described temperature range, the silicone oils can be roughly classified into a short gelation time group and a long gelation time group .
• a shift is preferably made to a next step of selecting any two of the amino equivalent, the viscosity at the normal temperature, and the both-terminal reactive functional group ratio according to a function required for the silicone oil and determining the remaining one factor on the basis of the approximate formula obtained at the required heating
• each of the steps may be performed in any order. Further, the step of designing the gelation time adjusting additive may be performed simultaneously or sequentially with the designing of the silicone oil. Note that, according to the exemplified designing method, it becomes possible to preferentially determine the structural factors important for expressing a function of the silicone oil and further efficiently adjust the gelation time so as to promote or prevent the gelation, at a high temperature without a restriction on the silicone oil. This is because the gelation time adjusting additive provided by the present invention acts only on the gelation time and the effects on the expression of the function of the silicone oil are
• the gelation time adjusting additive selected in the method for designing a silicone oil composition is selected on the basis of the following tendency shown by a silicone oil in response to the addition molar number of the polyoxyalkylene unit contained in the additive.
• polyoxyalkylene unit contained in the gelation time adjusting additive on the gelation time of the silicone oil composition at a high temperature of 160 to 300°C exhibits two different behaviors depending on the gelation time of the silicone oil alone. That is, in a silicone oil belonging to a group in which the gelation time is short at a predetermined heating temperature, when the addition molar number of the
• the gelation time of the silicone oil composition is longer than that of the silicone oil, and the amount of change in the gelation time tends to become larger as the addition molar number of the unit becomes smaller.
• the gelation time of the silicone oil composition is shorter than that of the silicone oil, and the amount of change in the gelation time tends to become larger as the addition molar number of the unit becomes larger.
• the addition molar number of the silicone oil is long at a predetermined heating temperature
• the gelation time of the silicone oil composition is shorter than that of the silicone oil, and the amount of change in the gelation time tends to become larger as the addition molar number of the unit becomes smaller.
• the gelation time of the silicone oil composition is longer than that of the silicone oil, and the amount of change in the gelation time tends to become larger as the addition molar number of the unit becomes larger.
• selection of the gelation time adjusting additive is based on a comparison of the gelation time obtained by the above-described approximate formula with the required gelation time in the silicone oil satisfying the appropriate structural factors and is performed in accordance with, for example, the following guideline that is based on a relation between the addition molar number of the polyoxyalkylene in the gelation time adjusting additive and the gelation time.
• a gelation time adjusting additive having the addition molar number of a polyoxyalkylene unit close to a lower or upper limit in the above-described range is selected, otherwise, a gelation time adjusting additive having the addition molar number of the
• polyoxyalkylene unit close to an intermediate value in the above-described range is selected.
• a gelation time adjusting additive in accordance with the required gelation time of the silicone oil can be selected.
• the gelation time adjusting additive needs to be a surfactant, and it is preferable that 100 parts by mass of the emulsion contain 1 to 10 parts by mass of the gelation time adjusting additive and 10 to 50 parts by mass of the silicone oil. If the components do not satisfy the respective ranges in terms of parts by mass, it is not possible to maintain high emulsion stability as an
• suitable known method can be adopted.
• a method of mixing the respective components constituting the emulsion may be mentioned a method of mixing the respective components constituting the emulsion, gradually injecting water into the mixture under an environment in which a
• antioxidants such as an acidic phosphate ester, phenol-based, amine-based, sulfur-based, phosphorus-based, and quinone-based
• antioxidants an antistatic agent such as a higher alcohol, a sulfonate, and an amine salt-type cationic surfactant; a preservative; and an acetic anhydride compound intended to suppress the yellowing of silicone oils containing amino groups at a high temperature.
• temperature of 160 to 300°C may include a mold release agent in rubber and plastic molding applications and aluminum die casting applications, a lubricant for movable parts of
• the viscosity thereof is the most important factor, with the preferable range of 350 mm 2 /s to 1,000 mm 2 /s.
• the mold releasing ability decreases in both the cases where the viscosity is lower than 350 mm 2 /s and where it is higher than 1,000 mm 2 /s.
• the second most important factor is the gelation time, and the silicone composition applied to a mold is quickly gelatinized by heating, so that a uniform mold
• the silicone oil is typically used at a predetermined heating temperature of 300°C, and the viscosity thereof is the most important factor, with the preferable range of around 10,000 mm 2 /s.
• the silicone oil is typically used in the temperature range of 100 to 200°C.
• the amino equivalent is the most important factor, and a high amino equivalent can impart high flexibility to the fibers, but yellowing over time becomes a problem. At low amino equivalents, flexibility can be
• the second most important factor is the both-terminal reactive functional group ratio. Since the higher the both-terminal reactive functional group ratio, the higher the obtained repulsion and slip property are, an appropriate both-terminal reactive functional group ratio is selected according to the purpose.
• the third most important factor is the gelation time.
• the gelation time is short, the volatilization of the silicone composition applied to the fibers can be suppressed, so that high-quality fibers can be produced.
• the gelation time is long, the silicone composition
• Viscosity is also important, and an appropriate viscosity is selected according to the purpose because the higher viscosity can improve the slip property.
• the silicone oil is typically used in the temperature range of 200 to 300°C, and the amino equivalent is the most important factor.
• the amino equivalent preferably falls within the range of 700 g/mol to 6,000 g/mol for strongly adhering the silicone composition to the carbon fibers.
• the second most important factor is the viscosity with the preferable range of 50 mm 2 /s to 5,000 mm 2 /s for the uniform application of the silicone composition onto the carbon fibers.
• the third most important factor is the gelation time. When the gelation time is short, the
• the silicone composition transferred onto the roller or the like is not gelatinized and does maintain fluidity, so that the frequency of equipment protection cleaning can be kept low and productivity can be increased.
• suppressed gelation of the silicone oil at a high temperature of about 200 to 300°C can extend the time for which the oil transferred to the roller or the like is kept in a fluidized state, so that the frequency of equipment protection cleaning can be kept low and productivity can be increased.
• the structural factors of the respective silicone oils and the factors to be weighted within the gelation time are different from one another, and the factors to be given priority are determined in certain numerical value ranges, respectively; however, the above-described approximate formula (1) can be applied to all of the numerical value ranges.
• A-l Amino-modified silicone, viscosity: 5,000 mm 2 /s, amino equivalent: 7,000 g/mol, and both-terminal reactive functional group ratio: 100%
• A-2 Amino-modified silicone, viscosity: 800 mm 2 /s, amino equivalent: 5,000 g/mol, and both-terminal reactive functional group ratio: 5%
• A-3 polydimethylsiloxane, viscosity: 6,000 mm 2 /s, both- terminal reactive functional group ratio: 100%
• B-3 Gelation time adjusting additive having a surfactant structure, 57 carbon atoms, and 200 polyoxyalkylene units
• a, b, c, and a were obtained using a plurality of amino-modified silicones containing the above-described components (A-l, 2).
• the gelation time of each component was measured by adopting the following method for measuring a gelation time (measured only at 250°C) . This measurement result and a viscosity at the normal temperature, a both-terminal reactive functional group ratio, and an amino equivalent of each component were used to obtain a, b, c, and a in the above- described formula (1) .
• a plurality of the compositions was prepared and tested multiple times under respective test conditions of 200°C and 250°C to measure the gelation time.
• the gelation time was determined by measuring the tack free time.
• the tack free time was a time until a sample touched with a metal rod did not stick to the rod any more.
• A-l and B-l were mixed by using a spatula in an aluminum cup so that A-l/B-1 became 1.8 g/ 0.2 g to prepare a silicone oil composition.
• the resulting silicone oil composition was allowed to stand at 200°C or 250°C, and the gelation time was measured while a rod was brought into contact therewith over time.
• Example 2 was performed in the same manner as that in Example 1 described above except that B-2 was used instead of B-l of Example 1.
• Example 3 was performed in the same manner as that in Example 1 described above except that B-3 was used instead of B-l of Example 1.
• Example 4 was performed in the same manner as that in Example 1 described above except that A-2 was used instead of A-l of Example 1.
• Example 5 was performed in the same manner as that in Example 4 described above except that B-2 was used instead of B-l of Example 4.
• Example 6 was performed in the same manner as that in Example 4 described above except that B-3 was used instead of B-l of Example 4.
• Example 7 was performed in the same manner as that in Example 1 described above except that A-3 was used instead of A-l of Example 1.
• Example 8 was performed in the same manner as that in Example 7 described above except that B-2 was used instead of B-l of Example 7.
• Example 9 was performed in the same manner as that in Example 7 described above except that B-3 was used instead of B-l of Example 7.
• an amino-modified silicone needed to be used at 250°C with the viscosity of 5,000 mm 2 /s, the both-terminal reactive functional group ratio of 100%, and the gelation time of 30 minutes at 250°C needed from the standpoint of a function required for the silicone.
• an amino-modified silicone needed to be used as well as the oil A-2 from the standpoint of a function required for the silicone with the gelation time of 180 minutes at 250°C needed.
• an amino-modified silicone needed to be used as well as the oil A-2 from the standpoint of a function required for the silicone with the gelation time of 250 minutes at 250°C needed.
• Comparative Example 2 Comparative Example 2 was performed in the same manner as that in Comparative Example 1 except that A-2 was used instead of A-l of Comparative Example 1.
• Comparative Example 3 was performed in the same manner as that in Comparative Example 1 except that A- 3 was used instead of A-l of Comparative Example 1.
• an amino-modified silicone needed to be used at 250°C with the viscosity of 5,000 mm 2 /s and the both-terminal reactive functional group ratio of 100% needed from the standpoint of a function required for the silicone. Further, the gelation time of the oil needed to be 35 minutes in this application.
• the only way to reach the gelation time of the target oil was to set the amino equivalent in a trial and error manner.
• an amino-modified silicone needed to be used at 250°C with the viscosity of 800 mm 2 /s and the both-terminal reactive functional group ratio of 5% needed from the standpoint of a function required for the silicone. Further, the gelation time of the oil needed to be 225 minutes in this application.
• the amino equivalent obtained by the above-described approximate formula (1) was 5,000 g/mol although the amino equivalent needed to be 7,000 to 9,000 g/mol.
• a silicone oil having the optimal structural factors that is, the amino equivalent of 7,000 to 9,000 g/mol, the viscosity of 800 mm 2 /s, and the both-terminal reactive functional group ratio of 5%, was selected and the structural factors were investigated multiple times within the numerical values or numerical value ranges defined above using the above-described approximate formula (1), the obtained gelation time did not satisfy the required gelation time. Further, without adding a gelation time adjusting additive to the silicone oil, it was difficult to adjust the gelation time to the required gelation time without sacrificing any of the amino equivalent, the viscosity, and the both-terminal reactive functional group ratio.
• the gelation time obtained in a silicone oil alone can be changed in multiple ways by a gelation time adjusting additive
• the component (B-l) which is a gelation time adjusting additive having the small addition molar number of the polyoxyalkylene unit, is simultaneously used with the silicone oil.
• the gelation time needs to be longer (for example, about 340 minutes) or the gelation time needs to be changed by about several minutes (for example, about 200 minutes) as compared with the gelation time obtained in the silicone oil alone, as shown in Example 12, a gelation time adjusting additive of each component (B-l, 2) is
• the gelation time can be adjusted.
• a gelation time adjusting additive does not need to be used. If not, a gelation time adjusting additive is used, allowing designing of a silicone oil and a silicone oil composition in which the gelation time has been adjusted to the required gelation time while the structural factors of the silicone oil are optimally maintained.
• a silicone oil cannot be efficiently designed without using any one of the above- described approximate formula (1) and the gelation time adjusting additive, making it difficult to design a silicone oil composition in which the gelation time has been adjusted while the structural factors are optimized.
• the silicone oil composition of the present invention in which a gelation time has been efficiently adjusted so as to promote or prevent gelation of the silicone oil under a high temperature condition can be suitably used for applications in which the silicone oil is used at a high temperature, such as a mold release agent in rubber and plastic molding
• lubricant for movable parts of machines exposed to high temperatures and high friction conditions a heat medium, an aramid-polyimide fiber treating agent, and a carbon fiber treating agent. Since the gelation time of a silicone oil at a high temperature can be adjusted, the technique can be expected to be used in various novel applications in the technical field which have not been known.

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