WO2020074277A1 - Silicone oil composition, gelation time adjusting additive, and method for designing silicone oil and silicone oil composition - Google Patents

Silicone oil composition, gelation time adjusting additive, and method for designing silicone oil and silicone oil composition Download PDF

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Publication number
WO2020074277A1
WO2020074277A1 PCT/EP2019/076242 EP2019076242W WO2020074277A1 WO 2020074277 A1 WO2020074277 A1 WO 2020074277A1 EP 2019076242 W EP2019076242 W EP 2019076242W WO 2020074277 A1 WO2020074277 A1 WO 2020074277A1
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Prior art keywords
silicone oil
gelation time
chemical formula
group
functional group
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PCT/EP2019/076242
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French (fr)
Inventor
Satoshi Ohno
Keiya HIGO
Kenji Igarashi
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Wacker Chemie Ag
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Publication of WO2020074277A1 publication Critical patent/WO2020074277A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • 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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Abstract

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.

Description

DESCRIPTION
SILICONE OIL COMPOSITION, GELATION TIME ADJUSTING ADDITIVE,
AND METHOD FOR DESIGNING SILICONE OIL AND SILICONE OIL COMPOSITION
TECHNICAL FIELD
[0001]
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.
BACKGROUND ART
[0002]
A silicone oil, which is generally a colorless
transparent liquid, is excellent in heat resistance and cold resistance, is chemically inactive, has little change in a viscosity with temperature, and has small surface tension as compared with a mineral oil and an organic oil such as a vegetable oil. Thus, 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.
In this regard, 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. However, for example, when the temperature of the silicone oil reaches a high temperature of 160 to 300°C, the silicone oil becomes thickened and gelatinized. In the above industrial fields, in a case where a silicone oil is used at a high temperature of 160 to 300°C, it is ideal that 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.
[0003]
Regarding this point, the technique described in Patent Literature 1 is focused on prevention of gelation at a high temperature when a silicone oil is used for a fiber
application .
More specifically, when a high performance carbon fiber is produced by using an acrylic fiber for carbon fiber
production as a precursor fiber and performing respective treatments of flameproofing and firing, 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.
In particular, when an amino-modified silicone oil agent having high thermal cross-linking properties is used, the amino-modified silicone oil agent is easily formed into a film or becomes adhesive on a fiber or a drying roller. In this regard, 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.
[0004]
However, the following technical problems exist in technique described in Patent Literature 1.
First, 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.
Second, the silicone oil agent is limited to the amino- modified silicone oil agent. More specifically, the compound having a primary amino group and an oxyalkylene group can prevent gelation of the amino-modified silicone oil agent having high thermal cross-linking properties in the presence of a surfactant. However, there is no description as to whether the same is applicable to a non-reactive silicone oil agent .
Third, 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.
Fourth, although gelation can be prevented by the compound having a primary amino group and an oxyalkylene group, it is still difficult to adjust a time of gelation of an amino-modified silicone oil agent caused by heating.
[0005]
Regarding this point, Patent Literature 2 discloses a fiber bundle to which a silicone oil is attached.
Specifically, 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. However, the disclosure is not directly focused on gelation, much less on a gelation time, of an oil agent at a high temperature.
[0006]
Regarding this point, Patent Literature 3 discloses an emulsion composition that restricts the viscosity of a
silicone oil aiming at the same effects as that of Patent Literature 2. However, Patent Literature 3 is not directly focused on a gelation time at a high temperature.
[0007]
Note that, in 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.
[0008]
Patent Literature 1: W02018/003347
Patent Literature 2: Japanese Patent Application Laid- Open No. 2016-199824
Patent Literature 3: Japanese Patent No. 6017109
SUMMARY OF INVENTION TECHNICAL PROBLEM
[0009]
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
composition .
Furthermore, another object of the present invention is to provide a method for designing a silicone oil or a silicone oil composition in which a structural factor important for expressing a function of the silicone oil is preferentially determined and further a gelation time can be efficiently adjusted so as to promote or prevent gelation at a high temperature without a restriction on the silicone oil.
SOLUTION TO PROBLEM
[0010]
As a result of extensive studies, the present inventors paid attention to a fact that a gelation time of a silicone oil particularly at a high temperature of 160 to 300°C is significantly influenced by three structural factors, namely, an amino equivalent, a viscosity at the normal temperature, and a both-terminal reactive functional group ratio, which govern a function to be performed by the silicone oil at the high temperature, and is changed by an additive containing a polyoxyalkylene unit. Consequently, the present inventors have found that 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.
[0011]
That is, the composition provided by the present
invention is a 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
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 .
Note that the required gelation time refers to a gelation time at a temperature to which the silicone oil or the
silicone oil composition is exposed in a use environment of the silicone oil.
[0012]
[Chemical Formula 1]
Figure imgf000007_0001
In the chemical formula (1), R1 to R6 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 having 1 to 14 carbon atoms, 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 1.
[0014]
[Chemical Formula 2]
R7 (- (O-R8-) r-OH) (2)
[0015]
In the chemical formula (2), R7 is a monovalent to trivalent saturated or unsaturated hydrocarbon functional group having 3 to 60 carbon atoms, and R8 is a divalent hydrocarbon group having 2 to 4 carbon atoms, r is an integer from 3 to 200, and s is an integer from 1 to 3.
[0016]
Furthermore, the gelation time adjusting additive of the present invention, which is to be added to the silicone oil, is defined by the following chemical formula (2) and
characterized in that the addition molar number of the
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. [0017]
[Chemical Formula 2]
R7 (- (O-R8-) r-OH) s (2)
[0018]
In the chemical formula (2), R7 is a monovalent to trivalent saturated or unsaturated hydrocarbon functional group having 3 to 60 carbon atoms, and R8 is a divalent
hydrocarbon group having 2 to 4 carbon atoms, r is an integer from 3 to 200, and s is an integer from 1 to 3.
[0019]
Furthermore, the method for designing a silicone oil of the present invention is a method for designing a silicone oil in which a gelation time has been adjusted, characterized by including the steps of:
selecting a required heating temperature, a required gelation time, and a type of a silicone oil according to an application of the silicone oil;
obtaining an approximate formula between three structural factors of an amino equivalent, a viscosity at the normal temperature, and a both-terminal reactive functional group ratio, and the gelation time at the required heating
temperature ;
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 at the required heating temperature; and
repeating the previous step using the approximate formula if the remaining one factor fails to satisfy the function required for the silicone oil.
[0020]
Still further, 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:
selecting a required heating temperature, a required gelation time, and a type of a silicone oil according to an application of the silicone oil;
obtaining an approximate formula between three structural factors of an amino equivalent, a viscosity at the normal temperature, and a both-terminal reactive functional group ratio, and the gelation time at the required heating
temperature ;
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 temperature;
repeating the previous step using the approximate formula if the remaining one factor fails to satisfy the function required for the silicone oil; and
adding a gelation time adjusting additive in which the addition molar number of the polyoxyalkylene unit has been adjusted according to the required gelation time at the required heating temperature.
EFFECTS OF INVENTION
[0021]
According to the present invention, there can be provided 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,
regardless of whether the silicone oil is a reactive or non reactive silicone oil.
According to the present invention, there can be provided the method for designing a silicone oil in which a gelation time has been adjusted, the method including the steps of:
selecting a required heating temperature, a required gelation time, and a type of a silicone oil according to an application of the silicone oil represented by the following chemical formula (1);
obtaining an approximate formula between three structural factors, namely, an amino equivalent, a viscosity at the normal temperature, and a both-terminal reactive functional group ratio, and the gelation time at the required heating temperature ;
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 at the required heating temperature; and
repeating the previous step using the aforementioned approximate formula if the remaining one factor fails to satisfy the function required for the silicone oil.
Furthermore, there can be provided the method for
designing a silicone oil composition in which a gelation time has been adjusted, the method including the steps of:
selecting a required heating temperature, a required gelation time, and a type of a silicone oil according to an application of the silicone oil;
obtaining an approximate formula between three structural factors, namely, an amino equivalent, a viscosity at the normal temperature, and a both-terminal reactive functional group ratio, and the gelation time at the required heating temperature ;
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 temperature;
repeating the previous step using the aforementioned approximate formula if the remaining one factor fails to satisfy the function required for the silicone oil; and
adding a gelation time adjusting additive in which the addition molar number of the polyoxyalkylene unit has been adjusted according to the required gelation time at the required heating temperature.
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.
[0022]
[Chemical Formula 1]
R3 R4 R5 R6
R1 S i O (S i O) p (S i O) , S i R2 (1)
CH3 CH3 CH3 CH3
[0023]
In the chemical formula (1), R1 to R6 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
1.
[0024]
[Chemical Formula 2]
R7 (- (O-R8-) r-OH) s (2)
[0025]
In the chemical formula (2), R7 is a monovalent to trivalent saturated or unsaturated hydrocarbon functional group having 3 to 60 carbon atoms, and R8 is a divalent
hydrocarbon group having 2 to 4 carbon atoms, r is an integer from 3 to 200, and s is an integer from 1 to 3.
Embodiments of Invention
[0026]
Hereinafter, the present invention will be described in detail. 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. Each of the components constituting the composition of the present
invention and the method for designing the silicone oil and the silicone oil composition will be described below.
[0027]
The composition of the present invention is characterized by containing a silicone oil represented by the aforementioned chemical formula (1) .
[0028]
In the aforementioned chemical formula (1), when the R1 to R6 are each a nitrogen-containing group, the nitrogen- containing group may be specifically represented by the following general chemical formula (3) .
[0029] [Chemical Formula 3]
-R9- (NH-R10) t-N-R1 1 (3)
R1 2
[0030]
In the chemical formula (3) , R9 to R10 are each a
saturated hydrocarbon group having 1 to 5 carbon atoms, R11 to R12 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 -CH2-CH2-CH2-NH (CH3) , -CH2-CH2-CH2-N (CH3) 2, -CH2-CH2-NH- CH2-CH2-NH2, -CH2-CH2-CH2-NH (CH3) , -CH2-CH2-CH2-NH-CH2-CH2-NH2, - CH2-CH2-CH2-NH-CH2-CH2-N (CH3) 2, -CH2-CH2-CH2-NH-CH2-CH2-NH (CH2CH3) , -CH2-CH2-CH2-NH-CH2-CH2-N (CH2CH3) 2, and -CH2-CH2-CH2-NH-CH2-CH2- NH (cyclo-C6Hn) .
[0031]
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) .
[0032]
In the chemical formula (2), R7 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
pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, and an icosyl group; and fatty acid ester groups having a hydroxyl group an alkoxy group such as an oleate group, and a hydrogenated or
nonhydrogenated castor oil.
[0033]
In the chemical formula (2), R8 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.
[0034]
In the chemical formula (2), p is an integer of 3 to 200, and q is an integer of 1 to 3. When p is 3 or more and 200 or less, volatilization of the gelation time adjusting additive is suppressed at a high temperature of 160 to 300°C, and an adjusting function for the gelation time of the silicone oil composition can be exhibited.
[0035]
As 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.
[0036]
The method for designing the silicone oil defined by the above-described formula (1) is a method for designing a
silicone oil in which a gelation time has been adjusted, characterized by including the steps of:
selecting a required heating temperature, a required gelation time, and a type of a silicone oil according to an application of the silicone oil;
obtaining an approximate formula between three structural factors of an amino equivalent, a viscosity at the normal temperature, and a both-terminal reactive functional group ratio, and the gelation time at the required heating
temperature ;
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 temperature; and
repeating the previous step using the approximate formula if the remaining one factor fails to satisfy the function required for the silicone oil.
[0037]
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:
selecting a required heating temperature, a required gelation time, and a type of a silicone oil according to an application of the silicone oil;
obtaining an approximate formula between three structural factors of an amino equivalent, a viscosity at the normal temperature, and a both-terminal reactive functional group ratio, and the gelation time at the required heating
temperature ;
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 temperature;
repeating the previous step using the approximate formula if the remaining one factor fails to satisfy the function required for the silicone oil; and
adding a gelation time adjusting additive in which the addition molar number of the polyoxyalkylene unit has been adjusted according to the required gelation time at the required heating temperature.
[0038]
The above-described methods for designing a silicone oil and a silicone oil composition are characterized in that both methods follow the same steps until halfway. On the other hand, these methods are distinguished according to whether a gelation time adjusting additive needs to be finally used or not to optimize three structural factors of the silicone oil and the gelation time. Thus, first, the common steps of the methods for designing a silicone oil and a silicone oil composition will be described below.
In the above-described methods for designing a silicone oil and a silicone oil composition, each of the above steps may be performed in any order. However, considering a
required function and a use environment, the most preferable designing method may be exemplified as follows.
[0039]
In the initial step of designing a silicone oil and a silicone oil composition, the type of a silicone oil is preferably selected according to a required heating
temperature and a required gelation time depending on an application of the silicone oil. Herein, the description is based on the premise that, in an application of using a silicone oil at a high temperature of 160 to 300°C, 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.
For example, in the application of using a silicone oil at a high temperature of 160 to 300°C, an appropriate heating temperature and gelation time are determined. Then, in a case where a silicone oil having an amino-modified group is
necessarily used from the standpoint of a function required for the silicone oil, a silicone oil having an amino-modified group is specified as the type of a silicone oil to be used.
[0040]
Next, a shift is preferably made to a step of obtaining an approximate formula. In this step, on the basis of the premise that the heating temperature within a temperature range of 160 to 300°C and the type of a silicone oil to be used have been determined, 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.
[0041]
This approximate formula can be obtained without
particularly being restricted by numerical value ranges of the amino equivalent, the viscosity at the normal temperature, and the both-terminal reactive functional group ratio of the silicone oil, and is characterized in that it can be obtained as a formula such as the following formula (1) using actual measurement values of the gelation time obtained from a plurality of silicone oils of the same type at a certain predetermined heating temperature within a temperature range of 160 to 300°C, and three structural factors of the amino equivalent, the viscosity at the normal temperature, and the both-terminal reactive functional group ratio.
[0042] (Formula 1)
G = a-Aa/ (Bb-Cc) (1)
[0043]
In the formula (1), G, A, B, and C represent a gelation time, an amino equivalent, a viscosity at the normal
temperature, and a both-terminal reactive functional group ratio, respectively, 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.
[0044]
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.
At a high temperature of 160 to 300°C, a phenomenon occasionally occurred that the gelation time of a silicone oil depended on the amino equivalent, the viscosity at the normal temperature, and the both-terminal reactive functional group ratio of the silicone oil. More specifically, a phenomenon occasionally occurred that as the amino equivalent of the silicone oil became larger or the viscosity at the normal temperature and/or the both-terminal reactive functional group ratio became smaller, the gelation time of the silicone oil at the aforementioned high temperature became longer. In view of this observation, the amino equivalent was used as a base to set an exponential function with a positive exponent, and the viscosity at the normal temperature and the both-terminal reactive functional group ratio were each used as a base to set an exponential function having a negative exponent. Then, the product of these three exponential functions was calculated. This made it possible to obtain a measurement value of the gelation time corresponding to each of a
plurality of silicone oils.
The above-described approximate formula (1) can also be obtained for a silicone oil without an amino-modified group.
In this case, an approximate formula is obtained by setting Aa in the right side of the above-described approximate formula (1) to 1 and using only the viscosity at the normal
temperature and the both-terminal reactive functional group ratio of the silicone oil. However, note that 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.
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 .
[0045]
After obtaining the above-described approximate formula (1), 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
temperature. In this step, the required gelation time
determined in the initial step is applied to the above- described approximate formula (1), and then two of the
structural factors defined into three were applied to the above-described approximate formula (1) to determine the remaining one factor. The optimal structural factors vary depending on an application of a silicone oil. However, they are often set as numerical value ranges. In this case, any values within the numerical value ranges are applied to the approximate formula to determine the remaining one structural factor which is lastly determined. In a case where the remaining one factor is also defined by a numerical value range, it is confirmed whether the lastly determined
structural factor is within the numerical value range, and, in a case where the remaining one factor is not defined by a numerical value range (but defined by a certain numerical value) , it is confirmed whether the lastly determined
structural factor matches with the numerical value. In both cases, in a case where the remaining one factor does not satisfy a function required for the silicone oil, a shift is made to a step of repeating the previous step in which any numerical values within the appropriate numerical value ranges are selected again for the two structural factors and applied to the above-described approximate formula (1) to examine whether the remaining one factor is an appropriate value using the above-described approximate formula.
[0046]
In a case where, after performing the above-described steps, the remaining one factor falls outside the appropriate numerical value range or the appropriate value determined according to the application of the silicone oil despite repeatedly performing investigation so as to obtain the required gelation time from the above-described approximate formula (1), a silicone oil in which all of the structural factors satisfy the appropriate numerical value ranges or the appropriate values is selected. The gelation time obtained by the above-described approximate formula (1) using the
structural factors of the silicone oil is deviated from the required gelation time. Thus, a shift is made to a step of using a gelation time adjusting additive as a silicone oil composition and a step of adjusting the gelation time to the required gelation time.
[0047]
That is, the above-described method for designing a silicone oil composition is a designing method to be performed when a silicone oil is designed by preferentially determining the structural factors of the silicone oil and then the gelation time obtained by applying the structural factors to the above-described approximate formula (1) is deviated from the required gelation time. This designing method can adjust only the gelation time by the addition molar number of the polyoxyalkylene unit in the gelation time adjusting additive even if the gelation time is deviated from the required gelation time by optimizing all of the structural factors, making it possible to adjust the gelation time to the required gelation time while optimizing the preferentially determined structural factors.
In the methods for designing a silicone oil and a silicone oil composition, 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
negligible in most cases. Further, in the present invention, it is found that the approximate formula (1) exemplified in the above is a useful relational formula for efficiently performing the step of designing a silicone oil.
[0048]
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.
The effect of the addition molar number of the
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
polyoxyalkylene unit contained in the gelation time adjusting additive is small, 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.
Conversely, when the addition molar number of a
polyoxyalkylene unit contained in the gelation time adjusting additive is large, 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. On the other hand, in a silicone oil belonging to a group in which the gelation time is long at a predetermined heating temperature, when the addition molar number of the
polyoxyalkylene unit contained in the gelation time adjusting additive is small, 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.
Conversely, when the addition molar number of the
polyoxyalkylene unit contained in the gelation time adjusting additive is large, 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.
Thus, 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.
[0049]
In a case of a silicone oil belonging to a group in which a gelation time is short at a predetermined heating
temperature, if the gelation time of the silicone oil at a high temperature of 160 to 300°C obtained by the approximate formula of a gelation time is shorter than the required gelation time, a gelation time adjusting additive having the small addition molar number of the polyoxyalkylene unit is selected. On the other hand, if the gelation time obtained by the approximate formula is longer than the required gelation time, a gelation time adjusting additive having the large addition molar number of the polyoxyalkylene unit is selected. In both cases, if the gelation time obtained by the
approximate formula is significantly deviated from the
required gelation time, a gelation time adjusting additive having the addition molar number of the polyoxyalkylene unit close to a lower or upper limit of 3 to 200 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. Under this guideline, a gelation time adjusting additive in accordance with the required gelation time of the silicone oil can be selected.
On the other hand, in a case of a silicone oil belonging to a group in which a gelation time is long at a predetermined heating temperature, if the gelation time of the silicone oil at a high temperature of 160 to 300°C obtained by the
approximate formula of a gelation time is shorter than the required gelation time, a gelation time adjusting additive having the large addition molar number of the polyoxyalkylene unit is selected. On the other hand, if the gelation time obtained by the approximate formula is longer than the
required gelation time, a gelation time adjusting additive having the small addition molar number of the polyoxyalkylene unit is selected. In both cases, if the gelation time
obtained by the approximate formula is significantly deviated from the required 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. Under this guideline, a gelation time adjusting additive in accordance with the required gelation time of the silicone oil can be selected.
[0050]
When the gelation time adjusting additive in which the addition molar number of the polyoxyalkylene unit has been adjusted is added to the silicone oil according to the above- described guideline, the additive is added preferably in an amount of 10 parts by mass relative to 10 to 99 parts by mass of the silicone oil (additive/silicone oil=10/10 to 99), and more preferably in an amount of 10 parts by mass relative to 10 to 90 parts by mass of the silicone oil (10/10 to 90) .
When the mass ratio of the additive/silicone oil does not fall within this range, the effect of adjusting the gelation time as the gelation time adjusting additive is not exhibited.
[0051]
The silicone oil compositions designed by the
aforementioned method are used in a case where the gelation time adjusting additive is added directly to the silicone oil and in a case where the composition is prepared as an oil-in water emulsion emulsified in water.
In the case of an emulsion, 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
emulsion .
At this time, a method of emulsifying and dispersing each of the components is not particularly limited, and any
suitable known method can be adopted. As examples of such a technique, 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
mechanical shearing force is applied by using a homogenizer, a homomixer, or the like, and phase-transfer emulsifying the mixture .
[0052] Other compounds may be added to the silicone oil composition of the present invention as long as they are not inconsistent with the spirit of the present invention.
Examples of such other compounds may include an antioxidant 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.
[0053]
The silicone oil composition of the present invention may contain a silicone oil such as an aminopolyether-modified silicone, an amide-modified silicone, an amide polyether- modified silicone, an alkyl-modified silicone, or an alkoxy- modified silicone, as long as the silicone oil belonging to the group in which the gelation time is short is not mixed with the silicone oil belonging to the group in which the gelation time is long. The silicone oil may be used alone or a plurality of the silicone oils may be used in combination.
[0054]
Among the four factors of structural factors and gelation time determined at the time of designing of the silicone oil and silicone oil composition, particularly important factors are described below for each application of the silicone oil. Examples of applications using silicone oils at a high
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
machines exposed to high temperatures and high friction conditions, a heat medium, an aramid-polyimide fiber treating agent, and a carbon fiber treating agent. Different factors are considered important depending on the respective applications. In addition, the numerical value ranges or numerical values of the structural factors to be optimized differ from each other.
[0055]
In rubber and plastic molding applications, the silicone oil is typically used in temperatures ranging from 100 to
250°C, and the viscosity thereof is the most important factor, with the preferable range of 350 mm2/s to 1,000 mm2/s. The mold releasing ability decreases in both the cases where the viscosity is lower than 350 mm2/s and where it is higher than 1,000 mm2/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
releasing effect can be obtained.
[0056]
In aluminum die casting applications, 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 mm2/s. When the
viscosity is low, volatilization by decomposition of the silicone oil is remarkable, and when the viscosity is high, emulsification is difficult. Thus, in both the cases, it is difficult to obtain a sufficient mold releasing effect. The gelation time is also attracting attention. Here, there are two cases where a homogeneous mold releasing effect is aimed at by quick gelation and where fluidity is maintained for a long time to prevent a decrease in operability due to
gelation. Thus, the silicone oils are selectively used
according to the purpose.
[0057]
In fiber treating applications such as aramid, polyimide, etc., 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
imparted and yellowing can be suppressed. 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. When 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. On the other hand, when the gelation time is long, 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. Viscosity is also important, and an appropriate viscosity is selected according to the purpose because the higher viscosity can improve the slip property.
[0058]
In carbon fiber treating applications, 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 mm2/s to 5,000 mm2/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
volatilization of the silicone composition applied to the fibers can be suppressed, so that high-quality fibers can be produced. On the other hand, if the gelation time is long, 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. In order to balance the respective advantages of the short and long gelation times, it is preferable to have a technique of increasing the gelation time, that is, suppressing gelation, from the intrinsic gelation time of the silicone composition. More specifically, 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.
[0059]
In the above-mentioned applications, 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.
Example :
[0060]
Examples of the present invention will be described in detail below, but the present invention is not limited to the following examples. All viscosity values are viscosity values at 25°C unless otherwise specified. The respective components used in the examples, derivation of the approximate formula, and the measurement method of the gelation time are described as follows.
The mass ratios of compositions in the respective Examples and Comparative examples and the evaluation results are shown in Table 1.
[0061]
Contents of components:
A-l: Amino-modified silicone, viscosity: 5,000 mm2/s, amino equivalent: 7,000 g/mol, and both-terminal reactive functional group ratio: 100%
A-2 : Amino-modified silicone, viscosity: 800 mm2/s, amino equivalent: 5,000 g/mol, and both-terminal reactive functional group ratio: 5%
A-3: polydimethylsiloxane, viscosity: 6,000 mm2/s, both- terminal reactive functional group ratio: 100%
B-l: Gelation time adjusting additive having a surfactant structure, 13 carbon atoms, and 6 polyoxyalkylene units
B-2 : Gelation time adjusting additive having a surfactant structure, 16 carbon atoms, and 25 polyoxyalkylene units
B-3: Gelation time adjusting additive having a surfactant structure, 57 carbon atoms, and 200 polyoxyalkylene units
[0062]
Derivation of approximate formula:
In the above-described approximate formula (1), a, b, c, and a were obtained using a plurality of amino-modified silicones containing the above-described components (A-l, 2). Specifically, 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) .
[0063]
Definition of gelation time:
The gelation time was defined by a tack free time of a silicone oil particularly at high temperatures of 200 and 250°C in a temperature range of 160 to 300°C of the silicone oil.
[0064]
Method for measuring gelation time:
For each composition in Examples and Comparative
examples, 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.
[0065]
Example 1 :
The above-described 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.
[0066]
Example 2 :
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.
[0067]
Example 3 :
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.
[0068]
Example 4 :
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.
[0069]
Example 5 :
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.
[0070]
Example 6:
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.
[0071]
Example 7 :
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.
[0072]
Example 8 :
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.
[0073]
Example 9:
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.
[0074]
Example 10 :
The variables specified in the above-described
approximate formula (1) satisfied a = 1, b = 0.5, c = 0.5, and a = 3 at 250°C.
In a certain application, an amino-modified silicone needed to be used at 250°C with the viscosity of 5,000 mm2/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.
On the basis of this matter, the remaining structural factor, the amino equivalent, was obtained using the
approximate formula expressed by the above-described formula (1) . As a result, the amino equivalent was 6, 000 g/mol. This amino equivalent was found to fall within the numerical value range in which a function expected from the silicone oil was sufficiently exhibited. Thus, there was no need to adjust the gelation time.
[0075]
Example 11 :
The variables specified in the above-described
approximate formula (1) satisfied a = 1, b = 0.5, c = 0.5, and a = 3 at 250°C.
An amino-modified silicone needed to be used at 250°C with the viscosity of 800 mm2/s, the both-terminal reactive functional group ratio of 5%, the amino equivalent of 7,000 to 8,000 g/mol, and the gelation time of 250 minutes or less at 250°C from the standpoint of a function required.
On the basis of this matter, optimization of the amino equivalent was performed using the approximate formula
expressed by the above-described formula (1) . The result was 5,000 g/mol. This amino equivalent was out of the range of 7,000 to 8,000 g/mol, and thus it was determined to use a gelation time adjusting additive.
Under such circumstances, an amino-modified silicone having an amino equivalent of 7,000g/mol was selected again so as to satisfy the above-described three structural factors. Then, considering a difference between the required gelation time and the gelation time of this silicone oil obtained by the approximate formula (1) as 320 minutes, a gelation time adjusting additive having the addition molar number of the polyoxyalkylene unit of 25 in an amount of 8 parts by mass was added to the amino-modified silicone oil in an amount of 10 parts by mass to produce a silicone oil composition. In this manner, the gelation time of this composition could be
adjusted to the required gelation time of 225 minutes.
[0076]
Example 12 :
In a certain application, 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.
When 3 parts by mass and 7 parts by mass of B-l and B-2, respectively, were added to A-2 as additives for adjusting the gelation time of the component (B) , the gelation time was 175 minutes .
[0077]
Example 13:
In a certain application, 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.
When 7 parts by mass and 3 parts by mass of B-2 and B-3, respectively, were added to A-2 as additives for adjusting the gelation time of the component (B) , the gelation time was 248 minutes .
[0078]
Comparative Example 1 :
Two grams of the above-described A-l was heated in an aluminum cup at 200°C or 250°C and the gelation times were measured .
[0079]
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.
[0080]
Comparative Example 3:
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.
[0081]
Comparative Example 4 :
In a certain application, an amino-modified silicone needed to be used at 250°C with the viscosity of 5,000 mm2/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 optimum value of the amino equivalent was not known 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.
[0082]
Comparative Example 5:
In a certain application, an amino-modified silicone needed to be used at 250°C with the viscosity of 800 mm2/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. However, even though 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 mm2/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.
[0083] [Table 1]
Figure imgf000037_0001
Figure imgf000038_0001
[0084]
As evident from Examples 1 to 9 in Table 1, the gelation time obtained in a silicone oil alone can be changed in multiple ways by a gelation time adjusting additive
simultaneously used with the silicone oil. This makes it possible to obtain a silicone oil composition in which the gelation time can be adjusted in multiple ways in both
directions of prevention and promotion of the gelation by the addition molar number of the polyoxyalkylene unit in the gelation time adjusting additive.
In contrast, as evident from Comparative Examples 1 to 3 in Table 1, in the case of not including a gelation time adjusting additive having a structure of a surfactant as an example, only one gelation time can be obtained.
[0085]
As evident from Examples 1 to 9, for example, it is supposed that, in an application in which a silicone oil is used at a high temperature of 250°C, a silicone oil having the structural factors such as shown in the component (A-2) is desired to be used from the standpoint of a function expected from the silicone oil. In this case, if the requited gelation time of the silicone oil in this application is close to the gelation time of 225 minutes obtained in the silicone oil alone, the component (A-2) can be used alone. If the gelation time needs to be shorter than the gelation time obtained in the silicone oil alone (for example, about 120 minutes) , 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. On the other hand, if 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
simultaneously used with the silicone oil. In this manner, the gelation time can be adjusted.
[0086]
As evident from Examples 10 and 11, in an application of a silicone oil, when two structural factors are applied to the above-described approximate formula (1) according to a function required for a silicone oil to determine the
remaining one factor under the required gelation time, if the remaining one factor falls within an appropriate numerical value range, 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. However, as evident from Comparative Examples 4 and 5, 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.
Industrial Applicability
[0087]
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
applications and aluminum die casting applications, a
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.

Claims

1. A silicone oil composition comprising a silicone oil defined by the following chemical formula (1) and a gelation time adjusting additive defined by the following chemical formula (2), wherein
an addition molar number of the 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:
[Chemical Formula 1]
R 3 R 4 R 5 R 6
R1 S i O (SiO) (SiO) Si R2 (l)
CH3 CH3 CH3 CH3
(in the chemical formula (1), R1 to R6 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 having 1 to 14 carbon atoms, 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 1),
[Chemical Formula 2]
R7 (- (O-R8-) r-OH) (2)
(in the chemical formula (2), R7 is a monovalent to trivalent saturated or unsaturated hydrocarbon functional group having 3 to 60 carbon atoms, and R8 is a divalent hydrocarbon group having 2 to 4 carbon atoms, r is an integer from 3 to 200, and s is an integer from 1 to 3) .
2. A gelation time adjusting additive which is to be added to a silicone oil and is defined by the following chemical formula (2) wherein an addition molar number of the
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:
[Chemical Formula 2]
R7 (- (O-R8-) r-OH) s (2)
(in the chemical formula (2), R7 is a monovalent to trivalent saturated or unsaturated hydrocarbon functional group having 3 to 60 carbon atoms, and R8 is a divalent
hydrocarbon group having 2 to 4 carbon atoms, r is an integer from 3 to 200, and s is an integer from 1 to 3) .
3. A method for designing a silicone oil which is defined by the following chemical formula (1) and in which a gelation time has been adjusted, the method comprising the steps of: selecting a required heating temperature, a required gelation time, and a type of a silicone oil according to an application of the silicone oil;
obtaining an approximate formula between three structural factors of an amino equivalent, a viscosity at a normal temperature, and a both-terminal reactive functional group ratio, and the gelation time at the required heating
temperature ;
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 a basis of the approximate formula at the required heating temperature; and
repeating the previous step using the approximate formula if the remaining one factor fails to satisfy the function required for the silicone oil:
[Chemical Formula 1]
R3 R 4 R 5 R 6
R1 Si-O- (SiO) p- (SiO) q-Si-R2 (l)
CH3 CH3 CH3 CH3
(in the chemical formula (1), R1 to R6 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 having 1 to 14 carbon atoms, 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 1) .
4. A method for designing a silicone oil composition
containing a silicone oil defined by the following formula (1) and a gelation time adjusting additive defined by the
following chemical formula (2) in which a gelation time has been adjusted, the method comprising the steps of:
selecting a required heating temperature, a required gelation time, and a type of a silicone oil according to an application of the silicone oil;
obtaining an approximate formula between three structural factors of an amino equivalent, a viscosity at a normal temperature, and a both-terminal reactive functional group ratio, and the gelation time at the required heating
temperature ;
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 a basis of the approximate formula obtained at the required heating temperature;
repeating the previous step using the approximate formula if the remaining one factor fails to satisfy the function required for the silicone oil; and
adding a gelation time adjusting additive in which an addition molar number of the polyoxyalkylene unit has been adjusted according to the required gelation time at the required heating temperature:
[Chemical Formula 1]
R3 R4 R5 R6
R1 S i O (SiO) - (SiO) -Si R2 (l)
CH3 CH3 CH3 CH3
(in the chemical formula (1), R1 to R6 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 having 1 to 14 carbon atoms, 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 1),
[Chemical Formula 2]
R7 (- (O-R8-) r-OH) s (2)
(in the chemical formula (2), R7 is a monovalent to trivalent saturated or unsaturated hydrocarbon functional group having 3 to 60 carbon atoms, and R8 is a divalent
hydrocarbon group having 2 to 4 carbon atoms, r is an integer from 3 to 200, and s is an integer from 1 to 3) .
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