JP2020059799A - Silicone oil composition, gelation time control additive, silicone oil and method for designing silicone oil composition - Google Patents

Abstract

To provide a silicone oil composition that has a gelation time controlled to promote or suppress gelation under a high temperature condition without limitation on silicone oil, or a gelation time control additive therefor.SOLUTION: A silicone oil composition contains silicone oil containing a siloxane structure, and a gelation time control additive defined by the following formula (2). In the gelation time control additive, the number of moles of added polyoxyalkylene units is controlled according to the silicone oil, and a requested gelation time of the silicone oil at a predetermined heating temperature. R(-(O-R-)-OH)(2) [in formula (2), Ris a univalent to trivalent saturated or unsaturated hydrocarbon functional group with 3-60 carbon atoms, Ris a divalent hydrocarbon with 2-4 carbon atoms. r is an integer of 3-200, s is an integer of 1-3].SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a silicone oil composition, a gelling time adjusting additive, a silicone oil and a method for designing a silicone oil composition, and more specifically, promoting and suppressing gelation under high temperature conditions without restriction on silicone oil. As described above, the present invention relates to a silicone oil or a silicone oil composition whose gelation time is efficiently adjusted, and a method for designing the same.

Silicone oils are generally colorless and transparent liquids, which are superior in heat resistance and cold resistance to organic oils such as mineral oil and vegetable oil, are chemically inert, and have little change in viscosity with temperature. Since it has a low surface tension, it exhibits excellent characteristics such as electrical properties, releasability, water repellency, defoaming properties, lubricity, etc., and is widely used in the fields of electrical, mechanical, chemical industries, etc.
In this respect, silicone oil is technically advantageous in that the viscosity changes little with temperature when the use environment is high or low, but for example, the temperature reaches a high temperature of 160 to 300 ° C. Then, thickening progresses and gels. In the above industrial fields, when silicone oil is used at a high temperature such as 160 to 300 ° C., this gelation may be accelerated or suppressed from the viewpoint of the function required of silicone oil. However, it has been ideal that the gelation time can be adjusted so that it can be operated.

In this regard, in Patent Document 1, when silicone oil is used for fiber applications, attention is focused on gelation suppression at high temperatures.
More specifically, when using an acrylic fiber as a precursor fiber for carbon fiber production and subjecting it to flameproofing and firing treatments, when producing high-performance carbon fiber, flameproofing at about 160 to 300 ° C is performed. During the treatment, in order to prevent fusion of the single fibers, it is performed to coat the filament with a silicone oil agent having excellent heat resistance, particularly when using an amino-modified silicone oil agent having high heat crosslinkability, Since it is easy to form a film or an adhesive on the fiber or on the drying roller, the amino-modified silicone, the surfactant, and the compound having a primary amino group and an oxyalkylene group are used in combination to permeate the fiber. It is described that the gelation of the amino-modified silicone can be suppressed while improving the property.

However, Patent Document 1 has the following technical problems.
First, the characteristic amount of the compound having a primary amino group and an oxyalkylene group causes a reduction in the amount of silicone over time. As a result, the function originally intended for the amino-modified silicone oil agent is impaired over time.
Secondly, the silicone oil agent is limited to amino modification. More specifically, the compound having a primary amino group and an oxyalkylene group is capable of suppressing gelation with respect to an amino-modified silicone oil agent having a high thermal crosslinkability in the presence of a surfactant, There is no mention that the same can be done for non-reactive silicone fluids.
Thirdly, the compound having a primary amino group and an oxyalkylene group only serves to suppress gelation only under a surfactant, and the surfactant is required even in applications where emulsification is not required. That is the point. Since this increases the number of components in the silicone oil agent, the quality of the silicone oil oil agent may become unstable and the manufacturing cost of the oil agent may increase.
Fourthly, the gelation is suppressed by the compound having the primary amino group and the oxyalkylene group, but the gelling time by heating the amino-modified silicone oil agent cannot be adjusted.

In this regard, Patent Document 2 discloses a fiber bundle to which silicone oil is attached. Specifically, it is disclosed that the heat fusion between the fibers caused by the thermal decomposition residue at a high temperature is suppressed by reducing the ratio of the non-silicone oil agent such as a surfactant to the silicone oil agent. However, it does not directly pay attention to the gelation of the oil under high temperature, let alone the gelation time.

In this regard, Patent Document 3 discloses an emulsion composition for limiting the viscosity of silicone oil for the same effect as Patent Document 2. However, Patent Document 3 does not directly pay attention to the gelation time at high temperature.

In Patent Document 3, the polyoxyethylene alkyl ether exhibiting an emulsifying function has other effects depending on the application, and is effective for gelation time at high temperature. Not even done.

WO2018 / 003347 JP, 2016-199824, A Patent No. 6017109

The object of the present invention relates to a silicone oil composition, a gelling time adjusting additive, a silicone oil and a method for designing a silicone oil composition, and more specifically, to promote gelation under high temperature conditions without restriction on silicone oil. Another object of the present invention is to provide a silicone oil composition in which the gelling time is adjusted so as to suppress it or a gelling time adjusting additive therefor.
Further, the subject of the present invention is to preferentially determine the important structural factors for expressing the function of the silicone oil at high temperature without restriction on the silicone oil, and to further promote and suppress the gelation time. It is an object of the present invention to provide a method for designing a silicone oil or a silicone oil composition capable of efficiently adjusting the above.

As a result of intensive studies by the present inventors, the gelling time of silicone oil at a high temperature of 160 to 300 ° C. determines the amino equivalent, the viscosity at room temperature and the reaction at both ends which influence the function of the silicone oil at that high temperature. It was noted that it was greatly affected by the three structural factors of the sexual functional group ratio and that it was changed by the additive containing the polyoxyalkylene unit. Therefore, in the present invention, the gelling time is adjusted according to the number of added moles of the polyoxyalkylene unit of the gelling time adjusting additive used in combination with the silicone oil, which is an important structural factor for expressing the function of the silicone oil. The present invention has been achieved by finding out what can be done after making a priority decision.

That is, the composition provided in the present invention is a silicone oil composition having a silicone oil defined by the following formula (1) and a gelling time adjusting additive defined by the following formula (2): The gelling time adjusting additive is a silicone oil and a silicone oil composition characterized in that the number of moles of addition of the polyoxyalkylene unit is adjusted according to the required gelling time of the silicone oil at a predetermined heating temperature. It is a thing.
The required gelling time means the gelling time at the temperature that the silicone oil or the silicone oil composition will have in the environment in which the silicone oil is used.

In the formula (1), R ^{1 to} R ⁶ are any of the same or different monovalent saturated or unsaturated hydrocarbon functional groups having 1 to 14 carbon atoms, a hydroxyl group, a nitrogen-containing group, a sulfur-containing group, and hydrogen. . Both p and q satisfy an arbitrary integer of 1 or more.

(Chemical formula 2)
_{^{R 7 (- (O-R}} 8 -) r -OH) s (2)

In the formula (2), R ⁷ is a saturated or unsaturated hydrocarbon functional group having a valence of 1 to 3, a carbon number of 3 to 60, and R ⁸ is a hydrocarbon having a valence of 2, The number is 2-4. r is an integer of 3 to 200, and s is an integer of 1 to 3.

That is, the gelling time adjusting additive of the present invention is a gelling time adjusting additive which is added to silicone oil and is defined by the following formula (2). The gelling time adjusting additive is characterized in that the number of added moles of the polyoxyalkylene unit is adjusted according to the required gelling time.

(Chemical formula 2)
_{^{R 7 (- (O-R}} 8 -) r -OH) s (2)

In the formula (2), R ⁷ is a saturated or unsaturated hydrocarbon functional group having a valence of 1 to 3, a carbon number of 3 to 60, and R ⁸ is a hydrocarbon having a valence of 2, The number is 2-4. r is an integer of 3 to 200, and s is an integer of 1 to 3.

That is, the method for designing the silicone oil of the present invention is
Selecting the required heating temperature, required gelling time, and type of silicone oil from the application of silicone oil,
Determining an approximate expression between the gelation time and three structural factors of amino equivalent, viscosity at normal temperature, and ratio of reactive functional groups at both ends under the required heating temperature;
A step of determining the remaining one from any two of the amino equivalent selected from the functions required for the silicone oil, the viscosity at room temperature, and the ratio of reactive functional groups at both ends under the required heating temperature based on an approximate expression. When,
When the remaining one does not satisfy the function required for the silicone oil, using the above approximate expression, repeating the above steps, and
A method for designing a silicone oil having a controlled gelation time, which comprises:

That is, the method for designing the silicone oil composition of the present invention,
Selecting the required heating temperature, required gelling time, and type of silicone oil from the application of silicone oil,
Determining an approximate expression between the gelation time and three structural factors of amino equivalent, viscosity at normal temperature, and ratio of reactive functional groups at both ends under the required heating temperature;
Based on the approximate formula obtained under the required heating temperature, one of the amino equivalents selected from the functions required for the silicone oil, the viscosity at room temperature, and the reactive functional group ratio at both ends is used to determine the remaining one. The decision stage,
When the remaining one does not satisfy the function required for the silicone oil, using the above approximate expression, repeating the above steps, and
A step of adding a gelling time adjusting additive in which the number of added moles of polyoxyalkylene units is adjusted according to the required gelling time at the required heating temperature,
And a method for designing a silicone oil composition having a controlled gelation time.

Action of the invention

According to the present invention, regardless of the reactive or non-reactive silicone oil, the gelling time of the silicone oil is calculated based on the required gelling time at a predetermined heating temperature of the silicone oil according to the use of the silicone oil, By adjusting the number of moles of polyoxyalkylene units of the gelling time adjusting additive, the silicone oil composition capable of promoting or suppressing gelation under high temperature without restriction on silicone oil, or gelling time therefor A conditioning additive can be provided.
According to the present invention, the required heating temperature, the required gelling time, and the type of silicone oil are selected from the applications of the silicone oil defined by the following formula (1):
Determining an approximate expression between the gelation time and three structural factors of amino equivalent, viscosity at normal temperature, and ratio of reactive functional groups at both ends under the required heating temperature;
Based on the approximate formula obtained under the required heating temperature, one of the amino equivalents selected from the functions required for the silicone oil, the viscosity at room temperature, and the reactive functional group ratio at both ends is used to determine the remaining one. The decision stage,
When the remaining one does not satisfy the function required for the silicone oil, using the above approximate expression, repeating the above steps, and
Or a method for designing a silicone oil with a controlled gelation time, or
Selecting the required heating temperature, required gelling time, and type of silicone oil from the application of silicone oil,
Determining an approximate expression between the gelation time and three structural factors of amino equivalent, viscosity at normal temperature, and ratio of reactive functional groups at both ends under the required heating temperature;
Based on the approximate formula obtained under the required heating temperature, one of the amino equivalents selected from the functions required for the silicone oil, the viscosity at room temperature, and the reactive functional group ratio at both ends is used to determine the remaining one. The decision stage,
When the remaining one does not satisfy the function required for the silicone oil, using the above approximate expression, repeating the above steps, and
A step of adding a gelling time adjusting additive in which the number of added moles of polyoxyalkylene units is adjusted according to the required gelling time at the required heating temperature,
By the method for designing a silicone oil composition having a controlled gelation time, the structure factor that is important for developing the function of the silicone oil at high temperature is given priority without restriction on the silicone oil. It is possible to provide a method of designing a silicone oil or a silicone oil composition, which can be efficiently determined and gelling time can be efficiently adjusted so as to accelerate and suppress gelation.

In the formula (1), R ^{1 to} R ⁶ are any of the same or different monovalent saturated or unsaturated hydrocarbon functional groups having 1 to 14 carbon atoms, a hydroxyl group, a nitrogen-containing group, a sulfur-containing group, and hydrogen. . Both p and q satisfy an arbitrary integer of 1 or more.

(Chemical formula 2)
_{^{R 7 (- (O-R}} 8 -) r -OH) s (2)

In the formula (2), R ⁷ is a saturated or unsaturated hydrocarbon functional group having a valence of 1 to 3, a carbon number of 3 to 60, and R ⁸ is a hydrocarbon having a valence of 2, The number is 2-4. r is an integer of 3 to 200, and s is an integer of 1 to 3.

Hereinafter, the present invention will be specifically described. The present invention relates to a gelling time-adjusted silicone oil composition, a gelling time adjusting additive, a silicone oil, and a method for designing a silicone oil composition. Each component constituting the composition of the present invention and a method for designing a silicone oil and a silicone oil composition will be described below.

The composition of the present invention is characterized by containing a silicone oil represented by the above formula (1).

When R ^{1 to} R ⁶ are nitrogen-containing groups in the above formula (1), the nitrogen-containing groups can be specifically represented by the following general formula (3).

In formula (3), R ^{9 to} R ¹⁰ are saturated hydrocarbon groups having 1 to 5 carbon atoms, and R ^{11 to} R ¹² are hydrogen or saturated hydrocarbon groups having 1 to 10 carbon atoms and are linear or It is branched or annular. t is an integer satisfying either 0 or 1, but is preferably 1 from the viewpoint of production of the composition. This satisfies functional groups for _{example, -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 -N (CH 2 CH 3) 2, -CH 2 -CH 2 -CH 2 -NH-CH 2 -CH 2 -NH (cyclo-C 6 H ₁₁ ), and the like.

The gelling time adjusting additive in the present invention plays a role of adjusting the gelling time of the silicone oil in the composition of the present invention. The structural formula is represented by the above formula (2).

In the formula (2), R ⁷ is a saturated or unsaturated hydrocarbon functional group having a valence of 1 to 3, a carbon number of 3 to 60, and an ester bond or an ether bond even if there is a branched structure inside. , May have a hydroxyl group, specifically, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group, and other alkoxy groups, oleate And fatty acid ester groups having a hydroxyl group such as hydrogenated or non-hydrogenated castor oil.

In formula (2), R ⁸ is a divalent hydrocarbon and is an alkylene group having 2 to 4 carbon atoms, and examples thereof include an ethylene group and a propylene group.

In formula (2), p satisfies an integer of 3 to 200 and q satisfies an integer of 1 to 3. When p is 3 or more and 200 or less, volatilization of the gelling time adjusting additive is suppressed at a high temperature of 160 to 300 ° C., and the adjusting function for the gelling time of the silicone oil composition can be brought out.

Examples of the compound satisfying the above formula (2) include organic compounds containing various polyoxyalkylene units, and examples thereof include polyoxyalkylene adducts of aliphatic alcohols such as polyoxyethylene dodecyl ether and polyoxyethylene olein. Examples thereof include fatty acid esters of polyoxyalkylenes such as acid esters, polyoxyethylene (hydrogenated) castor oil, and the like.

The method of designing the silicone oil defined by the above formula (1) is
Selecting the required heating temperature, required gelling time, and type of silicone oil from the application of silicone oil,
Determining an approximate expression between the gelation time and three structural factors of amino equivalent, viscosity at normal temperature, and ratio of reactive functional groups at both ends under the required heating temperature;
Based on the approximate formula obtained under the required heating temperature, one of the amino equivalents selected from the functions required for the silicone oil, the viscosity at room temperature, and the reactive functional group ratio at both ends is used to determine the remaining one. The decision stage,
When the remaining one does not satisfy the function required for the silicone oil, using the above approximate expression, repeating the above steps, and
A method for designing a silicone oil having a controlled gelation time, which comprises:

A method for designing a silicone oil composition containing a silicone oil defined by the above formula (1) and a gelling time adjusting additive defined by the above formula (2),
Selecting the required heating temperature, required gelling time, and type of silicone oil from the application of silicone oil,
Determining an approximate expression between the gelation time and three structural factors of amino equivalent, viscosity at normal temperature, and ratio of reactive functional groups at both ends under the required heating temperature;
Based on the approximate formula obtained under the required heating temperature, one of the amino equivalents selected from the functions required for the silicone oil, the viscosity at room temperature, and the reactive functional group ratio at both ends is used to determine the remaining one. The decision stage,
When the remaining one does not satisfy the function required for the silicone oil, using the above approximate expression, repeating the above steps, and
A step of adding a gelling time adjusting additive in which the number of added moles of polyoxyalkylene units is adjusted according to the required gelling time at the required heating temperature,
And a method for designing a silicone oil composition having a controlled gelation time.

The above-mentioned method of designing a silicone oil and a silicone oil composition is characterized by taking steps similar to each other up to the middle, while optimizing the three structural factors of the silicone oil and the gelation time. Therefore, there is a difference in that it is finally divided into a case where the gelling time adjusting additive is not used and a case where it is necessary to use it. Therefore, first, the steps common to the methods for designing silicone oils and silicone oil compositions will be described below.
The above-mentioned steps of the method for designing the silicone oil and the silicone oil composition may be performed in any order, but in view of the required function and use environment, the most preferable design method is as follows.

In the design of the silicone oil and the silicone oil composition, it is preferable to select the type of the silicone oil in the initial stage depending on the application of the silicone oil, the required heating temperature, and the required gelling time. Here, in the application where silicone oil is used at a high temperature of 160 to 300 ° C., it is premised that the specific heating temperature is determined within the above temperature range and the required gelling time of the silicone oil is further determined. Become. After determining these, the silicone oil to be used is determined.
For example, in the use of silicone oil at a high temperature of 160 to 300 ° C., the appropriate heating temperature and gelling time are determined, and from the viewpoint of the function required for the silicone oil, the silicone always has an amino-modified group. When it is desired to use an oil, a silicone oil having an amino-modified group is specified as the type of silicone oil to be used.

  Next, it is preferable to move to the step of obtaining an approximate expression. At this stage, it is premised that the heating temperature within the temperature range of 160 to 300 ° C. and the type of silicone oil to be used are determined, and the amino equivalent of the silicone oil, the viscosity at room temperature, and the reactive functional group ratio at both ends. An approximate expression is derived with the three variables as variables.

The approximate expression can be obtained without any particular designation in the numerical ranges of the amino equivalent of silicone oil, the viscosity at room temperature, and the ratio of reactive functional groups at both ends, and a certain heating temperature within a temperature range of 160 to 300 ° C. Below, the following formula (1) is used by utilizing the actual measurement value of gelation time obtained from a plurality of silicone oils of the same system and three structural factors of amino equivalent, viscosity at normal temperature and reactive functional group ratio at both ends. ) Is obtained as an expression of the form such as.

(Equation 1)
G = α · A ^a / (B ^b · C ^c ) (1)

In the formula (1), G indicates gelation time, A indicates amino equivalent, B indicates viscosity at room temperature, and C indicates both-end reactive functional group ratio. α is a proportional constant determined by the measured value of G. a, b, c and α are exponential and proportional constants required for fitting so that the measured gelation time is calculated, and are real numbers determined under the temperature at which the silicone oil is placed, and a ≧ 0, It is a real number that satisfies b ≧ 0, c ≧ 0, and α> 0.

The above formula (1) is characterized by being an approximate formula derived on the basis of the following phenomena relating to the gelation time and the structural factor.
At a high temperature of 160 to 300 ° C., it was observed that the gelling time of the silicone oil depends on the amino equivalent of the silicone oil, the viscosity at room temperature, and the ratio of reactive functional groups at both ends. More specifically, a phenomenon in which the gelling time of the silicone oil at high temperatures increases as the amino equivalent of the silicone oil increases or the viscosity at room temperature and / or the reactive functional groups at both ends decrease. Was scattered around. In view of this case, for amino equivalents, an exponential function whose index is positive with respect to that is used as a base, and for the viscosity at room temperature and the ratio of reactive functional groups at both ends, the exponential function is used with each as a base. When an exponential function having a negative value was set and the product of these three exponential functions was calculated, the actual gelation time corresponding to each of several silicone oils was obtained.
This approximate expression (1) can be obtained even in the case of a silicone oil having no amino-modifying group. In that case, A ^a of the term on the right side of the above expression (1) is set to 1 and the silicone oil is kept at room temperature. An approximate expression is obtained using only the viscosity and the reactive functional group ratio at both ends. However, the silicone oil having an amino-modified group and the silicone oil having no amino-modified group may have different b and c in the above formula (1) and a proportional constant α even under the same predetermined heating temperature.
When the gelling time when various silicone oils are placed at a high temperature within the above temperature range is measured, they can be roughly classified into a group having a short gelling time and a group having a long gelling time.

The above approximate expression (1) is obtained, and then, based on the approximate expression obtained under the required heating temperature, the amino equivalents selected from the functions required for the silicone oil, the viscosity at room temperature, and the reactive functional groups at both ends are calculated. It is preferable to move from any two to the step of determining the other one. In this stage, while applying the required gelling time determined in the first stage to the above approximate expression (1), two of the three structural factors defined are applied and the remaining one is determined. . The optimum structural factor depends on the use of the silicone oil, but is often set as a numerical range. In that case, an arbitrary value within the numerical range is applied to the approximate expression, and the remaining one structural factor finally determined is determined. If the remaining one is also specified by a numerical range, check whether the last determined structural factor exists in that numerical range, and if it is not specified by a numerical range (if specified by a certain numerical value, ) To see if it matches that number. In any case, if the remaining one does not satisfy the function required for the silicone oil, the above-mentioned approximate expression is used again by selecting arbitrary numerical values within the appropriate numerical ranges for the two structural factors using the above-mentioned approximate expression. Apply to (1) and move to the stage of repeating checking whether the remaining one is a proper value.

  After the above steps, the other one is out of the proper numerical range determined by the application of the silicone oil, even if it is repeatedly examined to obtain the required gelling time from the above approximate expression (1), or an appropriate value. If it is out of the range, select a silicone oil in which all of these structural factors satisfy the appropriate numerical range or appropriate values. The gelling time obtained by the above approximate expression (1) due to the structural factor of the silicone oil deviates from the required gelling time. Therefore, the step of using the gelling time adjusting additive as the silicone oil composition is performed. Move to the step of adjusting the gelling time to the required gelling time.

That is, in the method for designing the silicone oil composition, the structural factors of the silicone oil are preferentially determined, and as a result of designing the silicone oil, the gelling time obtained by applying the above approximate expression (1) is the required gelling time. This is the design method that should be implemented when there is a deviation from By this design method, even if the gelling time deviates from the required gelling time when all the structural factors are optimized, only the gelling time is adjusted by the number of moles of polyoxyalkylene unit of the gelling time adjustment additive. Therefore, it becomes possible to adjust the gelling time to the required gelling time while optimizing the structural factor that is preferentially determined.
Each step in the method for designing a silicone oil and a silicone oil composition can be performed in any order. In the step of designing the gelling time adjusting additive, the silicone oil may be designed at the same time or sequentially. However, according to the illustrated design method, it is possible to preferentially determine the important structural factors for expressing the function of the silicone oil at high temperature without restricting the silicone oil, and to further promote and suppress the gelation. The gelation time can be adjusted efficiently. This is because the gelling time adjusting additive provided in the present invention acts only on the gelling time, and the effect on the function expression of the silicone oil can often be ignored.
It has been found in the present invention that the approximate expression (1) shown in the above example is a useful relational expression in order to efficiently carry out the design stage of silicone oil.

The gelling time adjusting additive selected in the method for designing a silicone oil composition is selected based on the following tendency of the silicone oil with respect to the number of moles of polyoxyalkylene units added to the additive.
The effect of the number of moles of polyoxyalkylene units added by the gelling time adjusting additive on the gelling time of the silicone oil composition at a high temperature of 160 to 300 ° C. depends on the gelling time of the silicone oil alone. Shows the behavior of. That is, in the silicone oil belonging to the group where the gelling time at a predetermined heating temperature is short, the gelling time of the silicone oil composition is small when the number of added moles of the polyoxyalkylene unit contained in the gelling time adjusting additive is small. The gelation time for silicone oil becomes longer, and the amount of change tends to increase as the number of moles added to the unit decreases. On the contrary, when the number of added moles of the polyoxyalkylene unit possessed by the gelling time adjusting additive is large, the gelling time of the silicone oil composition becomes shorter than the gelling time of the silicone oil, and the change amount thereof is a unit. It tends to increase as the number of added moles of increases. On the other hand, in the silicone oil belonging to the group where the gelling time at the predetermined heating temperature is long, the gelling time of the silicone oil composition is small when the number of added moles of the polyoxyalkylene unit contained in the gelling time adjusting additive is small. The gelling time is shorter than that for silicone oil, and the amount of change tends to increase as the number of added moles of the unit decreases. On the contrary, when the number of added moles of the polyoxyalkylene unit possessed by the gelling time adjusting additive is large, the gelling time of the silicone oil composition becomes longer than the gelling time of the silicone oil, and the amount of change is a unit. It tends to increase as the number of added moles of increases.
Therefore, the selection of the gelling time adjusting additive is based on the assumption that the gelling time obtained by the above approximate expression and the required gelling time are compared with each other in the silicone oil satisfying the appropriate structural factors. It is carried out according to the following guidelines based on the relationship between the number of moles of polyoxyalkylene added as the adjusting additive and the gelation time.

In the case of a silicone oil belonging to a group having a short gelling time at a predetermined heating temperature, the gelling time obtained by an approximate expression of the gelling time of the silicone oil at a high temperature of 160 to 300 ° C. is shorter than the required gelling time. If so, select a gelling time adjusting additive having a small addition mole number of the polyoxyalkylene unit, and if the gelling time obtained by the approximate expression is longer than the required gelling time, the addition mole number of the polyoxyalkylene unit is Choose a larger gel time adjusting additive. In any case, when the gelling time obtained by the approximate expression largely deviates from the required gelling time, the gelling time adjusting additive in which the number of added moles of the polyoxyalkylene unit is close to the lower limit or the upper limit of 3 to 200 If not, and if not, the gelling time according to the required gelling time of the silicone oil is selected according to the guideline of selecting a gelling time adjusting additive in which the number of added moles of the polyoxyalkylenene unit is close to the middle of the above range. The choice of aging time adjusting additives is made.
On the other hand, in the case of a silicone oil belonging to a group having a long gelling time at a predetermined heating temperature, the gelling time obtained by an approximate expression of the gelling time of the silicone oil at a high temperature of 160 to 300 ° C. is the required gelling time. If it is shorter, the gelling time adjusting additive with a large addition mole number of polyoxyalkylene units is selected.If the gelling time obtained by the approximate expression is longer than the required gelling time, the addition mole number of polyoxyalkylene units is increased. Select a low number gelling time adjusting additive. In any case, when the gelling time obtained by the approximate expression deviates greatly from the required gelling time, the number of moles of addition of the polyoxyalkylene unit is close to the lower limit or the upper limit of the above range. The gelling time corresponding to the required gelling time of the silicone oil is selected according to the guideline of selecting the gelling time adjusting additive in which the number of added moles of the polyoxyalkylenene unit is close to the middle of the above range. A selection of conditioning additives is made.

When a gelling time adjusting additive in which the number of added moles of polyoxyalkylene units is adjusted according to the above guidelines, is added to silicone oil, the additive must be added as additive / silicone oil = 10/10 to 99 parts by mass. Is preferred, and more preferably 10/10 to 90 parts by mass is added. If the mass ratio of the additive / silicone oil is not within this range, the effect of adjusting the gelling time as a gelling time adjusting additive will not be exhibited.

The silicone oil composition designed by the above method is classified into the case where the gelling time adjusting additive is directly added to the silicone oil and the case where the oil-in-water emulsion is emulsified in water.
In the case of an emulsion, the gelling time adjusting additive needs to be a surfactant, and 1 to 10 parts by mass of the gelling time adjusting additive and 10 to 50 parts by mass of silicone oil are contained in 100 parts by mass of the emulsion. Preferably. If each does not satisfy this mass part range, high emulsion stability cannot be maintained as an emulsion.
At this time, the method of emulsifying / dispersing each is not particularly limited, and a known method can be adopted. Examples of the method include a method of mixing each component constituting the emulsion, gradually adding water under an environment of applying a mechanical shearing force using a homogenizer, a homomixer, etc., and performing phase inversion emulsification. .

Other compounds can be added to the silicone oil composition of the present invention as long as they do not violate the spirit of the present invention. Other compounds include antioxidants such as acidic phosphoric acid ester, phenol-based, amine-based, sulfur-based, phosphorus-based, and quinone-based antioxidants; antistatic agents such as higher alcohols, sulfonates, amine salt-type cationic surfactants, etc. Agents; antiseptics; acetic anhydride compounds for the purpose of suppressing yellowing of amino group-containing silicone oils at high temperatures.

Further, the silicone oil composition of the present invention is an aminopolyether-modified silicone, an amide-modified silicone, an amide polyether unless a silicone oil belonging to the group having a short gel time and a silicone oil belonging to the group having a long gel time are mixed. Silicone oils such as modified silicones, alkyl-modified silicones, and alkoxy-modified silicones may be included, and one type of silicone oil may be used, or a plurality of types may be used in combination.

Among the four factors of the structural factor and gelation time that are determined when designing the silicone oil and the silicone oil composition, the factors that are particularly important are described below for each application of the silicone oil. Applications of using silicone oil at high temperatures of 160 to 300 ° C. include, for example, mold release agents in rubber, plastic molding, and aluminum die casting applications, lubricants for machine moving parts exposed to high temperature and high friction conditions, and heat transfer media. , Aramid / polyimide fiber treating agent, carbon fiber treating agent, etc., and important factors are different in each application. Also, the numerical range or numerical value of the structural factor that is optimum for each is different.

For rubber and plastic molding applications, silicone oil is usually used within a temperature range of 100 to 250 ° C., viscosity is the most important, and 350 mm ² / s to 1000 mm ² / s is preferable. The releasability is lowered when the pressure is lower than 350 mm ² / s or higher than 1000 mm ² / s. Next, gelation time is important, and the silicone composition applied to the mold is rapidly gelated by heating, so that a uniform releasing effect can be obtained.

For use in aluminum die-casting, silicone oil is usually used at a predetermined heating temperature of 300 ° C., viscosity is the most important, and a viscosity of about 10,000 mm ² / s is preferable. When the viscosity is low, the volatilization due to the decomposition of the silicone oil is remarkable, and when the viscosity is high, the emulsification is difficult and it is difficult to obtain a sufficient releasing effect. The gelation time has also attracted attention.Here, there are cases of aiming for a uniform release effect by rapid gelation, and cases of preventing the deterioration of operability due to gel by keeping the fluidity for a long time. There is a proper use depending on the purpose.

For fiber treatment applications such as aramid and polyimide, silicone oil is usually used within a temperature range of 100 to 200 ° C., and amino equivalent is most important. It can be applied, but yellowing over time poses a problem. With a low amino equivalent, flexibility can be imparted and yellowing can be suppressed. Next to the amino equivalent, the ratio of reactive functional groups at both ends is important. The higher the ratio of reactive functional groups at both ends, the higher the resilience and slipperiness. Select a radix. Next, the gelation time is important, and when the gelation time is fast, volatilization of the silicone composition applied to the fibers is suppressed, so that high-quality fibers can be produced. On the other hand, when the gelation time is slow, the silicone composition transferred to the roller or the like maintains fluidity without gelation, and thus the frequency of equipment protection cleaning can be kept low and productivity can be increased. Viscosity is also important, and the higher the viscosity, the better the slipperiness. Therefore, an appropriate viscosity is selected according to the purpose.

In carbon fiber treatment applications, silicone oil is usually used within a temperature range of 200 to 300 ° C., the amino equivalent is the most important, and 700 g is used to firmly attach the silicone composition to the carbon fiber. The range from / mol to 6000 g / mol is preferred. Next, the viscosity is important, and 50 mm ² / s to 5000 mm ² / s is preferable in order to apply the silicone composition uniformly on the carbon fiber. Next, the gelation time is important, and when the gelation time is fast, volatilization of the silicone composition applied to the fibers is suppressed, so that high-quality fibers can be produced. On the other hand, when the gelling time is slow, the silicone composition transferred to the roller or the like maintains fluidity without gelation, and therefore the frequency of equipment protection cleaning can be kept low and productivity can be increased. This gelling time is longer than the original gelling time of the silicone composition, that is, a technique such as suppressing gelation is used in order to maintain a good balance between the advantages of fast and slow. It is preferable to exist. More specifically, by suppressing the gelling of silicone oil at a high temperature of around 200 to 300 ° C., the time for which the oil transferred to the roller or the like remains in a fluid state can be kept longer, so the frequency of equipment protection cleaning Can be raised and productivity can be increased.

In the above applications, the structural factors of the silicone oil and the factors to be emphasized in the gelation time are different, and the factors to be prioritized are each set in a certain numerical range. Can be applied in all of its numerical ranges.

Examples of the present invention will be described in detail below, but the present invention is not limited to the following examples. Further, all numerical values of viscosity are viscosities at 25 ° C. unless otherwise specified. The components used in the examples, the derivation of the approximate expression and the method for measuring the gelation time are as follows.
Table 1 shows the mass ratios of the compositions in each Example and Comparative Example, and the evaluation results.

<Contents of constituents>
A-1: Amino-modified silicone, viscosity 5000 mm ² / s, amino equivalent 7000 g / mol, both end reactive functional group ratio 100%
A-2: Amino-modified silicone, viscosity 800 mm ² / s, amino equivalent 5000 g / mol, both ends reactive functional group ratio 5%
A-3: Polydimethylsiloxane, viscosity 6000 mm ² / s, both end reactive functional group ratio 100%
B-1: a surfactant having a structure of 13 carbon atoms, a gelling time adjusting additive of a polyoxyalkylene unit 6 B-2: a surfactant having a structure of 16 carbon atoms, a polyoxyalkylene unit 25 gelation time adjusting additive B-3: gelling time adjusting additive having a surfactant structure and having 57 carbon atoms and polyoxyalkylene unit 200

<Derivation of approximate expression>
By using a plurality of amino-modified silicones containing the above components (A-1, 2), a, b, c, and α in the above approximate expression (1) were obtained. Specifically, the gelling time of each component was measured by adopting the following gelling time measuring method (only in the case of 250 ° C.), the measurement result, the viscosity of each component at room temperature, and the reaction at both ends. The a, b, c, and α of the above formula (1) were determined from the ratio of the functional group and the amino equivalent.

<Definition of gelation time>
The gelling time was regarded as the tack-free time of the silicone oil at a high temperature of 200 and 250 ° C. in the temperature range of 160 to 300 ° C. of the silicone oil.

<Measurement method of gelation time>
The gelation time was measured by preparing a plurality of each composition of Examples and Comparative Examples for each test condition of 200 ° C. and 250 ° C. and performing a plurality of tests. The gelation time was determined by measuring the tack free time. The tack free time was defined as the time when the sample was not attached to the sample by touching the sample with a metal rod.

<Example 1>
The above-mentioned A-1 and B-1 were mixed with a spatula in an aluminum cup so that A-1 / B-1 = 1.8 g / 0.2 g to prepare a silicone oil composition. The gelation time was measured by allowing this to stand at 200 ° C. and 250 ° C. and contacting it with a rod over time.

<Example 2>
In the second embodiment, B-1 in the first embodiment is changed to B-2.

<Example 3>
In the third embodiment, B-1 of the first embodiment is changed to B-3.

<Example 4>
In the fourth embodiment, A-1 in the first embodiment is changed to A-2.

<Example 5>
In the fifth embodiment, B-1 of the above-mentioned fourth embodiment is changed to B-2.

<Example 6>
In the sixth embodiment, B-1 in the above-mentioned fourth embodiment is changed to B-3.

<Example 7>
Example 7 is a modification of Example 1 from A-1 to A-3.

<Example 8>
In the eighth embodiment, B-1 of the above-mentioned seventh embodiment is changed to B-2.

<Example 9>
Example 9 is a modification of Example 1 from B-1 to B-3.

<Example 10>
The variables specified in the above approximate expression (1) satisfied a = 1, b = 0.5, c = 0.5, and α = 3 at 250 ° C.
In some applications, it is necessary to use amino-modified silicone at 250 ° C., from the viewpoint of the required function, the viscosity is 5000 mm ² / s, the reactive functional group ratio at both ends is 100%, and the gelling time is 250 ° C. It had to be 30 minutes.
Based on this, the amino equivalent, which is the remaining structural factor, was calculated using the approximate expression of the above formula (1), and it was 6000 g / mol. Since it was found that this amino equivalent was within a numerical range sufficient to exhibit the function expected of the silicone oil, it was not necessary to adjust the gel time.

<Example 11>
The variables specified in the above approximate expression (1) satisfied a = 1, b = 0.5, c = 0.5, and α = 3 at 250 ° C.
It is necessary to use amino-modified silicone at 250 ° C., the viscosity is 800 mm ² / s, the reactive functional group ratio at both ends is 5%, the amino equivalent is 7,000 to 8000 g / mol, and the gelation time is from the viewpoint of the required function. Had to be 250 ° C. or less for 250 minutes or less.
Based on this, when the optimization of the amino equivalent was tried using the approximate expression of the above formula (1), it was 5000 g / mol. Since this amino equivalent is not in the range of 7000 to 8000 g / mol, it was judged that a gelling time adjusting additive should be used.
Therefore, an amino-modified silicone having an amino equivalent of 7000 g / mol is again selected so as to satisfy the above three structural factors, and the required gelling time and the gelling time of 320 minutes obtained from this silicone oil by the approximate expression (1) are set. In view of the difference, when a silicone oil composition is prepared by adding 8 parts by mass of a gelling time adjusting additive having a polyoxyalkylene unit addition mole number of 25 to 10 parts by mass of an amino-modified silicone oil, the composition The gelling time could be adjusted to the required gelling time of 225 minutes.

<Example 12>
In some applications it is necessary to use amino-modified silicones, to use oil A-2 in view of its required function and to have a gel time at 250 ° C of 180 minutes.
As an additive for adjusting the gelation time of the component (B), 3 parts by mass and 7 parts by mass of B-1 and B-2 were respectively added to A-2, and the gelation time was 175 minutes. .

<Example 13>
In some applications, it is necessary to use amino-modified silicones, from the standpoint of their required functionality, to use oil A-2, and to gel the oil at 250 ° C for 250 minutes.
As an additive for adjusting the gelation time of the component (B), 7 parts by mass and 3 parts by mass of B-2 and B-3 were respectively added to A-2, and the gelation time was 248 minutes. .

<Comparative Example 1>
2.0 g of the above A-1 was heated at 200 ° C. and 250 ° C. in an aluminum cup, and the gelation time was measured.

<Comparative example 2>
In Comparative Example 2, A-1 in Comparative Example 1 was changed to A-2.

<Comparative example 3>
In Comparative Example 3, A-1 of Comparative Example 1 was changed to A-3.

<Comparative example 4>
In some applications, it is necessary to use the amino-modified silicone at 250 ° C., from the viewpoint of the required function, the viscosity needs to be 5000 mm ² / s and the reactive functional group ratio at both ends needs to be 100%. Moreover, the gel time of the oil should be 35 minutes for that application. The optimum value of amino equivalent was not known for this application.
The only way to reach the desired gel time of the oil was to set the amino equivalent by trial and error.

<Comparative Example 5>
In some applications, it is necessary to use the amino-modified silicone at 250 ° C., the viscosity is 800 mm ² / s, and the both end reactive functional group ratio is 5% from the viewpoint of the required function. In addition, the gel time of the oil should be 225 minutes for that application.
Although the amino equivalent obtained from the above approximate expression (1) was 5000 g / mol, this amino equivalent had to be 7,000 to 9000 g / mol. However, a silicone oil having an optimal structural factor of amino equivalent of 7,000 to 9000 g / mol, viscosity of 800 mm ² / s, and reactive functional groups at both ends of 5% is selected, and several times using the above approximate expression (1). Even if the structural factors were examined within the numerical values or numerical ranges defined above, the obtained gelling time did not match the required gelling time, and the gelling time adjusting additive was not added to the silicone oil. Therefore, the only way to adjust the gelling time to the required gelling time is to sacrifice any of the amino equivalent weight, the viscosity, and the reactive functional group ratio at both ends.

As can be seen from Examples 1 to 9 in Table 1, the gelling time obtained with the silicone oil alone can be changed in a plurality of ways by the gelling time adjusting additive used in combination therewith. It is possible to obtain a silicone oil composition that can be adjusted in a plurality of ways, both in the direction of suppressing gelation and in the direction of promoting gelation, depending on the number of moles of polyoxyalkylene units added of the addition agent for adjusting gelation time.
On the other hand, as can be seen from Comparative Examples 1 to 3 in Table 1, only one gelling time is obtained when the gelling time adjusting additive, which has a structure of a surfactant, is not contained. Absent.

As can be seen from Examples 1 to 9, for example, in applications in which silicone oil is used at a high temperature of 250 ° C., structural factors such as the component (A-2) are considered from the viewpoint of the function expected of the silicone oil. Suppose you want to use your own silicone oil. At this time, when the required gelling time of the silicone oil in the application is close to the gelling time of 225 minutes obtained with the silicone oil alone, the component (A-2) can be used alone. When a gelling time shorter than that of the silicone oil alone is required (for example, about 120 minutes), the component (B-1) which is a gelling time adjusting additive having a small number of added moles of polyoxyalkylene units is used. In Example 12, when a long gelation time is required (for example, around 340 minutes) or when it is desired to change the gelation time by several minutes (for example, around 200 minutes) as compared with the case of using silicone oil alone, As shown in, the gelation time can be adjusted by using the gelation time adjustment additive of each of the components (B-1, 2) together.

As can be seen from Examples 10 and 11, in the use of a certain silicone oil, the remaining 1 is obtained by the above approximate expression (1) from the two structural factors applied from the function required of the silicone oil under the required gelling time. When one of the two is determined to be within the appropriate numerical range, the gelling time adjusting additive may not be used, and if not, the gelling time adjusting additive may be used to remove the silicone oil. It is possible to design a silicone oil and a silicone oil composition in which the gelling time is adjusted to the required gelling time while maintaining the structural factors to be optimum. However, as can be seen from Comparative Examples 4 and 5, the silicone oil cannot be efficiently designed without using any one of the approximate expression (1) and the gelling time adjusting additive, and the structural factors are optimized. It is not possible to design silicone oil compositions with controlled gel times.

  Since the silicone oil composition of the present invention is a composition in which the gelling time is efficiently adjusted so as to promote and suppress the gelling of the silicone oil under high temperature conditions, it can be used for rubber, plastic molding, and aluminum die casting. Release agents, lubricants for moving parts of machinery exposed to high temperature and high friction conditions, heat media, aramid / polyimide fiber treatment agents, carbon fiber treatment agents, etc. It is possible and useful. Further, by adjusting the gelling time of silicone oil under high temperature, it is possible to develop new industrial uses that have not existed in the past.

Claims (4)

A silicone oil composition comprising a silicone oil defined by the following formula (1) and a gelling time adjusting additive defined by the following formula (2), wherein the gelling time adjusting additive is a silicone A silicone oil composition, wherein the number of moles of polyoxyalkylene units added is adjusted according to the required gelling time of the oil and the silicone oil at a predetermined heating temperature.

(In the formula (1), R ^{1 to} R ⁶ are the same or different monovalent saturated or unsaturated hydrocarbon functional groups having 1 to 14 carbon atoms, a hydroxyl group, a nitrogen-containing group, a sulfur-containing group, or hydrogen. Yes, both p and q satisfy an arbitrary integer of 1 or more.)
(Chemical formula 2)
_{^{R 7 (- (O-R}} 8 -) r -OH) s (2)
(In the formula (2), R ⁷ is a 1-3-valent saturated or unsaturated hydrocarbon functional group having 3 to 60 carbon atoms, and R ⁸ is a divalent hydrocarbon, The carbon number is 2 to 4. r is an integer of 3 to 200 and s is an integer of 1 to 3.) A gelling time adjusting additive, which is added to silicone oil and is defined by the following formula (2), wherein a polyoxyalkylene unit is added according to the required gelling time of silicone oil and a predetermined heating temperature of silicone oil. A gelling time adjusting additive characterized in that the number of added moles of is adjusted.
(Chemical formula 2)
_{^{R 7 (- (O-R}} 8 -) r -OH) s (2)
(In the formula (2), R ⁷ is a 1-3-valent saturated or unsaturated hydrocarbon functional group having 3 to 60 carbon atoms, and R ⁸ is a divalent hydrocarbon, The carbon number is 2 to 4. r is an integer of 3 to 200 and s is an integer of 1 to 3.) A method for designing a silicone oil defined by the following formula (1),
Selecting the required heating temperature, required gelling time, and type of silicone oil from the application of silicone oil,
Determining an approximate expression between the gelation time and three structural factors of amino equivalent, viscosity at normal temperature, and ratio of reactive functional groups at both ends under the required heating temperature;
Based on the approximate formula obtained under the required heating temperature, one of the amino equivalents selected from the functions required for the silicone oil, the viscosity at room temperature, and the reactive functional group ratio at both ends is used to determine the remaining one. The decision stage,
When the remaining one does not satisfy the function required for the silicone oil, using the above approximate expression, repeating the above steps, and
A method for designing a silicone oil having a controlled gelation time, which comprises:

(In the formula (1), R ^{1 to} R ⁶ are the same or different monovalent saturated or unsaturated hydrocarbon functional groups having 1 to 14 carbon atoms, a hydroxyl group, a nitrogen-containing group, a sulfur-containing group, or hydrogen. Yes, both p and q satisfy an arbitrary integer of 1 or more.) A method for designing a silicone oil composition comprising a silicone oil defined by the following formula (1) and a gelling time adjusting additive defined by the following formula (2),
Selecting the required heating temperature, required gelling time, and type of silicone oil from the application of silicone oil,
Determining an approximate expression between the gelation time and three structural factors of amino equivalent, viscosity at normal temperature, and ratio of reactive functional groups at both ends under the required heating temperature;
A step of determining the remaining one from any two of the amino equivalent selected from the functions required for the silicone oil, the viscosity at room temperature, and the ratio of reactive functional groups at both ends under the required heating temperature based on an approximate expression. When,
When the remaining one does not satisfy the function required for the silicone oil, using the above approximate expression, repeating the above steps, and
A step of adding a gelling time adjusting additive in which the number of added moles of polyoxyalkylene units is adjusted according to the required gelling time at the required heating temperature,
A method for designing a silicone oil composition having a controlled gelation time, which comprises:

(In the formula (1), R ^{1 to} R ⁶ are the same or different monovalent saturated or unsaturated hydrocarbon functional groups having 1 to 14 carbon atoms, a hydroxyl group, a nitrogen-containing group, a sulfur-containing group, or hydrogen. Yes, both p and q satisfy an arbitrary integer of 1 or more.)
(Chemical formula 2)
_{^{R 7 (- (O-R}} 8 -) r -OH) s (2)
(In the formula (2), R ⁷ is a 1-3-valent saturated or unsaturated hydrocarbon functional group having 3 to 60 carbon atoms, and R ⁸ is a divalent hydrocarbon, The carbon number is 2 to 4. r is an integer of 3 to 200 and s is an integer of 1 to 3.)