JP2774235B2 - Organosiloxane liquid composition and use thereof - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organosiloxane liquid composition containing a liquid organopolysiloxane as a main component and its use. More specifically, it relates to a film or fiber, a paint or a binder, a composite structure, The present invention relates to an organosiloxane liquid composition formed by contacting water or heat at a temperature of 300 ° C. or lower with a cured siloxane cured product having a polysiloxane bond as a main chain and applied to a composite sheet or a building material, and its use.

[0002]

2. Description of the Related Art Conventionally, when an organic polymer compound is handled, the presence of an organic solvent is important. In particular, the role of solvents in paints is important. From the viewpoint of the amount used, solvents account for 45 to 50% of the materials used for paints, and the major types are only 50 or more. . In particular, an organic solvent is an important and indispensable material for imparting fluidity by dissolving and dispersing a coating film forming material, and for providing coating suitability and coating film forming suitability. As described above, the organic solvent is at an inseparable edge for an organic polymer compound, particularly for a paint. However, organic solvents are highly flammable and have been designated as hazardous materials. In addition, when the human body comes into contact with organic solvents, various disorders such as anesthesia, central nervous system and autonomic nervous system disorders, liver and kidney disorders, (I.e., skin and eye inflammation), and its handling requires careful management and care.

[0003] The use or provision of such harmful organic solvents, which are flammable dangerous substances and cause harmful symptoms to the human body, in commodities widely used in the living environment has been considered to conserve the global environment. It is not something that is allowed from above.
Therefore, there is a strong demand for the development of solvent-free paints in the field of paints and the like. However, although water-based emulsion paints and powder paints have been developed as solventless paints, these paints still do not provide satisfactory film performance and are not satisfactory.

Generally, materials such as varnishes, paints, adhesives, and fibers are mainly composed of organic resins. However, in the changing living environment in recent years, the fields in which non-combustible, flame-retardant and non-polluting are required are becoming more and more widespread. Under these circumstances, it is considered that paints and the like use organic solvents which are dangerous and have harmful effects such as pollution, and that organic resins as main raw materials are susceptible to heat and fire and easily burn. There is a strong demand for the development of pollution-free and environmentally friendly alternative products that do not have these disadvantages.

[0005] Siloxane compounds having -Si-O- bonds are resistant to heat, light, and oxidation, and have excellent weather resistance and heat resistance. Some of the results have been put to practical use. Representative examples of the research results and problems of the prior art are listed below mainly in the fields of paints and coating materials. A popular example of applying organosiloxanes to paints is zinc rich paint developed during World War II. The paint is applied to a hydrolyzate such as tetraethoxysilane diluted with approximately the same amount of isopropyl alcohol solvent for about 2 hours.
This paint contains twice the amount of zinc powder. This paint is widely used as a rust preventive paint that forms a coating film when dried at room temperature.

[0006] It is a common practice to dilute a polymer of an organosiloxane or a modified organosiloxane thereof, and a copolymer with various organic compounds together with itself or other various organic resins into an organic solvent to form a coating. It is a common practice in the industry and most techniques have been developed as an application of this common practice. For example, a technique for preparing a modified tetraalkoxysilane in the presence of the same amount or more of a solvent as a film-forming agent, and then applying the same to air-dry or hot-air-drying to obtain a heat-resistant and rust-proof paint is disclosed in Japanese Patent Publication No. 63-28942. Japanese Patent Application Publication No. 63-58191 discloses a technique for forming a coating film from an organosiloxane in an organic solvent and forming the film at room temperature or under heating.

There are many technical examples in which an organic compound (organic resin) and an organosiloxane are simply compounded and applied to a coating material or the like, and most of them are formed by heating.
A typical example is a method in which tetraethoxysilane and methyltriethoxysilane are mixed with polyvinyl butyral butylated methylol melamine and applied, and the coated body is heated to 130 ° C. to obtain a coated film. No. 6,009,036. Many studies have attempted to use organosiloxanes as coating agents for heat-resistant paints.
Heat-resistant inorganic materials (aluminum phosphate, zinc molybdate, calcium carbonate, zinc silicate powder, etc.) were added with a slight amount of aluminum chelate compound to 50 to 80% by weight, and modified silicone resin was added to 20 to 50% by weight. JP-B-63-35183 can be mentioned as a technique for applying a paint to a substrate and baking it at 180 ° C. for heat-resistant coating.

Examples of applications of pure organosiloxanes include organopolysiloxanes, organotin compounds,
A technique for preparing a durable and stain-resistant transparent film made of volatile dimethylpolysiloxane (JP-A-3-68676) can be mentioned. In order to stably coexist the metal-containing organic compound used as a curing accelerator in the organosiloxane of the polymer-forming parent, a technique of combining a keto-enol type tautomer is known as a linear copolymer having a carboxyl group in the molecule. An example of a mixed composition of an aluminum alcoholate complex compound and a solvent is disclosed in JP-B-48-17859. A similar technique is to chelate an epoxy resin with an isocyanate group, a hydroxyl group, an epoxy group, a carboxyl group and an amino group, which are partially reacted with an alkoxysilane group or a hydroxysilane group, with the use of an organic solvent. Japanese Patent Application Laid-Open No. 1-129066 discloses a technique in which a keto-enol type tautomer is used in combination with a compound curing agent.

US Pat. No. 3,294,739 discloses a technique for curing a one-pack type organosiloxane composition at room temperature.
No. 3,647,917 and U.S. Pat. No. 4,111,890. However, in these patents, by limiting the concentration of metal elements such as silicon contained in the composition to a specific range, to improve the inorganic hardness and brittleness of the cured product that occurs when the metal element is at a high concentration, There is no disclosure of a technique for imparting flexibility to a cured body and further improving the adherence to a substrate or the like.

[0010] Further, there is no disclosure of a technique in which these cured products are applied to building materials, sheets, fibers, etc., and applied as flexible siloxane polymer materials, not limited to coating materials of coating materials. The present inventor has already given various specific conditions to the solvent-free organosiloxane composition,
Inventions (Japanese Patent Application Nos. 4-180127 and 4-36273) relating to polymer compositions which can be cured at room temperature or under heating and used for various effective applications such as coatings and binders have been made.

In these inventions, zinc, tin, boron, aluminum,
The total concentration of an element selected from the group consisting of silicon, titanium and zirconium (referred to as M element in the present invention)
It is characterized by containing at least 40% by weight based on the MOy _{/ 2} oxide standard. Thereafter, in the process of re-testing the invention, the present inventor found that the total M element concentration was less than 40% by weight. The siloxane liquid composition improves the inorganic hardness and brittleness of the cured body generated when the element M is at a high concentration, imparts flexibility to the cured body, and further improves the adherence followability to a substrate or the like. The knowledge was obtained and the present invention was completed.

[0012]

In the present specification, the organosiloxane liquid composition of the present invention refers to a siloxane cured product having a polysiloxane bond as a main chain formed by contact with water or heat of 300 ° C. or less. Siloxane polymer composition ". Further, in the present specification, elements selected from the group consisting of aluminum, boron, silicon, titanium, zirconium, zinc, and cobalt may be collectively referred to as an M element. Further, when expressing the concentration or content of the M element in terms of% by weight on an oxide basis, the display may be omitted and expressed as "MOy _{/ 2} % by weight". The term “adherence-following property” used in the present specification means that a polymer material is applied to a substrate (metal such as a steel plate, cement product such as an asbestos plate, wood, etc.) by applying, coating, bonding, or the like, and is applied in a natural environment. When exposed for a long period of time, adhesion / adhesion is achieved following changes in the expansion and contraction of the base material that occur under the long-term natural environment, and the state in which the adhesion is not destroyed.

The following terms used in this specification are defined as follows, and will be described in detail in the following specific description of the invention. In the present invention, the "siloxane polymer composition"
The shape polymer composition and adhesive polymer composition defined below, and the siloxane cured product constituting the composite structure, composite sheet and building material are collectively referred to. The `` shape polymer composition '' means that the organosiloxane liquid composition of the present invention alone was maintained in a film shape, a thin sheet shape, a fibrous shape, a string shape, a massive shape, a spherical shape, a square shape, or a specified shape. A polymer composition that forms a siloxane cured product in a shape. The term "adhesive polymer composition" means that the organosiloxane liquid composition of the present invention comprises a paint / varnish, a base material, a coating protective material having a certain thickness, an adhesive, a binder, a jointing agent, and various aggregates. A polymer that is used on the surface and inside of various base materials for applications such as hardening agents and bulking agents, as well as cementing materials and anchor fixing materials, and forms siloxane cured products with coatings and binders attached to the base materials Refers to a composition.

"Composite structure" means that the organosiloxane liquid composition of the present invention has a honeycomb shape, a bulk shape, a plate shape, a net shape,
It refers to a structure in which a complex integrated with a reinforcing agent, an aggregate, a molded body, a structurally processed body, or the like made of various base materials such as a fibrous or cloth-like material is formed through the intermediation of a cured siloxane. The term “composite sheet” refers to a cured siloxane formed in a state in which the organosiloxane liquid composition of the present invention is applied to and impregnated into a sheet base such as a film, a net, a net, a cloth, and a fabric, and is integrally formed into a sheet. Sheet "Building material" means that the organosiloxane liquid composition of the present invention is a metal product such as iron, a concrete product such as cement, a ceramic / clay product, an enamel product, a product such as wood / bamboo using natural materials, or a synthetic process thereof. A building material in which a siloxane cured body is formed while being coated on the surface of a building material such as a product.

As can be seen from the above prior art, the technique of applying an organopolysiloxane as a siloxane polymer to a paint or the like is excellent in coating film / film forming performance, diluting performance with a solvent, drying property after coating, and the like. The main material is an organic polymer or organic resin having a -CC- bond as the main chain, and in the application of these organic compounds to paints, the method and technology of supplementing and adding a siloxane compound for the purpose of compensating for its drawbacks have been started. Therefore, in these prior arts, the combined use of dangerous and obstructive organic solvents is unavoidable, and non-solvent, non-flammable and flame-retardant films and fiber-based polymer compositions, paints and the like are mainly composed of organosiloxanes. Actively produce siloxane polymer compositions such as adhesive polymer compositions such as adhesives and have not commercialized them. On the other hand, products have been developed in which the concentration of inorganic components such as silicon elements is increased to emphasize noncombustibility, flame retardancy and hardness. However, there has been seen a technique in which the concentration of the M element such as silicon contained is limited to a specific range to impart flexibility to the siloxane polymer composition and to improve adherence to a substrate or the like. Absent.

The present inventor has found that when conventionally used polymers are applied to films, fibers, paints, coating materials, binders, structures, sheets, building materials, etc., these polymers have the following problems. First of all, we focused on the lack of overcoming technologies that take into account the earth's environmental conservation and energy and labor savings. 1) In the case of a polymer mainly composed of an organic compound having a -CC- bond as a main chain; (a) Use of an organic solvent having danger and obstacles is inevitable. (b) Very weak against oxidation by heat and fire. (c) When flammable, emits toxic and harmful gases. (d) Very poor weather resistance. 2). Non-combustible polymer mainly composed of a silicon compound having a main chain of -Si-O- bonds; (a) Hard and inflexible due to lack of flexibility. (b) Strong reactivity with alkali metal elements and poor alkali resistance. (c) In the case of -Si-O-bonded cured product due to hydraulic property, pores are formed and lack water resistance. (d) Inorganic-Si-O-bonded materials have no adhesion to organic materials,
Cannot be applied repeatedly. In addition to the above, the present inventor has set forth the invention technology (Japanese Patent Application No.
In Japanese Patent Application No. 4-180127 and Japanese Patent Application No. 4-36273, it was noted that sufficient attention was not paid to ensuring adhesion that could follow changes in expansion and shrinkage of the substrate.

The present inventor has found that a siloxane bond (Si-O bond)
Basically, (a) the interatomic bond energy is large and resistant to heat, light, oxidation, etc., (b) the wavelength absorption in the ultraviolet region is small and the weather resistance is excellent, and (c) the interatomic bond distance is Assuming that it has features such as long length, low electron density, easy bonding rotation, and high flexibility, it is used for its application, especially for substrates that are exposed to the natural environment for a long time. As a result of intensive experiments and studies on the organopolysiloxane composition to be prepared, it has been found that the following properties are exhibited when a liquid composition of the specified organosiloxane is prepared.

The liquid composition comprising the specified organopolysiloxane liquid, the crosslinking agent for the organometallic compound, and the curing accelerator should be maintained in a solvent-free liquid composition. In particular, all metal elements in the organosiloxane liquid composition
When the amount is controlled in the range of 25% by weight or more and less than 40% by weight based on the MO _{y / 2} oxide standard, the heat resistance is ensured, the brittleness of the produced polymer is eliminated, and the base material during long-term exposure is removed. A siloxane polymer composition that effectively exhibits the adherence follow-up property of the polymer. When the metal-containing organic compound is allowed to coexist with the specified organosiloxane liquid composition and is brought into contact with heat or water, the effective siloxane cured polymer is formed by a moisture curing mechanism. The specified organosiloxane liquid composition has
Bond, Ti-O bond, Zr-O bond, etc.
Unprecedented high-performance performance is added to the polymer whose bond is the main chain.

[0019]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a flexible, heat-resistant and durable siloxane polymer composition formed by moisture curing, which can be used as a film, fiber, paint / varnish, adhesive, composite structure, composite In order to effectively apply to sheets and building materials, it is a specified material that does not substantially contain a solvent harmful to the human body that is environmentally friendly and can technically solve the above-mentioned problems that were not achieved by the prior art. An object of the present invention is to provide an organosiloxane liquid composition.

[0020]

DISCLOSURE OF THE INVENTION The present invention has been proposed to achieve the above-mentioned object, and is directed to a specific liquid organopolysiloxane (A), a crosslinking agent (B) and a curing accelerator ( C) is characterized by a mixed liquid composition comprising the three components. That is, according to the present invention, the liquid organopolysiloxane (A), a cross-linking agent (B) and a curing accelerator (C) is a mixed liquid composition comprising three components; the liquid organopolysiloxane (A), The following general formula (1) (Wherein, R ¹ is a hydrogen atom or a C ₁ to C ₅ alkyl group; R ² to R ⁶ are the same or different groups each selected from a hydrogen atom, an OR ¹ group or a monovalent hydrocarbon group, n
Is a number less than 15) or 2
A low-molecular-weight polysiloxane composed of a combination of at least two or more kinds, and the silicon concentration in the liquid organopolysiloxane is 50% by weight or more expressed on the basis of SiO ₂ oxide, and the crosslinking agent (B) is formula _{^{(2) R 7 p B ·}} (oR 1) 3-p ·········· (2) ( wherein: alkyl of R ¹ is or a C ₁ are hydrogen C _5; R ⁷ is a hydrogen atom, an OR ¹ group or a group selected from monovalent organic groups; p is an organic compound of boron represented by 2 or less, or the above (2) and the following formula (3) or (4) R ⁷ _p Al ・ (OR ¹ ) _3-p・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ (3) R ⁷ _m Q ・ (OR ¹ ) _4-m・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ (4) (Wherein Q is a silicon, titanium or zirconium element;
R ¹ is a hydrogen atom or a C ₁ to C ₅ alkyl group; R ⁷ is a hydrogen atom, an OR ¹ group or a group selected from monovalent organic groups;
An integer of 2 or less; m is an integer of 3 or less), wherein the curing accelerator (C) is zinc, aluminum,
A compound comprising one or more combinations selected from the group consisting of metal-containing organic compounds containing titanium, zirconium or tin, and zinc, tin, boron, aluminum, silicon of the ternary mixture composition (M element) selected from the group consisting of, titanium and zirconium
Wherein the total concentration of the organosiloxane liquid is in the range of 25% by weight or more and less than 40% by weight on the basis of MO _{y / 2} oxide (y is the valence of M element). .

According to the present invention, the crosslinking agent (B)
Is an organotrialkoxysilane composed of a monovalent organic group having at least an amino group. Further, according to the present invention, there is provided the above organosiloxane liquid composition, wherein the crosslinking agent (B) is blended in an amount of 70% by weight or less.
Further, according to the present invention, the liquid organopolysiloxane (A) or the cross-linking agent (B) alone or in the form of a mixed liquid composition contains an OR group (R is a hydrogen atom, C ₁ to C ₅ ) of a functional side chain. The organosiloxane liquid composition is provided, wherein the solid silicone resin having an alkyl group of the above is dissolved in an amount of 70% by weight or less.

According to the present invention, an activator, a filler, a pigment and a colorant are added to 100 parts by weight of the liquid organopolysiloxane (A) or the crosslinking agent (B) alone or in a mixture. The above organosiloxane liquid composition is provided, wherein one or more combination fillers (D) selected from the group are pre-complexed in the range of 1 to 500 parts by weight. Further, according to the present invention, there is provided the above organosiloxane liquid composition, wherein the activator is a powder of a combination of one or more of a boric acid-containing compound, a chromic acid-containing compound, and a phosphoric acid-containing compound.

According to the present invention, there is provided the above-mentioned curing accelerator.
Β having an alkyl group or a trifluoro group in (C)
A keto-enol type tautomeric compound composed of one or two or more selected from the group consisting of keto acid esters, β-diketone compounds and malonic esters, in an amount of 50% by weight or less. An organosiloxane liquid composition is provided.

Further, according to the present invention, the aforementioned curing accelerator
The above organosiloxane liquid composition, wherein (C) contains at least 50% by weight of an alcohol comprising one or a combination of two or more selected from the group of monohydric or polyhydric alcohols, Provided. According to the present invention,
The above-mentioned organo-compound, wherein the curing accelerator (C) comprising the metal-containing organic compound containing the keto-enol type tautomeric compound or the alcohol or the single metal-containing organic compound is blended in an amount of 10% by weight or less. A siloxane liquid composition is provided.

According to the present invention, the liquid organopolysiloxane (A), the crosslinking agent (B), the silicone resin or the thermoplastic resin and the filler (D) alone or in combination or in a composite liquid composition are The above-mentioned organosiloxane liquid composition, which has been previously subjected to a curing step at 100 ° C. or lower in the absence of water for 10 minutes or more to remove water content or silanol groups, and then containing a curing accelerator (C), is provided. Is done.

According to the present invention, the organosiloxane liquid composition is formed from a siloxane cured product having a polysiloxane bond as a main chain by contact with water or heat of 300 ° C. or less. A shaped polymeric composition is provided.

According to the present invention, the organosiloxane liquid composition is formed of a coating film or a binder having a polysiloxane bond as a main chain by contact with water or heat of 300 ° C. or less. An adhesive polymer composition is provided that features.

According to the present invention, one or two kinds selected from the group consisting of a reinforcing material, an aggregate and a molded body are used in an amount of 1 to 2000 parts by weight based on 100 parts by weight of the organosiloxane liquid composition. A composite structure in which the composite in which the above combination materials are preliminarily mixed is integrated with a cured siloxane having a polysiloxane bond as a main chain by contact with water or heat of 300 ° C. or less. Provided.

Further, according to the present invention, the above-mentioned organosiloxane liquid composition is applied and impregnated to a cloth-like or net-like sheet base, and a polysiloxane bond formed by contact with water or heat of 300 ° C. or less is bonded to the main chain. The composite sheet is characterized by being integrated into a sheet with the cured siloxane.

[0030]

What is important in the present invention is that a liquid composition mainly composed of an organopolysiloxane, which has good workability in workability without substantially allowing an organic solvent harmful to the human body to coexist as a raw material of the siloxane polymer composition. An object of the present invention is to provide a siloxane polymer composition which is prepared and cured to exhibit various physical properties, and to provide a polymer effective for each purpose of the present invention. In order to make the resulting siloxane polymer composition of the present invention nonflammable, flame-retardant and excellent in heat resistance, the flammable organic solvent component is eliminated, and the concentration of the organic component which is weak to heat is suppressed to a low level. In particular, it is necessary to increase the silicon concentration. On the other hand, if the total concentration of the M element selected from the group consisting of zinc, tin, boron, aluminum, silicon, titanium and zirconium is too high, the physical properties of the resulting siloxane polymer composition are infinitely inorganic, such as glass and ceramics. Hard and fragile as seen in
There is no tendency to be sticky and brittle. Therefore, the flexibility required for products and the ability to adhere to substrates are impaired,
The object of the present invention cannot be achieved.

In order to obtain a siloxane polymer composition which is the object of the present invention and which is flexible, has excellent adhesion following long-term exposure, and is heat-resistant, it is necessary to compensate for and improve the disadvantages of inorganic physical properties. . The inventors of the present invention have conducted intensive studies to develop a material having non-flammable / flame-retardant inorganic properties with excellent heat resistance, as well as organic properties such as flexibility and adhesion followability. As a result, the degree of polymerization is maintained in a specific range, the concentration of silicon is maintained in a liquid state at a certain level or more, and the liquid organo-organic silicon group is a monovalent hydrocarbon group while the functional group is a hydrogen atom or an alkoxy group. Polysiloxane (A)
In the above general formula (2) or (2) and (3) or (4) a specific crosslinking agent (B) containing boron as an essential component, and a specific curing accelerator (C) and In the mixed liquid composition composed of three components, the concentration of all M elements contained is expressed in terms of MOy _{/ 2} oxide, and is 25% by weight to 40% by weight.
When the amount is controlled to be less than the range, the hardness and brittleness seen in general inorganic materials are improved, and especially, the adhesiveness which can effectively follow the expansion and contraction of the base material in long-term exposure, and the general organic resin An organosiloxane liquid composition capable of forming a siloxane polymer having characteristics such as noncombustibility, flame retardancy and heat resistance maintained at a high level as compared with a polymer product comprising the same.

As an organosiloxane having an organosilicon group and an OR group as a functional side chain in the Si—O bond, methyltrimethoxysilane [CH ₃ Si (OCH ₃ ) ₃ ] having the least number of carbon atoms will be exemplified. The silicon concentration is 20.6% by weight as Si, which is equivalent to 44.1% by weight in terms of SiO ₂ . The silicon concentration of methyltrimethoxysilane [C ₂ H ₅ Si (OC ₂ H ₅ ) ₃ ] having more carbon atoms is 14.6% by weight as Si, which is 3% in terms of SiO _2.
This corresponds to a low value of 1.2% by weight. Naturally, if the organopolysiloxane (A) having a large number of carbon atoms of R ¹ to R ⁶ in the general formula (1) shown above is selected, the ratio of the organic component occupies further and the silicon concentration decreases. Is easily understood.

In order to maintain the silicon concentration of the organopolysiloxane (A) which can be maintained in a liquid state substantially without an organic solvent at a high concentration of 50% by weight or more, preferably 53% by weight or more in terms of SiO _2. Is possible by polymerizing an organosiloxane to an oligomer or more. That is, this is achieved by setting _{n in} the [-Si-O-] _n term of the general formula (1) to at least two or more polymers. For example, when 2 mol of methyltrimethoxysilane having a SiO ₂ concentration of 44.1% by weight shown above is subjected to a condensation reaction by dealcoholation to form a dimer, the silicon concentration is 24.7% by weight as Si,
This corresponds to 53.0% by weight in terms of O ₂ , and it is easily understood that the silicon concentration increases due to the condensation reaction and shifts to a higher concentration side.

On the other hand, when the number of n increases and the degree of polymerization increases, the liquid viscosity of the organopolysiloxane (A) increases, and no diluent such as an organic solvent for adjusting the liquid viscosity is added. Therefore, it is difficult to ensure good workability as a paint or the like. In addition, since the present invention aims to adopt materials and methods that are friendly to the global environment and is not in a position to use an organic solvent that causes various adverse effects, it is not possible to employ a dilution means using an organic solvent. Therefore, in order to ensure a good liquid state in the composition of the present invention and to guarantee the workability of the composition, the silicon concentration and the degree of polymerization of the organopolysiloxane (A) naturally have an upper limit.

The liquid organopolysiloxane (A) used in the present invention has an organic group in which an organic group is directly bonded to silicon without through oxygen. It is important in different ways. In particular, in order to effectively exhibit the flexibility, adhesion follow-up property, water repellency, water resistance and alkali resistance properties of a polymer not having an inorganic siloxane bond, an organic group large enough to cover the siloxane bond, For example, it is important to have a monovalent hydrocarbon organic group such as an alkyl group, a phenyl group, a glycidoxy group, a methacryloxy group, and an aminoalkyl group. In particular, an alkyl group or a phenyl group is preferable as the organic group.

In the prior art, the compound having a -Si-O- bond has poor alkali resistance irrespective of whether it is an inorganic or organic compound. However, as shown in Examples described later, it is surprising to show excellent alkali resistance. Although the reason is not clear, as described above, the cured polymer of the present invention forms a dense and strong network structure by the specified crosslinking reaction,
Moreover whereas Si-O bond has an average area of about 22 Å ^2, for example, since the -CH ₃ bond having an average area of about 12 Å ^2, at least -CH ₃ linking two organic When you are
From the above, it can be considered that the siloxane polymer composition of the present invention exhibits alkali resistance, since the Si-O bond can be sufficiently covered and protected in terms of area.

Further, the Si—O bond serving as the basic skeleton of the siloxane polymer composition of the present invention is a polymer having a structure of —Si—O—
The organopolysiloxane liquid, which has some -Si- bonds, not only increases its SiO ₂ concentration,
This is important in determining the basic structure of the desired polymer skeleton, predicting the structural form of the target siloxane cured product to some extent, and predicting the physical properties of the desired siloxane polymer composition. Furthermore, when a cured siloxane is to be formed in a short time by heat curing, a polymer that has undergone a certain degree of condensation reaction, an oligomer of general formula (1) in which n is 2 or more, or a polymer having a low molecular weight is used as a raw material. It is effective to choose.

In order to form the siloxane liquid composition of the present invention into a useful polymer in the range from room temperature to 300 ° C., the types and contents of the organopolysiloxane and the organometallic compound (crosslinking agent) constituting the liquid state are required. , Especially the type and composition of the organosilicon group, the hydroxyl group or the alkoxy group,
It is necessary to carefully select and control the silicon concentration, the degree of polymerization, the curing step, and the catalytic action of the compounded metal-containing organic compound.

Furthermore, in order to obtain a polymer cured product in which the polymer formed here effectively exerts useful physical properties, it is necessary to form a three-dimensionally spread network-like polymer densely and durably. However, for example, when the number of functional groups of the organosiloxane is two or less, only a linear polymer is formed, or the polymerization is terminated only at the terminal functional group portion of the polymer to form a three-dimensionally spread network polymer. Can not. In order to form a dense and durable three-dimensional network polymer, a cross-linking agent having at least three functional groups at an intermediate point of the organopolysiloxane serving as the basic skeleton base is used to cross-link or cross-link. -It is necessary to proceed in the left and right three-dimensional directions to form a three-dimensionally spread structure, not on a line or a plane.

Therefore, the role of the cross-linking agent used is important.
(2) R ⁷ _p B · (OR ¹ ) _3-p (where R ¹ is a hydrogen atom or a C ₁ to C ₅ alkyl group; R ⁷ is selected from a hydrogen atom, an OR ¹ group or a monovalent organic group) P is an integer of 2 or less), or the compound (2) and the general formula (3) R ⁷ _m Al · (OR ¹ ) _3-p or the general formula (4) R ⁷ _p Q · (OR ¹ ) _4-m (where Q is a silicon, titanium or zirconium element; R ¹ is a hydrogen atom or C ₁
An alkyl group of C ₅ ; R ⁷ is a group selected from a hydrogen atom, an OR ¹ group or a monovalent organic group; p is an integer of 2 or less and m is an integer of 3 or less); It has been found that an organic compound having an acidic functional group is effective.

Further, the inventor has determined that the crosslinking agent (B) of the present invention
When selecting a cross-linking agent having an aminoalkyl group in its monovalent organic group, a heat is generated due to a neutralization reaction with an acidic curing accelerator in which the basic amino group is blended, and the dehydration required for condensation polymerization is caused. It was found that the alcohol reaction accelerated. This property is particularly effective when it is necessary to quickly develop various physical properties of the polymer in a room temperature curing reaction.

Further, what is important for the crosslinking agent (B) of the present invention is that boron or boron and aluminum, silicon, titanium or zirconium of the crosslinking agent are directly bonded to the Si—O bond constituting the siloxane polymer. It also plays a role as one of its members. In particular, in the present invention, by containing these trivalent or tetravalent metal elements partially but in addition to the silicon element in the main chain of the polymer, the M element mainly composed of boron elements having different sizes and sizes can be obtained. Is partially mixed in the Si—O bond. As a result, the cured product itself changes from a completely regular structure to a partially irregular structure, causing play and extra space in the cured product structure, resulting in a toughness in the resulting polymer. It is possible to exhibit toughness.

Further, what is important about the crosslinking agent (B) of the present invention is that the crosslinking agent (B)
Or boron and an organometallic compound of boron and aluminum, titanium or zirconium are both a crosslinking agent and also have a function as a curing accelerator.
Therefore, when selecting the organometallic compound for the cross-linking agent (B), it is necessary to determine the content of the curing accelerator (C) in consideration of the content and the content of the curing accelerator (C).

Further, the organosiloxane liquid composition of the present invention basically differs from the case of an inorganic siloxane composition such as water glass in that it does not contain an alkali metal component. In addition, in the liquid composition of the present invention, the alkyl group or the like involved in the condensation is removed from the cyclohexane bond by dealcoholation, and is volatilized from the cured system. As a result, not only is the adverse effect caused by the alkali metal component remaining in the composition system occurring in the case of the inorganic siloxane composition eliminated, but also the electron around the Si-O bond of the produced siloxane polymer composition is reduced. The density decreases, the degree of freedom increases, and the Si—O bond of the cured siloxane becomes flexible. As a result, the cured siloxane of the present invention having a Si-O bond as a main chain is provided with flexibility, and becomes a coating material that can follow the bending of a flexible substrate such as a thin plate, a cloth or a sheet.

Further, the present inventor, when dissolving a polymerized solid silicone resin in an organosiloxane liquid and blending it into a liquid composition, is suitable as a liquid composition used for paints and binders. Was found. The solid silicone resin referred to in the present invention means a paste, flake, gel or powder non-flowable silicone resin. In this case, by mixing a silicone resin, which has a polymerized state in advance, in the liquid composition in a specific amount range, the liquid viscosity of the liquid composition can be adjusted in a thickening direction, thereby controlling workability. In addition to this, there is an advantage that the structural design and properties of the target siloxane polymer composition can be specified in advance.

The present inventor dissolves a thermoplastic resin, which is a linear organic polymer compound soluble in an organosiloxane liquid, in a range of 30% by weight or less, and prepares a liquid composition in which an organic polymer compound is previously compounded. It has been found that it can be suitably used in the present invention. In this case, when the organic polymer compound is blended, the concentration of all metal elements in the liquid composition tends to decrease, and nonflammability and flame retardancy tend to be reduced. However, when the siloxane composition of the present invention is required to be applied or bound on an organic material, the added thermoplastic resin has the advantage of improving the adhesion and adhesion to the organic compound-based material. is there.

As another means for improving the silicon concentration in the polymer cured product of the organosiloxane, a composite is prepared by adding solid colloidal or finely powdered silica or silicate to the starting organosiloxane. There are ways. However, in this case, the added silica or silicate or the like reacts with the starting organosiloxane to form one compound, and the formation of a polymer as a member of the siloxane bond cannot be expected. Therefore,
Even if the added silica or silicate etc. can be expected to be non-flammable or flame-retardant, as long as the siloxane polymer cured body that combines silica or silicate etc. does not have non-flammability or flame retardancy, this composite It is not possible to expect non-combustible / flame-retardant properties or heat resistance that can maintain the shape.

Further, the solvent-free liquid composition of the present invention may contain an activator generally used in the art depending on the purpose of use.
A filler (D) composed of a filler, a pigment, a colorant and the like can be selected according to the purpose and can be previously blended in a specified amount ratio. The filler (D) such as an activator, a filler, a pigment, a colorant and the like to be used is a powder having a size of 200 μm or less, preferably 100 μm or less.

A curing accelerator for accelerating the above crosslinking reaction
As (C), a metal-containing organic compound comprising a metal element such as zinc, cobalt, aluminum or tin is effective. Further, in the present invention, it is noted that the above-mentioned organic compound of the crosslinking agent (B) is a crosslinking agent and also functions as a hardening accelerator in combination with the above-mentioned metal-containing organic compound, thereby performing a dual role. Therefore, as described above, the curing accelerator (C)
Must be determined in consideration of this point.

The inventor of the present invention has intended to ensure one-pack preservability of the liquid composition of the present invention and to control and control the progress of the curing reaction occurring after application at desired time intervals. A blocking agent capable of blocking and blocking the curing accelerator (C) to be used is examined beforehand, and keto-enol type tautomeric compounds and alcohols satisfying the above conditions in an anhydrous state are effective as blocking agents. I found that.

Generally, a keto-enol type tautomeric compound has an equilibrium relationship between a keto type (β-ketobutyric acid ethyl ester) and an enol type (β-oxycrotonate ethyl ester) as represented by ethyl acetoacetate. And have the property of coexisting. Therefore, this keto
Since the enol-type tautomeric compound undergoes chelation by hydrogen bonding in the molecule, it is considered that hydrogen bonding between molecules hardly occurs and a blocking effect is exhibited without causing intermolecular association.

It is considered that the enol type of the keto-enol type tautomer is stabilized by chelation by hydrogen bonding. However, when water, a compound having a hydroxyl group such as alcohol or acetic acid coexists, the hydroxyl group easily forms a hydrogen bond with the oxygen atom of the keto-type carbonyl group, hinders the chelation of the metal element, and the blocking effect is eliminated. It is thought that it exerts a catalytic action by the element.

Further, in the present invention, it is effective to incorporate a monohydric or polyhydric alcohol in order to delay and control the reaction rate of curing. Although the reason is not clear, it is presumed that the coexistence of these alcohols suppresses a newly occurring dealcoholization reaction and delays the reaction rate.

Further, it is important for putting the present invention into practical use that one-pack preservability can be maintained even when the liquid composition of the present invention coexists with a curing accelerator. The liquid composition of the present invention may be applied in a so-called two-pack type method, but a one-pack type is preferable in terms of the workability without complexity. In order to enable this one-part type, it is important that R of the OR group in the organosiloxane liquid composition is only an organic group such as an alkoxy group or an acyloxy group which is stably present even in the presence of a curing accelerator. is there.

If the OR of the liquid organosiloxane stock solution,
When the group R has a so-called silanol group which is a hydrogen atom, the OH group of the silanol group is de-alcoholized with the co-existing alkoxy group when the curing accelerator coexists even in the absence of water. A reaction occurs, and the liquid composition changes in the direction of polymerizing. As a result, the one-pack preservability of the liquid composition is impaired, which makes it difficult to control the quality of the product, and requires careful attention since the product is a material in which the desired physical properties cannot be exhibited.

Therefore, when water or silanol groups are contained in the organosiloxane liquid composition and further in the composite liquid composition in which the filler (D) such as a coloring agent or a pigment is blended, as described above. In order to prevent moisture curing during storage, water and silanol groups need to be removed and eliminated in a pre-curing step. The curing process is
The prepared organosiloxane liquid composition or composite composition can be removed and extinguished by allowing it to stand beforehand at a temperature of 100 ° C. or lower and react with water contained therein or a silanol group coexisting with an alkoxy group. By utilizing this phenomenon, the step of dispersing and mixing a filler such as a coloring agent or a pigment in the organosiloxane liquid composition in an open state, which has been conventionally difficult, can be easily performed.

As described above, when the liquid composition of the present invention is exposed to the atmosphere and given moisture curing conditions, a condensation reaction is started to form a cured siloxane polymer. Of course, the reaction is sufficiently possible at room temperature,
Even if moisture curing conditions are given by heating at 300 ° C. or less, preferably 270 ° C. or less, the formation of the siloxane polymer composition is not impaired, but rather the dealcoholization reaction is promoted and the polymer formation is accelerated. Therefore, when the productivity of the reaction of the present invention is required to be improved under physical and time constraints such as in a factory line, the curing reaction under heating is very effective.

In the present invention, when a solvent-free organosiloxane liquid composition is used alone or by adding, blending or compounding various materials, and then moisture-cured at room temperature to 300 ° C. or less, the following results can be obtained. It is suitably provided for each of the applications shown. Single film, thin sheet, fiber, string, lump,
A shaped polymer composition that is maintained in a spherical, angular, etc. or specified shape. Various types of applications such as paints / varnishes, base materials, coating protective materials with a certain thickness, adhesives, binders, jointing agents, hardening agents and binders for various aggregates, cementing materials and anchor fixing materials An adhesive polymer composition which is used on the surface or inside of a substrate and exerts a desired effect by being adhered to the substrate. A composite structure integrated with a honeycomb, lump, plate, mesh, fiber, cloth, or other reinforcing agent, aggregate, molded body, structurally processed body, or the like. A composite sheet formed by coating and impregnating a sheet base such as a film, a net, a net, a cloth, and a fabric. Building materials painted on the surface of building materials, such as iron and other metal products, cement and other concrete products, ceramic ceramic and clay products, enamel products, wood and bamboo products and synthetic products made of natural materials.

[0059]

DETAILED DESCRIPTION OF THE INVENTION Liquid organopolysiloxane (A)
Is a basic matrix for preparing a liquid mixed composition without an organic solvent to form a cured polymer of the present invention. Therefore, the content of the liquid organopolysiloxane (A) is important in determining workability and physical properties of the resulting siloxane polymer composition, and it is necessary to conduct a thorough study on its selection.

X constituting the organosilicon group (X-Si) of the liquid organopolysiloxane (A) used in the present invention comprises a hydrogen atom or a monovalent hydrocarbon group and has a carbon number of ₁ to ₅ carbon atoms.
Wherein the group of X is a linear or branched alkyl group, fluoroalkyl group, vinyl group, allyl group, alkenyl group, phenyl group, xenyl group, naphthyl group, aryl group, cyclohexyl group, cyclohexenyl group, A benzyl group, an aralkyl group, an araryl group, an epoxy group, an aminoalkyl group and the like are preferable for achieving the object of the present invention. From the above organosilicon groups, the silicon concentration of the liquid organopolysiloxane (A) is as high as possible, and the total M element concentration in the liquid composition of the present invention is 25% by weight to 40% by weight on an oxide basis. When a good liquid state is secured in the workability, the desired physical properties, especially the flexibility and adhesion follow-up properties are exhibited, and various physical properties such as water repellency, alkali resistance and water permeability are exhibited. It becomes possible. It is effective for the present invention that the X atom group at this time is an alkyl methyl group, an ethyl group, or a phenyl group.

On the other hand, the OR group of the functional side chain possessed by the liquid organopolysiloxane (A) of the present invention is important as a functional group of a base for promoting a polymerization reaction by moisture curing.
Therefore, this OR group is important as a functional group that is de-alcoholized by hydrolysis with water to form a silanol group, or that promotes a polymerization reaction by a dealcoholization reaction with a siloxane having an OH group in the presence of a curing accelerator. . For this purpose, R of the OR group is preferably an alkyl group which is a monovalent C _n H _{2n + 1} atomic group, and therefore, the OR group is preferably an alkoxy group.

The incombustibility of the siloxane polymer composition of the present invention
To ensure flame retardancy, organopolysiloxane (A)
It is necessary to ensure a high silicon concentration of 50% by weight or more based on SiO ₂ oxide. Its purpose is to define the [-SiO] _n term of the liquid organopolysiloxane (A) represented by the general formula (1).
This is achieved by choosing an oligomer or polymer where n is a number greater than or equal to 2.

However, in order to ensure the liquid state of the organopolysiloxane (A), it is preferable that n in the general formula (1) is a number smaller than 15. By controlling the degree of polymerization of the organosiloxane used in this way, it is possible to secure the viscosity of the liquid to a level of 3000 centipoise or less so that it is easy to handle in construction. There is no need to adjust the viscosity, and the pure organosiloxane liquid composition alone can be used for construction as it is.

The fact that the liquid organopolysiloxane (A) is a compound obtained by polymerizing to a certain extent means that most of the skeleton of the cured product of the resulting siloxane is almost completed, and that the functional side chain has an OR group. This is effective because the siloxane polymer composition having the specified skeleton can be designed in advance. This liquid organopolysiloxane is composed of a siloxane compound of a D unit having two functional groups and a T unit having three functional groups each having a side chain alkyl group alone or a TD unit composed of a combination thereof. It is sufficient that n in the [-Si-O-] term of the formula (1) is at least 2 or more. On the other hand, the upper limit of n can be selected just before the polymer loses its fluidity. In general, it is preferable that the polysiloxane compound is a low molecular weight polysiloxane compound having a molecular weight of the order of 10 ² to 10 ⁵ .

The side chain (R) of the organic group including the OR group of the functional side chain in the liquid organopolysiloxane (A) has a Si—O bond.
Expressed in Si, its possible to the ratio of R / Si is not 1/3 is in the range of 2/2 keeping the SiO ₂ concentration to a high concentration, promoting the polymerization reaction efficiently enable polymer cured product of interest It is important in forming. As typical examples of the liquid organopolysiloxane (A) preferably used in the present invention, the following compounds, oligomers of methylmethoxysiloxane, the ratio of R / Si is 1/3
Alkyl group, fluoroalkyl group, vinyl group, allyl group, alkenyl group, phenyl group,
Organopolysiloxanes having a xenyl group, a naphthyl group, an aryl group, a cyclohexyl group, a cyclohexenyl group, a benzyl group, an aralkyl group, an araryl group, an epoxy group, an aminoalkyl group and the like, particularly preferably a methyl group or a phenyl group Organopolysiloxanes, oligomers of tetramethyl or ethyl orthosilicate, oligomers of methyl or vinyltriacetoxysilane, and the like. Moreover, these compounds are preferably used alone or in combination of two or more.

In order to make the liquid composition of the present invention a high-molecular polymer having a flexible, dense and strong three-dimensional network structure, not only the polymerization at the terminal of the polysiloxane but also various places in the middle of the polysiloxane. Therefore, a cross-linking agent (B) is required which can proceed cross-linking and cross-linking vertically and horizontally.
As a cross-linking agent (B) which can achieve this purpose, the present inventors have a general formula (2) having a functional side chain OR group capable of condensation reaction with an alkoxyl group or a silanol group, etc.R ⁷ _p B (OR ¹ ) liquid organic compounds of boron represented by _3-p, or the general formula (2) and the general formula _{^{(3) R 7 p Al ·}} (oR 1) aluminum-containing compound represented by the _3-p or the general formula (4) R ⁷ _m Q · (OR ¹ ) _4-m (Q,
R ¹ , R ⁷ , p, and m are as described above).
It is effective to use a liquid organic compound of titanium and zirconium in combination. Moreover, it is preferable that R ^{7 of the} organosilicon group is a compound having a large number of carbon atoms in order to exhibit flexibility and adhesion followability.

The following are typical examples of the crosslinking agent (B). In the general formula (2), p is an organometallic compound having a trialkoxy group R ¹ is methyl, ethyl or butyl with 0, In the general formula (3) is, p
Is preferably 0 and R ¹ is isopropyl or secondary butyl.

When Q in the general formula (4) is a silicon element,
R ⁷ is a methoxy group or an ethoxy group, tetramethyl or ethyl orthosilicate, methyltrimethoxysilane, methyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, γ-glycidoxypropylmethoxysilane , Dimethylmethyltrifluoropropylsilane, γ-
Organic metal compounds such as methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-ureidopropyltriethoxysilane, and γ- (2-aminoethyl) aminopropyltriethoxysilane are preferred.

When Q in the general formula (4) is a titanium element,
An organometallic compound such as tetra-i-propyl titanate and tetra-n-butyl titanate is preferred. When Q in the general formula (4) is a zirconium element, it is preferably an organometallic compound such as tetraethyl zirconate, tetra-i-propyl zirconate, or tetra-n-butyl zirconate.

It is preferable that these organometallic compounds are monomers in order to exhibit a crosslinking effect. However, the use of a compound such as a dimer, which has already started polymerization, also impairs the object of the present invention. Not valid. Further, it is preferable to use the above-mentioned organometallic compounds singly or in combination of two or more in accordance with the purpose and workability. The crosslinking agent (B) used in the present invention, when incorporated in the liquid composition at 70% by weight or less, preferably at 65% by weight or less, improves the crosslinking effect of the siloxane polymer composition,
It is effective for imparting flexibility and adhesion followability.

As described above, it is necessary to consider that the cross-linking agent (B) is a cross-linking agent and also functions as a curing accelerator. Therefore, the amount of these organic compounds, particularly aluminum, boron, titanium and zirconium compounds, is related to the type and the mixing ratio of the curing accelerator (C) of the present invention, but within 25% by weight in the composition of the present invention. It is desirable to limit the amount in order to control the one-part storage property, the curing speed, and the physical properties of the siloxane polymer composition.

Further, in the present invention, not only from the viewpoint of designing the basic skeleton of the produced siloxane polymer composition, but also from the viewpoint of adjusting the liquid viscosity of the liquid composition and controlling the workability,
Solid silicone resin can be selected and blended.
However, in this case, in view of handling the present composition in a liquid state, it is important to dissolve the solid silicone resin once with an organoshiroquine liquid before use. In this case, it is preferable that the silicone resin is blended in the liquid composition in an amount of 70% by weight or less, preferably 60% by weight or less in order to achieve the above object and secure good workability. It is. However, these silicone resins generally have a tendency to contain 3 to 8% by weight of silanol groups. Therefore, unless the silanol groups are preliminarily blocked and altered by a curing step as described above, they must be modified. It tends to be impossible to ensure liquid preservability.

Further, in the present invention, a thermoplastic resin can be dissolved and coexisted in the organosiloxane in order to improve the adhesion to the organic material and to make minor modifications as a coating material. As the thermoplastic resin used in the present invention, a linear organic polymer compound soluble in an organosiloxane is preferable. Examples thereof include resins such as acrylic resins, polystyrene resins, polyethylene resins, polyvinyl chloride resins, and celluloses and derivatives thereof, and copolymers of unsaturated carboxylic acids with non-aqueous solutions.

The monomers include ethylene, propylene,
Butadiene, isoprene, chloroprene, styrene, vinyl acetate, vinyl propionate, vinyl ether, vinyl chloride, vinylidene chloride, methyl or ethyl acrylate, or acrylate ester, and unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid , Itaconic acid, maleic anhydride and the like. These thermoplastic resins are blended in the raw organosiloxane liquid composition in an amount of 30% by weight or less, preferably 25% by weight or less, so that the above-mentioned object can be achieved and good workability can be ensured. It is suitable for performing.

The organosiloxane liquid composition of the present invention has the following properties required for the resulting siloxane polymer composition:
Fillers (D) selected from the group of powdered activators, fillers, pigments, colorants and the like having a particle size of 200 microns or less can be blended according to functionality, workability, purpose of use, and the like. These fillers (D) are used in an amount of 1 to 500 parts by weight, preferably 1 to 400 parts by weight, based on 100 parts by weight of the organosiloxane liquid composition, as long as the workability and various physical properties are not impaired.
(D) can be used alone or in combination of two or more. It is preferable to mix and disperse the compound before the addition of the curing accelerator (C). These fillers
When (D) has moisture, OH group, etc.
It is important to use it after a treatment step for removing the group, for example, drying or a curing step specified in the present invention.
An example of the filler (D) is shown below.

As the activator, a powdered product of a boric acid-containing compound, a chromic acid-containing compound or a phosphoric acid-containing compound can be selected. By premixing the activator with the organosiloxane composition, when selecting a metal such as iron as the base material, the adhesiveness between the coating material or the binder with the organosiloxane and the base material is improved. , Anti-corrosion properties can be expected. As the activator compound containing boric acid, chromic acid or phosphoric acid, borosilicate glass, zinc borate, boron phosphate, alkaline earth metal salt of boric acid, alkali metal salt of boric acid, zinc chromate, chromic acid It can be selected from powders of strontium, lead chromate, silicon phosphate, aluminum phosphate, zinc phosphate, alkaline earth metal salts of phosphoric acid and the like, or modified or processed products thereof.

As the filler, stainless steel, silicon,
Powders of metals and alloys such as zinc, aluminum and iron, glass powder, ceramic powder, diamond powder, silicon oxide (silica sand powder, silica powder, silica powder, silica fume, etc.), fused alumina powder, magnesium powder, calcium carbonate, zircon Sand, various clays (purified products such as bentonite, smectite, gailome, Kibushi clay), calcined clay (baked products such as bauxite, montmorillonite, kaolin), gypsum, calcium phosphate, magnesium phosphate,
Particle size of barium sulfate, aluminum fluoride, calcium silicate, magnesium silicate, barium silicate, barium carbonate, barium hydroxide, aluminum silicate, glaze of various composition contents, talc, mica, fly ash, etc. 2
It can be appropriately selected from powders of 00 microns or less.

Examples of the pigment include inorganic colored pigments such as titanium dioxide, red iron oxide, chromium oxide, graphite, carbon black, and ultramarine blue; fired pigments composed of metals, alloys, non-oxides, oxides, etc .; It can be selected from inorganic functional pigments such as system white carbon, alumina, zinc oxide, magnetic iron oxide, boron nitride, silicon carbide, various clay powders, etc., and organic pigments according to the purpose.

As the coloring agent, the above-mentioned inorganic pigments can be used. However, since the organosiloxane of the present invention has an organic group, known organic pigments and dyes commonly used in the art can be used alone. Alternatively, by selecting from a combination, a siloxane polymer composition having a desired hue can be obtained.

Each of the fillers (D) described above has a particle size composition, a shape, and the like in consideration of the purpose of use of the organosiloxane composition and the like.
Use materials that have been preliminarily dried, crushed, classified, mixed, sintered, refined, etc., with due consideration given to properties such as pore volume, specific surface area, water absorption and oil absorption, alone or in combination of two or more. Is preferred. In addition, powders in which these fillers are surface-treated with various coupling materials, surfactants, and the like can be selected according to the workability, the purpose of use, and the like.

The curing accelerator (C) used in the present invention is zinc,
It is preferable from the standpoint of achieving the object of the present invention that one or a combination of two or more of the metal-containing organic compounds composed of elemental cobalt, aluminum or tin is selected. Of course, as mentioned above, it is necessary to consider that the titanium or zirconium organic compound of the crosslinking agent (B) of the present invention also functions as a curing accelerator. Curing accelerator
Examples of the specific metal-containing organic compound as (C) include the following compounds. Zinc naphthenate, cobalt octylate, cobalt naphthenate, aluminum trimethoxide, aluminum tris (acetylacetate), aluminum tri-n-butoxide, diacetyltin diacetate, dibutyltin dilaurate, dibutyltin diacetate, dioctyltin dilaurate, Known and commonly used general hardening accelerators such as diacetyltin dioctoate and tin octylate can be used.

What is important in the present invention is that the curing accelerator (C) to be used is blocked with a keto-enol type tautomer in advance to form a liquid organopolysiloxane (A).
The composition of the present invention comprising a ternary mixed solution of the composition of the present invention and a crosslinking agent (B) and a curing accelerator (C) can reliably ensure the one-pack storage stability over a long period of time. As described in the section on action, keto-enol-type tautomers are compounds that coexist in an equilibrium between the keto- and enol-type compounds. I have. As this compound, ethyl acetoacetate is representative and is suitably used in the present invention. Other keto-enol type tautomeric compounds used in the present invention include malonic diester, acetylacetone such as β-diketones, benzoylacetone, dibenzoylmethane, β
Such as diacetone alcohol which is a ketone having a hydroxyl group at the position, methyl salicylate which is an ester having a hydroxyl group at the β position, and the like in which the alkyl group in the above compound is constituted by a trifluoro group. It can be cited as a valid example.

The amount of the keto-enol type tautomeric compound varies depending on the kind and the amount of the curing accelerator (C) to be used, the curing conditions and the like, but is easily determined by conducting a simple preliminary experiment in advance. can do. Generally, it is effective from the viewpoint of providing a blocking effect that it is blended in an amount of 50% by weight or less in the curing accelerator (C). More important in the present invention, the curing accelerator used (C)
Is capable of slowing down the condensation reaction rate with alcohols such as monohydric or polyhydric alcohols, whereby the curing rate at the time of forming a cured polymer in the present invention is controlled and controlled. Is made possible.

Examples of alcohols which are effectively used in the present invention as a retarder include monohydric alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, and amyl alcohol, and ethylene glycol, glycerin, erythritol and the like. Polyhydric alcohols can be mentioned. The alcohol used as a retarder for the condensation reaction rate varies depending on the type and amount of the curing accelerator (C) used, as well as the curing conditions and the degree of delay, but this can also be easily achieved by conducting preliminary preliminary experiments in advance. Can be determined. Generally, it is effective that the compound is added in advance in the curing accelerator (C) in an amount of 50% by weight or less, since the catalytic effect is not impaired. Of course, when the keto-enol type tautomeric compound of the blocking agent and the alcohol of the retarder are used in combination, the combined amount thereof is 50% by weight or less in the curing accelerator (C). It is preferred that they are blended.

A curing accelerator (C) blocked with the above keto-enol type tautomeric compound, a curing accelerator (C) containing an alcohol as a reaction retarder, and a single curing accelerator (C) The amount of used is liquid organopolysiloxane
Although it varies depending on the content, type and amount ratio of (A) and the cross-linking agent (B) and the content, type and combination of the curing accelerator (C), it is generally 0.1 to 10.0% by weight. Particularly when boron or an organometallic compound of boron and aluminum, titanium or zirconium is blended as the crosslinking agent (B), the amount of the curing accelerator (C) used may be as small as possible. By selecting the above blending conditions, the curing condensation reaction of the present invention proceeds smoothly, and the production of the siloxane polymer composition aimed at by the present invention can be suitably completed.

In the present invention, R in the OR group of the organopolysiloxane (A) may be a hydrogen atom.
Group), to ensure one-pack preservation of the liquid composition, before curing with the crosslinking agent (B),
A curing step for eliminating silanol groups is required. This process is used for silicone resin, thermoplastic resin, filler
It is equally important when (D) is used together.

In the curing step, a liquid organopolysiloxane (A), a crosslinking agent (B), a silicone resin, a thermoplastic resin, and a filler (D) are used alone or in combination or in a composite liquid composition in the absence of water. This is achieved by maintaining the mixture at room temperature or below 100 ° C. for at least 5 minutes, preferably 8 minutes or more, with stirring or standing. In this case, the condition maintained at room temperature for 24 hours is sufficient. Due to this curing, a dealcoholization reaction occurs between the silanol group and the alkoxy group or acyloxy group, and the silanol group disappears and is eliminated. When the filler (D) has a large amount of water, it is effective to remove most of the water contained in advance by a treatment such as heat dehydration before subjecting it to the curing step.

The liquid organopolysiloxane (A) of the present invention
And crosslinking agent (B), curing accelerator (C) and, if necessary, filler (D)
The mixed or composite liquid composition of the present invention starts a curing reaction upon contact with water. At this time, water in the air is sufficient, but the water may be positively brought into contact with the water. The condition for contact with water may be room temperature, or 300 ° C.
Below, preferably under heating at 270 ° C. or under pressure,
It is also possible to carry out under conditions such as degassing. Further, if desired, it is also possible to perform the work under reduced pressure in an atmosphere of an inert gas such as nitrogen gas. The point is that the OR group, which is a functional group in the liquid composition, is hydrolyzed by water to first generate a silanol group, which is an OH group, and then the silanol group remains.
It is sufficient that the conditions for causing a dealcoholation reaction with the OR group to cause a condensation reaction of the siloxane bond to occur.

According to the present invention, the composition of the mixed or complex liquid comprising the liquid organopolysiloxane (A), the crosslinking agent (B), the curing accelerator (C) and, if necessary, the filler (D) is specified as it is. When the siloxane polymer composition is formed by maintaining it in the proper shape, applying or impregnating it on the specified base material, or compounding it with various materials, it is exposed to the humid atmosphere. There is no need to worry about diffusing and contaminating harmful substances such as organic solvents in the working environment, and there is no generation of harmful or toxic gas even when exposed to combustion, and the composition of the present invention can be used as a material that is environmentally friendly. Is well understood.

The organosiloxane composition of the present invention includes:
In order to improve various properties such as dispersibility, impregnating property, defoaming property, fluidity, and coating property of the composition, a fluorine-based interface or the like is used as long as the physical properties and workability of the organosiloxane composition are not impaired. An activator, various organic compounds, resins and the like can be added and blended in advance. The mixing step of the organosiloxane mixed solution of the present invention and the filler described above must be performed under conditions avoiding moisture and moisture since the curing reaction starts when the composition comes into contact with moisture such as moisture. There is. For that purpose, it is necessary to consider that the mixing step is performed in dry air or under reduced pressure. Further, as another method, these fillers are mixed and compounded before adding the curing accelerator to the composition, and then subjected to the curing step described above for curing, and finally, the curing accelerator (C) is added. A method of adding a predetermined amount can also be adopted.

The mixing method is naturally different depending on the content of the organosiloxane liquid composition, the purpose of use, and the like.
Mixers commonly used in the cement, concrete, paint, food, and chemical manufacturing industries,
For example, mortar mixer, stirrer, mixer, roll,
The method may be appropriately selected from a homogenizer or the like, and a method capable of obtaining a homogeneous liquid, paste, or mortar-like mixture may be employed. The material (liquid part or powder part) before mixing is subjected to processing adjustment such as cooling or heating in advance in consideration of weather conditions and environmental conditions during mixing and work, such as winter and summer, before use. It is also effective.

The solvent-free organosiloxane liquid composition of the present invention can be used in a hot atmosphere at a temperature of, for example, 300 ° C. or lower while maintaining the fibrous or film-like shape of the liquid composition as it is or partially started with moisture curing. Exposure to 60 seconds or more can form a fibrous fiber or film of the shaped polymer composition. As a preferred example, after the liquid composition is flowed on a water surface to form a thin film, and then pulled up while the thin film is fluid, the liquid composition can be pulled up with a thread-like fiber. The fibrous polymer composition can be recovered by passing the fibrous fiber through a hot atmosphere at 300 ° C. or lower. In the case of a film, the film-form polymer composition can be easily collected by setting the film surface on the water surface.

Mortar mixed and prepared in a homogeneous liquid state,
Paste or liquid organosiloxane liquid composition of the present invention is a method known per se, for example, spraying method,
Automatic or manual using a common method in the industry such as spraying, brushing, roller coating, ironing, dipping, lifting, nozzle, winding, sinking, pouring, laying, and patching. In accordance with the purpose and use in the shape polymer composition, painting, coating, protection,
The adhesive polymer composition can be formed by bonding, hardening, putting together, applying an anchor or the like. Of course, it is sufficiently effective depending on the purpose, conditions, method and the like to apply the recoating or the undercoating and the overcoating in combination with liquid compositions of different contents and types.

In the present invention, the organosiloxane liquid composition may be used as a binder, depending on the workability, physical properties, functionality, purpose of use, etc. required for various structures, such as honeycomb, block, plate, net, etc. It is possible to provide a composite structure made of a composite cured product obtained by integrating a fibrous or cloth-like reinforcing agent, an aggregate, a molded product, a structurally processed product, and the like. At this time, the aggregate, reinforcing material, and molded body suitably used can be selected from a large powder having a particle size of 200 microns or more or the following materials. These materials are combined in a range that does not impair the purpose of use, workability, various physical properties, etc., for example, 100 to 2000 parts by weight of the organosiloxane composition in a wide range of 100 to 2000 parts by weight. A composite structure of a cured product can be obtained.

Suitable reinforcing materials, aggregates, moldings and the like having a particle size of 200 microns or more used in the present invention include, for example, silica stone, silica sand, wax stone, feldspar, chamotte, mullite, alumina, dolomite, magnesium, zirconia, Various aggregates such as calcium, zircon, carbon, graphite, carbonized or nitrided, various mica, asbestos, and flake-like metal powder can be used. In addition, artificially produced large and small glass beads, hollow glass fine particles, glass flakes,
Metal flakes, perlite, various synthetic lightweight aggregates, and powdered or granular artificial aggregates made of industrial waste such as slugs and fly ash can be used. Furthermore, wood, bamboo, vegetable fiber, flake or fibrous metal, glass fiber, rock wool, natural mineral fiber,
Stable, woven, sliver, net, net, mat, woven fabric, nonwoven fabric and other fibrous reinforcing materials and moldings of inorganic fibers such as carbon fibers and organic fibers can also be used. further,
It is also possible to use a honeycomb-shaped molded body formed by combining the above aggregates and the like as a raw material.

The above aggregates, reinforcing materials, moldings and the like used in the present invention have various particle sizes and shapes.
They can be appropriately selected and used depending on the purpose of use and required physical properties. Further, depending on the construction work, the purpose of use, and the like, a material previously treated with various coupling materials, surfactants, resins, or the like can be used. For these aggregates, reinforcing materials, molded articles, etc., there are various methods for forming a solidified or structured composite cured body obtained by integrating the organosiloxane composition of the present invention into a binder. Materials, molded bodies, etc. and the organosiloxane composition of the present invention are mixed together and then cured together in a fixed mold or container, or aggregates, reinforcing materials, molded bodies, etc. In a frame or container, or in a state of being left, or poured the composition of the present invention therein,
There is a method of impregnating, curing and integrating to obtain a composite cured product. These methods can be appropriately selected and adopted depending on the purpose, application, environmental conditions and the like.

In the present invention, various materials such as natural products,
A composite sheet obtained by coating and impregnating the organopolysiloxane liquid composition of the present invention on a sheet base such as a film, a net, a net, a cloth, and a fabric made of a synthetic product, a mineral product, a glass / ceramic product, etc. Can be formed.
Also, in the present invention, the present invention is applied to various building material surfaces such as metal products such as iron, concrete products such as cement, ceramic / clay products, enamel products, products such as wood / bamboo using natural materials, and synthetic products thereof. By applying the above organosiloxane liquid composition, various effective large and small building materials can be produced.

As will be understood from the above description, the solvent-free organosiloxane liquid composition of the present invention is used in a wide range of application fields, for example, in the social / life related, manufacturing / industrial, construction / civil engineering, service industries, etc. Although not particularly limited, the following objects and construction sites can be cited as examples. Parts composed of paper, pulp, metal such as iron, alloys such as stainless steel, rock, glass, gypsum, ceramics, slug, asphalt, wood, fiber, etc., various materials, structures, various devices, floors, walls, blocks,
Surfaces of chimneys, chimneys, furnaces and furnaces, roads, tunnels, bridges, building materials, buildings, etc .; surfaces of ingots and equipment that require lot marking; and various fabrics made of the above materials as objects to be impregnated , Molded articles, structures, honeycomb bodies, etc. can be cited as useful construction sites and objects.

The organosiloxane liquid composition of the present invention comprises:
It can be suitably used as a material such as repair, base treatment, pre-treatment, filling material, finishing material, plating material, slip resistant material, etc. in each of the above-mentioned locations. In addition, various ceramic materials, fibrous materials, abrasives, abrasion-resistant materials, various inorganic compounds, etc. are blended into the liquid composition of the present invention, and applied as a composite material that meets various needs such as water resistance, heat resistance, fire resistance, and acid resistance. It is possible to solidify materials, processing materials, adhesives, binders,
As a joint material, it can be applied to chemical factories, food factories, plating factories, hot springs, cafeterias, kitchens of hotels and the like, flue, drains, building materials and the like.

Furthermore, the organosiloxane liquid composition of the present invention can be used as a casting solidifying material for various molds, as a casting repair material for damaged parts such as refractory furnace materials, chimneys, boilers, structures, and the like. It can also be suitably used as an injection solidifying material for treating and disposing of industrial waste molded into a junk (irregular shape) or a specific shape, for example, solid waste of radioactive waste discarded from a nuclear power plant. . Furthermore, the organosiloxane liquid composition of the present invention can be used for anchoring materials such as tanks, towers, structures such as buildings and devices, and also in places where embedding and plastic patching materials in the above-described fields are required. It can also be suitably used as a fixed cement material.

[0101]

According to the present invention, flexibility and excellent adhesion followability, which are effectively applied to composite structures, composite sheets, building materials, etc., such as films or fibers, paints, varnishes or binders, etc. Provided is an organosiloxane liquid composition containing no organic solvent that is environmentally friendly and forms a siloxane polymer composition having excellent weather resistance by moisture curing.

[0102]

EXAMPLES Hereinafter, the solvent-free organosiloxane liquid composition of the present invention and its use will be described with reference to specific examples. In this example, the raw material liquid organopolysiloxane (A) was “OS-A”, the two-component composition of OS-A and the crosslinking agent (B) was “OS-AB”, and the curing accelerator was compounded. The solvent-free organosiloxane liquid composition of the present invention thus prepared is abbreviated as “OS liquid composition”. The percentages are given by weight.

Example 1 (I) Raw materials of the liquid composition of the present invention (OS liquid composition) and preparation and contents of the liquid composition. 1) Liquid organopolysiloxane (A) The liquid siloxane raw material used for (OS-A) and its silicon concentration (SiO ₂ %) are shown in Table 1. a): Manufacturer TD; Toray Dow Corning Silicone
SS: Shin-Etsu Chemical TM: Tama Chemical

2) Table 2 shows the raw materials of the cross-linking agent (B) and the metal element concentration (MO _{y / 2} %) thereof. b): TM: Tama Chemical Industry SS: Shin-Etsu Chemical Industry
KK: Koriyama Kasei NS: Nippon Soda CM: Commercial reagent DC: Daihachi Chemical TD: Toray Dow Corning Silicone

3) The raw materials of the solid silicone resin and the thermoplastic resin, and the silicon concentration (SiO ₂ %) are also shown in Table 3. These resins were dissolved in the crosslinking agent (B) shown in Table 4 and then blended with OS-A to form an OS.
-Prepared AB. In this example, a resin composition of a solid silicone resin or a thermoplastic resin was dissolved in phenyltrimethoxysilane (tentative name: B-FTM) as a crosslinking agent (B) at a concentration of 50% by weight to obtain a liquid composition (tentative name: BSR-MF1, BSR-MF2, BHR-
AC, BHR-PE) and blended with OS-AB. c): Manufacturer TD; Dow Corning Toray Silicone
MR; Mitsubishi Rayon

4) Composition of a two-component liquid mixture prepared from OS-A shown in Table 1, a crosslinking agent (B) shown in Table 2, and a resin material dissolved in phenyltrimethoxysilane at a concentration of 30% by weight Table 4 shows the content of the product (OS-AB), its MO _{y / 2} concentration (%), and the conditions of each curing step. On the other hand, the composition of Comparative Example (AB-11, 12) is also shown. In this example, the MO _{y / 2} concentration (%) of the overall curing accelerator [including blocking agent and reaction retarder] described below was all
Since the content is 40% by weight or less and the content thereof is 10% by weight or less, the MOy _{/ 2} concentration (%)
It was shown for convenience at the S-AB composition stage and used as a reference.

5) The curing accelerator (C) used in this example The metal-containing organic compound as a raw material, the blocking agent and the reaction retarder were each selected from commercially available reagents and are shown in Table 5. Table 5 also shows the metal element concentration in the metal-containing organic compound in terms of _{MOy / 2} concentration (% by weight).

6) Table 6 shows the composition of the total curing accelerator (C) obtained by combining the metal-containing organic compound, the blocking agent and the reaction retarder. Note that the metal element concentration
Table 6 also shows the _{y / 2} concentration.

Example 2 (II) Organosiloxane Liquid Composition and Siloxane Polymer Composition Table 7 shows 17 kinds of organosiloxane liquid compositions prepared in this example. The following six types were selected as comparative examples. A liquid composition containing a silicone resin having an OH group (OS-
When the AB sample number: AB-3) was not subjected to the curing step (sample number: H-1), a two-part mixture composition (OS-AB sample number) having a metal element concentration of 40% by weight or more was used. AB
-10) (Sample number: H-2)
In the case of a two-liquid mixture composition (OS-AB sample number: AB-11) of 25% by weight or less (sample number: H-3), a two-liquid mixture composition (OS-AB sample number: AB-3) ), No cross-linking agent was added (Sample No .: H-4), or in the case of general-purpose paints (commercially available) acrylic paints using organic compounds as raw materials (Sample No .: H-5), commercially available In the case of a bake-hardening water-glass type paint of the product (sample number: H-6) was selected. The one-pack preservability of the organosiloxane liquid composition was confirmed by the test method shown below, and then the cured siloxane was performed under the curing conditions shown in Table 7. The test was conducted for the properties, and each material was evaluated. The results are shown in Table 7.

Test method: One-part storage Place the organosiloxane liquid composition of the sample in a sealed container.
And leave it at room temperature for one month.
One-pack preservation “Yes” when not gelled, gelling or skinning
The case where a phenomenon or the like occurred was defined as "one-pack storage stability".Heat-resistant In accordance with the general paint test method described in JIS K 5400, JIS G
The sample liquid is placed on a 0.4 mm thick steel base material specified in 3141.
The composition is applied at a film thickness of about 30 microns by a spraying method,
Samples were applied to the steel sheet by film forming and curing under the curing conditions shown in Table 7.
The prepared specimen was prepared. Keep the specimen at 250 ° C
After exposure for 24 hours in a heated electric furnace, the surface condition of the specimen was observed.
No abnormal condition such as crack, peeling, discoloration, etc. was confirmed.
If yes, heat resistance "Yes"; if there is an abnormal state, heat resistance
It was evaluated as "none".Adherence tracking 0.4mm thick steel base material prepared in heat resistance test method
Using the specimen on which the sample was applied and the film was cured, JIS
K 5400 Using a bending tester described in 6.16, adjust the mandrel 4 mmφ
Bend through the surface of the test piece.
No abnormalities such as cracks or peeling
Certain conditions were rated "none".

[0111]

As a result, the organosiloxane liquid composition of the present invention was prepared without solvent by controlling the total metal component concentration within the range of 25% by weight or more and less than 40% by weight in terms of MOy _{/ 2} oxide. It is well understood that when a liquid composition having preservability is prepared, the resulting siloxane polymer composition is given both physical properties such as heat resistance and adhesion followability. On the contrary, the liquid composition which was not subjected to the curing step did not have one-liquid storage property and gelled in one week. In addition, in a liquid composition having a metal element concentration of 40% by weight or more based on MO _{y / 2} oxide,
When the film was bent at 3 mmφ, the coating film was cracked and did not have adhesion followability. At a metal element concentration of 25% by weight or less based on _{MOy / 2} oxide, there was no heat resistance. Further, when the liquid composition did not contain a cross-linking agent, it did not cure at all even when left at room temperature for a long time (one week), and did not form a film. Organic resin-based coatings had no heat resistance. The water-glass type paint had no adhesion followability at all.

Example 3 (III) Application as Shaped Polymer Composition A liquid composition selected from the organosiloxane liquid compositions (OS liquid compositions) shown in Table 7 was maintained alone in the form of a film or fiber. An example in which a siloxane cured product is formed and applied to a siloxane polymer composition will be described. In the case of a thin film form: A liquid composition selected from the OS liquid compositions shown in Table 7 is flowed on a plasticizer-containing soft vinyl chloride plate so as to form a thin film having a thickness of about 25 μm, and left at room temperature for 72 hours. A thin film was formed to obtain a thin film specimen composed of a cured siloxane. In the case of a fiber form: a liquid composition selected from the OS liquid compositions shown in Table 7 is allowed to flow in a thin film state of about 10 μm thick on the surface of the water in which it is immersed, and left at room temperature for 1 hour to form a liquid composition. Partially promotes polymerization in a thin film state to make it a highly viscous state, pulls it up to form a thread-like fiber with a thickness of about 0.1 mmφ, and passes this thread-like fiber through a heating section maintained at about 200 ° C. Was formed to obtain a fiber specimen composed of a cured siloxane. The physical properties of the siloxane polymer composition were evaluated by the heat resistance test and the flexibility test shown below for the thin film sample and the fiber sample, and the results are shown in Table 8.

Test method: (1) After exposing the heat-resistant specimen to an electric furnace maintained at 250 ° C. for 24 hours, observe the state of the exposed specimen, and shrink, break, melt, discolor, etc. When no abnormal state was confirmed, the heat resistance was evaluated as “Yes”, and when there was an abnormal state, the heat resistance was evaluated as “No”. (2) Flexibility When the specimen is wound around a 3 mmφ mandrel, the specimen does not break or break, and the state where no abnormality is observed when it is spread again in the form of a film or fiber is flexible. The sex was evaluated as “Yes”, and the abnormal state was evaluated as “No”.

[0115] As described above, it is well understood that when the organosiloxane liquid composition of the present invention is formed into a film or a fiber and cured, it is possible to produce a film or a fiber having heat resistance and flexibility. Is done.

Example 4 (IV) Application as Adhesive Polymer Composition A liquid composition selected from the organosiloxane liquid compositions (OS liquid compositions) shown in Table 7 was used alone or in combination with a filler or the like to paint. Alternatively, application examples will be described as an adhesive polymer composition when a siloxane cured product is formed for each application as a binder binder.

IV-1 In the case of a transparent coating film: A clear organosiloxane liquid composition selected from the OS liquid compositions in Table 7 was applied to a steel sheet by the method described in the test method in section (II) Heat resistance. Under the curing conditions shown in Table 9, a siloxane cured product was formed from a transparent coating film to obtain a coated plate sample. For this transparent film coated plate specimen, a siloxane polymer as an adhesive polymer composition according to the following surface hardness, adhesion, heat resistance, non-flammability, water resistance, acid resistance, acid resistance, alkali resistance, flexibility, weather resistance test method shown below The physical properties of the composition were evaluated, and the results are shown in Table 9.

Test method: (1) The surface hardness of the coated plate specimen was measured by the pencil scratching test method described in JIS K 5400, 6.14, and the result was expressed as a pencil hardness symbol in Table 9.
Are also shown. (2) In accordance with the grid test method described in Section 6.15 of JIS K 5400, the adhesive coated plate specimen is cut into six grid-shaped notches at 1.0 mm intervals on the coated surface of the coated plate with a cutter knife. , Adhere the cellophane tape on the cut grid and peel off. Observe the peeling state of the coating surface at this time.
25/25, the number of grids where peeling or damage occurred was 25/2
It is shown by subtracting from the numerator of 5. (3) Heat resistance In the same manner as described in the heat resistance test method in section (II), the coating film specimen was exposed to an electric furnace at 250 ° C for 24 hours, taken out of the electric furnace, and allowed to cool to room temperature. By observing the film surface of the test specimen, the heat resistance was evaluated as “Yes” when the film was in a robust state without swelling, cracking or peeling, and “No” when abnormal. (4) Exposing the non-combustible coating film specimen in an electric furnace at 450 ° C through which oxygen sufficiently passes, and the non-combustible When there was no such change, it was judged as non-flammable “Yes”. (5) Spread the sample on which the sample was applied using Toyo Filter Paper No. 6 as the material to be coated on a natural filtration funnel, pour water into the funnel, determine the amount of water passing through the sample at this time, and determine the amount of water passing No water permeability was defined as "presence" when there was no water permeability, and water permeability resistance was determined as "absent" when there was even a small amount of passing water. (6) Specimens coated with acid-resistant sheet glass as the material to be coated were subjected to JIS K
In accordance with the test method described in 7.5 of 5400, immerse in a 5% by weight sulfuric acid solution at 20 ° C for 30 days, and swell, wrinkle, peel, hole, soften, and dissolve on the surface of the test plate. Acid resistance "Yes", when there was an abnormality, acid resistance "No". (7) Alkali resistance ( Na resistance ) Caustic soda (NaOH) adjusted to pH 10 on the coated surface of the specimen
Place about 5 cc of the solution, cover it with a curved watch glass to prevent volatilization, leave it at room temperature for 24 hours, wash the coated surface, observe changes on the coated surface, and withstand when there is no change When there was a change such as alkalinity "presence" or melting, the alkali resistance "no" was determined. (8) Flexibility The test specimen was bent using a bending tester described in 6.16 of JIS K 5400 through a round rod of 3 mm in diameter of the mandrel. ”, And the case where there was an abnormality was designated as“ flexible ”. (9) Weather resistance to (weatherometer) QUV formula weather meter (not wavelength range 280 specimens 32
0 nm) at 55 ± 15 ° C with 2500 cycles of irradiation and condensation
Exposure for a time, measure the gloss of the coating surface of the test specimen after exposure,
The gloss reduction rate (%) in comparison with the gloss of the coating film surface of the specimen before exposure was calculated and shown. When the gloss reduction rate was within 10%, the weather resistance was "presence", and when the reduction rate was 10% or more, the weather resistance was "no".

[0119] As a result, the solvent-free organosiloxane liquid composition of the present invention forms a transparent cured film by moisture curing when applied to a steel sheet, and the transparent film has a certain surface hardness and is heat resistant. Adhesive polymer that is excellent in acid resistance, alkali resistance, flexibility, weather resistance, etc.
It is well understood that it is useful as a protective film for a substrate.

IV-2 In the case of a filler-containing coating film or a binder Table 10 shows the fillers used in this example. In addition, these fillers were previously subjected to a drying treatment at about 200 ° C., and dehydration treatment before use.

A liquid composition in which powder fillers (activators, fillers, pigments, colorants) of 200 microns or less shown in Table 10 were selected from OS-AB compositions (combination combinations are shown in Table 11).
And put into an SG mill using alumina balls for about 1 hour to disperse the filler. The liquid composition obtained by dispersing and mixing the filler was subjected to a curing process under the conditions shown in Table 11 to stabilize, and then a curing accelerator was mixed and compounded (combination combinations are shown in Table 11), and the paint or paint was obtained. A material sample of a fluid or plastic binder was used. Sample number PE-
1, PE-2 and PE-3 are sprayed by air gun, sample number PE-4 is rolled, sample numbers PE-5, PE-6, P
E-7 was installed on a blasted steel plate with an iron. Table 11 shows a sample of the OS liquid composition in which the filler was dispersed and mixed.
The composition was cured under the curing conditions shown in (1) and formed into a coating film or a binder to obtain a specimen. IV-
A siloxane polymer composition according to the surface hardness, adhesion, heat resistance, nonflammability, water permeability, acid resistance, alkali resistance, deflection, weather resistance test method described in item 1 and the adhesion test method (10) described below. Was evaluated and the results are shown in Table 11. (10) Adhesion test method Pour the mixed solution composition prepared in a mold prepared so as to have a size of 40 × 40 × 15 cm on a steel plate substrate, cure at 25 ° C for 7 days, and cure the siloxane cured product on the steel plate. A specimen to which is adhered is prepared. Next, in accordance with the adhesion test method of the Ministry of Construction Building Research Institute, the tester attachment was adhered with an epoxy resin-based adhesive, pulled upward by the hydraulic pressure of the tester, and the adhesive between the adherend and the cured siloxane The adhesive force (kg / cm ² ) was measured from the load (P) when the adhesive surface was peeled off, and the binding property was evaluated.

[0122]

As a result, the solvent-free organosiloxane liquid composition of the present invention has a one-pack preservability, and a cured siloxane polymer is formed into a useful coating film, coating or binder by moisture curing. Adhesive polymer has surface hardness,
It is well understood that it is heat-resistant, non-flammable, and excellent in acid resistance, alkali resistance, flexibility, weather resistance, adhesiveness and the like.

Example 5 (V) Application as Composite Structure The materials used in this example, such as reinforcing materials, aggregates, and molded products, are shown in Table 12.
Shown in These reinforcing materials, aggregates, molded bodies, etc. were used after having been subjected to a drying treatment at about 200 ° C. and sufficiently dehydrated.

A material (reinforcing material, aggregate, molded product) having a size of 200 microns or more shown in Table 12 was mixed with a powder filler (activator,
A composite composition was obtained by integrating with a mixed OS liquid composition (PE series shown in Table 11) in which a filler, a pigment, and a coloring agent) were mixed and mixed. The composite composition was subjected to the curing conditions shown in Table 13 to form a cured siloxane in the composite composition, thereby obtaining a specimen of a composite structure. With respect to this test specimen, the physical properties of the structure composited with the siloxane polymer were evaluated by the following heat resistance, nonflammability, weather resistance, and compression strength test methods. The results are shown in Table 13. Test method: (1) Heat resistance , (2) Nonflammability and (3) Weather resistance Same as in the test method for transparent coating film (4) Compression strength Conforms to the method described in JIS A 1108 Then, a composite composition integrated with the liquid composition of the present invention was prepared in a rectangular mold (2 × 2 × 8 cm), left at room temperature for 7 days, and then demolded to form a composite structure. Specimen. Using a compression tester based on the method described in JIS A 1132, this square specimen was subjected to compression strength (kg /
cm ² ).

[0126]

As a result, a material capable of forming a composite structure such as various reinforcing materials, aggregates, molded articles, etc. using the solventless organosiloxane liquid composition of the present invention and a mixture of fillers. When combined with moisture-curing, a composite structure in which a siloxane polymer cured body is formed as a binder is a floor material with excellent heat resistance, non-combustibility, weather resistance, and compressive strength.
It is well understood that it is effectively used for building material structures, waste disposal, and the like.

[0128]

[0129]

[0130]

[0131]

[0132]

Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 83/06 C08L 83/06 C09D 183/05 C09D 183/05 183/06 183/06 ZAB ZAB // C08J 5/18 C08J 5/18 ( 56) References JP-A-3-26735 (JP, A) JP-A-3-287664 (JP, A) JP-A-2-286748 (JP, A) JP-A-63-258964 (JP, A) JP JP-A-57-165453 (JP, A) JP-A-50-154747 (JP, A) JP-A-48-10158 (JP, A) JP-A-64-1769 (JP, A) JP-A-63-137958 (JP, A) , A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C08L 83/05 C04B 24/42 C04B 41/64 C08J 3/12 CFH C08J 5/04 CFH C08L 83/06 C09D 183/05 C09D 183/06 C08J 5/18 CFH C08G 77/00 CA (STN) REGISTRY (STN)

Claims (14)

(57) [Claims] 1. A mixed liquid composition comprising a liquid organopolysiloxane (A), a crosslinking agent (B) and a curing accelerator (C), wherein the liquid organopolysiloxane (A) has the following general formula: (1) (Wherein, R ¹ is a hydrogen atom or a C ₁ to C ₅ alkyl group; R ² to R ⁶ are the same or different groups each selected from a hydrogen atom, an OR ¹ group or a monovalent hydrocarbon group, n
Is a number less than 15) or 2
A low-molecular-weight polysiloxane composed of a combination of at least two or more kinds, and the silicon concentration in the liquid organopolysiloxane is 50% by weight or more based on SiO ₂ oxide, and the crosslinking agent (B) is as follows: formula _{^{(2) R 7 p B ·}} (oR 1) 3-p ·········· (2) ( wherein: alkyl of R ¹ is or a C ₁ are hydrogen C _5; R ⁷ is a hydrogen atom, an OR ¹ group or a group selected from monovalent organic groups; p is an organic compound of boron represented by 2 or less, or the above (2) and the following formula (3) or (4) R ⁷ _p Al ・ (OR ¹ ) _3-p・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ (3) R ⁷ _m Q ・ (OR ¹ ) _4-m・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ (4) (Wherein Q is a silicon, titanium or zirconium element;
R ¹ is a hydrogen atom or a C ₁ to C ₅ alkyl group; R ⁷ is a hydrogen atom, an OR ¹ group or a group selected from monovalent organic groups;
An integer of 2 or less; m is an integer of 3 or less), wherein the curing accelerator (C) is zinc, aluminum, titanium, zirconium or tin. A compound comprising one or more combinations selected from the group of metal-containing organic compounds containing an element, and from the zinc, tin, boron, aluminum, silicon, titanium and zirconium of the ternary mixture composition. The total concentration of the element (M element) selected from the group consisting of: is not less than 25% by weight and less than 40% by weight, expressed in terms of MO _{y / 2} oxide (y is the valence of M element). Organosiloxane liquid composition. 2. The organosiloxane liquid composition according to claim 1, wherein the crosslinking agent (B) is an organotrialkoxysilane composed of a monovalent organic group having at least an amino group. 3. The organosiloxane liquid composition according to claim 1, wherein the crosslinking agent (B) is blended in an amount of not more than 70% by weight. 4. The liquid organopolysiloxane (A)
Or alone or a mixture composition of the crosslinking agent (B), OR group functional side chains in the amount of solid silicon resin is 70 wt% or less with (R is a hydrogen atom, an alkyl group of C ₁ to C ₅₎ The organosiloxane liquid composition according to any one of claims 1 to 3, wherein the composition is dissolved. 5. The liquid organopolysiloxane (A)
Alternatively, one or more combination fillers (D) selected from the group of activators, fillers, pigments and colorants are added to 1 to 100 parts by weight of the cross-linking agent (B) alone or as a mixture, and The organosiloxane liquid composition according to any one of claims 1 to 4, which is previously compounded in an amount of 500 parts by weight. 6. The organosiloxane according to claim 1, wherein the activator is one or a combination of two or more powders of a boric acid-containing compound, a chromic acid-containing compound, and a phosphoric acid-containing compound. Liquid composition. 7. A β-keto acid ester having an alkyl group or a trifluoro group in the curing accelerator (C),
A keto comprising one or a combination of two or more selected from the group consisting of diketone compounds and malonic esters;
The organosiloxane liquid composition according to any one of claims 1 to 6, wherein the enol-type tautomeric compound is blended in an amount of 50% by weight or less. 8. The hardening accelerator (C) contains 50% by weight or less of an alcohol composed of one or a combination of two or more selected from monohydric or polyhydric alcohols. The organosiloxane liquid composition according to any one of claims 1 to 7, wherein 9. A curing accelerator (C) comprising the metal-containing organic compound containing the keto-enol type tautomeric compound or the alcohol or a single metal-containing organic compound.
9. The organosiloxane liquid composition according to claim 7, which is blended in an amount of 10% by weight or less. 10. The liquid organopolysiloxane as described above.
(A), a cross-linking agent (B), a silicone resin or a thermoplastic resin and a filler (D) alone or in combination or a composite liquid composition in a curing step for 10 minutes or more at 100 ° C. or less in the absence of water in advance. The organosiloxane liquid composition according to any one of claims 1 to 10, further comprising a curing accelerator (C) after the removal of water content or silanol groups. 11. The method according to claim 1, wherein
4. A shaped polymer composition, characterized in that the organosiloxane liquid composition described in the above item is formed from a cured siloxane having a polysiloxane bond as a main chain by contact with water or heat of 300 ° C. or lower. 12. The method according to claim 1, wherein
An adhesive polymer composition, characterized in that the organosiloxane liquid composition according to the above item is formed from a coating film or a binder having a polysiloxane bond as a main chain by contact with water or heat of 300 ° C. or less. . 13. The method according to claim 1, wherein
1 to 2000 parts by weight of one or more combination materials selected from the group consisting of a reinforcing material, an aggregate and a molded article are mixed in advance with 100 parts by weight of the organosiloxane liquid composition described in the above item. A composite structure, wherein the composite obtained is integrated with a cured siloxane having a polysiloxane bond as a main chain by contact with water or heat of 300 ° C. or lower. 14. The method according to claim 1, wherein
The organosiloxane liquid composition described in the above item is coated and impregnated on a cloth-like or net-like sheet base, and formed into a sheet with a cured siloxane having a polysiloxane bond as a main chain formed by contact with water or heat of 300 ° C or less. A composite sheet characterized by being integrated.