JP6031008B2 - Method for producing room temperature curable organopolysiloxane composition, and automobile oil seal, architectural sealant and method for producing electrical and electronic parts using cured product of said composition - Google Patents

Description

  The present invention relates to a method for producing a room temperature curable organopolysiloxane composition that cures to an elastomer solid, an automobile oil seal, a building sealant, and an electrical / electronic component using the cured product of the composition.

  Room temperature curable organopolysiloxane compositions that cure to elastomeric solids are well known. Typically, such compositions include polydiorganosiloxanes having reactive end groups (eg, silanol groups), organosilanes for polydiorganosiloxanes such as alkenyloxysilane, oxime silane, acetoxysilane, alkoxysilane, or aminosilane. It is obtained by mixing with a crosslinking agent. When these materials are exposed to atmospheric moisture at room temperature, the organosilane cross-linking agent that has reacted with the polydiorganosiloxane is hydrolyzed and released by releasing the corresponding gas. Important applications of such room temperature curable organopolysiloxane compositions include, for example, automotive oil seals, architectural waterproof seals, and electrical and electronic parts. For this reason, such a composition is generally required to have good appearance for maintaining design properties, properties for workability, physical properties as an elastomer, and adhesion to equipment.

  In the room temperature curable organopolysiloxane composition as described above, a filler is used in order to give rubber properties, chemical resistance, and adhesiveness that cannot be obtained by using an elastomer alone. In general, the filler has various particle diameters, and the surface thereof is untreated or treated with a treating agent such as fatty acid. Examples of such fillers include dry silica, calcined silica, precipitated silica, heavy calcium carbonate, colloidal calcium carbonate, alumina, aluminum oxide, aluminum hydroxide, carbon black, titania, zinc oxide, zinc carbonate, clay and Examples include mica, and all of them are used for the purpose of imparting mechanical strength, chemical resistance, and adhesiveness to the cured product.

  Furthermore, the room temperature curable organopolysiloxane composition as described above is intended to enhance adhesion to various substrates, particularly metals (aluminum, iron, etc.) and plastics (polybutylene terephthalate, polycarbonate, modified polypropylene oxide, etc.). It is common to add an adhesion promoter. Examples of the adhesion promoter used as standard include alkoxysilanes such as aminoalkylalkoxysilanes, epoxyalkylalkoxysilanes, mercaptoalkylalkoxysilanes, and derivatives thereof.

（式中、Ｄ置換基の１つは、−Ｒ−Ｓｉ（Ｒ^４）_ｐ（ＯＲ^４）_３−ｐ（ここでＲは、アルキレンアリーレン、アルキレン、シクロアルキレン及びそれらのハロゲン置換誘導体から選択される二価の炭化水素基であり、Ｒ^４は、８個以下の炭素原子を有するアルキル又はハロアルキル基であり、ｐは、０〜３である。）であり、残りのＤ置換基は、上述の−Ｒ−Ｓｉ（Ｒ^４）_ｐ（ＯＲ^４）_３−ｐ、スチリル、ビニル、アリル、クロロアリル又はシクロヘキセニルから選択される基である。） Another group of compounds that have been used as adhesion promoters is, for example, silicon compounds containing isocyanurate as shown in Patent Documents 1 to 3. Such a compound typically contains a structure represented by the following general formula (3).

Wherein one of the D substituents is —R—Si (R ⁴ ) _p (OR ⁴ ) _3-p (where R is selected from alkylene arylene, alkylene, cycloalkylene and their halogen substituted derivatives. R ⁴ is an alkyl or haloalkyl group having 8 or fewer carbon atoms, and p is 0 to 3, and the remaining D substituents are as described above. the _{^{-R-Si (R 4) p}} (oR 4) 3-p, styryl, vinyl, allyl, a group selected from chloroallyl or cyclohexenyl.)

  However, if an adhesion promoter is added to the room temperature curable organopolysiloxane composition, the expected adhesiveness is not always obtained. Therefore, in order to obtain the expected adhesiveness, a filler is often used in combination. However, by using the filler, when dispersed in the silicone oil, the fillers aggregate together, impairing the design, and the thixotropy decreases due to the decrease in dispersibility, and the shape retainability deteriorates (flowing) Etc.) may occur. In order to reduce this tendency, for example, a filler whose surface is hydrophobized with a hydrophobizing agent such as fatty acid, organochlorosilane, organopolysiloxane, and hexamethyldisilazane is used. By using such a surface-treated filler, shape retention is improved to some extent, but on the other hand, the effect is not sufficient, and the price of the surface-treated filler increases. .

  Moreover, as a technique for controlling the properties of the room temperature curable organopolysiloxane composition, methods for changing the process and the raw material addition method have been proposed so far. As an example, Patent Document 4 proposes that the fluidity is improved by adding an aminosilane coupling agent, which is an adhesion promoter, before the filler. In Patent Document 5, the titanium catalyst, which is a curing catalyst, is first added to the curable base oil, and then silica powder, which is an inorganic filler, is added to improve the storage stability, transparency, and low-temperature curability. In addition, it has been proposed that an increase in viscosity over time can be suppressed.

  As a technique for improving the shape retention, in Patent Document 6, an oxime silane is added to an organopolysiloxane having hydroxyl groups at both ends, and an inorganic filler and a curing catalyst are prepared in this order, whereby a room temperature curable organopolysiloxane is prepared. Proposals have been made that the thixotropy of the composition is increased and the shape retention can be improved. However, in this method, only a deoxime type room temperature curable organopolysiloxane composition can be obtained, and there is a limitation that it cannot be applied to other curing types such as a deacetone type, a dealcohol type and a deacetic acid type.

  Recently, in order to solve the problem, in Patent Document 7, an organosilane and a curing catalyst are added to an organopolysiloxane having hydroxyl groups at both ends, and then added and mixed in the order of a filler and an adhesion promoter, thereby obtaining thixotropy. It has been proposed that room temperature-curable organopolysiloxane compositions of various curing types having a high temperature can be obtained. However, in this proposal, particularly in batch processes, highly reactive organosilanes such as alkenyloxysilanes such as vinyltriisopropenoxysilane and phenyltriisopropenoxysilane, vinyltris (methylethylketoxime) silane, vinyltris (methylisobutylketo) When oxime silanes such as oxime) silane, vinyltris (methylpropylketoxime) silane, tetra (methylethylketooxime) silane, tetra (methylisobutylketoxime) silane, tetra (methylpropylketoxime) silane are used, they are added simultaneously. A part where the curing proceeds rapidly due to the curing catalyst, a cured gel is generated in the kettle, curing proceeds with moisture in the air when adding a filler, and curing with moisture contained in the filler Progress And will be, at room temperature curable organopolysiloxane composition obtained or become highly viscous, cured gel has occurred a problem that the design is impaired for incorporation.

US Pat. No. 3,571,001 US Pat. No. 3,708,467 U.S. Pat. No. 4,100,129 JP-A-8-104816 JP 2005-247923 A Japanese Patent No. 2613446 Japanese Patent No. 4351816

  The present invention has been made to solve the above problems, and produces various curing type room temperature curable organopolysiloxane compositions having high thixotropy, good appearance, and excellent viscosity stability. It aims to provide a method.

In order to solve the above problems, according to the present invention,
A batch process for producing a room temperature curable organopolysiloxane composition comprising:
1) A step of preparing a blend by dispersing a polymer (A) having two or more hydroxyl groups bonded to silicon and an organosilane (B) represented by the following general formula (1) in a mixer. ,
(R ¹ ) _(4-n) Si (OR ² ) _n (1)
(Wherein R ¹ is a halogen-substituted or unsubstituted alkyl group, alkenyl group or aryl group having 1 to 6 carbon atoms, R ² is an organic group having 1 to 6 carbon atoms, and n is 2, 3 or 4)
2) A step of adding and dispersing the curing catalyst (C1) to the blend,
3) Further, one or more fillers (D) selected from the group consisting of calcium carbonate, alumina, aluminum oxide, aluminum hydroxide, silica, carbon, titania, zinc oxide, zinc carbonate, clay and mica are added, Producing a base by dispersing,
4) a step of further adding and dispersing the curing catalyst (C2) to the base, and 5) further adding one or more adhesion promoters (E) represented by the following general formula (2), Dispersing until the product is sufficiently homogeneous,
(R ³ O) _(3-q) (R ³ ) _q Si-X (2)
Wherein R ³ is independently a hydrogen atom or a halogen-substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, X is amino, ketimino, mercapto, epoxy, isocyanate, ureido, acryloxy, methacryloxy and their A saturated, unsaturated or aromatic hydrocarbon group functionalized with a group selected from the group consisting of a mixture, q is an integer of 0-3.)
A process for producing a room temperature curable organopolysiloxane composition having the following is provided.

  If it is the manufacturing method of the room temperature curable organopolysiloxane composition of this invention, it can obtain room temperature curable organopolysiloxane composition of various hardening type with high thixotropy, good external appearance, and excellent viscosity stability. it can.

  Moreover, it is preferable to add so that the addition amount of the said curing catalyst (C1) and the said curing catalyst (C2) may become C1 <= C2.

  By adding the component (C1) and the component (C2) in such amounts, the room temperature curable organopolysiloxane composition is hard to be mixed with the cured gel, so that the room temperature curing has good design properties and rubber properties. An organopolysiloxane composition can be obtained.

  At this time, it is preferable to perform an operation of removing a volatile component in one or more of the steps 2) to 5).

  By performing the operation of removing volatile components in this way, it is possible to remove bubbles mixed in during mixing, and it can be expected that the storage stability of the resulting composition is improved.

  At this time, the adhesion promoter (E) is preferably selected from aminoalkylalkoxysilanes, ketiminoalkylalkoxysilanes, epoxyalkylalkoxysilanes, mercaptoalkylalkoxysilanes, and ureidoalkylalkoxysilanes.

  With such an adhesion promoter (E), a room temperature curable organopolysiloxane composition with better adhesion can be obtained.

  At this time, the organosilane (B) is vinyltriisopropenoxysilane, phenyltriisopropenoxysilane, vinyltris (methylethylketoxime) silane, vinyltris (methylisobutylketoxime) silane, vinyltris (methylpropylketoxime). It is preferably selected from silane, tetra (methylethylketoxime) silane, tetra (methylisobutylketoxime) silane, and tetra (methylpropylketoxime) silane.

  If it is a manufacturing method of the room temperature curable organopolysiloxane composition of this invention, thixotropy is used as organosilane (B) using the alkenyloxysilane and oxime silanes with high reactivity in such a batch process. A room temperature-curable organopolysiloxane composition that is high, has good appearance, and is excellent in viscosity stability can be obtained.

  The present invention also provides an automobile oil seal using a cured product of a room temperature curable organopolysiloxane composition obtained by the above production method.

  Moreover, this invention provides the sealant for buildings using the hardened | cured material of the room temperature curable organopolysiloxane composition obtained with the said manufacturing method.

  Moreover, this invention provides the electrical / electronic component using the hardened | cured material of the room temperature curable organopolysiloxane composition obtained by the said manufacturing method.

  Thus, if it is a hardened | cured material of the room temperature curable organopolysiloxane composition obtained by the manufacturing method of this invention, it can use suitably as a motor vehicle oil seal, a building sealant, an electrical and electronic component, etc.

  If it is a manufacturing method of the room temperature curable organopolysiloxane composition of the present invention, thixotropy is good even in a composition blending that is conventionally reduced in thixotropy, and the appearance is good, so it is excellent in design and viscosity stability. Various excellent curing type room temperature curable organopolysiloxane compositions can be obtained. Moreover, in the manufacturing method of this invention, since the addition amount of a curing catalyst can be determined freely, adjustment of sclerosis | hardenability of room temperature curable organopolysiloxane composition is very simple. Moreover, the room temperature curable organopolysiloxane composition obtained by the production method of the present invention can be suitably used as an oil seal, an architectural sealant, and an electric / electronic component.

  As described above, there has been a demand for the development of a method for producing various curing type room temperature curable organopolysiloxane compositions having high thixotropy, good appearance, and excellent viscosity stability.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have previously mixed and dispersed the polymer (A) having at least two hydroxyl groups bonded to silicon and the organosilane (B), and then at least By adding a limited amount of the curing catalyst (C1), the hydroxyl group of the polymer (A) and the organosilane (B) can be allowed to react gently, so that the mixing of the cured product gel can be prevented. I found it. Further, a filler (D) is then added, and a highly thixotropic mixture is obtained by mixing and dispersing, and an additional curing catalyst (C2) is added according to the purpose in order to obtain quick curing according to the purpose. By adding an adhesion promoter (E) to obtain adhesiveness, a room temperature curable organopolysiloxane composition having fast curability and adhesiveness according to the purpose while maintaining high thixotropy can be obtained. The present invention was completed by finding that it can be produced without mixing.

  Hereinafter, although embodiment of this invention is described, this invention is not limited to these.

The present invention
A batch process for producing a room temperature curable organopolysiloxane composition comprising:
1) A step of preparing a blend by dispersing a polymer (A) having two or more hydroxyl groups bonded to silicon and an organosilane (B) represented by the following general formula (1) in a mixer. ,
(R ¹ ) _(4-n) Si (OR ² ) _n (1)
(Wherein R ¹ is a halogen-substituted or unsubstituted alkyl group, alkenyl group or aryl group having 1 to 6 carbon atoms, R ² is an organic group having 1 to 6 carbon atoms, and n is 2, 3 or 4)
2) A step of adding and dispersing the curing catalyst (C1) to the blend,
3) Further, one or more fillers (D) selected from the group consisting of calcium carbonate, alumina, aluminum oxide, aluminum hydroxide, silica, carbon, titania, zinc oxide, zinc carbonate, clay and mica are added, Producing a base by dispersing,
4) a step of further adding and dispersing the curing catalyst (C2) to the base, and 5) further adding one or more adhesion promoters (E) represented by the following general formula (2), Dispersing until the product is sufficiently homogeneous,
(R ³ O) _(3-q) (R ³ ) _q Si-X (2)
Wherein R ³ is independently a hydrogen atom or a halogen-substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, X is amino, ketimino, mercapto, epoxy, isocyanate, ureido, acryloxy, methacryloxy and their A saturated, unsaturated or aromatic hydrocarbon group functionalized with a group selected from the group consisting of a mixture, q is an integer of 0-3.)
It is a manufacturing method of the room temperature curable organopolysiloxane composition which has this.

[(A) component]
The polymer having two or more hydroxyl groups bonded to silicon as component (A) is represented by various structures. For example, the simplest structure among them is represented by the following general formula (4). Can be mentioned.
HO (R ⁵ ₂ SiO) _L H (4)
(In the formula, each R ⁵ is independently an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a part of hydrogen atoms thereof being a halogen atom. A substituted group, and L is an integer of 10 or more.)

Specific examples of such R ⁵ include alkyl groups such as methyl, ethyl, propyl and cyclohexyl groups, alkenyl groups such as vinyl and allyl groups, aryl groups such as phenyl groups, 3, 3, 3- And halogen substituents such as a trifluoropropyl group.

  L is an integer of 10 or more, and the number of the diorganopolysiloxane having a viscosity at 23 ° C. in the range of 100 to 200,000 mPa · s is preferable, more preferably the viscosity at 23 ° C. is 500 to 100,000 mPa. -A number in the range of s.

  Moreover, it is preferable to mix | blend the polymer of (A) component in the quantity of about 30-90 mass% with respect to the whole composition, More preferably, it is about 40-60 mass%. By blending the polymer of the component (A) in an amount of about 30% by mass or more, it is possible to suppress a decrease in mechanical properties of the room temperature curable organopolysiloxane composition obtained. Moreover, the fall of the shape retention of the room temperature curable organopolysiloxane composition obtained can be suppressed by mix | blending in the quantity of 90 mass% or less.

[Component (B)]
The organosilane that is component (B) is represented by the following general formula (1).
(R ¹ ) _(4-n) Si (OR ² ) _n (1)
(Wherein R ¹ is a halogen-substituted or unsubstituted alkyl group, alkenyl group or aryl group having 1 to 6 carbon atoms, R ² is an organic group having 1 to 6 carbon atoms, and n is 2, 3 or 4)

R ¹ in the above formula is a halogen-substituted or unsubstituted alkyl group, alkenyl group or aryl group having 1 to 6 carbon atoms, and as such R ¹ , a methyl group, a vinyl group, a phenyl group and the like are preferable.

  (B) The organosilane of the component reacts with the hydroxyl group of the component (A) to become a hydrolyzable group, and is a raw material for removing the filler (D) described later and moisture mixed during production, and It becomes a crosslinking agent of the room temperature curable organopolysiloxane composition obtained. Such an organosilane crosslinking agent is preferably selected from silanes having an alkenyloxy group, an oxime group, an acetoxy group, and an alkoxy group. Of these, silanes having an alkenyloxy group or an oxime group are more preferable.

Specific examples of such organosilanes as component (B) include alkenyloxysilanes such as vinyltriisopropenoxysilane and phenyltriisopropenoxysilane, vinyltris (methylethylketoxime) silane, methyltris (methylethylketoxime) silane, Phenyltris (methylethylketoxime) silane, vinyltris (methylisobutylketoxime) silane, methyltris (methylisobutylketoxime) silane, phenyltris (methylisobutylketoxime) silane, vinyltris (methylpropylketoxime) silane, methyltris (methylpropylketo) Oxime) silane, phenyltris (methylpropylketoxime) silane, tetra (methylethylketoxime) silane, tetra (methyli) Butyl ketoxime) silane, tetra (methyl propyl ketoxime) oxime silanes such as silane, vinyl triacetoxy silane, methyl triacetoxy silane, include acetoxy silanes such as phenyl triacetoxysilane.
Among them, vinyltriisopropenoxysilane, phenyltriisopropenoxysilane, vinyltris (methylethylketoxime) silane, vinyltris (methylisobutylketoxime) silane, vinyltris (methylpropylketoxime) silane, tetra (methylethylketoxime) silane, tetra It is preferably selected from (methylisobutylketoxime) silane and tetra (methylpropylketoxime) silane.

  The amount of the organosilane (B) added is preferably 0.5 to 5% by mass, more preferably 1.5 to 3% by mass. (B) Addition of the organosilane in an amount of 0.5% by mass or more to reduce the storage stability of the resulting room temperature-curable organopolysiloxane composition over time, and design by mixing with a cured product gel or the like Deterioration can be suppressed. Moreover, the fall of the mechanical characteristic of the room temperature curable organopolysiloxane composition obtained and the delay of hardening can be suppressed by adding in the quantity of 5 mass% or less.

[(C1) component and (C2) component]
The curing catalyst as component (C1) is added for the purpose of promoting the reaction between the hydroxyl group contained in component (A) and the organosilane as component (B). The (C2) component curing catalyst is added for the purpose of imparting rapid curability to the room temperature curable organopolysiloxane composition obtained.

  Here, it is preferable to mix | blend so that the addition amount of a curing catalyst (C1) and a curing catalyst (C2) may become C1 <= C2. By setting it as such addition amount, it can suppress that hardened | cured material gel mixes in the room temperature curable organopolysiloxane composition obtained, and the stability of the design property or rubber | gum physical property is impaired.

  Moreover, the curing catalyst of the component (C1) and the curing catalyst of the component (C2) may be the same or different. The curing catalyst may be any catalyst type as long as it accelerates the reaction process. Examples of such a catalyst include an amine compound and a metal organic salt. More specifically, when an organosilane having an alkenyloxy group is used as the component (B), an amine catalyst is preferable. When an organosilane having an oxime group, an acetoxy group or an alkoxy group is used, it is preferable to use a metal organic salt.

  Specific examples of such a catalyst include primary amines such as methylamine, ethylamine, propylamine, butylamine and octylamine, secondary amines such as dimethylamine, diethylamine, dipropylamine, dibutylamine and dioctylamine, Tertiary amines such as trimethylamine, triethylamine, tripropylamine, tributylamine, trioctylamine, 1,1,3,3-tetramethylguanidine, 1,1,3,3-tetramethyl-2- [3- ( Trimethoxysilyl) propyl] guanidine and other amines having a guanidine skeleton, dimethyldimethoxytin, dibutyltin diacetate, dibutyltin dioctoate, dibutyltin dibenzyl malate, dioctyltin diacetate, dioctyltin diversate, etc. Compounds, organic titanium compounds such as titanium tetraisopropoxide, titanium tetranormal butoxide, titanium tetra-2-ethyl hexoxide, titanium tetra tert-butoxide, tert-amyl titanate, titanium acetylacetonate, titanium ethyl acetoacetate , Organic zirconium compounds such as normal propyl zirconate, normal butyl zirconate, zirconium tetraacetyl acetate and zirconium monoacetyl acetate, organoaluminum compounds such as aluminum tetraisopropoxide and aluminum acetylacetoate, bismuth octylate, neodecanoic acid Organic bismuth compounds such as bismuth, and other metal salts of naphthenic acid and octylic acid (specifically, zinc, calcium, manganese, cobalt, Potassium, nickel, iron, lithium, barium, zirconium, etc.).

  The total addition amount of the curing catalysts (C1) and (C2) varies depending on the catalyst species, but is preferably 0.01 to 1.0% by mass, more preferably 0.02 to 0.7% by mass. That is, the amount of the curing catalyst (C1) is preferably 0.01% by mass or more and less than 0.5% by mass. By adding the curing catalyst in an amount of 0.01% by mass or more, it is possible to prevent the resulting room temperature-curable organopolysiloxane composition from being deteriorated or uncured. Moreover, since the sclerosis | hardenability of the room temperature curable organopolysiloxane composition obtained by adding in the quantity of 1.0 mass% or less is moderate, workability deterioration and the design property by mixing of hardened | cured material gel are included. The decrease can be suppressed.

[(D) component]
The filler selected from the group consisting of (D) component calcium carbonate, alumina, aluminum oxide, aluminum hydroxide, silica, carbon, titania, zinc oxide, zinc carbonate, clay and mica is a rubber-like elastic body after curing It is added for the purpose of imparting mechanical strength and hardness. These fillers may be used alone or in combination of two or more.

  The surface treatment of these fillers is not limited, but it is preferable to use a filler that has been subjected to a surface treatment in order to further improve the shape retention. However, an untreated filler may be used if the surface treatment increases the price. Specific examples of calcium carbonate include heavy calcium carbonate and colloidal calcium carbonate. Specific examples of silica include fumed silica and precipitated silica.

  (D) As for the addition amount of the filler of a component, 2-60 mass% is preferable, More preferably, it is 5-58 mass%, More preferably, it is 8-53 mass%. By adding the filler of component (D) in an amount of 2% by mass or more, it is possible to suppress a decrease in shape retention of the resulting room temperature curable organopolysiloxane composition. Moreover, by adding it in an amount of 60% by mass or less, workability deteriorates due to an increase in the viscosity of the room temperature curable organopolysiloxane composition obtained, and it becomes easy to cure during production, resulting in a cured gel. It is possible to suppress a decrease in design properties due to mixing.

[(E) component]
The adhesion promoter as component (E) is represented by the following general formula (2).
(R ³ O) _(3-q) (R ³ ) _q Si-X (2)
Wherein R ³ is independently a hydrogen atom or a halogen-substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, X is amino, ketimino, mercapto, epoxy, isocyanate, ureido, acryloxy, methacryloxy and their A saturated, unsaturated or aromatic hydrocarbon group functionalized with a group selected from the group consisting of a mixture, q is an integer of 0-3.)

  The said adhesion promoter is added in order to give favorable adhesiveness to the room temperature curable organopolysiloxane composition obtained. One type of adhesion promoter may be used, or two or more types may be used in combination.

  As the adhesion promoter, a known one having a designated functional group at X in the general formula (2) can be used. Specific examples thereof include N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3- Aminoalkylalkoxysilanes such as aminopropyltriethoxysilane, 3-trimethoxysilyl-N- (1,3-dimethylbutylidene) -1-propanamine partial hydrolyzate, 3-triethoxysilyl-N- ( 1,3-dimethylbutylidene) -1-propanamine partially hydrolyzed ketiminoalkylalkoxysilanes, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyldimethoxysilane and other mercaptoalkylalkoxysilanes, 3 -Glycidoxypropyltrimethoxysilane, 3-glyci Epoxyalkylalkoxysilanes such as xylpropyltriethoxysilane, isocyanatealkylalkoxysilanes such as 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, and ureidoalkylalkoxysilanes such as 3-ureidopropyltriethoxysilane And acryloxyalkylalkoxysilanes such as 3-acryloxypropyltrimethoxysilane, and methacryloxyalkylalkoxysilanes such as 3-methacryloxypropyltrimethoxysilane and 3-methacryloxypropyltriethoxysilane.

  Moreover, among these, it is preferable that it is a thing selected from aminoalkyl alkoxysilane, ketimino alkyl alkoxysilane, epoxy alkyl alkoxysilane, mercapto alkyl alkoxysilane, and ureido alkyl alkoxysilane.

  (E) 0.2-2 mass% is preferable, and, as for the addition amount of the adhesion promoter of a component, More preferably, it is 0.3-1.5 mass%, More preferably, it is 0.4-1.2 mass%. . By adding the adhesion promoter (E) in an amount of 0.2% by mass or more, it is possible to suppress a decrease in adhesiveness of the room temperature curable organopolysiloxane composition obtained. Moreover, by adding it in an amount of 2% by mass or less, it is economical because a decrease in mechanical properties of the resulting room temperature curable organopolysiloxane composition can be suppressed and the addition amount is small.

[Optional ingredients]
In the manufacturing method of this invention, arbitrary components other than the said (A)-(E) component can be added according to the objective. Specific examples include plasticizers that are terminal non-reactive polymers for adjusting rubber physical properties, pigments and dyes for coloring, metal powders for imparting electrical conductivity and heat dissipation, and improved extrusion workability. Viscosity modifiers, UV absorbers, fungicides, heat resistance improvers, flame retardants, etc., and these various additives may be added to produce room temperature curable organopolysiloxane compositions. .

[Manufacturing process]
The manufacturing method of the room temperature curable organosiloxane composition of this invention is performed by a batch process. The batch process of the present invention
1) A step of preparing a blend by dispersing the polymer of component (A) and the organosilane of component (B) in a mixer,
2) adding and dispersing the curing catalyst (C1) to the blend;
3) Further, a step of adding one or more fillers (D) and dispersing them to produce a base,
4) Step of adding and dispersing the curing catalyst (C2) to the base, and 5) Adding one or more types of the adhesion promoter (E), and the final product becomes sufficiently homogeneous. The process of dispersing to
Have

  In the present invention, a polymer (A) having at least two hydroxyl groups bonded to silicon and an organosilane (B) are mixed in advance to obtain a mixed solution, and then a curing catalyst (C1) is mixed, and a filler ( D) is added. Thereafter, a room-temperature curable organopolysiloxane composition having a fast curing property and adhesiveness according to the purpose by adding a necessary amount of a curing catalyst (C2) and an adhesion promoter (E) depending on the application to be used. Can be obtained.

  Further, the curing catalyst (C2) and the adhesion promoter (E) component may be added simultaneously or separately. Although there is no restriction | limiting when adding a curing catalyst (C2) and an adhesion promoter (E) component simultaneously, It is preferable to add a curing catalyst (C2) and an adhesion promoter (E) without mixing beforehand.

Moreover, it is preferable to perform operation which removes a volatile component in one or more processes among said process 2) -5).
That is, the operation of removing the volatile component may be performed every time in each of the steps 2), 3), 4), and 5). For example, the volatile component is removed only in the steps 2) and 3). The operation may be performed, or the operation of removing volatile components may be performed only in step 4) and step 5).

  Here, the “volatile component” includes by-products generated during the process, air and other bubbles that may be mixed during mixing. By performing the operation of removing volatile components in this way, by-products generated during the process, air bubbles mixed in during mixing, and the like can be removed, and the storage stability of the resulting composition is improved. I can also expect that.

  Here, “dispersion” ideally means that the internally added components are preferably uniformly dispersed, but the method of confirming this takes time. Therefore, mixing the internally added components added to the mixer at a certain rotation speed (rpm) for a certain period of time was defined as “dispersion”. The number of rotations is preferably mixed and dispersed for about 1 minute or more at 2 rpm or more, and more preferably mixed and dispersed for about 5 minutes or more at 5 rpm or more.

  If the method for producing the room temperature curable organopolysiloxane composition of the present invention is as described above, the thixotropy is good even in the composition blending in which the thixotropy is lowered, and the appearance is good, so the design is excellent and the viscosity is high. Various curing types of room temperature curable organopolysiloxane compositions having excellent stability can be obtained. Moreover, in the manufacturing method of this invention, since the addition amount of a curing catalyst can be determined freely, adjustment of sclerosis | hardenability of room temperature curable organopolysiloxane composition is very simple.

  Moreover, the room temperature curable organopolysiloxane composition obtained by the method for producing the room temperature curable organopolysiloxane composition of the present invention includes an automobile oil seal, an architectural sealant, and an electrical / electronic component (for example, an electrical / electronic adhesive). Can be suitably used. Moreover, as a form of a seal | sticker or adhesion | attachment, FIPG (Formed In Place Gaskets), a sealing material, an adhesive agent etc. are mentioned, for example.

EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated concretely, this invention is not limited to these.
All examples and comparative examples were performed by a batch process, and a planetary mixer (manufactured by Inoue Seisakusho Co., Ltd.) was used as a mixer. Moreover, all the parts in an Example represent a mass part. Further, physical properties such as viscosity, which are not particularly described, show values at 23 ° C.

Example 1
1) 100 parts by mass of α, ω-bis-dihydroxy-dimethylpolysiloxane having a viscosity of 20,000 mPa · s as component (A) and 5 parts by mass of vinyltriisopropenoxysilane as component (B) were dispersed and mixed. Later
2) 0.2 part by mass of 1,1,3,3-tetramethyl-2- [3- (trimethoxysilyl) propyl] guanidine was added as the component (C1), and vacuum degassing mixing was performed.
3) Thereafter, 100 parts by mass of precipitated silica (trade name; Crystallite VXS-2, manufactured by Tatsumori Co., Ltd.) as component (D), fumed silica (trade name; MU-215, Shin-Etsu Chemical Co., Ltd.) 7 parts by mass) was added, and vacuum degassing dispersion mixing was performed.
4) Thereafter, 0.6 parts by mass of 1,1,3,3-tetramethyl-2- [3- (trimethoxysilyl) propyl] guanidine was further added as the component (C2), and vacuum degassing dispersion mixing was performed. .
5) Thereafter, 2 parts by mass of 3-aminopropyltriethoxysilane was added as the component (E), and vacuum defoaming dispersion mixing was performed to obtain the intended composition (i).
In addition, the mass% of each component is A; 46.56 mass%, B: 2.33 mass%, C1: 0.09 mass%, C2: 0.28 mass%, D: 49.81 mass%, E : 0.93 mass%.

(Example 2)
1) Add 100 parts by mass of α, ω-bis-dihydroxy-dimethylpolysiloxane having a viscosity of 20,000 mPa · s as component (A) and add 6 parts by mass of vinyltris (methylpropylketoxime) silane as component (B) to disperse. After mixing,
2) 0.1 parts by mass of dibutyltin dibenzyl malate was added as component (C1), and vacuum degassing dispersion mixing was performed.
3) Thereafter, 100 parts by mass of heavy calcium carbonate (trade name; Whiten SSB, manufactured by Shiraishi Calcium Co., Ltd.) as component (D), fumed silica (trade name; MU-215, Shin-Etsu Chemical Co., Ltd.) 7 parts by mass) was added and degassed and dispersed under reduced pressure.
4) Thereafter, 0.4 parts by mass of dibutyltin dibenzyl malate was further added as component (C2), and vacuum degassing dispersion mixing was performed.
5) Thereafter, 1.5 parts by mass of 3-aminopropyltriethoxysilane was added as component (E), and vacuum defoaming dispersion mixing was performed to obtain the intended composition (ii).
In addition, the mass% of each component is A; 46.51 mass%, B: 2.79 mass%, C1: 0.05 mass%, C2: 0.19 mass%, D: 49.76 mass%, E : 0.70% by mass.

(Comparative Example 1)
In Example 1 except that step 2) was omitted, the same operation as in Example 1 was performed to obtain the target composition (iii).

(Comparative Example 2)
In the above Example 1, 0.2 part by mass of 1,1,3,3-tetramethyl-2- [3- (trimethoxysilyl) propyl] guanidine was added as the component (C1) during step 1). The intended composition (iv) was obtained by operating in the same manner as in Example 1 except that the step 2) was omitted.

(Comparative Example 3)
1 ′) 100 parts by mass of α, ω-bis-dihydroxy-dimethylpolysiloxane having a viscosity of 20,000 mPa · s as component (A)
3 ′) 100 parts by mass of precipitated silica (trade name; Crystallite VXS-2, manufactured by Tatsumori Co., Ltd.) as component (D), fumed silica (trade name; MU-215, Shin-Etsu Chemical Co., Ltd.) 7 parts by mass) was added and degassed and dispersed under reduced pressure.
Then, after adding 5 mass parts of vinyl triisopropenoxysilane as (B) component and mixing,
4) Thereafter, 0.4 parts by mass of 1,1,3,3-tetramethyl-2- [3- (trimethoxysilyl) propyl] guanidine was further added as component (C2), and vacuum degassing dispersion mixing was performed. .
5) Thereafter, 2 parts by mass of 3-aminopropyltriethoxysilane was added as the component (E), and vacuum defoaming dispersion mixing was performed to obtain the intended composition (v).

(Comparative Example 4)
In Example 1 above, 0.2 parts by mass of 1,1,3,3-tetramethyl-2- [3- (trimethoxysilyl) propyl] guanidine as the component (C1) and Example as the component (C2) All of 0.6 parts by mass of 1,1,3,3-tetramethyl-2- [3- (trimethoxysilyl) propyl] guanidine used in step 4) of step 1) ) And 4) were omitted, and the same operation as in Example 1 was performed to obtain the target composition (vi).

[Test method]
After producing a room temperature curable organopolysiloxane composition by the batch process described above, the presence or absence of a cured product gel was visually confirmed inside the produced kettle. As for the viscosity of the obtained composition, the apparent viscosity at 23 ° C. was measured according to ASTM D1092 immediately after production and after storage at 70 ° C. for 5 days. Also, the compositions (i) to (vi) obtained in Examples 1 and 2 and Comparative Examples 1 to 4 were poured into a 2 mm mold, and cured for 4 days at 23 ° C. and 50% RH. A rubber sheet was obtained. At that time, the appearance of the obtained rubber sheet was visually confirmed, and the presence or absence of a cured product gel or filler aggregate was confirmed. The tack-free time (touch drying time) was measured according to the method specified in JIS A 5758, and the rubber physical properties were measured from a 2 mm thick sheet according to JIS K6249. In addition, a shear adhesion test specimen having an adhesion area of 2.5 mm ² and an adhesion thickness of 1 mm was prepared from this composition using an aluminum adherend having a width of 25 mm and a length of 100 mm, and was subjected to 4 days at 23 ° C. and 50% RH. Curing and measurement were performed to confirm the shear adhesive strength and cohesive failure rate. In the curing rate test method, a glass petri dish having an inner diameter of 10 mm was filled with a sample, and the thickness cured from the portion exposed to air after one day at 23 ° C. and 50% RH was measured. As a fluidity confirmation test, immediately after mixing and twice as long as that, or after 20 minutes of mixing, the liquid composition was filled into an aluminum channel 20 × width 150 × depth 10 mm, and immediately leaned vertically. The distance at which the liquid composition flows was measured, and a moving distance of 3 mm or less was determined to be acceptable. The test results of the compositions (i) to (vi) obtained in Examples 1 and 2 and Comparative Examples 1 to 4 are shown in Table 1 below.

  As shown in Table 1, in the compositions prepared in Examples 1 and 2, no cured product gel was observed in the apparatus or in the composition, and no fluidity was produced. Furthermore, even after 5 days from the production of the composition, there was little change in viscosity immediately after the production. On the other hand, since the step 2) was omitted in Comparative Example 1, the reaction was not performed only in the state of the polymer (A) and the organosilane (B), and fluidity was generated. Further, in Comparative Examples 2 and 4, since the curing catalyst was added during step 1), the reaction between the polymer (A) and the organosilane (B) rapidly progressed, and the cured product gel in the apparatus and in the composition. Occurred and mixed. In Comparative Example 3, since the polymer (A) and the filler (D) were mixed and then mixed in the order of the organosilane (B), the curing catalyst (C2), and the adhesion promoter (E), the organosilane (B ) Reacted not only with the hydroxyl group at the terminal of the polymer (A) but also with the hydroxyl group on the surface of the filler (D), and fluidity was generated. Furthermore, since the adhesion promoter (E) also reacted with the surface of the filler (D), the adhesion decreased. Moreover, in Comparative Examples 1-4, the viscosity increased significantly after 5 days from the production of the composition.

  As described above, according to the method for producing the room temperature curable organopolysiloxane composition of the present invention, a cured product gel does not occur in the apparatus or in the composition, so that the appearance is good and fluidity does not occur. A room temperature-curable organopolysiloxane composition (that is, good thixotropy), good adhesion, and excellent viscosity stability can be obtained.

  From the above, if it is a manufacturing method of the room temperature curable organopolysiloxane composition of the present invention, the thixotropy is good even in the composition blending in which the conventional thixotropy is reduced, and the appearance is good, so the design is excellent, It was revealed that room temperature curable organopolysiloxane compositions of various curing types having excellent viscosity stability can be obtained.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has any configuration that has substantially the same configuration as the technical idea described in the claims of the present invention and that exhibits the same effects. Are included in the technical scope.

Claims (13)

A batch process for producing a room temperature curable organopolysiloxane composition comprising:
1) A polymer (A) having two or more hydroxyl groups bonded to silicon , and an organo having a hydrolyzable group selected from alkenyloxy, oxime and acetoxy groups represented by the following general formula (1) Silane (B) is dispersed in a mixer to produce a blend,
(R ¹ ) _(4-n) Si (OR ² ) _n (1)
(In the formula, R ¹ is a halogen-substituted or unsubstituted alkyl group, alkenyl group or aryl group having 1 to 6 carbon atoms, OR ² is a carbon number of 1 to 3 selected from an alkenyloxy group, an oxime group and an acetoxy group . 6 is a hydrolyzable group , and n is 2, 3 or 4.)
2) A step of adding and dispersing the curing catalyst (C1) to the blend,
3) Further, one or more fillers (D) selected from the group consisting of calcium carbonate, alumina, aluminum oxide, aluminum hydroxide, silica, carbon, titania, zinc oxide, zinc carbonate, clay and mica are added, Producing a base by dispersing,
4) a step of further adding and dispersing the curing catalyst (C2) to the base, and 5) further adding one or more adhesion promoters (E) represented by the following general formula (2), Dispersing until the product is sufficiently homogeneous,
(R ³ O) _(3-q) (R ³ ) _q Si-X (2)
Wherein R ³ is independently a hydrogen atom or a halogen-substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, X is amino, ketimino, mercapto, epoxy, isocyanate, ureido, acryloxy, methacryloxy and their A saturated, unsaturated or aromatic hydrocarbon group functionalized with a group selected from the group consisting of a mixture, q is an integer of 0-3.)
A process for producing a room temperature curable organopolysiloxane composition characterized by comprising: Hydrolyzable group OR in the organosilane (B) ² Is a alkenyloxy group or an oxime group, The manufacturing method of the room temperature curable organopolysiloxane composition of Claim 1 characterized by the above-mentioned. The curing catalyst (C1) and (C2) is at least one selected from amine compounds, organotin compounds, organotitanium compounds, organozirconium compounds, organoaluminum compounds, and organobismuth compounds. The manufacturing method of the room temperature curable organopolysiloxane composition of Claim 1 or Claim 2. The room temperature-curable organo according to any one of claims 1 to 3, wherein the addition amount of the curing catalyst (C1) and the curing catalyst (C2) is C1 ≦ C2. A method for producing a polysiloxane composition. The room temperature-curable organopolysiloxane composition according to any one of claims 1 to 4, wherein an operation of removing a volatile component is performed in one or more of the steps 2) to 5). Manufacturing method. The adhesion promoter (E) is an amino alkyl alkoxy silane, stingy aminoalkyl alkoxysilanes, epoxy alkoxysilanes, mercaptoalkylalkoxysilane, claims 1 to 5, characterized in that it is selected from ureidoalkyl alkoxysilane The manufacturing method of the room temperature curable organopolysiloxane composition as described in any one of these. The organosilane (B) is vinyltriisopropenoxysilane, phenyltriisopropenoxysilane, vinyltris (methylethylketoxime) silane, vinyltris (methylisobutylketoxime) silane, vinyltris (methylpropylketoxime) silane, tetra (methylethylketo) 7. Room temperature-curable organopoly according to any one of claims 1 to 6 , characterized in that it is selected from oxime) silane, tetra (methylisobutylketoxime) silane, and tetra (methylpropylketoxime) silane. A method for producing a siloxane composition. The method for producing a room temperature curable organopolysiloxane composition according to any one of claims 1 to 7, wherein the room temperature curable organopolysiloxane composition is used for automobile oil seals. The method for producing a room temperature curable organopolysiloxane composition according to any one of claims 1 to 7, wherein the room temperature curable organopolysiloxane composition is for an architectural sealant. The method for producing a room temperature curable organopolysiloxane composition according to any one of claims 1 to 7, wherein the room temperature curable organopolysiloxane composition is used for electric and electronic parts. To produce a pre-Symbol RTV organopolysiloxane composition in the manufacturing method according to any one of claims 1 to 7, an automobile oil seal, characterized in that it consists of curing the composition Manufacturing method . To produce a pre-Symbol RTV organopolysiloxane composition in the manufacturing method according to any one of claims 1 to 7, architectural sealant, characterized in that it consists of curing the composition Manufacturing method . To produce a pre-Symbol RTV organopolysiloxane composition in the manufacturing method according to any one of claims 1 to 7, the electrical and electronic components, characterized in that it consists of curing the composition Manufacturing method .