JPH0813888B2 - Silicone resin and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION Industrial Field of the Invention The present invention relates to a silicone resin, particularly a monofunctional organosiloxane unit (M unit) and a trifunctional siloxane unit (T
Unit) and a tetrafunctional siloxane unit (Q unit), and is excellent in compatibility with an organopolysiloxane composed of a bifunctional siloxane unit (D unit). The present invention relates to a silicone resin composed of MTQ units which is useful as a reinforcing agent and a method for producing the same.

(Prior Art) Various kinds of organosiloxane resins have been conventionally known, for example, monofunctional siloxane units (hereinafter abbreviated as M units) and tetrafunctional siloxane units (hereinafter abbreviated as Q units). The copolymer consisting of is called MQ resin, which is used as a raw material for silicone pressure-sensitive adhesives, or silicone rubber that requires transparency in particular,
Above all, it is used as a strength enhancer for room temperature curable (hereinafter abbreviated as RTV) silicone rubber, and a copolymer obtained by further introducing a bifunctional siloxane unit (hereinafter abbreviated as D unit) into this MQ is also MDQ. Called resin,
It is known that this also has an effect which is not inferior to that of MQ resin.

However, the MTQ resin in which a trifunctional siloxane unit (hereinafter abbreviated as T unit) is introduced into this MQ resin is difficult to manufacture because the siloxane of this T unit is easy to gel especially during hydrolysis, and thus obtained. Also contains a gelled product, and the yield is extremely poor. Furthermore, this MTQ resin has poor compatibility with other organopolysiloxanes and organic resins other than silicone, and it does not stick when applied to pressure-sensitive adhesives. The strength is low, and the reinforcing effect of the silicone rubber as a reinforcing agent is hardly recognized. Therefore, this material has not been industrially put to practical use.

(Structure of the Invention) The present invention relates to an MTQ resin and a method for producing the same, in which such a disadvantage is solved, in which the repeating unit is M unit: R ¹ ₃ SiO _1/2 (wherein R ¹ is unsubstituted or Substituted same or different monovalent hydrocarbon group), Q unit: SiO ₂ and T unit: R ² SiO _3/2 (wherein R ² is an unsubstituted or substituted same or different monovalent hydrocarbon group, 30 mol% or more thereof is a group having 2 or more carbon atoms), M units are in a molar ratio of M / Q = 0.4 to 2.0 with respect to Q units, and T units are contained in 1 to 20 mol%, A silicone resin having a molecular weight of 500 to 100,000, and 1) the general formula R ¹ _a Si (OR ³ ).
Organo represented by _4-a (R ¹ is an unsubstituted or substituted same or different monovalent hydrocarbon group, R ³ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and a is a positive number of 2.6 to 3.0) A hydroxysilane, an organoalkoxysilane and / or an organosiloxane represented by the general formula (R ¹ _a Si) ₂ O _4-a (R ¹ and a are the same as above); and 2) a general formula Si (OR ⁴ ) ₄ ( Here
R ⁴ is an alkyl group having 1 to 5 carbon atoms) and / or a partial hydrolysis-condensation product thereof, and 3) the general formula R ² _b Si (OR ⁴ ) _4-b (R ² is 30 mol thereof) % Or more is a group having 2 or more carbon atoms, and is an unsubstituted or substituted monovalent hydrocarbon group of the same or different type, and R ⁴ is the same as the above) and mixed with an organoalkoxysilane and / or a hydrolyzed condensate thereof. Then, the present invention relates to a method for producing a silicone resin, which comprises subjecting this to co-hydrolysis and polycondensation reaction.

That is, as a result of various investigations by the present inventors to develop a highly industrially useful MTQ resin, when the monovalent hydrocarbon group R ² of the T unit of this MTQ resin is all methyl groups, It has no compatibility with organopolysiloxanes composed of difunctional siloxane units (D units) represented by the formula R ⁵ ₂ SiO (wherein R ⁵ is an unsubstituted or substituted same or different monovalent hydrocarbon group). When applied to silicone pressure-sensitive adhesives, it has low adhesiveness and is not practical, and when used as a reinforcing agent for silicone rubber, almost no reinforcing effect is observed, and compared with the MQ resins and MDQ resins described above. R ² is 30
When the mol% is a monovalent hydrocarbon group having 2 or more carbon atoms, this MTQ resin has excellent compatibility with the organopolysiloxane composed of the D unit siloxane described above, and is suitable for silicone pressure-sensitive adhesives. It was found that when it is applied, it shows excellent adhesiveness, and when it is applied as a silicone rubber reinforcing agent, it also shows excellent reinforcing effect, and this is a defoaming agent based on organopolysiloxane. When added to, the defoaming effect is improved,
It has the effect of maintaining defoaming properties, and when compounded in various plastics, it improves foaming prevention during molding, flow properties (flow characteristics), and mold release properties, and at the same time improves printability and surface gloss of molded products.
It was confirmed that it has the effect of improving the mechanical properties, and further improving its moisture resistance, water resistance and heat resistance when compounded in a molding compound composed of epoxy resin and various inorganic fillers. The present invention has been completed by conducting research on the type of each unit used, the polymerization ratio, and the manufacturing method. This will be described in detail below.

M which is the first component constituting the silicone resin of the present invention
Unit: In R ¹ ₃ SiO _1/2 , R ¹ is a methyl group, an ethyl group, a propyl group, an alkyl group such as a butyl group, a cycloalkyl group such as a cyclohexyl group, a vinyl group, an alkenyl group such as an allyl group, a phenyl group, Selected from an aryl group such as a tolyl group, or a chloromethyl group obtained by substituting a part or all of hydrogen atoms bonded to carbon atoms of these groups with a halogen atom, a cyano group, a trifluoropropyl group, a cyanoethyl group, etc. It is assumed to be an unsubstituted or substituted monovalent hydrocarbon group of the same or different type.

The second component constituting the silicone resin of the present invention represented by the Q unit: SiO ₂ is, for example, a compound represented by the general formula Si (O 2
An alkyl silicate represented by R ⁴ ) ₄ (R ⁴ is an alkyl group having 1 to 5 carbon atoms) is most suitable.

T unit as the third component constituting the silicone resin of the present invention: In R ² SiO _3/2 , R ² is the same unsubstituted or substituted monovalent hydrocarbon group which is the same as or different from that exemplified for R ^1. However, if all of the R ² are methyl groups, the target MTQ resin will not be compatible with the organopolysiloxane composed of D units of siloxane units, and this MTQ resin will be a silicone pressure-sensitive adhesive or silicone. It cannot be used as a reinforcing agent for rubber. Therefore, if the MTQ resin has 30 mol% or more of groups having 2 or more carbon atoms, in other words, 30 mol% or more of groups other than methyl groups, D
Compatibility with organopolysiloxane consisting of siloxane units of units becomes poor, and raw material of silicone pressure-sensitive adhesive,
Not qualified as a reinforcing agent for silicone rubber. It is preferable that 60 mol% or more is a group having 2 or more carbon atoms, but the organic matter increases as the carbon number increases or the mol% increases. Since there is an advantage that the affinity with organic resins other than silicone is improved, it is necessary that 30 mol% or more of R ² is a group other than a methyl group, that is, a group having 2 or more carbon atoms.

The silicone resin of the present invention comprises the above M, T, and Q units. The polymerization ratio is such that the M unit is M / Q = 0.4 to 2.0 in a molar ratio with respect to the Q unit, and the T unit is 1-20
It is supposed to be contained by mol%. When M / Q is less than 0.4, compatibility dispersibility in organic resins other than organopolysiloxane and silicone added to the MTQ resin of the present invention deteriorates, and when 2.0 or more, mechanical strength of the compound, other If the T unit is less than 1 mol% when applied to a silicone pressure sensitive adhesive,
No significant effect was observed in its performance, especially in adhesive strength, and when it was used as a reinforcing agent for silicone rubber, the result was no different from that of MQ resin.
This is because the MTQ resin itself becomes unstable, and it may stick or gel during the manufacturing process.

Incidentally, if the molecular weight of this silicone resin is 500 or less, preferable physical properties as a reinforcing agent cannot be obtained, and if it exceeds 100,000, the solubility in a solvent and the compatibility with dimethylpolysiloxane are lowered, and therefore, in terms of styrene.
It may be 500 to 100,000, preferably 1,000 to 50,000. MT of the present invention produced by copolymerization at such a ratio
Silicone resin as Q resin is blended in this T
Since the siloxane unit as a unit contains not only a methyl group but also a monovalent hydrocarbon group having 2 or more carbon atoms in an amount of 30 mol% or more, for example, other than an organopolysiloxane composed of a siloxane unit as a D unit or silicone. It has a good compatibility with other organic resins, and shows excellent adhesive strength when used as a silicone pressure-sensitive adhesive, and also has an excellent reinforcing effect when used as a reinforcing agent for silicone rubber. When added to a resin, it is effective in improving its moldability and physical properties of molded products.

This T unit is an aliphatic unsaturated group, for example When this MTQ resin containing groups is vulcanized with an organic peroxide as a catalyst, the degree of cross-linking between the CH ₂ = CH- double bond and the organic group of the silicone rubber is further increased, so that the reinforcing property is improved. When it is used as a silicone pressure-sensitive adhesive, the cohesive force is improved, and the effect of improving physical constitution is further increased. When an organohydrogenpolysiloxane and a platinum- or palladium-based catalyst are added to this, The addition reaction between the heavy bond and the hydrogen atom bonded to the silicon atom provides the advantage that the various physical properties are improved. Also, for the conventionally known MQ resin, this M unit It is also known that a vinyl group is introduced at the end of the molecular chain using a siloxane represented by and an organosiloxane represented by (CH ₃ ) ₃ SiO _1/2, which is expensive as a raw material for this dimethylvinylsiloxane unit. Since the tetramethyldivinylsiloxane, dimethylvinylalkoxysilane, and dimethylvinylchlorosilane are used, this MQ resin becomes expensive, and thus its application range is limited, but the silicone resin of the present invention is used. Is this MT
Since vinyltrichlorosilane, vinyltrialkoxysilane, etc. can be used as the T unit source when making the Q resin, this can be obtained at a low cost, and therefore it is widely used outside the limited application range up to now. The advantage is given that it can be used.

The silicone resin of the present invention is made of the copolymer of the above-mentioned first to third components as described above, and the production of this may be carried out, for example, by the following method. That is, the M unit source of the first component in this production method is represented by the general formula R ¹ _a Si (OR ³ ) _4-a , R ¹ and a are as described above, and R ³ is a hydrogen atom or a carbon atom. An alkyl group of the formulas 1 to 5, which is represented by a triorganosilanol, a triorganoalkoxysilane and / or a general formula (R ¹ _a Si) ₂ O _4-a , and R
¹ , a is hexaorganodisiloxane as described above, specifically trimethylsilanol, trimethylmethoxysilane, trimethylethoxysilane, toluethylmethoxysilane, toluethylethoxysilane, toluethylsilanol, hexamethyldisiloxane, hexaethyl Disiloxane, hexaisopropyldisiloxane and mixtures thereof may be used.

Next, the Q unit source of this second component is represented by the general formula Si (OR ⁴ ) ₄ , and R ⁴ is an alkyl silicate having 1 to 5 carbon atoms, such as methyl silicate, ethyl silicate, propyl silicate, Butyl silicate and / or a partially hydrolyzed condensate thereof may be used.

The T unit source of this third component is represented by the general formula R ² _b Si (OR ⁴ ).
_4-b , R ₂ , R ₃ and b are as defined above for organotrialkoxysilanes such as methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, vinyltrimethoxysilane, propyltrimethoxysilane. Methoxysilane, butyltrimethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, propyltriethoxysilane, butyltriethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, phenyltrimethoxysilane, etc., or their partial hydrolysis Examples of the condensate include, for the third component, 30 mol% or more of the siloxane unit is required to be a monovalent hydrocarbon group having 2 or more carbon atoms. It is required to use the selected combination.

The silicone resin of the present invention can be obtained by mixing the organosilane and / or the organosiloxane for constituting the above-mentioned first to third components, and co-hydrolyzing and polycondensing them. May be blended in such a manner that the polymerization ratio of the first to third components in the desired silicone resin is achieved. Therefore, as described above, the M / Q (molar ratio) is 0.4 to 2.0 and the T unit is 1 to 20 mol. It should be set to%. However, these respective components are mixed, and conventionally known hydrolysis, polycondensation method, for example, hydrolysis is performed by adding an inorganic acid and a necessary amount of water in the presence of an alkyl alcohol which is added as necessary, When hydrolyzed and heavy-bonded by a method of washing with neutralized water, the MTQ resin obtained becomes poor in compatibility and dispersibility with other organopolysiloxanes and organic resins other than silicone, and the physical properties of each resin added Since it becomes difficult to improve, the hydrolysis and polycondensation were carried out by sufficiently adding an alkyl alcohol, an aromatic solvent, and an inorganic acid such as hydrochloric acid and sulfuric acid to the mixture of the above-mentioned components and thoroughly stirring them. After that, the amount of water required for hydrolysis is added to carry out hydrolysis, the condensed alcohols are removed by a usual method, and the acid is neutralized by replacing it with a nonpolar solvent such as toluene or xylene. In order to neutralize by adding an amount of alkali more than necessary for increasing the temperature, then polycondensate using the excess alkali as a catalyst, and then acid more than the amount necessary to neutralize the alkali. After neutralization by adding, the polycondensation is carried out again using an acid added in excess at a temperature of 20 to 140 ° C as a catalyst, and then the acid content is neutralized with an alkali or removed by washing with water to neutralize. However, the order of the polycondensation with alkali and the polycondensation with acid may be reversed. The thus obtained MTQ resin silicone resin has excellent compatibility and dispersibility with other organopolysiloxanes and organic resins other than silicone,
When it is used as a silicone pressure-sensitive adhesive, it exhibits excellent adhesiveness, and when it is used as a reinforcing agent for silicone rubber, it exhibits an excellent reinforcing effect. This has the advantage of improving the moldability of the resin and improving the strength and other physical properties of the resulting molded product.

Next, examples of the present invention will be given. In the examples, parts are parts by weight, and viscosity and specific gravity are measured values at 25 ° C., and the silicone pressure-sensitive adhesives given in Reference Examples are shown. The physical properties of are the results of measurement by the following measuring methods.

〔Adhesive force〕

Lightly affixed to the center of the stainless steel plate (SUS27cp, 280 grit) with the adhesive layer side of the test piece facing down, and covered with a rubber layer with a thickness of about 6 mm from this top weight 2,000 ± 50 g, diameter 80 mm
The test piece is crimped by reciprocating the metal roller of 1 times at a crimping speed of 300 mm / min, and then the test piece is 23 ± 2 ° C., 60 ± 5
After leaving it in a room at a constant temperature and humidity of% RH for 16 hours, the play part was folded back at an angle of 180 °, and the peeling force when peeled off continuously at a speed of 300 mm / min was measured.

[Ball tack]

Roll the steel ball (SUJ2 of JIS G4805) from the approach distance of 10 cm on the slope with an inclination angle of 30 °, and indicate the maximum diameter of the steel ball that stops within the range of 10 cm of the adhesive layer (inclination formula Ball tack measurement method).

In addition, No. 32 was 1 inch and No. 24 was 24/32 inch, and the measurement was carried out in a constant temperature and constant humidity chamber at 23 ± 2 ° C. and 60 ± 5% RH.

[Cohesive force]

Attach a test piece with an area of 20 mm in length and 10 mm in width on the above-mentioned stainless steel plate, suspend a load of 1,000 ± 10 g, and 23 ± 2 ° C.
The deviation distance is shown after the sample was left in a constant temperature and humidity room of 60 ± 5% RH for 30 minutes.

Example 1 Ethyl polysilicate (SiO ₂ content 40%), which is a partially hydrolyzed condensate of orthoethyl silicate, was placed in a four-necked flask equipped with a thermometer, a reflux condenser and a stirrer.
g, hexamethyldisiloxane 122.5 g, vinyltrimethoxysilane 66.3 g and ethanol 20 g were charged, and kept at 20 ° C., 10 g of 35% hydrochloric acid water and 90 g of water were added dropwise over 30 minutes, and stirred at 76 ° C. for 4 hours to add water. After the decomposition, 200 g of toluene and 10 g of sodium hydrogen carbonate were added, and toluene was added while stripping ethanol by heating to obtain a toluene solution having a nonvolatile content of 60%.

Then, using excessively added sodium hydrogen carbonate as a catalyst, alkali polymerization was performed at 114 ° C. for 4 hours, and after cooling, 95% sulfuric acid was added.
0 g was added and acid-polymerized at 50 ° C. for 4 hours, sodium hydrogen carbonate was added thereto, and the mixture was stirred at 40 ° C. for 3 hours to neutralize sulfuric acid, and water in the system was dehydrated with anhydrous sodium sulfate and then passed through. However, nonvolatile content 60.3%, viscosity 17.2cS, specific gravity 1.050,
A colorless and transparent toluene solution having a hydroxyl group content of 0.02 mol / 100 g resin was obtained, and as a result of analysis, this product had an M / Q molar ratio of 0.6 and contained 10 mol% of CH ₂ = CHSiO _3/2 as a T unit. It was confirmed to be MTQ resin (hereinafter abbreviated as MTQ-I), and when this was distilled off toluene, it became a colorless and transparent solid resin.

Next, 100 parts of this MTQ-I and 100 parts of dimethylpolysiloxane having an average polymerization degree of 4,000 in which the molecular chain end is blocked with a hydroxyl group are thoroughly mixed with a mixer, and after defoaming under reduced pressure, the thickness is 8 mm on a glass dish. So that
When the transparency of the mixture after evaporating the solvent was examined, it was confirmed that this was completely transparent and that MTQ-I was compatible with the diorganopolysiloxane.

Example 2 The amount of hexamethyldisiloxane, vinyltrimethoxysilane, and ethanol added to 378 g of ethyl polysilicate in Example 1 was changed to hexamethyldisiloxane 15.
Non-volatile components were obtained after treating in the same manner as in Example 1 except that 3 g, 73.1 g of vinyltrimethoxysilane and 15 g of ethanol were used.
60.0% viscosity 11.8 cS, specific gravity 1.051, hydroxyl group content 0.03 mol /
A colorless and transparent 60% toluene solution, which is 100 g resin, was obtained. As a result of the analysis, this was an MTQ resin (M / Q molar ratio of 0.75 and containing 10 mol% of CH ₂ = CHSiO _3/2 as a T unit (hereinafter referred to as MTQ resin). (Abbreviated as MTQ-II) was confirmed, and when this was volatilized with toluene, it became a colorless and transparent solid resin.

When this MTQ-II was mixed with dimethylpolysiloxane as in Example 1, it was confirmed that this MTQ-II had excellent compatibility with dimethylsiloxane.

Example 3 The amount of hexamethyldisiloxane, vinyltrimethoxysilane, and ethanol added to 378 g of ethyl polysilicate in Example 1 was changed to hexamethyldisiloxane 16.
3.3g, vinyltrimethoxysilane 74.6g, ethanol 10g
Was treated as in Example 1 except that the nonvolatile content was 60.8, the% viscosity was 11.5 cS, the specific gravity was 1.050, and the hydroxyl group content was 0.02.
A colorless and transparent 60% toluene solution of 100 mol / 100 g resin was obtained, which was analyzed and found to have an M / Q molar ratio of 0.85 and T
It was confirmed to be an MTQ resin containing 10 mol% CH ₂ = CHSiO _3/2 as a unit (hereinafter abbreviated as MTQ-III), and when toluene was volatilized, it became a colorless and transparent solid resin. .

The MTQ-III was examined for compatibility with dimethylpolysiloxane in the same manner as in Example 1, and as a result, it showed excellent compatibility.

Example 4 The amount of hexamethyldisiloxane, vinyltrimethoxysilane, and ethanol added to 378 g of ethyl polysilicate in Example 1 was changed to hexamethyldisiloxane 20.
4.1g, vinyltrimethoxysilane 82.9g, ethanol 10g
Was treated in the same manner as in Example 1 except that the non-volatile content was 59.8%, the viscosity was 10.2 cS, the specific gravity was 1.051, and the hydroxyl group content was 0.02.
A colorless and transparent 60% toluene solution of 100 mol / 100 g resin was obtained, which was analyzed and found to have a M / Q molar ratio of 1.00 and T
It was confirmed to be an MTQ resin containing 10 mol% of CH ₂ = CHSiO _3/2 as a unit (hereinafter abbreviated as MTQ-IV), and when this was volatilized with toluene, it was colorless and transparent and had a little stickiness. It became a tinged solid resin.

Further, regarding this MTQ-IV, the compatibility with dimethylpolysiloxane was examined by the same method as in Example 1, and
It showed excellent compatibility.

Example 5 The amount of hexamethyldisiloxane, vinyltrimethoxysilane, and ethanol added to 378 g of ethyl polysilicate in Example 1 was changed to hexamethyldisiloxane 22.
The same treatment as in Example 1 was conducted except that 4.5 g, 87 g of vinyltrimethoxysilane and 10 g of ethanol were used.
61.9%, viscosity 9.8cS, specific gravity 1.052, hydroxyl group content 0.03mol
A colorless and transparent 60% toluene solution of 100/100 g resin was obtained, and the result of analysis showed that MTQ resin (MQ ratio of 1.10 and 10 mol% of CH ₂ ═CHSiO _3/2 as T unit ( Hereinafter, it is abbreviated as MT-V), and when toluene was volatilized, it became a colorless and transparent viscous solid solution resin.

The MTQ-V was tested for compatibility with dimethylpolysiloxane in the same manner as in Example 1,
It showed excellent compatibility.

Examples 6 to 9 In a four-necked flask equipped with a thermometer, a reflux condenser, and a stirrer, methyl polysilicate (SiO ₂ content 51%), which is a partial hydrolyzed condensate of orthomethyl silicate.
Hexamethyldisiloxane and isobutyltrimethoxysilane were added in the mixing ratio shown in Table 1, 20 g of isopropyl alcohol was added, and the temperature in the system was adjusted to 40
Keep the temperature at ℃, add 5g of 35% hydrochloric acid water and the amount of water shown in Table 1 to this to hydrolyze, and age at 70 ℃ for 3 hours, then add 100g of water and 200g of toluene and add toluene resin. The layer and the methanol / isopropyl alcohol / water / hydrochloric acid layer were separated and separated, and toluene was added to the toluene resin layer to make the nonvolatile content 60%.
Perform alkaline polymerization at 4 ° C for 4 hours, then add 8g of 35% hydrochloric acid water and perform acid polymerization at 90 ° C for 6 hours, wash with water to remove hydrochloric acid, and dehydrate with anhydrous sodium sulfate to remove non-volatile matter. 60
When adjusted to%, a colorless transparent liquid was obtained. These exhibited the properties as shown in Table 2.

The silicone resins obtained here are all MTQ
Regarding the resins, the compatibility of these resins with dimethylpolysiloxane was examined in the same manner as in Example 1, and all showed excellent compatibility.

Examples 10 to 13 In a four-necked flask equipped with a thermometer, a reflux condenser, and a stirrer, methyl polysilicate (SiO ₂ content 51%), which is a partial hydrolyzed condensate of orthomethyl silicate, and hexamethyldichloride. Siloxane, methyltrimethoxysilane and isobutyltrimethoxysilane were added at the compounding ratio shown in Table 3, and 20 g of isopropyl alcohol was added.
Was added to maintain the temperature inside the system at 10 ° C, and then add 35% hydrochloric acid
Hydrolyze by adding 5 g of water and the amount of water shown in Table 1 to 70
After aging at ℃ for 3 hours, 100g of water and 200g of toluene are added to separate into a toluene resin layer and a methanol / isopropyl alcohol / water / hydrochloric acid layer. Toluene is added to the toluene resin layer to obtain a nonvolatile content of 60%. Then, after adding 2 g of sodium hydrogen carbonate, alkali polymerization was carried out at 114 ° C. for 4 hours, then 8 g of 35% hydrochloric acid water was added and acid polymerization was carried out at 90 ° C. for 6 hours, followed by washing with water to remove hydrochloric acid content. After that, dehydration was performed with anhydrous sodium sulfate to adjust the non-volatile content to 60%, and colorless and transparent liquids were obtained, which exhibited the properties as shown in Table 4.

The silicone resins obtained here are all MTQ
Regarding the resins, the compatibility with dimethylpolysiloxane was examined in the same manner as in Example 1 for these resins.
All of them showed excellent compatibility.

Examples 14 to 17 methyl polysilicate, hexamethyldisiloxane,
The mixing ratio of methyltrimethoxysilane and isobutyltrimethoxysilane and the addition amount of water for hydrolysis were set in Example 10.
The same procedure as in Table 3 in Examples 13 to 13 was carried out in the same manner as in Examples 10 to 13 to obtain a toluene resin layer obtained by hydrolysis, aging, and adding toluene. After acid polymerization for 6 hours, the mixture was cooled to 50 ° C., and then 6.5 g of sodium hydrogen carbonate was gradually added to neutralize it, and then alkali polymerization was carried out at 115 ° C. for 4 hours using excess sodium hydrogen carbonate as a catalyst. 100g of water containing 3.7g of 35% hydrochloric acid water at 60 ° C
After cooling to 80 ° C, add slowly and heat to 80 ° C for 1 hour to neutralize, wash with water to remove excess hydrochloric acid and generated sodium chloride, dehydrate with anhydrous sodium sulfate, add toluene and add Then, I made MTQ resin by adjusting the nonvolatile content to 60%. This product showed the results as shown in Table 5.

The MTQ resin obtained here was used in Example 1.
When the compatibility with dimethylpolysiloxane was examined by the same method as above, all of them showed excellent compatibility.

Comparative Example 1 Ethyl silicate 37 used in Example 1 was placed in a four-necked flask equipped with a thermometer, a reflux condenser and a stirrer.
8 g, hexamethyldisiloxane 153 g and ethanol 15
Charge g, add 10g of 35% hydrochloric acid water and 90g of water to this to hydrolyze, aged at 76 ° C for 4 hours, add 203g of toluene to dissolve, and wash with water several times to remove hydrochloric acid content. After dehydration with anhydrous sodium sulfate, it was colorless and transparent and had a nonvolatile content of 6
0.1%, viscosity 4.3cS, specific gravity 1.050, hydroxyl group 1.8mol / 100g
A liquid which was a resin was obtained. As a result of the analysis, it was confirmed that the liquid was an MQ resin having an M / Q molar ratio of 0.75. The compatibility with dimethylpolysiloxane was confirmed in Example 1 When the mixture was examined in the same manner as in 1., it was found that the mixture had a slightly cloudy appearance and thus had poor compatibility with dimethylpolysiloxane.

Reference Example 1 To 125 parts of the solid content of MTQ-III obtained in Example 3, 100 parts of dimethylpolysiloxane raw rubber having an average polymerization degree of 6,500 and having both ends of the molecular chain blocked with hydroxyl groups was added, and toluene was added. The solid pressure was reduced to 60% and the mixture was stirred for 10 hours at a temperature of 100 ° C to produce a silicone pressure-sensitive adhesive, which was colorless and transparent, had a nonvolatile content of 60.1% and a viscosity of 136,000. It showed the physical properties of cS.

Then, 2 parts of benzoyl peroxide and 50 parts of toluene were added to 100 parts of this silicone pressure-sensitive adhesive and stirred well to obtain a sample having a width of 25 mm and a thickness of 0.025 mm and a thickness of 40 μm using an applicator. Then, the test piece was prepared by baking it at 180 ° C. for 3 minutes and measuring the adhesive strength, ball tack and cohesive strength, and the results shown in Table 6 were obtained.

In addition, 100 parts of this silicone pressure-sensitive adhesive contains 20 mol% of hydrogen atoms bonded to silicon atoms and has a viscosity of 55 cS, methylhydrogen polysiloxysan, and 5 parts of platinum catalyst as an addition reaction catalyst. 30 ppm and toluene 5
A sample obtained by adding 0 parts and stirring well was applied to the same polyimide film as above using an applicator and a thickness of 40 μm.
The test piece was prepared by vulcanizing it at 100 ° C. for 5 minutes and then air-drying it for 5 minutes and measuring the adhesive strength, ball tack, and cohesive strength, and the results shown in Table 6 were obtained. It was

However, instead of MTQ-III used above for comparison, the M / Q molar ratio is 0.8 and the organic group is a methyl group, the nonvolatile content is 60.5%, the viscosity is 9.3 cS, the hydroxyl group content is 0.04 mol. /
When a silicone pressure sensitive adhesive was made in the same manner as above using MQ resin which is 100 g resin, this was a colorless transparent viscous toluene solution having a nonvolatile content of 60.4% and a viscosity of 102,000 cS, This product was vulcanized with benzoyl peroxide in the same manner as described above, applied to a polyimide film, air-dried and baked, and the tackiness, ball tack, and cohesion were as shown in Table 6.

Reference Example 2 MTQ resin (MTQ-II) obtained in Example 2 and Comparative Example 1
Each of 100 parts of the obtained MQ resin was blocked at both ends with a vinyldimethylsilyl group, and the average degree of polymerization of vinyl groups bonded to the silicon atom of the main chain was 2 per molecule on average.
1,000 linear dimethylpolysiloxane containing vinyl groups 1
After mixing 00 parts with each other and stripping the solvent toluene, both ends were blocked with hydrogen dimethyl silyl groups, and the hydrogen atoms bonded to the silicon atoms in the main chain were 1
35 parts of linear hydrogen dimethyl polysiloxane containing an average of 20 molecules in a molecule are mixed by 35 parts each, and 30 ppm of platinum catalyst is added to the mixture as platinum amount and mixed, and degassed under reduced pressure and then 100 Cured at ℃ for 2 hours, thickness 1
I made a mm rubber sheet. Then, as a result of cutting this sheet into a predetermined size and conducting a tensile test, MTQ-II
The rubber sheet containing the above was a transparent rubber sheet having a tensile strength of 35 kg / cm ² .

However, the one containing the MQ resin prepared in Comparative Example 1 was a milky white opaque rubber sheet having a tensile strength of 20 kg / cm ² , and thus MTQ-II exhibits excellent performance as a reinforcing agent for silicone rubber. It was confirmed to be a thing.

Comparative Example 2 The amount of vinyltrimethoxysilane in Example 1 was 25
We tried to synthesize 6g of resin with M / Q ratio of 0.6 and T unit of 30 mol%, but MTQ resin was unstable due to too many T units.
Gelled in the strip.

Comparative Example 3 Example 3 except that 68.6 g of methyltrimethoxysilane was used instead of the vinyltrimethoxysilane in Example 3.
When treated in the same manner as above, nonvolatile content 60.1%, viscosity 25.2c
A colorless and transparent 60% toluene solution having S, a specific gravity of 1,050 and a hydroxyl group content of 0.04 mol% / 100 g resin was obtained. As a result of analysis, this product has an M / Q molar ratio of 0.85 and CH ₃ SiO _3/2 as the T unit.
Was confirmed to be an MTQ resin containing 10 mol% of
When this toluene was distilled off, it became a colorless and transparent solid resin. The compatibility of this product with dimethylpolysiloxane was examined by the same method as in Example 1. As a result, the mixture had a slightly cloudy appearance, and the compatibility with dimethylpolysiloxane was not good.

Comparative Example 4 The amount of hexamethyldisiloxane in Example 1 was changed to 6
1.2 g, the amount of vinyltrimethoxysilane was 54.0 g, and the M / Q ratio was 0.3 and the T unit was the same as in Example 1.
An attempt was made to synthesize 10 mol% resin, but MTQ resin was unstable and thickened and gelled during aging.

Comparative Example 5 The amount of hexamethyldisiloxane in Example 1 was changed to 51
The same treatment as in Example 1 was conducted except that 0.3 g and the amount of vinyltrimethoxysilane were changed to 145.1 g.
Viscosity 2.3 cS, specific gravity 1,030, hydroxyl group content 0.01 mol% / 100 g
A colorless and transparent 60% toluene solution which is a resin was obtained.
As a result of analysis, it was confirmed that this was an MTQ resin having an M / Q molar ratio of 2.5 and containing 10 mol% of T unit. When this toluene was distilled off, it became a colorless and transparent liquid resin. An attempt was made to manufacture a pressure-sensitive adhesive from this resin in exactly the same manner as in Reference Example 1, but it did not exhibit the properties of a pressure-sensitive adhesive at all.

Claims (3)

[Claims] 1. Repeating units are M units: R ¹ ₃ SiO _1/2 (wherein R ¹ is an unsubstituted or substituted monovalent hydrocarbon group of the same or different type), Q units: SiO ₂ and T units: R ² SiO _3/2 (here
R ² is an unsubstituted or substituted monovalent hydrocarbon group of the same or different type, 30 mol% or more of which is a group having 2 or more carbon atoms), and M unit is M / Q in molar ratio to Q unit. = 0.4 to 2.0
And, the T unit is contained in 1 to 20 mol% and the molecular weight is 500.
Silicone resin characterized by being ~ 100,000. 2. A compound represented by the general formula R ¹ _a Si (OR ³ ) _4-a (R ¹ is an unsubstituted or substituted monovalent hydrocarbon group of the same or different type, R ³ is a hydrogen atom or a carbon number of 1 to 5). Of the formula (a is a positive number of 2.6 to 3.0), an organohydroxysilane, an organoalkoxysilane and / or a general formula (R ¹ _a Si) ₂ O
An organosiloxane represented by _4-a (R ¹ and a are the same as above), and 2) an alkyl silicate represented by the general formula Si (OR ⁴ ) ₄ (wherein R ⁴ is an alkyl group having 1 to 5 carbon atoms) And / or its partial hydrolysis-condensation product, and 3) the general formula R ² _b Si (OR ⁴ ) _4-b (R ² is an unsubstituted or substituted group in which 30 mol% or more is a group having 2 or more carbon atoms. The same or different monovalent hydrocarbon groups, R ⁴ is the same as described above), and the organoalkoxysilane and / or its partial hydrolysis-condensation product are mixed, and this is subjected to co-hydrolysis and polycondensation reaction. The method for producing a silicone resin according to claim 1. 3. Co-hydrolysis and polycondensation reactions are carried out from the first component to the third component.
The mixture of components is hydrolyzed by adding an inorganic acid and water, and polycondensates in the presence of an alkali catalyst and then polycondensates in the presence of an acid catalyst, or after polycondensation in the presence of an acid catalyst and then an alkali catalyst. The method for producing a silicone resin according to claim 2, wherein polycondensation is performed in the presence of the silicone resin.