JP2022010421A - Polyorganosiloxane, polyorganosiloxane composition and cured product thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyorganosiloxane excellent in high elasticity, high strength, dimensional stability, easiness of handling and the like and to provide a composition including the polyorganosiloxane.

SOLUTION: The polyorganosiloxane has an M unit content (R¹R²R³SiO_1/2) of 10 mol% or more relatively to the total silicon and a T unit content (R⁶SiO_3/2) of 80 mol% or less relatively to the total silicon and has an alkoxy group and a reactive functional group other than an alkoxy group each bonded to silicon, in which the content of the alkoxy group bonded to silicon relatively to the total weight of the polyorganosiloxane is 0.07 to 4 wt%; the number of the reactive functional groups bonded to silicon is 3 to 12 per 1,000 in the molecular weight of the polyorganosiloxane; and the weight loss of the polyorganosiloxane is 5 wt% or less when heated under a reduced pressure of 0.15 torr at 110°C for 2 hours.

SELECTED DRAWING: None

COPYRIGHT: (C)2022,JPO&INPIT

Description

The present invention relates to a polyorganosiloxane having a novel structure.

Polyorganosiloxane is used in many industries because it has a high degree of freedom in design and can have various functions.
For example, Patent Document 1 discloses a polyorganosiloxane having a polyhedral structure, and proposes a polyorganosiloxane having improved heat resistance, light resistance, chemical stability, molding processability, and the like.

Further, Patent Document 2 discloses silsesquioxane having a cage-shaped structure, exhibiting good low-temperature fluidity, and is suitably used for encapsulation of semiconductors and the like.

Japanese Unexamined Patent Publication No. 2015-129288 Japanese Unexamined Patent Publication No. 2012-233174

Although the polyorganosiloxane disclosed in Patent Document 1 is a polyorganosiloxane having improved heat resistance, light resistance, chemical stability, molding processability, etc., it has mechanical properties such as elastic modulus and hardness and ignition. No consideration has been given to the points.
Further, the silsesquioxane disclosed in Patent Document 2 is suitable for encapsulation of semiconductors and the like, and although the hardness has been studied, it is insufficient, and the flash point has not been studied here either.
Further, polyorganosiloxane having a polyhedral structure as described in Patent Document 1 and Patent Document 2 is generally a solid, and even if it is a liquid, its viscosity is very high.

An object of the present invention is to provide a new polyorganosiloxane that is different from the already proposed polyorganosiloxane, focusing on mechanical characteristics, flash point, linear expansion coefficient, viscosity, and the like.

As a result of focusing on the flash point and viscosity of the polyorganosiloxane having a reactive functional group, and the mechanical properties and linear expansion coefficient of the cured product, the present inventors have determined that the weight loss rate when heated is a constant amount. In the following cases, it was found that the flash point is remarkably increased, the linear expansion coefficient of the cured product is decreased, and the amount of the curable functional group is in a specific range, so that the strength of the cured product is remarkably improved. .. Further, they have found that the maximum absorbed wavenumber in a specific wavenumber region in infrared absorption spectrum analysis has a great influence on the viscosity of polyorganosiloxane, and completed the present invention.

That is, the present invention is as follows.
(1) The content of M units (R ¹ R ² R ³ SiO _1/2 ) with respect to total silicon is 10 mL% or more, and the content of T units (R ⁶ SiO _3/2 ) with respect to total silicon is 80 mL% or less. It is a polyorganosiloxane having an alkoxy group bonded to silicon and a reactive functional group other than the alkoxy group, and the content of the alkoxy group bonded to silicon is 0.07 to the total weight of the polyorganosiloxane. When it is 4% by weight, the number of reactive functional groups bonded to silicon is 3 to 12 per 1000 molecular weight of polyorganosiloxane, and it is heated at 110 ° C. for 2 hours under a reduced pressure of 0.15 torr. Polyorganosiloxane, wherein the weight loss of the polyorganosiloxane is 5% by weight or less.
(2) The polyorganosiloxane according to (1), wherein the content of the M unit with respect to total silicon is 60 mL% or less.
(3) A polyorganosiloxane that requires a Q unit represented by (SiO _4/2 ) and has a reactive functional group other than an alkoxy group bonded to silicon, and is silicon per 1000 molecular weight of the polyorganosiloxane. The number of reactive functional groups bonded to is 3 to 12, and in infrared absorption spectrum analysis, it has the maximum absorption wave number of Si—O expansion and contraction vibration in the region of wave number 1030 to 1060 cm ^-1 , and the pressure is 0.15 torr. Polyorganosiloxane having a weight loss of 5% by weight or less of the polyorganosiloxane component when heated at 110 ° C. for 2 hours under reduced pressure. (4) The polyorganosiloxane according to (1) to (3), wherein the content of M units with respect to total silicon is 10 mol% or more and 60 mol% or less.
(5) The reactive functional group bonded to silicon is at least one selected from the group consisting of an alkenyl group, a methacryloyl group, an acryloyl group, an acyl group, and a cyclic ether group, and a hydrogen atom forming a hydrosilyl group with silicon. The polyorganosiloxane according to (1) to (4), which comprises one group.
(6) The polyorganosiloxane according to (1) to (5), wherein the reactive functional group is a vinyl group.
(7) The polyorganosiloxane according to (1) to (5), wherein the reactive functional group is a methacryloyloxypropyl group.
(8) The polyorganosiloxane according to any one of (1) to (7), which is liquid at 40 ° C.
(9) The polyorganosiloxane according to any one of (1) to (8), wherein the viscosity at 25 ° C. is 5 mPa · s or more and 20000 mPa · s or less.
(10) The polyorganosiloxane according to any one of (1) to (9), wherein the GPC measurement result in terms of polystyrene has a number average molecular weight Mn of 600 or more and 5000 or less.
(11) The polyorganosiloxane according to any one of (1) to (10), wherein the M unit contains at least a trimethylsiloxy group or a dimethylsiloxy group.
(12) The polyorganosiloxane according to any one of (1) to (11), which is an MQ resin.
(13) The polyorganosiloxane according to any one of (1) to (11), which is an MTQ resin.
(14) The composition containing the polyorganosiloxane according to any one of (1) to (13).
(15) A cured product obtained by curing either the polyorganosiloxane according to any one of (1) to (13) or the composition according to (14).
(16) The cured product according to (15), which has a haze of less than 1%.
(17) The cured product according to (15), which has a yellow index of 0 to 10 after being treated at 85 ° C. and a relative humidity of 85% for 168 hours.

As a result of focusing on the flash point and viscosity of the polyorganosiloxane having a reactive functional group, and the mechanical properties and linear expansion coefficient of the cured product, the present inventors have determined that the weight loss rate when heated is a constant amount. In the following cases, it was found that the flash point is significantly increased, the linear expansion coefficient of the cured product is decreased, and the amount of the curable functional group is in a specific range, so that the mechanical properties of the cured product are significantly improved. rice field. Further, they have found that the maximum absorbed wavenumber in a specific wavenumber region in infrared absorption spectrum analysis has a great influence on the viscosity of polyorganosiloxane, and completed the present invention.

According to the present invention, a polyorganosiloxane is obtained, which is a cured product having a high flash point before curing, a small temperature dependence of elastic modulus after curing, and a small weight loss during heating. If the flash point is low, it may be difficult to handle safely under normal conditions, and the Fire Service Act also classifies dangerous goods with a higher degree of danger, resulting in higher storage and transportation costs. Therefore, the merit of obtaining a polyorganosiloxane having a high flash point is very large. In addition, the low coefficient of linear expansion of the cured product is equivalent to exhibiting stable performance over a wide range of temperatures, and is also excellent in mechanical properties, which greatly contributes to the reliability of the product. Further, since the weight loss when the cured product is heated is small, embrittlement due to heat thinning or change with time is unlikely to occur.

Further, according to the present invention, a polyorganosiloxane having a low viscosity was obtained. The low viscosity significantly improves handleability and process flexibility, significantly reduces the time required for weighing, mixing, and molding, shortens the cleaning time, and reduces the amount of cleaning agent. You can expect it. The greatly improved thermal impact resistance of the cured product makes it possible to withstand more processes than before, and the degree of freedom in process design is significantly improved.

Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to the following embodiments, and can be variously modified and implemented within the scope of the gist thereof.
The polyorganosiloxane refers to a polymer having a siloxane bond as a main chain, and is represented by, for example, the general composition formula (1) shown below.
(R ¹ R ² R ³ SiO _1/2 ) _a (R ⁴ R ⁵ SiO _2/2 ) _b (R ⁶ SiO _3/2 ) _c (SiO _4/2 ) _d (O _1/2 R ⁷ ) _e ( O _1/2 H) _f ... (1)
Here, in the above formula (1), R ¹ to R ⁶ are independently selected from an organic functional group and a hydrogen atom, and a + b + c + d = 1 is satisfied. Further, R ⁷ is selected from organic groups having 1 to 7 carbon atoms.

One of the polyorganosiloxanes according to the present embodiment has an M unit (R ¹ R ² R ³ SiO _1/2 ) content of 10 mL or more with respect to total silicon, and a T unit (R ⁶ SiO ₃ ) with respect to total silicon. _{/ 2} ) is a polyorganosiloxane having a content of 80 mL or less and having an alkoxy group bonded to silicon and a reactive functional group other than the alkoxy group, and is bonded to the silicon with respect to the total weight of the polyorganosiloxane. The content of alkoxy groups is 0.07 to 4% by weight, the number of reactive functional groups bonded to silicon per 1000 molecular weight of polyorganosiloxane is 3 to 12, and the pressure is reduced to 0.15 torr. Below, polyorganosiloxane (hereinafter, may be referred to as polysiloxane A) has a weight loss of 5% by weight or less when heated at an internal temperature of 110 ° C. for 2 hours. Further, the other polyorganosiloxane according to the present embodiment is a polyorganosiloxane which requires a Q unit represented by (SiO _4/2 ) and has a reactive functional group bonded to silicon, and is poly. The number of reactive functional groups bonded to silicon per 1000 molecular weight of organosiloxane is 3 to 12, and in infrared absorption spectrum analysis, the maximum absorption of Si—O expansion and contraction vibration in the region of wave number 1030 to 1060 cm ^-1 . Polyorganosiloxane having a wave number and having a weight loss of 5% by weight or less of the polyorganosiloxane component when heated at 110 ° C. for 2 hours under a reduced pressure of 0.15 torr (hereinafter sometimes referred to as polysiloxane B). Is.

In the polyorganosiloxane A, a, which means the ratio of M units in the formula (1), is 0.1 or more, preferably 0.2 or more. Further, a is less than 1, preferably 0.6 or less, and more preferably 0.3 or less. By setting a to 0.1 or more, that is, setting the M unit to an appropriate upper limit or less, the molecular weight of the polyorganosiloxane can be easily controlled, and more specifically, the molecular weight can be easily set to an appropriate range not too small. Therefore, it is preferable because it is possible to suppress the increase of the low boiling point component and prevent the flash point from being lowered.

Further, in the formula (1), c indicating the T unit ratio is 0 or more, preferably 0.15 or more, more preferably 0.4 or more, and c is 0.8 or less as the upper limit. Yes, preferably 0.65 or less. When c in the formula (1) is in the above range, it is preferable that the cured product when the polyorganosiloxane A is cured has appropriate rigidity. Further, it is particularly preferable to set the value of c to 0.8 or less because the viscosity of the polyorganosiloxane can be easily maintained within an easy-to-handle range and the brittleness of the cured product is improved.

The polyorganosiloxane A may contain a Q unit represented by (SiO _4/2 ), that is, d in the formula (1) is preferably 0 or more, preferably 0.7 or less, and more preferably 0.5. It is as follows. When d in the formula (1) is in the above range, it is preferable to prevent the viscosity of the polyorganosiloxane from becoming too high and to give appropriate rigidity to the cured product when the polyorganosiloxane A is cured. .. Further, the polyorganosiloxane A may contain a D unit represented by (R ⁴ R ⁵ O _2/2 ), that is, b in the formula (1) can be 0 or more, but preferably 0.3. It is less than or equal to, more preferably 0.1 or less. By setting it in such a range, it becomes easy to keep the rigidity of the cured product high.

That is, the polyorganosiloxane A may be an MQ resin composed of M units and Q units, an MT resin composed of M units and T units, and an MDT composed of M units, D units and T units. It may be a resin, an MDQ resin consisting of M units, D units and Q units, an MTQ resin consisting of M units, T units and Q units, and M units, D units, T. It may be an MDTQ resin consisting of a unit and a Q unit. When the MTQ resin is used as a composition for various purposes, it is preferable that the MT resin is contained in an amount of 60% by weight or less based on the total amount of the polyorganosiloxane composition. By containing an appropriate amount of MT resin, appropriate flexibility can be imparted.

However, in the polyorganosiloxane A consisting of only M units and D units, when the M unit exceeds 10 mol% with respect to the total silicon, that is, a in the formula (1) exceeds 0.1 and b is larger than 0. When c and d are 0, the boiling point is low, and the weight loss when heated at an internal temperature of 110 ° C. for 2 hours under a reduced pressure of 0.15 torr is large, so that it is not included in the present invention.
The polyorganosiloxane A is a polyorganosiloxane having an alkoxy group bonded to silicon, and the content of the alkoxy group bonded to silicon with respect to the total weight of the polyorganosiloxane A is 0.07% by weight or more, preferably 0.5. It is 0% by weight or more, 4% by weight or less, preferably 2% by weight or less. Polyorganosiloxane A containing an alkoxy group having a content in the above range suppresses aggregation of polyorganosiloxane A molecules due to steric repulsion due to the alkoxy group, so that it does not become a solid but becomes a liquid and exhibits appropriate fluidity. Therefore, it becomes easy to mix with other resins and the like, and there is an advantage that the productivity in producing the composition is greatly improved. If the amount of alkoxy groups is too small from the lower limit specified in the present invention, the viscosity may become too high or the solid may become solid, and the above-mentioned merit of improving productivity cannot be received. On the other hand, by setting the content of the alkoxy group to the upper limit or less, the stability due to long-term storage is improved, and the phenomenon that the alkoxy group is desorbed by heating to generate alcohol is suppressed, so that the safety of the operator And good for health. In addition, when the cured product is heated, the alkoxy groups are less likely to be desorbed, so that embrittlement due to the thinning of the cured product is less likely to occur. This also leads to less embrittlement due to aging.

The type of the alkoxy group is not particularly limited, but a methoxy group, an ethoxy group, an isopropoxy group and the like are preferable and typical, but the type is not limited thereto.
Polysiloxane A is a polysiloxane having a reactive functional group bonded to silicon other than an alkoxy group, and has 3 or more reactive functional groups bonded to silicon per 1000 molecular weight of polyorganosiloxane A as a lower limit value. More preferably, the number is 4 or more, the upper limit is preferably 12 or less, and more preferably 9 or less. By setting the reactive functional group to the lower limit value or more, it is easy to improve the strength of the cured product when the polysiloxane is cured. On the other hand, by setting the reactive functional group to the upper limit or less, the brittleness of the cured product when the polysiloxane is cured is improved.

The content of the alkoxy group bonded to silicon of the polyorganosiloxane and the number of reactive functional groups bonded to silicon per 1000 molecular weight are calculated as follows. Further, the number of trimethylsiloxy groups per 1000 molecular weight can be measured in the same manner.
Weigh 50 mg of the polyorganosiloxane to be measured, add 15 mg of toluene as an internal standard, and weigh accurately. Further, 1 g of deuterated chloroform is added and dissolved, and measurement is performed by setting the Relaxation Delay to 20 seconds by 400 MHz ¹ H-NMR (AL-400 manufactured by JEOL Ltd.). Depending on the ratio of the signal intensity of each component to the signal intensity of the internal standard toluene and the weighed value, the content of alkoxy groups and the content of functional groups per gram (mmol / g), that is, the molecular weight of polyorganosiloxane. The number of functional groups per 1000 is calculated. At this time, impurities such as organic substances, water, and metals that are not bound to polyorganosiloxane must be removed to less than 0.1% by weight so as not to affect the measurement results, and exceed 0.1% by weight. If so, prepare the sample after removal by distillation, filtration or other purification method and measure ¹ H-NMR. If removal is difficult, ¹ Calculate the impurity content by H-NMR measurement or other analytical method, and subtract the weight of the impurity from the weighed sample weight so that it is not calculated as part of the polyorganosiloxane. Is used in the calculation as the true sample amount. As the internal standard, any substance that does not react with polyorganosiloxane, such as N, N-dimethylformamide and tribromoethane, can be used in addition to toluene.

The weight loss of the polysiloxane A when heated at an internal temperature of 110 ° C. for 2 hours under a reduced pressure of 0.15 torr is 5% by weight or less, preferably 3% by weight or less. By setting the weight reduction under the above conditions to be equal to or lower than the above upper limit, the flash point of the polyorganosiloxane can be kept relatively high. As a result, it is possible to avoid difficulty in handling safely under normal conditions, which is a risk when the flash point is low, and it is also classified as a dangerous goods under the Fire Service Act with a lower degree of risk. , Storage and transportation costs can also be reduced. In addition, since the weight loss of the cured product during curing is small, the temperature dependence of the storage elastic modulus of the cured product is small, the usable temperature range is widened, and embrittlement due to wall thinning is unlikely to occur. be able to.

The weight loss during vacuum heating can be measured as follows.
^{1 1} H-NMR is measured, and the weight of components other than polyorganosiloxane, such as an organic solvent, is calculated. Place the rotors in an eggplant-shaped flask and weigh them. Then, the polyorganosiloxane is placed in the eggplant-shaped flask and the weight of the polyorganosiloxane is measured. The eggplant-shaped flask is heated in an oil bath, the rotor is rotated by a magnetic stirrer to stir until the liquid level flows, and the pressure is reduced by an oil type vacuum pump. After 2 hours, the mixture was cooled to room temperature, returned to normal pressure, the oil adhering to the eggplant-shaped flask was sufficiently wiped off, the weight of the polyorganosiloxane in the eggplant-shaped flask was measured, and the eggplant that had been measured earlier was measured. The weight of the flask and the rotor is subtracted, and the weight volatilized by the operation is calculated. ¹ H-NMR of the polyorganosiloxane after the operation is measured, and the weight of a component other than the polyorganosiloxane such as an organic solvent is calculated. From the weight loss before and after the operation and the measurement result of ¹ H-NMR, the amount of components other than polyorganosiloxane and the volatilization amount of polyorganosiloxane are calculated from the volatilized weight. Further, the entire amount of the volatilized distillate may be recovered by a cold trap or the like, and the weight and ¹ H-NMR may be measured.

Polyorganosiloxane B, another embodiment of the present invention, contains a Q unit represented by (SiO _4/2 ) as an essential component. That is, in the formula (1), d is larger than 0, preferably 0.1 or more, and more preferably 0.15 or more in the polyorganosiloxane B. Further, d is less than 1, preferably 0.7 or less, more preferably 0.5 or less, and further preferably 0.3 or less. Having a Q unit, preferably more than the above lower limit value, improves the strength of the cured product when cured. Further, by setting the Q unit to the above upper limit value or less, the viscosity of the polyorganosiloxane does not become too high, and the cured product is less likely to become brittle.

The polyorganosiloxane B is a polysiloxane having a reactive functional group bonded to silicon other than the alkoxy group, and the content of the reactive functional group is preferably in the same range as that of the polyorganosiloxane A, and the reason is also the same. be.
Polyorganosiloxane B has a maximum absorbed wave number of Si—O stretching vibration in the region of wave number 1030 to 1060 cm ^-1 in infrared absorption spectrum analysis. In the infrared absorption spectrum analysis, by having the maximum absorbed wave number of Si—O stretching vibration in the wave number region, it is possible to avoid an extremely hard structure such as a cage-type silsesquioxane. The maximum absorbed wave number means the wave number that gives the maximum absorbance in a specific region, and in the present embodiment, the wave number that gives the maximum absorbance in the region of 1000 to 1200 cm ^-1 is defined as the maximum absorbed wave number.

The maximum absorbed wavenumber by infrared absorption spectrum analysis can be measured by the ATR method (total reflection measurement method) using a Fourier transform infrared spectroscope.
Further, in infrared absorption spectrum analysis, it is preferable that there is no absorption peak of Si—O expansion / contraction vibration in the region of wave number 1070 to 1150 cm ^-1 . By not having the maximum absorption wavenumber of Si—O expansion and contraction vibration in the wavenumber region, it is possible to avoid an extremely hard structure such as a cage-type silsesquioxane. In the case of a rigid structure such as cage-type silsesquioxane, the cured product does not deform to external stress and behaves as a single rigid body, so there is little conversion to heat energy inside the resin and the repulsive force is small. It doesn't become. In addition, a characteristic absorption band derived from an organic molecule other than Si—O may exist in the region of wave number 1070 to 1150 cm ^-1 . Examples of characteristic absorption bands derived from organic molecules are C—O-derived hydroxyl groups, COC-derived esters, COC-derived acid anhydrides, COC-derived ethers, and amines. C-N-derived, sulfonic acid, sulfoxide, fluorine compound CF-derived, phosphorus compound P = O or PO ^- derived, inorganic salt SO ₄ ^2- or ClO _4- derived from, have high absorption strength. Known as the structure. Care must be taken not to confuse these with the attribution of Si—O expansion and contraction vibration.

The weight loss of the polyorganosiloxane B when heated at an internal temperature of 110 ° C. for 2 hours under a reduced pressure of 0.15 torr is 5% by weight or less, preferably 3% by weight or less. When the weight loss under the above conditions is large, the flash point of the polyorganosiloxane becomes low. If the flash point is low, it may be difficult to handle safely under normal conditions, and the Fire Service Act also classifies dangerous goods with a higher degree of danger, resulting in higher storage and transportation costs. .. In addition, since the weight of the cured product is greatly reduced during curing, the temperature dependence of the storage elastic modulus of the cured product is large and the usable temperature is limited, and embrittlement due to wall thinning is likely to occur. In some cases.

In the polyorganosiloxane B, a, which means the ratio of M units in the formula (1), is preferably 0.1 or more, and more preferably 0.2 or more. Further, a is less than 1, preferably 0.6 or less, and more preferably 0.3 or less. By setting a to the above-mentioned lower limit value or more, that is, by including an appropriate amount or more of M unit amount, it is possible to easily control the molecular weight and prevent the viscosity from becoming too high. On the other hand, by setting a to the upper limit or less, that is, to the range where the M unit does not become too large, it becomes easy to make the molecular weight of the polyorganosiloxane in an appropriate range which is not too small, and the increase of the low boiling point component is suppressed to ignite. It is preferable because it can prevent the point from being lowered.

The type of the alkoxy group bonded to silicon in the polyorganosiloxane A and the polyorganosiloxane B is not particularly limited and may include a branched structure and a cyclic structure. However, when an alkoxy group having a large molecular weight is used, the polyorgano is used. Since the weight of the desorbed alkoxy group when the siloxane or its cured product is heated increases, an alkoxy group having a small molecular weight is preferable. Specifically, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a tert-butoxy group and the like are preferable.

The type of the reactive group other than the alkoxy group bonded to silicon in the polyorganosiloxane A and the polyorganosiloxane B is not particularly limited and may include a branched structure and a cyclic structure, but an alkenyl group may be included from the viewpoint of reactivity. , A methacryloyl group, an acryloyl group, an acyl group, a cyclic ether group, and a hydrogen atom forming a hydrosilyl group with silicon, and may be used alone or in combination of two or more. The alkenyl group is particularly preferably a vinyl group, the methacryloyl group is particularly preferably a methacryloyloxypropyl group, the acryloyl group is particularly preferably an acryloyloxypropyl group, and the cyclic ether group is particularly preferably a group having an epoxy group. As the epoxy group, a glycidyloxy group, an alicyclic epoxy group, an alkenyl group converted into an epoxy group by oxidation, or the like is preferably used.

Among the polyorganosiloxane A and the polyorganosiloxane B, the type of M unit is not particularly limited, and may contain a reactive functional group. In particular, from the viewpoint of storage stability of the polyorganosiloxane, it is preferable that at least one M unit is a trimethylsiloxy group, and more specifically, the number of trimethylsiloxy groups per 1000 molecular weight is 1 to 4. preferable. If the number of trimethylsiloxy groups is too small, the number of M units other than trimethylsiloxy groups, that is, M units containing reactive groups tends to increase automatically, so from the viewpoint of storage stability of polyorganosiloxane, trimethylsiloxy groups Is preferably in the above range. On the other hand, from the viewpoint of the reactivity of the polyorganosiloxane, it is preferable that the amount of the trimethylsiloxy group in the polyorganosiloxane or in the M unit is small, and specifically, the number of trimethylsiloxy groups per 1000 molecular weight is 1 or less. Is preferable, and it is more preferable that the trimethylsiloxy group is not contained. If there are too many trimethylsiloxy groups, the amount of the reactive functional groups will be small. Therefore, when the function (curability and the like) of the reactive functional groups is important, one or less trimethylsiloxy groups are preferable.

The polyorganosiloxane A and the polyorganosiloxane B are preferably liquid at 40 ° C. (under normal pressure). Normal pressure means pressure equal to atmospheric pressure, which is almost one atmospheric pressure. The liquid means a fluid state. Further, from the viewpoint of molding processing, it is more preferable that the liquid is liquid at 25 ° C. (under normal pressure).
The viscosity of the polyorganosiloxane at 25 ° C. is not particularly limited as long as the polyorganosiloxane is liquid at 40 ° C. (under normal pressure), but is usually 5 mPa · s or more, preferably 50 mPa · s or more, more preferably at 25 ° C. Is 100 mPa · s or more, and is usually 20000 mPa · s or less, preferably 2000 mPa · s or less, and more preferably 500 mPa · s or less. By setting the viscosity within this range, it is possible to reduce dripping from the nozzle, dripping during coating, repelling, etc., and it has appropriate fluidity and facilitates processing.

The molecular weight of the polyorganosiloxane is not particularly limited, but the number average molecular weight Mn is usually 600 or more, preferably 800 or more, more preferably 900 or more, still more preferably 950 or more, and usually 10,000 or less, preferably 5000 or less. It is preferably 2000 or less. The weight average molecular weight Mw is usually 800 or more, preferably 900 or more, more preferably 1000 or more, and usually 20000 or less, preferably 10000 or less, more preferably 4000 or less. By setting the number average molecular weight or weight average molecular weight to the above lower limit or higher, the volatile components are reduced, the flash point rises, the liquid drips from the nozzle by optimizing the viscosity, and the liquid drips during application is prevented. There are various merits such as. On the other hand, by setting the number average molecular weight or the weight average molecular weight to the upper limit or less, it is possible to prevent the viscosity from increasing and, in some cases, to become a solid, and it becomes easy to mix and process with other components.

The number average molecular weight Mn and the weight average molecular weight Mw can be measured by gel permeation chromatography (GPC) under the following conditions and shown as standard polystyrene-equivalent values. The sample uses a THF solution of about 10% by weight and is filtered with a 0.45 μm filter before measurement. Equipment: TOSOH HLC-8220 GPC Column: KF-G, KF-401HQ, KF-402HQ, KF-402.5HQ (manufactured by Showa Denko KK), Column temperature 40 ° C. Eluent: Tetrahydrofuran, Flow rate 0.2 mL / min Another embodiment of the present invention is a cured composition containing the polyorganosiloxane described above, and a cured product obtained by curing the cured composition. The curing mode includes an addition polymerization curing type, a polycondensation curing type, a chain polymerization curing type, and the like, but any of them may be used. Hydrosilylation (addition polymerization curing type), which does not generate desorption components such as water and alcohol and the reaction is not reversible, and similarly, it does not generate desorption components and is used as a chain polymerization initiator such as a radical polymerization initiator. Polyorganosiloxane (chain polymerization type) that cures with ultraviolet rays or heat is easy to use. This is because when desorbed components such as water and alcohol are generated due to polymerization during curing, they remain as bubbles in the cured product, the pressure inside the container is increased during molding, and the desorbed components volatilize. This is because there is a tendency for shrinkage and distortion to occur.

The curable composition containing the polyorganosiloxane described above may appropriately contain a curing catalyst or a chain polymerization initiator depending on the curing mode. The curing catalyst and the chain polymerization initiator are not particularly limited as long as they can cure the polyorganosiloxane described in the present application.
Examples of addition polymerization catalysts include platinum black, second platinum chloride, platinum chloride acid, a reaction product of platinum chloride acid and a monovalent alcohol, a complex of platinum chloride acid and olefins, and platinum-based platinum bisacetacetate. Catalyst, platinum (0) complex with 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclo Examples thereof include platinum (0) complexes with siloxane, platinum-based catalysts, and platinum-group metal catalysts such as rhodium-based catalysts. The blending amount of the addition polymerization catalyst is usually 1 ppm or more, preferably 2 ppm or more, and usually 100 ppm or less, preferably 50 ppm or less, more preferably 20 ppm or less, based on the total weight of the polyorganosiloxane as a platinum group metal. As a result, the catalytic activity is high and the transparency of the cured product can be made high. In addition, one type of addition polymerization catalyst may be used alone, or two or more types may be used in combination.

As the catalyst for condensation polymerization, acids such as hydrochloric acid, nitric acid, sulfuric acid and organic acids, bases such as ammonia and amines, metal chelate compounds and the like can be used, and Ti, Ta, Zr, Al and Hf are suitable. , Zn, Sn, Pt, In, and any one or more of them can be used as a metal chelate compound. Among them, the metal chelate compound preferably contains any one or more of Ti, Al, Zn, Zr, Pt, and In, and more preferably contains Zr and Pt.

The blending amount of the catalyst for condensation polymerization is usually 1 ppm or more, preferably 2 ppm or more, and usually 300 ppm or less, preferably 200 ppm or less, still more preferably 150 ppm or less, based on the total weight of the polyorganosiloxane as a metal. As a result, the catalytic activity is high, and the weight loss when the cured product is heated can be reduced. Further, one type of condensation polymerization catalyst may be used alone, or two or more types may be used in combination.

Examples of the chain polymerization initiator include a radical polymerization initiator, a cationic polymerization initiator, an anionic polymerization initiator and the like, but a method using a radical polymerization initiator is common.
As the radical polymerization initiator, a photopolymerization initiator and a thermal polymerization initiator can be used.
As the photopolymerization initiator, an alkylphenone-based photopolymerization initiator, an acylphosphine oxide-based photopolymerization initiator, an intramolecular hydrogen abstraction type photopolymerization initiator, an oxime ester photopolymerization initiator, or the like can be used, which is suitable. As such, an alkylphenone-based photopolymerization initiator can be used.

Conventionally known peroxides and azo compounds can be used as the thermal polymerization initiator.
Examples of the organic peroxide include diacyl peroxide, peroxydicarbonate, peroxyester, peroxyketal, dialkyl peroxide, hydroperoxide, silyl peroxide and the like, and more specifically, cumylper. Oxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, 1-cyclohexyl-1-methylethylperoxynoedecanoate, t-hexylperoxyneodecanoate, t -Butylperoxyneodecanoate, t-butylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-di ( 2-Ethylhexanoylperoxy) hexane, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyneoheptanoate, t-amylper Oxy-2-ethylhexanoate, di-t-butylperoxyhexahydroterephthalate, t-amylperoxy-3,5,5-trimethylhexanoate, 3-hydroxy-1,1-dimethylbutylperoxyneo Decanoate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-amylperoxyneodecanoate, t-amylperoxy-2-ethylhexanoate, t- Hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl-2,5- Di (3-methylbenzoylperoxy) hexane, t-butylperoxy-2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t- Examples thereof include butylperoxybenzoate, dibutylperoxytrimethyl adipate, t-amylperoxynormal octoate, t-amylperoxyisononanoate, t-amylperoxybenzoate, lauroyl peroxide and the like.

Examples of the azo compound include 2,2'-azobis-2,4-dimethylvaleronitrile, 1,1'-azobis (1-acetoxy-1-phenylethane), and 2,2'-azobisisobutyronitrile. , 2,2'-azobis (2-methylbutyronitrile), dimethyl-2,2'-azobisisobutyronitrile, 4,4'-azobis (4-cyanovaleric acid), 1,1'-azobis ( 1-Cyclohexanecarbonitrile) and the like.

The radical polymerization initiator may be used alone or in combination of two or more.
The curing composition may contain other components such as a filler, a curing control agent, and a viscosity modifier. These components can be appropriately contained within a range that does not interfere with the rebound resilience reducing effect of the cured product of the polyorganosiloxane according to the present embodiment.

Further, the viscosity of the cured composition is not particularly limited, and may be an appropriate viscosity according to the molding method.
The polyorganosiloxane curable composition may be in the form of containing MT resin as described above, or may be in the form of containing cage-type silsesquioxane. When the cage-type silsesquioxane is contained in the polyorganosiloxane curable composition, the content of the cage-type silsesquioxane is preferably less than 5% by weight. By setting the content of the cage-type silsesquioxane to the above-mentioned upper limit or less, the cage-type silsesquioxane is less likely to precipitate, the transparency is easily increased, and the haze of the cured product described later is easily suppressed. It is also easy to maintain the liquid phase.

A cured product obtained by curing the cured composition is also another embodiment of the present invention. The curing method is not particularly limited, and a known method such as heat and ultraviolet rays can be appropriately applied depending on the type of polyorganosiloxane.
The cured product obtained by curing the cured composition preferably has a haze of less than 1%, more preferably 0.6% or less. Within such a range, the influence of light diffusion is reduced, so that the transparency can be used for optical resin applications.

For the measurement of haze, "Plastic-Test method for total light transmittance of transparent material-Part 1 Single beam method / compensation method (JIS K 7361)", "Plastic-How to obtain haze of transparent material (JIS K 7136)" It can be measured with a measuring device (haze meter) that complies with.
The cured product obtained by curing the cured composition preferably has a yellow index of 0 to 10 and more preferably 0 to 5, and 0 to 3 after being treated at 85 ° C. and 85% relative humidity for 168 hours. It is more preferable to have. Within such a range, when used for optical applications, the durability under the influence of ambient temperature and humidity is improved, and the cured product can be used for optical applications.

The yellow index can be measured with a measuring device compliant with "Plastic-How to determine the degree of yellowness and yellowing (JIS K 7373)".
The method for producing a polyorganosiloxane according to the present embodiment is not particularly limited as long as a polyorganosiloxane having the above structure can be obtained. For example, a method for condensing a disiloxane compound or a disilazan compound and its hydrolyzate, an alkoxysilane compound, a hydrolyzate thereof, or a partially hydrolyzed condensate, a method for condensing a chlorosilane compound or a hydrolyzate thereof, or a method for condensing a partially hydrolyzed condensate. , A method of ring-opening polymerization of a cyclic siloxane compound, a chain polymerization including anionic polymerization, or any other production method may be used, and a plurality of production methods may be used in combination. Further, polyorganosiloxane having a desired reactive functional group weight or molecular weight may be fractionated and used by column chromatography, GPC, extraction with a solvent, distillation of unnecessary components, or the like. Further, when the weight loss of the polyorganosiloxane component when heated at 110 ° C. for 2 hours under a reduced pressure of 0.15 torr exceeds 5% by weight, that is, when a large amount of low boiling point components occur, heating or The low boiling point component can be removed by reducing the pressure to obtain the polyorganosiloxane according to the present embodiment.

The method for introducing the reactive functional group into the polyorganosiloxane according to the present embodiment is not particularly limited. For example, a disiloxane compound having a reactive functional group, a disilazan compound having a reactive functional group, an alkoxysilane compound having an M unit, a D unit or a T unit having a reactive functional group, an M unit having a reactive functional group, A reactive functional group can be introduced by using a D-unit or T-unit chlorosilane compound, a cyclic siloxane compound having a reactive functional group, or the like as a raw material. Further, the introduced reactive functional group may be converted into another reactive functional group by a chemical method. For example, a method of converting a polyorganosiloxane having an alkenyl group and a monofunctional thiol having a reactive functional group into another kind of reactive functional group by a reaction, oxidizing the alkenyl group with an oxidizing substance and converting it into an epoxy group. Method, a method of converting a polyorganosiloxane having a hydrogen atom directly connected to a silicon atom into another kind of reactive functional group by a reaction with a vinyl compound having a reactive functional group, a cyclic ether group introduced into the polyorganosiloxane. It can be converted into another kind of reactive functional group and used by opening the ring and converting it into an alcoholic hydroxyl group. The polyorganosiloxane according to the present embodiment has a low viscosity and a small amount of weight loss during depressurization and heating, so that it is extremely easy to handle, and the polyorganosiloxane according to the present embodiment is cured by curing. Since the object has high strength and high thermal shock resistance, it can be used for various purposes. For example, viscosity modifiers, compatibilizers, lubricants, dispersants, flocculants, adhesives, adhesives, mold release agents, water repellents, oil repellents, coating materials, surface modifiers, optical members, metal surface repairs. It can be used as an agent, a flame retardant-imparting agent, a semiconductor device encapsulant such as an inorganic or organic light emitting element, a base material, and a coating material.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited thereto. The materials used in the examples and the measurement methods for the evaluation items are as follows. Parts and% in the examples are based on mass unless otherwise specified.
[Measuring method]

1. 1. Measurement of Reactive Functional Group Amount and Alkoxy Group Amount in Polyorganosiloxane Weighed 50 mg of the polyorganosiloxane to be measured, added 15 mg of toluene as an internal standard, and weighed precisely. Further, 1 g of deuterated chloroform was added and dissolved, and the measurement was carried out by 400 MHz ¹ H-NMR (AL-400 manufactured by JEOL Ltd.) with the Relaxation Delay set to 20 seconds. Depending on the ratio of the signal intensity of each component to the signal intensity of the internal standard toluene and the weighed value, the content of alkoxy groups and the content of functional groups per gram (mmol / g), that is, the molecular weight of polyorganosiloxane. The number of functional groups per 1000 was calculated. At this time, impurities such as organic substances, water, and metals that are not bound to polyorganosiloxane must be removed to less than 0.1% by weight so as not to affect the measurement results, and exceed 0.1% by weight. If so, prepare the sample after removal by distillation, filtration or other purification method and measure ¹ H-NMR. If removal is difficult, ¹ Calculate the impurity content by H-NMR measurement or other analytical method, and subtract the weight of the impurity from the weighed sample weight so that it is not calculated as part of the polyorganosiloxane. Is used in the calculation as the true sample amount. As the internal standard, any substance that does not react with polyorganosiloxane, such as N, N-dimethylformamide and tribromoethane, can be used in addition to toluene.

2. 2. Measurement of Silicon Bonded Alkoxy Group Content and Number of Functional Groups per 1000 Molecular Weight Weighed 50 mg of each polyorganosiloxane and added 15 mg of toluene as an internal standard. Further, 1 g of deuterated chloroform was added and dissolved, and the relaxation delay was measured in 20 seconds by 400 MHz ¹ H-NMR (AL-400 manufactured by JEOL Ltd.). Estimate the reactive functional group content (mmol / g) per 1 g from the ratio of the signal intensity of each component to the signal intensity of the internal standard toluene and the weighed value, and calculate the number of reactive functional groups per 1000 molecular weight. did.

3. 3. ²⁹ Si-NMR measurement method Equipment: JEM-ECS400, TUNABLE (10), Si-free, AT10 probe measurement conditions manufactured by JEOL Ltd .: Relaxation Delivery / 15 seconds, SCAN frequency / 1024 times, measurement mode / non-gated decoupler pulse Method (NNE), spin / none, measurement temperature / 25 ° C
-Sample preparation: Tris (2,4-pentanedionato) chromaIII was added to deuterated chloroform so as to be 0.5% by weight to obtain a solvent for ²⁹ Si-NMR measurement. 1.5 g of the organopolysiloxane to be measured was weighed, 2.5 ml of the above ²⁹ Si-NMR measurement solvent was added and dissolved, and the mixture was placed in a 10 mmΦ Teflon (registered trademark) NMR sample tube.

4. Measurement of Molecular Weight The number average molecular weight Mn and weight average molecular weight Mw of each polyorganosiloxane were measured by gel permeation chromatography (GPC) under the following conditions and shown as standard polystyrene-equivalent values. As a sample, a THF solution of about 10% by weight was used, and a sample filtered through a 0.45 μm filter before measurement was used.
Equipment: TOSOH HLC-8220 GPC
Column: KF-G, KF-401HQ, KF-402HQ, KF-402.5HQ (manufactured by Showa Denko KK), column temperature 40 ° C.
Eluent: Tetrahydrofuran, flow rate 0.2 mL / min

5. Infrared absorption measurement (IR measurement)
-Fourier Transform Infrared Spectroscopy
-Device: Nic-Plan manufactured by Thermo Fisher Scientific Co., Ltd.
・ Resolution: 4 cm ^-1
-Number of integrations: 64 times The maximum absorbed wave number was measured by the ATR method (Attenuated Total Reflection, total reflection measurement method).

6. Measurement of weight loss during decompression heating
¹ Measure 1 H-NMR and calculate the weight of components other than polyorganosiloxane, such as organic solvent. Place the rotors in an eggplant-shaped flask and weigh them. Then, the polyorganosiloxane is placed in the eggplant-shaped flask and the weight of the polyorganosiloxane is measured. Heat the eggplant-shaped flask in an oil bath, rotate the rotor with a magnetic stirrer to stir to the extent that the liquid level flows, raise the temperature until the internal temperature reaches 110 ° C, and reduce the pressure with an oil-type vacuum pump. .. As the depressurizing capacity of the oil type vacuum pump, one having a decompression capacity of 0.15 Torr is used. After 2 hours, the mixture was cooled to room temperature, returned to normal pressure, the oil adhering to the eggplant-shaped flask was sufficiently wiped off, the weight of the polyorganosiloxane in the eggplant-shaped flask was measured, and the eggplant that had been measured earlier was measured. The weight of the flask and the rotor is subtracted, and the weight volatilized by the operation is calculated. ¹ H-NMR of the polyorganosiloxane after the operation is measured, and the weight of a component other than the polyorganosiloxane such as an organic solvent is calculated. The amount of the polyorganosiloxane weight loss was calculated by subtracting the amount of components other than the polyorganosiloxane from the volatilized weight.

7. How to check the properties at 40 ° C Put 100 g of each polyorganosiloxane and a rotor with a diameter of Φ8 mm and a length of 30 mm in a 500 ml eggplant-shaped flask, and while stirring with a magnetic stirrer, the internal temperature is 40 with an oil bath. Heated to ° C. After that, when the polyorganosiloxane is touched with a glass rod, the oil adheres to the glass rod, and after 30 minutes by tilting the eggplant-shaped flask sideways 90 °, the liquid 90 from the bottom surface to the side surface of the flask. Those that moved by% or more were judged to be liquid.

8. Measurement of Viscosity at 25 ° C. A value at a temperature of 25 ° C. was measured using an RV type viscometer RVDV-2 + Pro manufactured by Brookfield.

9. Flash point measurement method (to be described)
When the flash point is 80 ° C or less, the flash point is measured by the Penske Martins sealed type according to JIS K 2265-3: 2007 or ISO 2719: 2002, and the flash point is 80 ° C.
In the above cases, the value measured by the Cleveland opening method according to JIS K 2265-4: 2007 or ISO 2592: 2000 was used as the flash point. In addition, SILTECH COR. For VQ2012 manufactured by the company, SILTECH COR. The flash point was 49 ° C, which is the company catalog value.

10. Linear expansion coefficient measurement method The linear expansion coefficient of the cured product is measured with the following equipment, mode and temperature program using a thickness of 1 mm, and the average linear expansion coefficient from 50 ° C to 100 ° C at the time of the second temperature rise is measured. It was set as a value. Equipment: TMA / SS6100 manufactured by SII Nanotechnology Co., Ltd.
Mode: Compression mode Temperature program: Temperature rise from 1.30 ° C to 120 ° C at 5 ° C / min
2. Hold at 120 ° C for 5 minutes
3. Lower temperature from 120 ° C to 30 ° C at 50 ° C / min
4. Hold at 30 ° C for 5 minutes
Temperature rise from 5.30 ° C to 120 ° C at 5 ° C / min
6. Hold at 120 ° C for 5 minutes

11.3 Point flexural modulus measuring method Equipment: Shimadzu Corporation, desktop precision universal testing machine AG-Xplus
Load cell: 5kN
Measuring jig: Plastic 3-point bending test jig Test piece: Thickness 2 mm, width 14.25 mm, length 30 mm
Distance between lower fulcrums: 17.6 mm
Load speed: 0.5 mm / min

12. Shore D hardness Measured according to JIS K 6253 using an Asker rubber altimeter type D.

[Silicone resin used]
The reagents and solvents used for the synthesis are as follows.
Hexamethyldisiloxane (manufactured by NuSil Technology, product name: S-7205)
1,3-Divinyltetramethyldisiloxane (manufactured by NuSil Technology, product name: PLY-70)
Tetraethoxysilane (manufactured by Kishida Chemical Co., Ltd.)
Ethyl silicate ES-40 (manufactured by Corcote Co., Ltd.)
Methyl silicate MS-51 (manufactured by Mitsubishi Chemical Corporation)
(3-Methoxyloyloxypropyl) Trimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-503)
Tetrahydrofuran (manufactured by Kishida Chemical Co., Ltd.)
Toluene (manufactured by Kishida Chemical Co., Ltd.)
Ethanol (manufactured by Kishida Chemical Co., Ltd.)
Methanol (manufactured by Kishida Chemical Co., Ltd.)
1N Hydrochloric Acid (manufactured by Kishida Chemical Co., Ltd.)
Heptane (manufactured by Kishida Chemical Co., Ltd.)

(1) Polyorganosiloxane 1
Hexamethyldisiloxane 18.3 parts by weight, 1,3-divinyltetramethyldisiloxane 64.3 parts by weight, and tetraethoxysilane 105 parts by weight were dissolved in 187 parts by weight of tetrahydrofuran, and then 1N hydrochloric acid was added to 24.7 parts by weight. A mixture of 24.7 parts by weight of ethanol was added, and the mixture was stirred at 40 ° C. for 4 hours. After diluting with 374 parts by weight of heptane, it was washed with demineralized water. The solvent was distilled off under a reduced pressure of 76 ° C. and a pressure of 15 Torr using a rotary evaporator until the solvent was not distilled out visually. Subsequently, the mixture was heated at 110 ° C. under a reduced pressure of 0.15 torr for 2 hours to obtain 85.7 parts by weight of the desired polyorganosiloxane 1.

(2) Polyorganosiloxane 2
After dissolving 18.3 parts by weight of hexamethyldisiloxane, 64.3 parts by weight of 1,3-divinyltetramethyldisiloxane, and 74.7 parts by weight of ethyl silicate ES-40 in 157 parts by weight of tetrahydrofuran, 1N hydrochloric acid 17. A mixture of 9 parts by weight and 17.9 parts by weight of ethanol was added, and the mixture was stirred at 40 ° C. for 4 hours. After diluting with 315 parts by weight of heptane, the same treatment as in the synthesis of the above-mentioned polyorganosiloxane 1 was performed to obtain 87.2 parts by weight of the desired polyorganosiloxane 2.

(3) Polyorganosiloxane 3
After dissolving 277 parts by weight of 1,3-divinyltetramethyldisiloxane and 132 parts by weight of methylsilicate MS-51 in a mixed solvent of 205 parts by weight of toluene and 205 parts by weight of methanol, 46.0 parts by weight of 1N hydrochloric acid and 37 parts of methanol were used. .6 parts by weight of the mixture was added and stirred at 40 ° C. for 4 hours. After diluting with 409 parts by weight of heptane, the same treatment as in the synthesis of the polyorganosiloxane 1 described above was carried out to obtain the desired polyorganosiloxane 3.

(4) Polyorganosiloxane 4
2.6 parts by weight of hexamethyldisiloxane, 9.16 parts by weight of 1,3-divinyltetramethyldisiloxane, 8.24 parts by weight of methylsilicate MS-51, 10.0 parts by weight of toluene and 10.0 parts by weight of methanol. After dissolving in the mixed solvent, a mixture of 5.10 parts by weight of 1N hydrochloric acid and 2.55 parts by weight of methanol was added, and the mixture was stirred at 40 ° C. for 4 hours. After diluting with 17.5 parts by weight of heptane, the same treatment as in the synthesis of the above-mentioned polyorganosiloxane 1 was performed to obtain 13.2 parts by weight of the desired polyorganosiloxane 4.

(5) Polyorganosiloxane 5
33.8 parts by weight of hexamethyldisiloxane, 295 parts by weight of (3-methacryloyloxypropyl) trimethoxysilane, and 11.4 parts by weight of methyl silicate MS-51 are dissolved in a mixed solvent of 170 parts by weight of toluene and 170 parts by weight of methanol. Then, a mixture of 79.2 parts by weight of 1N hydrochloric acid and 79.2 parts by weight of methanol was added, and the mixture was stirred at 40 ° C. for 4 hours. After diluting with 466 parts by weight of toluene, the same treatment as in the synthesis of the above-mentioned polyorganosiloxane 1 was performed to obtain 216 parts by weight of the desired polyorganosiloxane 5.

(6) Polyorganosiloxane 6
It was synthesized in the same manner as polyorganosiloxane 1 except that the treatment was not carried out at 110 ° C. and a pressure of 0.15 torr under reduced pressure to obtain 100 parts by weight of the desired polyorganosiloxane 6.

(7) Polyorganosiloxane 6
SILTECH COR. The Silver VQ2012 manufactured by the same company was used as it was as the polyorganosiloxane 7. This is sold as a liquid vinyl group-substituted MQ resin, and is considered to be a commercially available product closest to the present invention.

(8) Polyorganosiloxane 8
After dissolving 207 parts by weight of hexamethyldisiloxane, 87.5 parts by weight of 1,3-divinyltetramethyldisiloxane, and 186 parts by weight of methylsilicate MS-51 in a mixed solvent of 180 parts by weight of toluene and 180 parts by weight of methanol, A mixture of 37.7 parts by weight of 1N hydrochloric acid and 37.7 parts by weight of methanol was added, and the mixture was stirred at 40 ° C. for 4 hours. After diluting with 151 parts by weight of heptane, the same treatment as in the synthesis of the above-mentioned polyorganosiloxane 1 was performed to obtain 196 parts by weight of the desired polyorganosiloxane 8.

(9) Polyorganosiloxane 9
After dissolving 210 parts by weight of hexamethyldisiloxane, 17.9 parts by weight of 1,3-divinyltetramethyldisiloxane, and 172 parts by weight of methylsilicate MS-51 in a mixed solvent of 200 parts by weight of toluene and 200 parts by weight of methanol, A mixture of 107 parts by weight of 1N hydrochloric acid and 53.7 parts by weight of methanol was added, and the mixture was stirred at 40 ° C. for 4 hours. After diluting with 350 parts by weight of heptane, the same treatment as in the synthesis of the above-mentioned polyorganosiloxane 1 was performed to obtain 204 parts by weight of the desired polyorganosiloxane 9.

(10) Polyorganosiloxane 10
HYBRID PLASTICS INC. The trade name Vinyl POSS Cage Mixture (OL1170) manufactured by the same company was used as it was as polyorganosiloxane 10.

(11) Polyorganosiloxane 11
HYBRID PLASTICS INC. The trade name Methally POS Cage Mixture (MA0735) manufactured by the same company was used as it was as the polyorganosiloxane 11.

[Method for creating cured product 1]
80 parts by weight of polyorganosiloxane synthesized by the above method, 20 parts by weight of vinyl group-containing silicone (manufactured by NuSil Technology, trade name: PLY7511), dicumyl peroxide (manufactured by NOF Corporation, trade name: Park Mill D) 0 .5 parts by weight were mixed. The obtained mixed solution was sandwiched between glass plates having a gap between them with a 1 mm spacer, the temperature was raised from 40 ° C. to 140 ° C. at 5 ° C./min, and the mixture was held at 140 ° C. for 2 hours. After allowing to cool to 40 ° C., the upper glass plate was removed, the temperature was further raised from 40 ° C. to 190 ° C. at 5 ° C./min, and the temperature was maintained at 190 ° C. for 2 hours. After allowing to cool to 40 ° C. or lower, the other remaining glass plate was removed to obtain a cured product of the polyorganosiloxane composition.

[Curing product preparation method 2]
100 parts by weight of the polyorganosiloxane synthesized by the above method and 3 parts by weight of 2-hydroxy-2-methylpropiophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed. The obtained mixed solution was sandwiched between glass plates having a gap with a 1 mm spacer, and was irradiated with light using a FUSION UV SYSTEMS, INC I6P1 / LH with a high-pressure mercury lamp (cumulative light amount 3000 mJ / cm2), and then used glass. The plate was removed to obtain a cured product of polyorganosiloxane.

[Method for creating cured product 3]
Hydrosilyl group-modified silicone (NuSil Technology) with respect to 100 parts by weight of polyorganosiloxane having a vinyl group synthesized by the above method and 100 parts by weight of bi-terminal vinyl group-modified silicone (manufactured by NuSil Technology, trade name: PLY-7500). A company-manufactured product, trade name: XL-1) was added so that the material amount ratio of the vinyl group and the hydrosilyl group was 1: 1. Further, a 2 wt% xylene solution (manufactured by Aldrich) of the Karstedt catalyst was added so as to have a platinum weight of 3 ppm, and 1-ethynyl-1-cyclohexanol was added at 6 ppm. The mixture thus obtained is referred to as a mixture A. For 15 parts by weight of the mixture A, 83 parts by weight of spherical silica (manufactured by Denka Co., Ltd., trade name: FB-5D) and terminal trimethylsilyl group-modified fumed silica (manufactured by Nippon Aerosil Co., Ltd., trade name RX-200) as an inorganic filler. ) 2 parts by weight was added, mixed using a centrifugal defoaming mixer, and then filled into a mold having a width of 14.25 mm, a length of 30 mm, and a thickness of 2 mm. Then, it was pressed at 200 ° C. and a pressure of 50 kg / cm ² for 3 minutes to obtain a cured product of the polyorganosiloxane composition.

[Examples and Comparative Examples]
Table 1 shows various measured values of polyorganosiloxane prepared according to the above-mentioned method, and various measured values of the cured product prepared according to the cured product preparation methods 1 to 3.
The polyorganosiloxane of Comparative Example 1 has a large number of alkoxy groups bonded to silicon, and also has a large weight loss when heated at 110 ° C. for 2 hours.

The polyorganosiloxane of Comparative Example 2 is a commercially available product closest to the present invention as far as the applicant knows, but the weight loss is large when heated at 110 ° C. for 2 hours.
In Comparative Examples 3 and 4, the amount of functional groups is insufficient with respect to the provisions of the present invention.
Comparative Examples 5 and 6 have different maximum absorption wave numbers of Si—O vibration in infrared absorption spectrum analysis, and are cage-type silsesquioxane having a substituent. These are substantially solid.

Consideration [Line expansion coefficient]
The polyorganosiloxanes 1, 2, and 4 used in Examples 1, 2, and 4 have a content and reactive functionality of each silicon species of the polyorganosiloxane as compared with the polyorganosiloxane 6 used in Comparative Example 1. Although the basic species and the amount are close to each other, in Examples 1, 2 and 4, the amount of weight loss during heating and depressurization is extremely small. In such a case, it was found that the linear expansion coefficient of the cured product became small. From this, it can be seen that when the weight loss during heating and depressurization is small, there is an advantage that a cured product having good dimensional stability can be produced in a wide range of temperatures.

[flash point]
Compared with the polyorganosiloxane 7 used in Comparative Example 2, the polyorganosiloxane 4 used in Example 4 has a similar content, reactive functional group species, and amount of each silicon species, but is heated. The amount of weight loss during depressurization is small. In such a case, it was found that the flash point rises significantly. When applied to the Fire Service Act Dangerous Goods Classification, Poiorganosiloxane 6 is Class 4 Second Petroleum (water-insoluble), while Polyorganosiloxane 4 is Class 4 Third Petroleum (water-insoluble). Is. From this, if the amount of weight loss during heating and depressurization is small, it can be handled more safely, and even in the Fire Service Act dangerous goods classification, it is classified as less dangerous, so the cost for storage and transportation It can be seen that there is a merit of lowering.

[viscosity]
The polyorganosiloxane 10 and polyorganosiloxane 11 used in Comparative Examples 5 and 6 were found in the wavenumber 1030 to 1150 cm-1 region in the infrared absorption spectrum analysis, and in the wavenumber ^1075-1150 cm ^-1 region peculiar to the cage structure. It has the maximum absorbed wave number of Si—O expansion and contraction vibration. On the other hand, the polyorganosiloxane used in the other examples and comparative examples has a maximum absorption wave number of Si—O expansion and contraction vibration in the region of wave number 1030 to 1070 cm ^-1 in the infrared absorption spectrum analysis, and is a cage type. Does not have the structure of. As a result of measuring the viscosities of these, polyorganosiloxane having the maximum absorbed wave number of Si—O expansion and contraction vibration in the region of wave number 1030 to 1070 cm ^-1 , that is, poly having no cage-shaped structure. Organosiloxane was found to have a low viscosity. On the other hand, the polyorganosiloxane having the maximum absorption wavenumber of Si—O expansion / contraction vibration in the region of wavenumber 1075 to 1150 cm ^-1 , that is, the polyorganosiloxane having a cage-shaped structure has a high viscosity or is It turned out to be solid. Therefore, since the polyorganosiloxane of the present invention is a low-viscosity liquid, it is easy to handle, the time required for weighing, mixing, and molding is significantly shortened, the time required for cleaning is shortened, the cleaning agent is reduced, and the like. There are merits.

[3-point flexural modulus and shore D hardness]
The polyorganosiloxanes 3 and 4 used in Examples 3 and 4 have vinyl groups as reactive functional groups in the range of 3 to 12 per 1000 molecular weight of the polyorganosiloxane. On the other hand, the polyorganosiloxanes 8 and 9 used in Comparative Examples 3 and 4 have the same kind of reactive functional groups as the polyorganosiloxanes 3 and 4, but the content is less than the range of 3 to 12. As a result of producing a cured product using these polyorganosiloxanes, the number of reactive functional groups is 3 to 12 per 1000 molecular weight of the polyorganosiloxane, so that the three-point bending elastic modulus and the shore D hardness are increased. I understood. Therefore, by producing a cured product using the polyorganosiloxane of the present invention, there is an advantage that a material having high elasticity and high hardness can be obtained.

Claims (15)

The content of M units (R ¹ R ² R ³ SiO _1/2 ) with respect to total silicon is 10 mL or more, and the content of T units (R ⁶ SiO _3/2 ) with respect to total silicon is 80 mL or less. Moreover, it is a polyorganosiloxane having an alkoxy group bonded to silicon and a reactive functional group other than the alkoxy group, and the content of the alkoxy group bonded to silicon is 0.07 to 4% by weight based on the total weight of the polyorganosiloxane. The number of reactive functional groups bonded to silicon per 1000 molecular weight of polyorganosiloxane is 3 to 12, and the polyorgano is heated at 110 ° C. for 2 hours under a reduced pressure of 0.15 torr. A polyorganosiloxane having a siloxane weight loss of 5% by weight or less. The polyorganosiloxane according to claim 1, wherein the content of the M unit with respect to total silicon is 60 mL% or less. A polyorganosiloxane having a reactive functional group other than the alkoxy group bonded to silicon, which requires the Q unit represented by (SiO _4/2 ) and is bonded to silicon per 1000 molecular weight of the polyorganosiloxane. The number of reactive functional groups is 3 to 12, and in infrared absorption spectrum analysis, the maximum absorption wave number of Si—O expansion and contraction vibration is in the region of wave number 1030 to 1060 cm ^-1 , and the pressure is reduced to 0.15 torr. , Polyorganosiloxane having a weight loss of 5% by weight or less of the polyorganosiloxane component when heated at 110 ° C. for 2 hours. The polyorganosiloxane according to any one of claims 1 to 3, wherein the content of M units with respect to total silicon is 10 mol% or more and 60 mol% or less. The reactive functional group bonded to silicon comprises at least one group selected from the group consisting of an alkenyl group, a methacryloyl group, an acryloyl group, an acyl group, and a cyclic ether group, and a hydrogen atom forming a hydrosilyl group with silicon. The polyorganosiloxane according to any one of claims 1 to 4, which comprises. The polyorganosiloxane according to any one of claims 1 to 5, wherein the reactive functional group is a vinyl group. The polyorganosiloxane according to any one of claims 1 to 5, wherein the reactive functional group is a methacryloyloxypropyl group. The polyorganosiloxane according to any one of claims 1 to 7, which is liquid at 40 ° C. The polyorganosiloxane according to any one of claims 1 to 8, wherein the viscosity at 25 ° C. is 5 mPa · s or more and 20000 mPa · s or less. The polyorganosiloxane according to any one of claims 1 to 9, wherein the GPC measurement result in terms of polystyrene has a number average molecular weight Mn of 600 or more and 5000 or less. The polyorganosiloxane according to any one of claims 1 to 10, wherein the M unit contains at least a trimethylsiloxy group or a dimethylsiloxy group. The polyorganosiloxane according to any one of claims 1 to 11, which is an MQ resin. The polyorganosiloxane according to any one of claims 1 to 11, which is an MTQ resin. The composition containing the polyorganosiloxane according to any one of claims 1 to 13. A cured product obtained by curing any of the polyorganosiloxane according to claim 1 to 13 or the composition according to claim 14.