JPH05230375A - Heating type solvent-free, catalyst-free organosiloxane composition and its use - Google Patents

Abstract

PURPOSE:To obtain an one pack-type, solvent-free and catalyst-free heating type organosiloxane composition consisting of a precursor composed of an organosiloxane and a specific crosslinking agent. CONSTITUTION:The objective composition is obtained by blending (A) 100 pts.wt. precursor consisting of a compound group [blending 2 10wt.% low molecular weight polysiloxane) composed of a combination of two or more kinds of an organic silicon group of the formula R<1>Si (R<2> is monovalent hydrocarbon) and a liquid organopolysiloxane of formula I (R<3> to R<7> are H, OR<2>, etc.; (n) is <=15) with (B) <=100 pts.wt. crosslinking agent consisting of one or more kinds of organic compounds of a liquid silicon, titanium or zirconium having a functional group consisting of one or more from alkoxy, acyloxy and oxime and expressed by formula II [M is silicon, titanium or zirccpium; R<8> is H, OR<1>, etc.; (m) is <=3] (containing >=40% metallic element component based on MO2 oxide).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heating type solvent-free catalyst-free organosiloxane composition containing liquid organosiloxane as a main component, which can be stored in one liquid, and its use. , Non-combustible / flame-retardant and heat-resistant, which is applied to transparent films, coating materials, binders, structures, etc.
TECHNICAL FIELD The present invention relates to a one-pack type solventless catalystless organosiloxane composition capable of producing a cured polymer having a polysiloxane bond as a main chain, which is imparted with water permeation resistance and has flexibility, and its use.

[0002]

2. Description of the Related Art Organosiloxane is an organosilicon compound having a Si--O bond and is a generic name given to organosilane compounds and polymers of this organosilane compound. The organosiloxane compound is composed of an organosilicon group (R.Si-) and a functional side chain (-OR) [hereinafter, the functional side chain may be abbreviated as "functional group"]. , R ₃ SiO (R ₂ Si
Rational formulas such as (O) _n SiR ₃ and (R ₂ SiO) _n are generally given.
As described above, the organosiloxane has an organic group (alkyl group,
A phenyl group, an aryl group, an alkoxy group, an acyloxy group, etc.). When the ratio [R / Si] of the organic group (R) and silicon (Si) directly bonded to silicon in this compound without intervening oxygen is 1/1,
It is called the T unit, and the case of 2/1 is called the D unit.

[0003] Organosiloxanes have this T unit or
It is a compound consisting of a single product, a mixture, and a polymer in the range of D unit. Of these, compounds consisting only of D units are called silicone oils, compounds consisting only of T units are called silsesquioxanes, and a special example of silsesquioxanes is a ladder polymer with a regular structure. is there. Also, as a copolymer of TD units, the ratio of R / Si is 1.0
The high molecular weight polymer compounds listed in 1 to 1.7 are called silicone resins. The physical properties of organosiloxane mainly consist of the silanol bond (-Si-OH), which is an inorganic compound, because it is a compound that has a siloxane bond as the main bond, but the side chain has a -CC- bond or a CO bond. Since it has the following organic group, it also has the property of an organic compound.

On the other hand, when the related interatomic bond energies were examined, siloxane, which is the main bond of organosiloxane, was investigated.
The (Si-O) bond is 108 kcal / mol, while the CC bond, which is a structural unit bond of an organic compound, is 84.9 kcal / mol, and the CO bond is 80.9 kcal / mol. That is, the interatomic bond energy of the siloxane bond is about 25% larger than the interatomic bond energy of the constitutional unit bond of the organic compound. Therefore, the organosiloxane having a siloxane bond as a main bond has a higher thermal energy than the organic compound. It is easily understood that it is much more stable to energy such as light.

Further, since organic resins have a sensitivity wavelength range in the wavelength range of 300 to 350 nm, radical decomposition tends to occur in the ultraviolet range wavelength. On the other hand, methyl-based silicone resins have almost no wavelength absorption in the ultraviolet region [Takarada: Rust prevention control, p 244-25.
2 (1991)] is known, and it has been proved that it is inactive to ultraviolet rays and exhibits excellent super weatherability. It is said that about 50% of siloxane bonds are ionic bonds, and since the bond distance is long and the electron density is low, the bond rotation is easy and the bond angle changes with a relatively small energy. Therefore, the chain due to the siloxane bond is
It is a material that is more flexible and flexible than the chain formed by CC bonds, and is also highly resistant to impact by physical energy such as heat and force, and is highly flexible.

[0006] As described above, the organosiloxane having a Si-O bond shows properties different from organic compounds composed of a -CC- bond or a CO bond in many points. In particular, it can be clearly distinguished from organic compounds that are vulnerable to oxidation and combustion. Crosslinking polymerization of organosiloxane-
Organosilicon polymer compounds having a Si-O-Si- bond as the main chain are called organopolysiloxas under the name of silicone or silicone resin.
It is widely used for many purposes because of its excellent properties such as weather resistance, cold resistance, and electrical insulation. In addition, organopolysiloxanes having two different functional groups in the same molecule are generally collectively referred to by the name of silane coupling agents, and are widely used as surface treatment agents, modification treatment agents, additives, etc. for inorganic and organic materials. It is commonly used.

The mechanism by which the organosiloxane polymerizes to form a cured product is believed to be due to the hydrolysis reaction of the reactive siloxane and water and the subsequent condensation reaction or addition reaction. Polymerization of the organosiloxane related to the present invention is carried out by crosslinking the functional group of the reactive organosiloxane to a silanol group by contact with water or moisture in the first step, and crosslinking with the silanol group-containing organosiloxane in the second step. It is said to be due to a so-called moisture curing mechanism by condensation with an agent by a reaction such as dealcoholization, deoxime and deacetic acid. Each of the above reactions is rate-controlled by the heating temperature, and the reaction rate is accelerated. Therefore, it becomes possible to complete the formation of the polymer cured body in a short time.

In general, materials such as varnish, paint, and adhesive are mainly composed of organic resins made of organic compounds and organic solvent. However, in the changing living environment and social environment in recent years, nonflammable / flame retardant and pollution-free fields are increasingly widespread. Under these circumstances, organic compounds having a -CC- bond as the main chain are vulnerable to heat and fire, and the organic solvent in which organic resins are dissolved is a hazardous substance to the human body and has harmful effects such as pollution. Has been regarded as a problem. As a material for solving these problems, siloxane compounds composed of -Si-O- bonds, which have flexibility and are strong against physical energy such as heat and light and chemical energy such as oxidation, are in the spotlight. A lot of applied research on compounds is being conducted.

The present inventors have previously conducted a study entitled "Solventless Room Temperature Curable Organosiloxane Compositions and Their Uses" and found that one-component storability is maintained regardless of the presence of solventless curing catalysts. By curing the specified organosiloxane composition at room temperature in the presence of water, we found the conditions for forming a polymer cured product having a polysiloxane bond as the main chain, and found that this polymer cured product was non-combustible / flame-retardant. With heat resistance,
It has been found that it is useful for applications such as transparent films, coating materials, binders and structures because it has water permeability resistance and flexibility (Japanese Patent Application No. 3-145960).
However, the research results of this room temperature curing type organosiloxane composition also have problems when it is applied in the following industrial cases, and these problems are solved to meet the needs in the production line. Not not.

That is, when the organosiloxane composition is to be applied to an industrial production line, for example, assuming that a coating material is continuously applied to a long thin steel plate or the like, the prepared organosiloxane composition is In general, the paint is poured into a paint storage tank in an open state of the production line in a sufficient amount, and then continuously supplied to the coated surface of the steel sheet to be applied. Therefore, the paint stored in the paint storage tank is always exposed to the atmosphere containing moisture. At this time, if the paint is a moisture-curing type, this paint causes a temporary hardening reaction to proceed in the paint storage tank, deteriorating the quality of the paint, and the intended production cannot be completed. Moreover, the paint used at this time is
It is required to form a coating in a short time on the order of "minutes".

Some typical examples of the research results of applying other organosiloxanes and problems in the prior art will be listed below mainly in the field of paints and coating materials. A popular example of applying organosiloxane to paint is zinc rich paint developed during World War II. This paint is a paint in which hydrolyzate such as tetraethoxysilane diluted with approximately the same amount of isopropyl alcohol is mixed with approximately twice the amount of zinc powder. This paint is dried at room temperature to form a coating film, iron, etc. It is widely used as an anticorrosive paint for base materials. An example of the improvement of this technique is disclosed in Japanese Examined Patent Publication No. 63-61987. Similarly, Japanese Patent Application Laid-Open No. 56-121824 discloses a heat-resistant paint technique in which enameled frit or the like is mixed with tetraethoxysilane diluted with isopropyl alcohol and dried at room temperature.

It is common practice to dilute a polymer of organosiloxane or a modified organosiloxane thereof or a copolymer with various organic compounds together with itself or other various organic resins into an organic solvent to prepare a coating material. It is a common practice in the industry and most technologies have been developed as an application of this common practice. For example, a technique of preparing a modified tetraalkoxysilane in the presence of an equal amount or more of a solvent as a film-forming agent, applying it, and then naturally drying or hot-air drying to obtain a heat-resistant and rust-preventive coating is disclosed in JP-B-63-28942. Japanese Patent Laid-Open Publication No. Hei 10 (1999) -1999 discloses a coating in which a ladder type silicon oligomer is diluted with an organic solvent.
It is disclosed in Japanese Patent Publication No. 1-115966.

Japanese Examined Patent Publication No. 63-33512 discloses that the average molecular weight is
2000 to 30000 and 5 of high molecular weight organosiloxane
Or 20% by weight of the content of copolymerization beforehand, add a curing catalyst such as amine compounds and metal-containing compounds, and leave at room temperature or 60
There is disclosed a coating composition which is baked at 150 ° C. to form a coating film. Japanese Patent Publication No. 64-10551 discloses a technique of removing frozen water from the surface of a cured product by adding a titanate catalyst diluted with a solvent such as hexane to a carboxy-functional siloxane and drying at room temperature.

In Japanese Patent Laid-Open No. 1-152167, the polymerization degree n is
A technology that uses phenyl (diethyl ketoxime) silane as a cross-linking agent based on a diorganopolysiloxane compound having a considerably high value of 5 to 5000, and uses dibutyltin dilaurate as a curing agent to perform room temperature curing, and uses this cured product as an electrolytic corrosion inhibitor. It is disclosed. In this case, the liquid viscosity of the diorganopolysiloxane compound used is considerably high at 6000 centipoise, and even though it is suitable for use as an electrolytic corrosion inhibitor, in the liquid state of the technology, it is generally used as a paint without a diluent such as a solvent. It is not suitable for application work. Moreover, the diorganopolysiloxane compound used has a silanol group, and when it coexists with the curing agent in this state, the condensation reaction starts immediately and the viscosity increases, so the mixture is a one-pack type. No measures have been taken to ensure shelf life.

Japanese Unexamined Patent Publication (Kokai) No. 1-123861 discloses that an organosiloxane having an aminosilane group containing 40 to 75% by weight of aluminum trihydrate uses a metal-containing oxide as a condensation catalyst, and the humidity in the atmosphere is A technique of a coating agent having excellent electric characteristics, which uses a moisture curing method of curing using (moisture), is disclosed.

Further, a method is adopted in which a paint, a coating material or the like is applied at room temperature without adding curing conditions such as heating, and a curing agent or the like is added immediately before the application in order to promote polymerization on the spot. There is. In this method, the construction material must be a two-liquid type, and the material preparation, storage, work management, construction procedure, etc. immediately before construction must be complicated. For these reasons, there is a strong demand for materials that can be used as a one-pack type. From such a demand, in the case of a type in which a polymer of organosiloxane is formed by moisture curing with a one-pack type paint or the like, the material is stored in a container capable of blocking air, for example, a tube or a cartridge, in order to secure shelf life thereof. In addition, the method of opening to the air at the time of use is adopted.

There are a great many examples of the technology in which an organosiloxane and an organic compound are simply compounded and applied to a coating material and the like, and most of them are formed by heating. As a typical example, 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 coating film is disclosed in JP-B-55-41274. Japanese Patent Laid-Open Publication No. 64-16868 and Japanese Laid-Open Patent Publication No. 1-115966 disclose many similar techniques.

There have been many studies to use organosiloxane as a coating agent for heat-resistant paints, and as a typical example thereof, heat-resistant inorganic materials (aluminum phosphate, zinc molybdate, calcium carbonate, zinc silicate powder, etc.) 50 to 80
Add a small amount of aluminum chelate compound to wt%,
Japanese Patent Publication No. 63-35183 can be cited as a technique for coating a base material with a coating containing 20 to 50% by weight of a modified silicone resin and baking it at 180 ° C. for heat-resistant coating. Further, as a technique similar to this, there is JP-A-63-23975.

A technique for applying a hydrolyzate of an organosiloxane to the surface of a plastic product and curing it by heating at 60 to 120 ° C. to form a coating film having excellent surface hardness is disclosed in Japanese Examined Patent Publication No. 50-39449. Japanese Patent Publication No. 51-2343, Japanese Patent Publication No. 55
-4148, JP 55-40631, JP 55-41271
JP-A-55-41272, JP-B-55-41273 and JP-A-64-11167. Further, as an example in which alkoxysilane itself is used as a coating agent for forming a coating film by heat curing similar to the above, Japanese Patent Publication No. 53-1
5743 and Japanese Patent Publication No. 55-36216.

Further, a technique in which a reaction product of a silane compound of organosiloxane and alkoxytitanium is used as an inorganic coating agent is described in JP-A-63-12671, and tetraalkoxysilane and zirconium tetraalkoxide. Japanese Patent Publication No. 3-71472 discloses a technique for preparing a coating composition by mixing and with an organic solvent.

Furthermore, as an application example of a combination of an organosiloxane and a fluorine-containing compound, there is disclosed a technique in which a silicone varnish is blended with an organosiloxane having a polyfluoroalkyl group to prepare a paint.
Japanese Patent Publication No. 77405/1999, and other similar techniques to Japanese Patent Publication No. 1-16405 and Japanese Patent Laid-Open No. 63-320 are disclosed.

An example of the application of pure organosiloxane is a technique (Japanese Patent Publication No. 1-58148) in which dimethyl silicone oil or silicone oil containing a linear alkyl group is used as a water repellent agent for concrete addition. be able to.

As a technique for improving the silicon concentration in the paint, a technique of using colloidal silica in combination is disclosed in Japanese Examined Patent Publication No. 52-396.
It is disclosed in Japanese Patent Publication No. 91, Japanese Patent Publication No. 53-5914, Japanese Patent Publication No. 55-8548. However, the silica in this case is a solid SiO ₂ colloidal silica, which is different from the silicon elements such as silanol groups and organosilicon groups bonded to the organosiloxane, and is in a mixed state after all. Therefore, even if improvement in noncombustibility / flame retardancy can be expected due to the added silica or silicate, etc., as long as the polymer itself that combines the silica or silicate is not noncombustible / flame retardant. , Intrinsic non-combustibility / flame retardancy cannot be expected in the produced polymer.

Next, in order to allow the metal-containing chelate compound used as a curing catalyst to coexist stably in the base material for forming various resins, a technique of combining keto-enol type tautomeric compounds has a carboxyl group in the molecule. An example of a mixed composition of a linear copolymer, an aluminum alcoholate complex compound and a solvent is disclosed in JP-B-48-17859. In addition, a similar technique is applied to a mixture of a resin having a functional group such as an isocyanate group, a hydroxyl group, an epoxy group, a carboxyl group, and an amino group, which is partially reacted with an alkoxysilane group or a hydroxysilane group, and an organic solvent of an epoxy resin. Japanese Patent Application Laid-Open No. 1-129066 discloses a technique in which a keto / enol type tautomeric compound is used in combination with a chelating compound curing agent.

In these cases, the application of the keto-enol type tautomeric compound is limited to the use as a curing agent for an organic resin dispersed in an organic solvent or an organic resin partially having a siloxane bond. However, there is no disclosure of an application technique using a pure organosiloxane system in which organic resins and organic solvents are not used in combination. Further, Japanese Patent Application Laid-Open No. 64-1769 discloses an application technique in which various resins containing an organosiloxane are previously reacted with β-diketones together with water.

[0026]

DISCLOSURE OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION The present inventors have previously studied "solvent-free room temperature-curable organosiloxane composition and its use". However, this research result also does not solve the problems when applied to the production line as described above. That is, (a) ensuring liquid state storability in an open state at room temperature, (b) curing the organosiloxane composition within a short time, and (c) having a solventless room temperature curable organosiloxane composition. It is necessary to satisfy all of the three conditions of maintaining and securing the characteristics, and the application technology of the organosiloxane composition which answers these requirements has not been completed yet.

In addition to the above, the technical problems of the prior art organosiloxane composition and its application and the current state thereof are summarized as follows. Most of the technologies that apply organosiloxanes in the fields of paints, etc., are excellent in coating / film forming performance, solvent dilution performance, and drying characteristics after coating, such as organic polymers with a CC-bond as the main chain. When using organic resins, siloxane compounds are added in order to compensate for the drawbacks of these organic compounds, and the applied technology is to add the characteristics of the siloxane bond.

In recent years, in advanced living and social environments, the emergence of non-combustible / flame-retardant materials is strongly desired. However, in the conventional technology for making non-combustible / flame-retardant polymer materials using organosiloxane as a raw material, the polymer constituent main chain is polysiloxane bond.
Only [(-Si-O-) _n ] is required, and the concentration of the contained silicon component is increased, or the total metal element component of the compounded organic compound of silicon, titanium or zirconium is represented by MO ₂ oxide standard of 40 By maintaining a high concentration of more than weight%,
There is no idea or technical idea to heat-cure such a non-catalyst organosiloxane composition to exert the effect of noncombustibility and flame retardancy.

Further, in order to meet the needs for applied materials such as coating materials as described above, attention is paid to completion of a material comprising an organosiloxane composition under solvent-free and pollution-free conditions, and techniques and techniques therefor. There is no disclosure that specifically states. In addition, when applying a moisture-curable organosiloxane composition in the paint industry, the shelf life of the material in a one-liquid state is safely secured (one-liquid storability). It is also very important for handling construction work.

However, in the prior art, in order to enable shelf life with one liquid of the moisture-curable organosiloxane composition and to secure the pot life in the open state, the organosiloxane compound group as the main raw material is used. Specified without adding a special compound after devising such as preliminarily erasing the silanol groups in the system by applying a specified curing process, etc., or ensuring stability with a non-catalyst organosiloxane composition No idea is found for polymerizing under the set curing conditions. Further, in order to safely secure shelf life and pot life in one solution, there is no idea to use a keto / enol type tautomeric compound in combination with a solventless catalystless organosiloxane composition.

Further, these conventional techniques are aimed at paying attention to blending a filler such as a pigment or a colorant with a moisture-curing type organosiloxane composition which is easily cured in the air without any trouble. I can't find any technology disclosure to complete the material product. Furthermore, in the prior art, it is generally known that an organosiloxane is polymerized and cured by heating. However, a solvent-free, non-catalyst, one-pack type organosiloxane composition is treated in a short time under heating conditions to make the coating film or coating film beautiful and glossy without impairing the adhesion to the substrate. There is no disclosure of specific technology to finish. Furthermore, the polymer formed by the polysiloxane bond has flexibility while having a main chain of -Si-O- bond, and has physical properties such as flame resistance / noncombustibility, heat resistance, and water permeability. I have not yet seen the technology that has been completed as a material.

Among the above, the present inventors have found that it is indispensable to use an organic solvent having a harmful effect on the human body in the application technology of organosiloxane according to the prior art. Type of energy-saving and labor-saving technology that enables short-time construction has not yet been completed, and it is non-combustible / flame-retardant, has beautiful / glossy properties, and can be used for coating materials, paints, etc. Many problems remain in environmental problems such as the fact that materials are not widely used, that toxic and harmful gases are generated when they are burned in material products that are based on organic compounds, and energy and labor saving technology. I paid attention to that.

In the present specification, when the concentration or content of silicon, titanium and zirconium components is expressed by weight% based on oxides, titanium and zirconium are omitted and represented by "silicon, etc." May be shown. In addition, in this specification, in order to express the storage stability of the liquid organosiloxane composition, it is assumed that the storage stability of the liquid state is ensured during the construction work in the open state to ensure the "pot life", and the sealing is performed. The fact that long-term storability is ensured in the state is expressed separately from the assurance of "shelf life".

[0034]

OBJECT OF THE INVENTION The present invention is a resource-saving and global environment-friendly material and method, which technically solves the above-mentioned problems which have not been achieved by the prior art, and provides a transparent film or coating in a short time under heating conditions. Polysiloxane suitable for applications such as materials, binders and structures
It is an object of the present invention to provide an organosiloxane composition which forms a polymer having a (-Si-O-) _n bond as a main chain and is solventless, catalyst-free, and has one-liquid storability.

[0035]

[Means for Solving the Problems] The inventors of the present invention have conducted extensive studies to achieve the above-mentioned objects of the present invention.
The invention has been completed. According to the invention,
In a mixed liquid composition of a precursor (A) composed of an organosiloxane and a cross-linking agent (B); R ¹ · Si group in which the precursor (A) is an organosilicon group (R ¹ is a monovalent hydrocarbon Group) and a functional side chain OR ² group (R ² is a hydrogen atom or a C ₁ to C ₅ alkyl group or an acyl group), which is a combination of two or more kinds of liquid organosiloxanes and is crosslinked. The agent (B) is one or a combination of two or more kinds of organic compounds of liquid silicon, titanium or zirconium having a functional group consisting of at least one alkoxy group, acyloxy group or oxime group, and a mixture of the two. The metal element content of the liquid composition is based on the MO ₂ oxide standard (M
Is silicon, titanium or zirconium)
A heating type solventless catalystless organosiloxane composition containing 40% by weight or more is provided.

According to the invention, the precursor (A) is
The following general formula (1) (In the formula, R ² is a hydrogen atom or a C ₁ to C ₅ alkyl group or an acyl group; R ³ to R ⁷ are each a hydrogen atom, O
A low molecular weight poly-organic composed of one or a combination of two or more liquid organopolysiloxanes represented by R ² groups or the same or different groups selected from monovalent hydrocarbon groups and n is a number smaller than 15). Provided is a heating-type solventless catalyst-free organosiloxane composition which is a compound group containing siloxane in an amount of 10% by weight or more.

According to the present invention, the precursor (A) further comprises
R ¹ · Si group that is an organosilicon group (R ¹ is a monovalent hydrocarbon group)
And a compound in which a silicone resin having an OR ² group (R ² is a hydrogen atom, a C ₁ to C ₅ alkyl group or an acyl group) as a functional side chain is dissolved and blended in an amount of 10% by weight or more. A group of heated solventless catalystless organosiloxane compositions is provided.

According to the present invention, the thermoplastic resin of the linear organic polymer compound having a carboxyl group is dissolved in the liquid organosiloxane of the precursor (A) in an amount of 30% by weight or less. A solventless catalystless organosiloxane composition of the type is provided.

According to the invention, the cross-linking agent (B) is
General formula R ⁸ _m M ・ (OR ² ) _4-m (2) (wherein M is a silicon, titanium or zirconium element; R ² is a hydrogen atom or a C ₁ to C ₅ alkyl group, an acyl group or an oxime group. ; R ⁸
Is a hydrogen atom, a group selected from an OR ¹ group or a monovalent hydrocarbon group, and m is an integer of 3 or less), and is one or a combination of two or more organic compounds of liquid silicon, titanium or zirconium. Certain heated solventless catalystless organosiloxane compositions are provided.

According to the present invention, the crosslinking agent (B) further comprises
From one or more combinations of keto-enol tautomeric compounds selected from the group of β-keto acid esters, β-diketone compounds and malonic acid esters, which optionally have an alkyl group or a trifluoro group The present invention provides a heating type solventless catalystless organosiloxane composition containing the reaction blocking agent in an amount of 80% by weight or less.

According to the invention, the cross-linking agent (B) is
A heating-type solventless catalyst-free organosiloxane composition is provided, which is blended in an amount of 100 parts by weight or less based on 100 parts by weight of the precursor (A).

Further, according to the present invention, the above-mentioned precursor (A) alone or a mixture with the cross-linking agent (B) is preliminarily added in the absence of water.
Provided is a stabilized heating-type solvent-free catalyst-free organosiloxane composition capable of being stored as a one-component solution when subjected to a curing step under treatment conditions of 100 ° C. or lower for 10 minutes or longer.

Further, according to the present invention, there is provided a transparent film comprising a polymer having a polysiloxane bond as a main chain, which is produced by heating the above-mentioned heating type solventless catalystless organosiloxane composition at 40 ° C. or higher. It

Further, according to the present invention, with respect to 100 parts by weight of the heating type solvent-free catalyst-free organosiloxane composition,
After mixing 1 or 2 or more kinds of combination fillers selected from the group of activators, fillers, pigments, and colorants in an amount of 400 parts by weight or less, 100 ° C or less in the absence of water, if necessary. It is formed by a polymer having a polysiloxane bond as the main chain, which is formed by heating a stabilized paint-like mixture that can be stored in a one-component storable solution by subjecting it to a curing step for 10 minutes or longer at 40 ° C or higher. A coating material comprising a composite cured body is provided.

Further, according to the present invention, with respect to 100 parts by weight of the heating type solvent-free catalyst-free organosiloxane composition,
A fluid or plastic mixture pre-blended with one or more kinds of combination fillers selected from the group of activators, fillers, pigments and colorants in an amount of 500 parts by weight or less is heated to 40 ° C or more. A binder comprising a composite cured product formed of a polymer having a polysiloxane bond as a main chain is provided.

Furthermore, according to the present invention, 100 to 2000 parts by weight of one or more kinds of combination materials selected from the group consisting of a reinforcing material, an aggregate and a molded body are previously added to 100 parts by weight of the fluid or plastic mixture. There is provided a structure comprising a composite cured product formed by using as a binder a polymer having a polysiloxane bond as a main chain, which is produced by heating a composite compounded and combined in a range of parts by weight to 40 ° C. or higher.

The transparent film used in the present specification, the covering material,
The terms binder and structure are defined as follows, and will be described in detail in the detailed description of the invention described below. Transparent film: A transparent film that is used as a base material (plastics, metal,
Inorganic materials, etc.), coating materials, protective materials, etc. Coating materials: paints, varnishes, base materials and coating protective materials with a certain thickness. Binder: An adhesive, a binder, a jointing agent, a hardening agent and a sizing agent for various aggregates, a cementing material and an anchor fixing material. Structures: building materials, floor / wall materials, structural processed materials such as various block, plate, net, fibrous, woven, etc. reinforcing materials, aggregates, solidified bodies and structures that integrate processed molding materials, etc. ..

[0048]

[Operation] In order to suppress the curing reaction of the organosiloxane composition in the atmosphere containing moisture at room temperature and to secure the pot life, the present inventors have determined that the functional group serving as a reaction base is a silanol group because of its curing mechanism. Does not contain (-Si ・ OH), or does not create conditions that easily change silanol groups, that the polymerization reaction is blocked at room temperature, that the polymerization reaction proceeds without catalyst, etc. The inventors have earnestly studied to solve the above condition and arrived at the present invention.

The present inventors have previously proposed a method for eliminating silanol groups serving as reaction sites in the organosiloxane composition system by using the precursor of the present invention alone or in a mixture with a crosslinking agent at 100 ° C. or lower for 10 minutes or more. It was found that the reactive silanol groups contained therein were erased during the curing process by treatment. Moreover, the organosiloxane composition from which the silanol groups have been eliminated in this way does not easily undergo a curing reaction even when exposed to normal temperature in an atmosphere containing moisture without a catalyst (see the experimental results in Table 1 below). (See).

As a matter of course, when a curing catalyst is allowed to coexist with the organosiloxane composition of the present invention from which the silanol groups have been eliminated, the curing reaction proceeds at room temperature. Therefore, the organosiloxane composition of the present invention needs to be in a non-catalyst state in order to safely secure the liquid state storability (pot life) in an open state at room temperature. Moreover, regarding the crosslinking agent to be added to the present composition, as will be described later, it is necessary to fully consider the relationship such as the crosslinking ability, type and amount.

The present inventors have found appropriate conditions for the cross-linking agent to be added to the non-catalyst organosiloxane composition, and to add a keto-enol type tautomeric compound that blocks the reactivity of the cross-linking agent used at room temperature. Found the conditions. Further, the present inventors have found that even in the case of a non-catalyst organosiloxane composition in which silanol groups are eliminated, when a specified cross-linking agent is used in combination, it is possible to polymerize easily and in a short time under heating conditions of 40 ° C. or higher. The conditions under which the reaction proceeds and a cured product is formed were found.

The following experiment was conducted to confirm the curing conditions by this heat treatment. The time required for the coating film coated with the catalyst-free liquid composition (Sample No. AB-1) in this example to reach a certain hardness (H hardness) or more was measured in relation to temperature. The results are shown in Table 1 below. From this result and the results of Examples described later, it is understood that the curing rate of the organosiloxane composition is limited by the heat treatment temperature regardless of the addition of the curing catalyst. Moreover, since the heating temperature exceeds 40 ° C, it is preferably 60
The curing speed is rapidly accelerated from the stage of exceeding ℃,
It is well understood that in the liquid organosiloxane composition of the present invention, the curing rate by heat treatment is much more preferentially limited than the curing rate by catalyst addition.

[0053]

The above composition of the present invention can be applied by a so-called two-pack type method in which a curing catalyst is added and used, but the composition can secure shelf life and pot life. It is needless to say that the one-liquid type is advantageous because there is no complexity in management of various construction processes regardless of the construction on the production line as described above. Moreover, the one-component type general organosiloxane composition that is premised on curing basically has a moisture curing function, and thus the curing by contact with moisture is slow regardless of the temperature, and is avoided regardless of the speed. I can't. As a result, the pot life during construction workability with such a composition is impaired, quality control becomes difficult, process control on the production line becomes complicated, and the desired physical properties of the product cannot be expected.

Therefore, as described above, the organosiloxane composition of the present invention is non-catalytic, and moreover, the content of the organosiloxane group, the special curing process, the selection of the cross-linking agent, the combined use of the blocking agent and the like are devised techniques. It is fully understood that the addition of the above-mentioned can secure the pot life safely in the production line and make the work management in various construction processes advantageous.

In order to develop a non-combustible / flame-retardant product having excellent heat resistance by using an organosiloxane in which an organic group is bonded to a Si—O bond, it is necessary to suppress heat-sensitive organic components to a low concentration. It is necessary to maintain the content of silicon content at a high concentration of 45% by weight or more, preferably 50% by weight or more based on the SiO ₂ oxide. As will be described later, of course, in the organosiloxane, dealcoholization occurs in the process of polymer formation due to the polymerization reaction, and a part of the alkoxy groups bonded to the organosiloxane is removed as alcohol to the outside of the system. As a result, the silicon content in the produced polymer tends to be higher than that in the raw material.

The mixed liquid composition of the present invention comprising the precursor (A) made of an organosiloxane and the crosslinking agent (B) is also used in the mixed liquid composition containing all of silicon, titanium and zirconium. The metal element component is at least 40% by weight or more, preferably 45% by weight based on MO ₂ oxide.
When the above high concentration is maintained, it becomes possible to develop products that are incombustible / flame-retardant and have excellent heat resistance. As a matter of course, the content of the metal element component in the completed cured polymer product is higher than that in the raw material, as described above.

As an organosiloxane having an organosilicon group and an OR group which is a functional side chain, methyltrimethoxysilane [CH ₃ Si (OCH ₃ ) ₃ ] having the smallest number of carbon atoms is taken as an example. The content of Si is 20.6% by weight, which corresponds to 44.1% by weight in terms of SiO ₂ . Taking ethyltriethoxysilane [C ₂ H ₅ Si (OC ₂ H ₅ ) ₃ ] with one more carbon number as an example, the silicon content was calculated to be 14.6% by weight as Si and 31.2% by weight in terms of SiO _2. It corresponds to a low value such as%. Moreover, if an organosiloxane having a large number of carbon atoms in the R ² to R ⁷ group in the general formula (1) shown above is selected, the proportion of the organic component further increases and the silicon content decreases. It is difficult to expect that a compound having a silicon content of 45% by weight or less in terms of SiO ₂ will exhibit nonflammability, flame retardancy, and heat resistance.

The content of silicon in the organosiloxane is
In order to obtain a high concentration of 40% by weight or more in terms of SiO ₂ , it is preferable to polymerize the organosiloxane to at least an oligomer to reduce the number of organic groups. That is, it is achieved by using a polymer in which _{n in} the [-Si-O-] _n term of the general formula (1) shown above is at least 2 or more. For example, when 2 mol of methyltrimethoxysilane having a SiO ₂ concentration of 44.1% by weight shown above is condensed into a dimer compound, the silicon component content of the compound is 24.7% by weight as Si,
It corresponds to 53.0 wt% in terms of SiO ₂ , and it is understood that the silicon component content increases and shifts to the high concentration side.

On the other hand, when the number of n is large and the degree of polymerization is too large, the liquid viscosity of the organopolysiloxane liquid is improved, and it is preferable to use a diluent such as an organic solvent for adjusting the liquid viscosity. It will be difficult to secure workability. Generally, when applying an organic polymer compound or organic resin having a high degree of coating performance to paints, etc., the polymer compound or organic resin is applied to a diluting means with an organic solvent, etc. The film physical properties are secured.
However, since the present invention is aimed at development with materials and methods that are friendly to the global environment, it is not possible to employ harmful organic solvents as diluents and the like. Therefore, in order to secure a good liquid state and guarantee the workability of the composition of the present invention, the upper limit naturally occurs in the silicon content and the degree of polymerization.

From the above viewpoints, the present inventors have selected a compound in which condensation of organosiloxane is suppressed to a low molecular weight polymer, the number of bonded organic groups is reduced, and the number of carbon atoms in the organic group is small. The inventors have found the conditions under which the SiO ₂ concentration of the composition can be maintained at 45% by weight or more while maintaining the liquid state of the composition within a specific range suitable for workability. Further, as a raw material for the Si-O bond, which is the basic skeleton of the cured polymer of the present invention, it is preferable to select an organopolysiloxane that has already formed a three-dimensional structure to some extent with the -Si-O-Si- polymer bond. Is. That is, by selecting a specific organopolysiloxane as a raw material, not only the concentration of silicon component is increased as described above, but also the basic structure of the desired polymer skeleton can be preset to some extent.
Moreover, it is important in that the structural morphology of the target polymer can be predicted and controlled to some extent.

The organopolysiloxane which is condensed to a certain degree to form a —Si—O—Si— bond is an oligomer having n of 2 or more in the general formula (1) prepared for increasing the concentration of silicon component, or a low oligomer. Although it is possible to select a polymer having a molecular weight, it is also possible to select a silicone resin which is a polymer compound which is polymerized and still has a functional side chain. What is very important for the present invention is to select, as a liquid compound for preliminarily dissolving these low molecular weight polymers or polymerized silicone resins, a corresponding organosilane compound of a monomer having an organosilicon group and an OR group. It has been found to be achieved by

That is, the inventors have found the conditions under which a high molecular weight organosilicon compound can be dissolved with the same kind of organosilicon compound without dissolving a high molecular weight organosilicon compound using a so-called harmful organic solvent. It is possible to eliminate the highly dangerous organic solvent, maintain the silicon component concentration at a high concentration, maintain the composition in a workable liquid state, and set the structural skeleton of the produced polymer in advance. I chose

In order to efficiently form a polymer cured product aimed at by the present invention under heating conditions and to exert its characteristics fully, a precursor in which an organosiloxane as a raw material is blended by selecting it from the group. It is important to summarize the above in advance and then subject it to the curing process under the processing conditions specified in the present invention.

As can be understood from the above description, the precursor of the organosiloxane group of the present invention is (a) an organosilane compound having a silanol group-removing ability,
(b) an oligomeric or polymeric organopolysiloxane compound, (c) a liquid organosilane compound capable of dissolving these oligomeric or polymeric siloxanes, and (d) an organosiloxane having different organic group contents bonded thereto. It is important that at least two or more kinds of compounds and the like are selectively combined.

In selecting the precursor, the physical properties of the desired polymer cured product, the constitutional content and blending ratio of the organosiloxane group, especially the type and composition of the organosilicon group, hydroxyl group or alkoxy group or acyloxy group to be contained, silicon It can be completed only after carefully examining the content concentration of components, the degree of polymerization, the viscosity of the liquid, etc., and carefully controlling the curing process.

Moreover, in order for the polymer formed here to exhibit excellent physical properties and be a dense and durable cured product,
It is necessary to form a three-dimensionally spread network polymer rather than a linear polymer. However, when the polymerization is performed only at the terminal functional group portion of the organosiloxane, only a linear polymer is formed, and a three-dimensionally spread network polymer cannot be formed. In order to form a three-dimensional reticulated polymer, functional groups that exist at various points in the middle of the organopolysiloxane compound, which is the basic matrix, are used to promote bonding by cross-linking or cross-linking or reinforcing. , It is necessary to create a wide variety of bonds at many points.

For that purpose, it is necessary to make the precursor (A) of the liquid organosiloxane as a raw material coexist with the cross-linking agent (B) capable of functioning as a bridge or a crosslink. A cross-linking agent that effectively plays this role is represented by the general formula (2) [R ⁸ _mM
It is a liquid organic compound of silicon, titanium or zirconium represented by (OR ² ) _4-m ], and it is essential that it has a functional group of —OR 2.

What is important about the cross-linking agent (B) of the present invention is that the silicon, titanium or zirconium of the organic compound of the cross-linking agent (B) is bonded to the Si—O bond constituting the cured polymer so as to be a member. The point is to play a role as a member. Therefore, the object of the present invention cannot be achieved if the crosslinking agent used in the present invention is free without binding to the Si-O bond. Such a binding reaction of these metal-containing organic compounds is basically different from the phenomenon that occurs when a general curing catalyst is used.

In the present invention, in particular, in the main chain of the cured polymer, in addition to the silicon metal component, a metal component of titanium or zirconium, although partially, is contained.
The fact that the bonded parts of the metal components of different sizes and sizes are mixed, although partially, will cause the cured product itself to change from a completely regular structure to a partially disordered state, and the cured product structure will have play and allowance. This results in the formation of the space, and as a result, the toughness of the cured product is exhibited. This fact is extremely important in achieving and completing the purpose of the present invention.

Further, what is important about the cross-linking agent (B) of the present invention is that the organic compound of titanium or zirconium of the cross-linking agent (B) is a cross-linking agent and also has a function as a reaction accelerator. Need to pay attention. In the present invention, as described above, it is necessary to suppress the curing reaction in the atmosphere at room temperature. Therefore, when a titanium or zirconium organic compound is selected as one component of the raw material for the cross-linking agent (B), it is necessary to give sufficient consideration to the combination with a keto / enol type tautomeric compound which is a blocking agent described later. However, on the other hand, in consideration of the fact that the titanium or zirconium organic compound plays a role of facilitating the condensation reaction in combination with the heating conditions, when selecting the crosslinking agent in the present invention, the curing content of the composition, the curing conditions, the curing point It is necessary to decide the content of the compound with due consideration of the above.

It is important that the organosiloxane of the present invention has an organic silicon group in which an organic group is directly bonded to silicon without interposing oxygen, as a fundamental difference from the physical properties of a polymer having an inorganic siloxane bond. Is. In particular, in order to effectively exhibit water repellency, water resistance, and compactness, which are not possessed by a polymer based on an inorganic siloxane bond, an organic group having a size sufficient to protect the siloxane bond, for example, an alkyl group or a phenyl group It is important to have an organosilicon group.

The reason why such physical properties are ensured is not clear, but as described above, the cured polymer of the present invention forms a strong network structure by the specified crosslinking reaction, and Whereas the Si-O bond has an average area of about 22 Angstroms ² , for example -CH ₃
The bonds have an average area of about 12 angstroms ² , so at least two -CH ₃ bonds have at least two Si atoms.
It is considered that the -O bond can be sufficiently covered and protected in terms of area. From the above, it is considered that the cured polymer of the present invention can exhibit compactness with excellent water repellency and water permeation resistance.

Further, the organosiloxane composition of the present invention is basically different from the inorganic siloxane composition such as water glass in that it does not contain an alkali metal component. Moreover, in the organosiloxane composition of the present invention, the alkyl group and the like involved in the condensation are removed from the siloxane bond by dealcoholization and volatilized from the cured system. As a result, not only the adverse effects caused by the residual alkali metal components or the like occurring in the case of the inorganic siloxane composition remaining in the cured product are eliminated, but in the organosiloxane composition, the electrons around the Si-O bond are eliminated. Low density and high degree of freedom. Therefore, flexibility occurs in the Si-O bond due to the organosiloxane composition, flexibility is imparted to the polymer cured product having the Si-O bond of the present invention as the main chain, and a useful material that can follow the bending of the substrate. Can be used as

What is further important in the present invention is that when the organosiloxane composition is applied to applications such as paints, it is necessary to mix and disperse the filler such as colorants and pigments in the organosiloxane composition in a homogeneously dispersed state. However, the organosiloxane composition originally has a moisture curing function as described above, and the step of dispersing and mixing the necessary fillers such as colorants and pigments in the open state in the organosiloxane composition without curing is performed. It's not easy.

However, the present inventors removed the silanol groups in the composition by previously subjecting it to the curing step specified in the present invention as described above, and ensured the pot life in one liquid without catalyst. In view of the above, the curing action of the organosiloxane composition of the present invention has been found to be a condition under which the curing rate is extremely slow as long as it is not accompanied by heating, and by utilizing this phenomenon, the organosiloxane composition is not It has been found that it is possible to easily carry out the dispersive mixing step of the filler which has been difficult.

In the present invention, in view of forming a polymer cured product from an organosiloxane composition under heating conditions, a thermoplastic resin is dissolved and combined with the liquid composition of the present invention to complete the polymerization. It has been found that the combined thermoplastic resin can be composited in the organosiloxane cured product in a homogeneous dispersion state by the process. The thermoplastic resin used at this time is preferably a linear organic polymer compound having a carboxyl group because it can be dissolved in organosiloxanes.

Furthermore, the inventors of the present invention ensure the pot life and shelf life of the one-pack type composition of the present invention safely, and manage and control the progress of the curing reaction occurring after construction at desired time intervals. In addition, it was examined that the cross-linking agent (B) used in advance was blocked by blocking. Moreover,
The blocking agent used at this time is to allow the metal component to stably exist in the liquid organosiloxane coexisting at a high concentration of 40% by weight or more in terms of MO ₂ , and to decompose the metal-containing organic compound in the organosiloxane during storage. It is important that there is no such thing, that the blocking action can be released under the heating conditions at the start of construction, and that the above three properties can be secured. As a result of intensive research conducted by the present inventors, as a reaction blocking agent satisfying the above conditions,
It was found that keto-enol type tautomeric compounds are effective.

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-oxycrotonic acid ethyl ester) as represented by acetoacetic acid ethyl ester. It has the property of coexisting while maintaining. Since this keto-enol tautomeric compound undergoes chelation due to hydrogen bond in the molecule, hydrogen bond between molecules is unlikely to occur and intermolecular association does not occur, and it is considered that the compound exhibits a blocking effect.

The enol form of the keto-enol tautomeric compound is stabilized by chelation due to hydrogen bonding [Sumio Umezawa “Organic Chemistry I” (Maruzen) p. 209 (195).
4) Reference] is considered. However, when water, a compound having a hydroxyl group such as alcohol or acetic acid coexists,
This hydroxyl group easily forms a hydrogen bond with the oxygen atom of the keto-type carbonyl group, and interferes with chelation of the metal element.

Therefore, it is considered that when the hydroxyl group coexists in this way, the blocking effect is eliminated, and the catalytic action which is the original role of the compound having a metal element is exhibited. As described above, when the organosiloxane of the present invention initiates a condensation reaction by the action of water, a dealcoholation reaction occurs and alcohols are by-produced in the system. It is considered that the generation of this by-product alcohol releases the metal element that has been blocked by blocking and exerts the original role of crosslinking.

As described above, in view of the fact that the composition of the present invention is non-catalytic in order to secure pot life and the like, it is necessary to apply heating conditions of 40 ° C. or higher in order to proceed the curing reaction. is there. As is clear from the above-mentioned experiment, the polymerization reaction of the liquid organosiloxane is rapidly accelerated by heating, which enables formation of a cured product from the desired network polymer.

The curing mechanism of the composition of the present invention is such that when the liquid organosiloxane composition is heated to 40 ° C. or higher under the condition of being in contact with humid atmosphere or water, one of the alkoxy groups and the acyloxy groups in the composition is The part first undergoes hydrolysis to form the Si-OH group of the silanol group, and then is composed of a condensation reaction that occurs continuously between this silanol group and the functional group such as the alkoxy group of the cross-linking agent. It is considered that the crosslinking reaction proceeds rapidly by a series of condensation reactions to form a three-dimensional and sturdy network polymer to form a cured product.

By carrying out the present invention described so far, it is possible to perform short-time construction in a production line, and it is possible to generate a dense and durable polymer under heating conditions. The excellent water repellency is related to the fact that a polymer that exhibits non-combustible / flame-retardant properties that are excellent in heat resistance, adhesion, etc. can be obtained, and that some organic silicon groups are bonded to the polymer. It is possible to obtain a water-permeable and dense polymer with high flexibility, and the flexibility of the -Si-O-Si- binding polymer is very flexible. Be done.

The polymer formed from the above-mentioned heating type solvent-free catalyst-free organosiloxane composition of the present invention has a structure in which a general polymer compound composed of an organic compound forms a film, serves as a binder, and has a structure. It can be effectively used for these various uses as it is used as a solidifying material constituting a body, and various problems that have not been solved in the past can be solved.

Particularly when the organosiloxane liquid composition of the present invention is heated to 40 ° C. or higher in a humid atmosphere, it easily forms a transparent film made of a polymer having a siloxane bond as a main chain. The transparent film formed here has useful physical properties such as weather resistance, heat resistance, water permeability resistance, flexibility, etc., so it is a transparent coating / protective film for various materials and base materials regardless of organic or inorganic. It can be effectively used as a film or a film.

Further, in the solventless one-pack type curing composition of the present invention, an activator, a filler, a pigment, a colorant and the like are appropriately selected according to the purpose of use, and the amount is specified in advance in a specified amount ratio. Prepare a blended paint-like or fluid or plastic mixture and keep the mixture at 40 ° C in a humid atmosphere.
When heated to the above temperature, a polymer having a siloxane bond as a main chain is produced, and a composite cured product with an activator, a filler, a pigment, a colorant, etc. is formed. This composite cured product has heat resistance of 300 ° C or higher, and has useful physical properties such as weather resistance, heat resistance, water permeability, flexibility, etc., so that it can be used for both organic and inorganic materials and metals. It can be effectively used for various applications such as coating materials for various materials and base materials, paints, coating protective materials, binders, binders, jointing agents, anchor materials, cementing materials and the like.

Further, in the present invention, a suitably selected reinforcing agent, aggregate, molded body or the like is blended with a mixture such as a paint in which the above-mentioned activator, filler, pigment, colorant and the like are blended in advance. When heated to 40 ° C or higher in a humid atmosphere, the polymer having siloxane bonds as the main chain formed here becomes a binder, and is integrated with the reinforcing agent, aggregate, molded body, etc. which are blended. Form a composite cured body. Since this composite cured product has heat resistance of 300 ° C or higher and useful physical properties such as weather resistance, heat resistance, water permeability, flexibility, etc., it can be used for building materials, civil engineering industry materials, and various materials. It can be effectively used as a solidified body or a structure.

[0089]

DETAILED DESCRIPTION OF THE INVENTION The precursor (A) consisting of the organosiloxane group is a basic matrix that forms the cured polymer skeleton of the present invention. Therefore, selection of the composition of the organosiloxane group is important in determining workability and physical properties of the cured product of the polymer, and it is necessary to give due consideration and attention to the composition content.

R of the organosilicon group (R-Si) of the liquid organosiloxane group consisting of a combination of two or more kinds selected from the precursors of the present invention has R 1 which is a monovalent hydrocarbon group and has a carbon number of C ₁
To the range of C _8, atomic alkyl groups R, fluoroalkyl group, alkyl group having an allyl group, a vinyl group, an allyl group, an alkenyl group, a phenyl group,
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 and the like are preferable, and an alkyl methyl group, an ethyl group and a phenyl group are particularly preferable. Is preferred. The above-mentioned organosiloxane group having an organic group is preferable in terms of enabling the physical properties targeted by the present invention, in particular, water repellency, water permeation resistance, adhesiveness, flexibility and the like to be exhibited.

On the other hand, the OR group of the functional side chain possessed by the liquid organosiloxane group selected in the present invention is important as a functional group at the base where the condensation reaction proceeds by heat curing in a humid atmosphere. Therefore, this OR group is a functional group that is dealcoholized by hydrolysis with water to form a silanol group, or that promotes a condensation reaction due to dealcoholization with the produced siloxane having a Si—OH group. For that purpose, R of this OR group has a carbon number of a monovalent hydrocarbon group in the range of C ₁ to C ₈ , and is represented by an alkyl group such as a C _n H _{2n + 1} -atom group, an acetyl group, or the like. It is preferable that it is an acyl group of -CO.R atomic group, or a ketoxime group which is -NCR ₂ atomic group, and thus the OR group is an alkoxy group,
It is preferably an acyloxy group or an oxime group. In particular, an organosiloxane having a methoxy or ethoxy functional side chain in which R 1 is a methyl group or an ethyl group is preferable from the viewpoint of production process and availability.

The organosiloxane group selected as the precursor of the present invention is the organosilicon group R in this organosilicon compound.
And the ratio [R / Si] of Si is in the range of T units of 1/1 to D units of 2/1, especially T units lying between 1.0 and 1.8.
A polymer compound (organopolysiloxane siloxane) that is a mixture with D units or a copolymer of TD units keeps the concentration of silicon component at a high concentration and efficiently promotes the polymerization reaction and the cross-linking reaction. It is suitable for effectively forming a cured polymer.

In general, organosiloxanes, especially polymer compounds thereof (organopolysiloxane siloxanes), tend to partially contain 1 to 10% by weight of silanol groups in which R 2 of OR group is a hydrogen atom. In the present invention, an organosiloxane in which R 2 of the OR group is a hydrogen atom can also be selected. However, when the silanol group (Si—OH group) is composed of hydrogen atoms as described above, it is difficult to secure the preservability of the liquid organosiloxane composition as one liquid.
Therefore, in such a case, it is necessary to carry out a modification treatment for eliminating the silanol group by applying the curing step specified in the present invention. This modification treatment is completed by a simple curing step in which a silane compound having a reactive alkoxy group is allowed to coexist and is treated at 100 ° C. or lower in the absence of water for at least 10 minutes or longer.

In order to secure the cured polymer of the present invention with noncombustibility and flame retardancy, the MO ₂ concentration consisting of a bond of oxygen with a metal element of silicon, titanium or zirconium constituting the main chain of the polymer is 40. It is necessary to secure a high concentration of not less than wt%, preferably not less than 45 wt%. In order to maintain the MO ₂ concentration in the composition of the present invention at such a high concentration at such a high concentration, considering that a crosslinking agent or the like having a low metal component concentration is mixed, SiO in the precursor is considered. It is necessary that the ₂ concentration is 45% by weight or more, preferably 50% by weight or more. In order to secure the SiO ₂ concentration in the precursor at a high concentration of 45% by weight or more, the liquid organosiloxane used as the raw material is
The necessity of selecting an oligomer or a low molecular weight polymer represented by the general formula (1), in which _n of the [-SiO-] _n term is 2 or more, is as described above.

However, if the degree of polymerization of the organopolysiloxane becomes too large, it becomes impossible to secure the organopolysiloxane in a liquid state. Thus, n in the general formula is preferably a number smaller than 15. By controlling the degree of polymerization of the organopolysiloxane used in this way, it becomes possible to secure a state in which the viscosity of the liquid is 3000 centipoise or less and is easy to handle in construction,
It is not necessary to adjust the liquid viscosity with a diluent such as an organic solvent as in the prior art, and it is possible to perform the construction using a material made of organosiloxane alone.

Further, the organosiloxane of the precursor of the present invention can be selectively blended with a high molecular weight organopolysiloxane which has undergone polymerization to some extent. It is effective to select the organopolysiloxane in the precursor in this way because the structural skeleton of the cured polymer is preliminarily finished in a large frame. Moreover, the organopolysiloxane of choice is a polymer compound that is a copolymer of TD units,
The composition of a solventless organosiloxane composition is a silicone resin that retains an OR group of a functional side chain and has a molecular weight of 10 ² to 10 ⁵ and is soluble in a low molecular weight silicone compound or a silane compound. It is suitable for enabling.

Representative examples of the organopolysiloxane preferably selected for the precursor of the present invention include a methyl group, an ethyl group, a phenyl group and a fluoroalkyl group as the organic group, and a methoxy group or an ethoxy group as the functional group. Such oligomers and polymer compounds are common and easily available. It is an object of the present invention that these organopolysiloxane compounds are dissolved in a monomeric organosilane compound and are allowed to coexist in the precursor in an amount of 10% by weight or more while ensuring good workability. Is effective in achieving

As shown above, the organosiloxane selected as one component of the precursor is a silane compound having the ability to eliminate silanol groups, and an orgomer or a polymeric organopolysiloxane that is the basis of the cured product structure. It is preferable to select and select from organosiloxanes having different organic group contents, in a combination of two or more kinds under the conditions and ranges that enable the above-described object of the present invention.

Further, in the present invention, it is possible to dissolve and coexist the thermoplastic resin in the precursor in view of allowing the polymerization reaction to proceed by heating. As the thermoplastic resin used in the present invention, a linear organic polymer compound having a carboxyl group soluble in organosiloxane is preferable, and a resin such as acrylic resin, polystyrene resin, polyethylene resin, polyvinyl chloride resin, or cellulose and A derivative thereof, a copolymer with an unsaturated carboxylic acid in a non-aqueous solution, and the like can be selected.

As the monomer, ethylene, propylene,
Butadiene, isoprene, chloroprene, styrene, styrene resin, vinyl acetate, vinyl propionate, vinyl ether, vinyl chloride, vinylidene chloride, methyl or ethyl acrylate, acrylic ester or methacrylic ester resin, etc. Examples thereof include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic anhydride and the like.

Generally, when a polymer is condensed and produced, only a linear polymer is produced by polymerization with only the terminal group of the monomer, and it is not expected that a polymer having a three-dimensionally developed network structure is produced. In order for the cured product according to the present invention to be a polymer having a dense network structure as a base, it is necessary to complete the connecting crosslinks, cross-links, and reinforcing bonds at various places in the middle of the polymer.

A cross-linking agent may be mentioned as a compound that achieves this purpose and serves as a bridge between polymers. The conditions as the cross-linking agent (B) used in the present invention are represented by the general formula (2) [R ⁸ _mm M (OR which has a functional side chain OR group capable of undergoing a condensation reaction with a silanol group formed by contact with water. ² ) _4-m ] is preferably a liquid organic compound of silicon, titanium or zirconium.

In particular, when the cross-linking agent (B) is an organic compound of titanium or zirconium, as described above, these compounds function not only as the cross-linking agent in the organosiloxane composition but also as the reaction accelerator. Need to be considered. On the other hand, however, direct reaction bonding of titanium or zirconium element in the siloxane bond is effective in finishing the resulting cured polymer as a tough and tough material, as described in the section of action, and in the siloxane bond, It is preferable to select a liquid organic compound of titanium or zirconium having an OR group of a reactive functional group which is bound and incorporated.

It is preferable that these organic compounds are monomers in a liquid state in order to exert a crosslinking effect, but if a compound such as a dimer that has started polymerization is partially in a liquid state, It can be used effectively without impairing the purpose. The above organic compounds of silicon, titanium or zirconium can be used alone or in combination of two or more in accordance with the purpose and workability.

The cross-linking agent (B) used in the present invention is blended in an amount of 50% by weight, preferably 45% by weight or less, relative to the precursor (A) consisting of the liquid organopolysiloxane group, and thus the crosslinkage of the cured polymer. It is effective in improving the effect. When the above-mentioned crosslinking agents are used in the composition of the present invention in a combination of two or more kinds, it is preferable that the combination composition is subjected to a curing step in advance to be stabilized and then used in order to effectively achieve the crosslinking effect. Is.

Representative examples of suitable cross-linking agents selected in the present invention are shown below. When M in the general formula (2) is a silicon element, tetramethyl or ethyl orthosilicate in which R ⁸ is a methoxy group or an ethoxy group, methyltrimethoxysilane, methyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane. Examples thereof include silane, phenyltrimethoxysilane, γ-glycidoxypropylmethoxysilane, and dimethylmethyltrifluoropropylsilane. When M in the general formula (2) is a titanium element, tetra-i-propyl titanate, tetra-n-butyl titanate and the like can be mentioned as examples. When M in the general formula (2) is a zirconium element, tetraethyl zirconate, tetra-i-propyl zirconate, tetra-n-butyl zirconate and the like can be mentioned as examples.

What is important in the present invention is to prevent the reaction between the liquid organosiloxane and the crosslinking agent at room temperature by blocking the coexisting crosslinking agent with a keto-enol tautomeric compound in advance. However, it has been found that the composition of the present invention can surely secure the liquid preservation stability in the open state at room temperature and the one-component storage stability during storage for a long period of time.

As described above, the keto-enol type tautomeric compound is a compound that coexists in an equilibrium relationship between the keto type and the enol type, and chelation by hydrogen bond occurs in the molecule. .. Acetoacetic acid ethyl ester is a typical example of this compound and is preferably used in the present invention. Other examples of the keto-enol type tautomeric compound used in the present invention include malonic acid diester, β-diketones such as acetylacetone, benzoylacetone, dibenzoylmethane, and diacetone alcohol which is a ketone having a β-position hydroxyl group. Examples thereof include methyl salicylates, which are esters having a hydroxyl group at the β-position, and the like, and examples in which the alkyl group in the above compound is composed of a trifluoro group.

The amount of the keto-enol tautomeric compound used varies depending on the type and amount of the cross-linking agent used, the curing conditions, etc., but can be easily determined by conducting a simple preliminary experiment in advance. .. Generally in the cross-linking agent
It is preferable that the crosslinking agent used in an amount of 80% by weight or less, preferably 60% by weight or less, is preliminarily blended and prepared in order to obtain a blocking effect and to complete the condensation reaction.

The binary liquid mixture composition of the precursor (A) and the cross-linking agent (B) of the present invention is heated to 40 ° C. or higher, preferably 60 ° C. or higher under the condition that it can contact with water. The reaction rate of polymerization is rapidly increased to complete the reaction as described in the section of the action. The amount of moisture at this time is sufficient as the amount of moisture in the atmosphere, but it may be positively brought into contact with water. Conditions for contacting the liquid composition of the present invention with water,
It may be at room temperature, but any temperature in the range of 40 ° C to 250 ° C may be used, and this condition may be applied under pressure or under deaeration.
If desired, it can be carried out under a partial reduced pressure or 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 mixed liquid composition, is hydrolyzed by water to first produce a silanol group, which is a Si-OH group, and the silanol group then remains with the OR group, which is a functional group, to undergo a dealcohol reaction It suffices to have a condition for causing the condensation of the siloxane bond to occur.

According to the present invention, the precursor (A) and the crosslinking agent (B)
Even when the construction material consisting of the two-component mixed liquid composition is applied in a general work environment such as coating and then heat-treated in a humid atmosphere, harmful substances such as organic solvents diffuse and contaminate the work environment. The composition of the present invention can be safely used as a material that is kind to the global environment. Moreover, the cured polymer of the present invention is resistant to heat and fire, and there is no fear of harmful effects due to toxic or harmful gas generated when a material made of an organic compound is exposed to fire. It is well understood that is a material that is kind to the global environment.

As described above, the heating type solventless catalystless organosiloxane composition of the present invention is carried out in a liquid composition which can be stored in a liquid state at room temperature, and when the liquid composition is heated to 40 ° C. or higher. Makes it possible to coat various useful substrates with a film of non-combustible / flame-retardant material that has a transparent or beautiful / glossy siloxane bond as the main chain. It can be used for applications such as adhesives. In particular, the background of the base material is expressed as it is, and the background can be protected from heat, ultraviolet rays, other physical energy, and various conditions (oxidation, acidity, alkalinity, salts, etc.). In addition, since the produced film has flexibility, it is also effective as a protective film for various base materials that are required to be flexed or bent in terms of being able to follow the flexure or bending of the base material.

The organosiloxane composition of the present invention comprises:
Depending on the physical properties, functionality, workability, purpose of use, etc. required for the cured product, powdered or liquid activators, fillers, pigments and colorants of 200 microns or less can be blended and used as fillers. .. These fillers are used in an amount of 500 parts by weight or less based on 100 parts by weight of a mixed solution of two components containing organosiloxane as a main raw material, as long as the workability and various physical properties are not impaired, and the filler is used alone according to the purpose. Alternatively, a composite cured product can be produced by adding and blending two or more kinds in advance in advance, and then conducting a condensation reaction under heating conditions of 40 ° C. or higher to form a polymer. Some of the specific applications are shown below.

As the activator to be used, a powdered product of a boric acid-containing compound or a phosphoric acid-containing compound can be selected. By pre-blending this activator into the organosiloxane composition, for example, when selecting a metal such as iron as the base material,
It tends to improve the adhesion between the base material and the coating material or binder made of organosiloxane. As an activator of the boric acid-containing compound or phosphoric acid-containing compound, boric acid, borosilicate glass, zinc borate, boron phosphate, alkaline earth metal salts of boric acid, alkali metal salts of boric acid, silicon phosphate,
Powders of aluminum phosphate, zinc phosphate, alkaline earth metal salts of phosphoric acid and the like, and boric acid compounds having an organic group, for example, liquid form of boric acid alcoholate which is polyc tributyl ester are preferably used. Can be used.

As other active agents, toxic effects such as an antibacterial agent, an antiseptic agent, a fungicide, and an algae inhibitor composed of an inorganic compound, an organic compound or a composite compound thereof can be exerted on each object. By selecting a drug or the like and mixing it in the liquid composition of the present invention in a required amount range in advance, the resulting cured polymer coating film or the like can be used for antibacterial, disinfectant, antifungal, antialgal, etc. It can give an effect.

As the filler, stainless steel, silicon,
Powder of metal and alloy such as zinc, aluminum, copper, lead and iron, glass powder, ceramic powder, diamond powder, silicon oxide (silica sand powder, silica powder, silica powder, silica fume, etc.), fused alumina, magnesia, talc, Calcium carbonate, zircon sand, zinc oxide, lead oxide, various clays (bentonite, smectite, gyrrome, kibushi clay and other refined products), calcined clay (calcined products such as bauxite, montmorillonite, kaolin), cuprous oxide, gypsum, Calcium phosphate, magnesium phosphate, barium sulfate,
Aluminum fluoride, calcium silicate, magnesium silicate, barium silicate, calcium carbonate, barium carbonate, aluminum silicate, glaze with various composition contents, mica, fly ash, etc. with a particle size of 200 microns or less, one kind or It is possible to appropriately select and use two or more kinds in combination or in combination.

Further, antistatic agents, conductive agents, heat conductive agents, strong conductive materials, radiation shielding materials, abrasion resistant materials, anticorrosive agents, antireflection agents, strong agents, which are already commercially available in the art with their respective purposes stated. A functional filler composed of an inorganic compound, an organic compound, or a composite compound thereof prepared for the purpose of a magnetic material or the like may be used alone or in combination or in combination of two or more, and selected and blended in the same manner as above. it can.

Examples of the pigment include inorganic colored pigments such as titanium dioxide, red iron oxide, chromium oxide, yellow lead, carbon black and ultramarine blue, silica-based white carbon, alumina, zinc oxide, magnetic iron oxide, boron nitride, silicon carbide and various pigments. Inorganic functional pigments commonly used in the art, such as clay powder, and organic pigments can be used according to the purpose.

As the colorant, 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 generally used in the art can be used alone. Alternatively, they can be used in combination of two or more, and can impart a desired hue to the cured polymer of the present invention.

Each of the above fillers has a particle size composition, a shape, a pore volume, and the like in consideration of the purpose of use of the liquid composition of the present invention.
It is important to use materials that have been pulverized, classified, mixed, sintered, refined, etc. either singly or in combination of two or more in consideration of powder properties such as specific surface area, water absorption and oil absorption. When these fillers contain water,
It must be handled with care because it accelerates the condensation reaction of the organosiloxane. Thus, in the case of a filler containing water, it is possible to remove the water content by subjecting it to a treatment such as heat dehydration in advance, or by subjecting it to a curing step specified in the present invention if a small amount of water is present. It is preferable from the standpoints of liquid storage and single liquid storage. In addition, fillers that are surface-treated with various known coupling materials, antistatic agents, surfactants, etc. and modified into functional powders according to workability and purpose of use are also used for their respective purposes. Can be used accordingly.

The organosiloxane composition of the present invention comprises:
In order to improve various properties such as dispersibility, impregnation property, defoaming property, fluidity and coating property of the composition, an interface such as a fluorine-based interface is provided as long as the physical properties and workability of the organosiloxane composition are not impaired. An activator, various organic compounds, a resin and, if necessary, a solvent can be added and blended in advance.

The mixing method naturally varies depending on the content of the organosiloxane composition, the purpose of use, etc. because the liquid composition of the present invention has sufficient one-liquid storability, but in general, the civil engineering industry, cement industry, concrete Mixer used in the industry, paint industry, food industry, chemical manufacturing industry, etc., for example, mortar mixer, stirrer, mixer, kneading roll, homogenizer, etc., selected as a homogeneous liquid, paste It may be mixed under the condition that a mixture in the form of mortar or mortar is obtained. In consideration of weather conditions and environmental conditions at the time of mixing and working, such as winter and summer, it is also possible to perform pretreatment adjustment such as cooling or heating of the materials before mixing before use.

Mortar-like compound prepared by mixing into a homogeneous liquid state,
The liquid composition of the present invention in a paste form or a liquid form can be prepared by a method known per se, for example, spraying method, spraying method, brush coating, roller coating, iron coating, flow coating, pouring, coating method, patching method, etc. It is possible to apply coating, coating, protection, adhesion, hardening, gathering, molding materials, anchors, etc., automatically or manually according to the purpose and application by the construction method generally used in. Of course, it is also sufficiently effective depending on the purpose, conditions, method, etc. to perform overcoating or to combine the undercoat and the topcoat with different compositions and compositions.

In the present invention, the liquid composition of the present invention is used as a kind of binder, and an aggregate, a reinforcing material, a molded body, etc. are prepared according to the workability, physical properties, functionality, purpose of use, etc. required of the cured product. It is possible to provide a solidified body or structure of an integrated composite cured body. At this time, the aggregate, the reinforcing material, and the molded body which are preferably used can be selected from powders having a particle size of 200 μm or more or the following materials.
These materials are integrated by contacting in an amount within a wide range of 100 to 2000 parts by weight with respect to 100 parts by weight of the organosiloxane composition so as not to impair the purpose of use, workability and various physical properties. It can be a solidified body or structure of a cured body.

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

The above-mentioned aggregates, reinforcing materials, molded bodies and the like used in the present invention have various grain sizes and shapes.
They can be appropriately selected and used depending on the purpose of use and various physical properties required. Further, depending on the construction work, purpose of use, etc., it is also possible to use a material which has been previously treated with various coupling materials, surfactants, resins and the like. There are various methods for forming a solidified body or a structure of a composite cured body in which the organosiloxane composition of the present invention is integrated with a binder for these aggregates, reinforcing materials, molded bodies and the like. Materials, molded bodies, etc. and the liquid composition of the present invention are mixed together, and then the whole is cured together in a fixed mold or container, and further aggregates, reinforcing materials, molded bodies, etc. Alternatively, there is a method in which the composition of the present invention is poured into the container or left in a container or left to stand, or is impregnated and cured to be integrated into a composite cured product. These methods can be appropriately selected and adopted depending on the purpose, application, environmental conditions and the like.

As can be understood from the above contents, the base material for which the composition of the present invention is used for the purpose of use such as a binder, a covering material, and a structure is wide, and it is related to society / life, manufacturing / industry industry. , The construction / civil engineering industry, the service industry, etc. can be selected as required, and the following construction sites and objects can be cited as examples, although not particularly limited thereto.

Parts made of paper, pulp, metal such as iron, alloys such as stainless steel, rock, glass, gypsum, ceramics, slug, asphalt, wood, fibers, various materials, structures, various devices, floors, walls , Blocks, flues, chimneys, furnaces and surroundings, surfaces of roads, tunnels, bridges, building materials, structures, etc .; and surfaces of ingots and equipment, etc. that require lot marking; Various woven fabrics, molded bodies, structures, honeycomb bodies, etc. according to the above can be cited as useful construction sites and objects.

Further, the liquid composition of the present invention can be usefully used as a material for repairing, undercoating, pretreating, filling material, finishing material, dressing material, anti-slip material, etc. at the above-mentioned respective places. Furthermore, various ceramic materials, fibrous materials, abrasives, abrasion-resistant materials, various inorganic compounds, etc. are mixed in the liquid composition of the present invention to form composite materials that meet various needs such as water resistance, heat resistance, fire resistance, and acid resistance. It can be applied as a solidifying material, processing material, adhesive, binder, joint material, etc. of various materials similar to the above, as a chemical factory, food factory, plating factory, hot spring, dining room, kitchen etc. It can be applied to roads, drains, building materials, etc.

Further, the liquid composition of the present invention is used as a casting solidifying material for various molding materials, as a casting repair material for damaged parts such as refractory furnace materials, chimneys, boilers, structures, etc. It can also be usefully used as an injection solidifying material for treating and disposing of (irregular shape) or a specific shape of industrial waste, for example, a solid body of radioactive waste discarded from a nuclear power plant or the like. Furthermore, the liquid composition of the present invention is an anchor fixing material for a structure such as a tank, a tower, and a building, an equipment fixing device, and the like, a fixing cement in a place where embedding or a plastic patching material in each of the above fields is required. It can also be used as a material.

[0131]

According to the present invention, a liquid precursor composed of an organosiloxane group having a high concentration of silicon component is mixed with a crosslinking agent composed of a liquid organic compound of silicon, titanium, and zirconium to obtain an organosiloxane composition. By heating under contact with, non-combustible / flame retardant and heat resistant,
It forms a polymer with a siloxane bond as the main chain, which has flexibility and flexibility with water permeation resistance, and is effectively applied to applications such as transparent films, coating materials, binders and structures. A solvent-free, catalyst-free organosiloxane composition that is heat-friendly and environmentally friendly is provided in a one-pack type.

[0132]

EXAMPLES The heating type solvent-free catalyst-free organosiloxane composition of the present invention and its use will be described below with reference to specific examples.

I. Raw Materials for Liquid Organosiloxane Compositions and Their Preparation. 1). The raw materials for the precursor (A) are shown in Table 2, the content of the precursor (A) and the silicon component concentration (SiO 2
₂ (%)) Table 3 shows the curing conditions of the curing process. Manufacturing Company SS: Shin-Etsu Chemical Co., Ltd. MR: Mitsubishi Rayon TD: Toray Dow Corning Silicone

[0134]

2). Table 4 shows raw materials for the crosslinking agent (B). Manufacturer TM: Tama Chemical Industry SS: Shin-Etsu Chemical NS: Nippon Soda CM: Commercial Reagent TD: Toray Dow Corning Silicone

3). Pre-prepared precursor (A) and cross-linking agent
Table 5 shows the contents of the organosiloxane composition prepared in (B) and the MO ₂ concentration (%).

II. Pot Life, Shelf Life and Curing Conditions of the Composition of the Present Invention Regarding the pot life and shelf life of one liquid of the liquid organosiloxane composition of this example shown in Table 5, each test shown below Tested by law. On the other hand, a test plate coated with the liquid composition was prepared by the method described below, and immediately subjected to the curing heating conditions shown in Table 6, and the surface hardness of the coating film formed at that time was measured by the following test method. The above results are also shown in Table 6. As a comparative example, a composition containing a silicone resin (SR-MF) having an OH group (sample number: A-4), which was not subjected to a curing process (sample number: H-1)
And a precursor containing no cross-linking agent (sample number: A-1
) Only liquid composition (sample number: H-2) was selected, and an acrylic paint (sample number: H-3) was selected from general-purpose paints (commercially available products) using organic compounds as raw materials and evaluated.

Test method for pot life: The liquid organosiloxane composition of the sample was placed in an open container in a thermostatic chamber at 20 ° C., and the surface state of the sample was observed at each lapse of time. The time until the tension phenomenon occurred was calculated. The sample in which the skin was not stretched even after 24 hours had passed was regarded as “good” because it had a sufficient pot life.

Test method for shelf life with one solution : One sample was prepared by placing the liquid organosiloxane composition as a sample in a sealed container and leaving it at room temperature for 6 months without any change. The shelf life was "Yes", and the case where gelation or skinning phenomenon occurred was "No".

Preparation method of coating test plate: According to the general coating paint test method described in JIS K 5400, a liquid composition of a sample was sprayed onto a steel plate base material specified in JIS G 3141 to obtain a film thickness of about 20. It was applied to have a size of micron and immediately cured in a heating oven at a predetermined temperature. Coating surface hardness test method: JIS for test pieces subjected to curing conditions
It was measured by the pencil scratch test method described in 6.14 of K 5400, and is shown by the pencil hardness symbol at that time.

[0141]

III. Application as transparent film A test piece was prepared by coating the liquid organosiloxane composition of this example shown in Table 5 with a transparent film by the following method, and the test piece was subjected to each test shown below. It evaluated by the method. In addition, the same test was performed for two types of comparative examples (sample numbers: H-1 and H-3). The results of these tests are also shown in Table 7.

Method for producing transparent film test piece: According to the general test method for paints described in JIS K 5400, the liquid composition of the sample was sprayed onto the steel plate base material defined in JIS G 3141 to obtain a film thickness of about A test piece was prepared by applying 20 μm of the coating and curing it under heating conditions of 200 ° C. for 10 minutes.

Test method for each item : Adhesion: A test piece was attached to the coated surface of the test coated plate with a cutter knife in accordance with the cross-cut test method described in JIS K 5400, 6.15.
Make 6 grid-shaped notches with 1.0 mm intervals, and attach the cellophane tape on the cut board and then peel it off.
The peeling state of the coating film surface at this time was observed, and the case where there was no peeling or scratching was evaluated by 25/25, and the number of grids with peeling or damage was reduced from the number of 25/25 molecules. Was displayed. Heat resistance: The test piece is exposed to an electric furnace at 250 ° C for 60 minutes according to the coating film heating test method described in 7.1 of JIS K 5400, taken out of the electric furnace, and allowed to cool at room temperature. When there is no swelling, cracking, or peeling on the film surface and the film is in a tough state, the heat resistance is “present”. Incombustibility: The test piece is exposed to an electric furnace at 500 ℃ where oxygen sufficiently passes according to the JIS K 5400 7.1 coating film heating test method, at which time the test piece does not burn by itself. The case was defined as “non-combustible”. Water permeation resistance: A test piece coated with Toyo Filter Paper No. 6 as a base material is laid on a funnel for natural filtration, water is put in the funnel, and the amount of water passing through the test piece at this time is determined. Was evaluated as having water permeability. Acid resistance: JIS glass is used for test pieces prepared from plate glass.
5% by weight at 20 ° C according to the test method described in 7.5 of K 5400.
Dipping in a concentrated sulfuric acid solution for 30 days, swelling on the surface of the test plate,
Acid resistance was defined as "present" when no blisters, peeling, holes, softening, or elution occurred. Alkali resistance: Place about 5 cc of supersaturated calcium hydroxide solution on the coated surface of the test piece, cover it with a curved watch glass to prevent volatilization and leave it at room temperature, and wash the coated surface after 24 hours. At this time, the change on the coated surface was observed, and when there was no change, the alkali resistance was “present”. Flexibility: Using a bending tester described in 6.16 of JIS K 5400, the test piece is bent through a round bar with a diameter of 10 mmφ, and if there is no abnormality on the coating film surface due to the bending, it is "resistant" to bending. And Weather resistance: 55 ± 15 using a QUV weather meter (wavelength range 280 to 320 nm) on the test piece.
Exposure to 2500 ° C in a cycle of irradiation and condensation at ℃, measure the glossiness of the test piece application surface after exposure, and compare the glossiness decrease rate (%) with the glossiness of the test piece application surface before exposure. Asked and showed. Weather resistance is "Yes" when the gloss reduction rate is within 10%
And

As a result of the above, the solventless catalystless liquid organosiloxane composition of the present invention rapidly forms a transparent cured film by heat curing, and the transparent film has heat resistance, acid resistance, alkali resistance, flexibility and weather resistance. It is well understood that it is excellent in sex.

[0146]

IV. Application as coating material or binder Two liquid compositions (sample numbers: AB-2, AB-5) were selected from the liquid organosiloxane compositions of this example shown in Table 5, and the liquid compositions were selected. Disperse powdery fillers (activators, fillers, pigments, colorants, etc.) of 200 micron or less in 100 parts by weight in an amount ratio (parts by weight) shown in Table 9 in a paint or paste form using a disper. After mixing and preparing, a composite cured product was prepared in which a polymer having a siloxane bond as a main chain was produced by heating and curing each of which was left at 40 ° C. for 24 hours. The composite cured product prepared here was evaluated as a coating material, a binder and the like by the following test methods. The above results are also shown in Table 9. The fillers used in this example are listed in Table 8. These fillers were used after being thoroughly dehydrated in advance by a drying treatment at about 200 ° C.

[0148]

Test methods for each item : Heat resistance: Same as for transparent film test method Non-combustibility: Same as for transparent film test method Alkali resistance: Same as for transparent film test method Weather resistance (weather meter): Transparent Similar to the case of the film test method Adhesion: A sample prepared in a mold made to have a size of 40 × 40 × 15 cm on the base material using the same steel plate as that used in the preparation of the transparent film test piece. Pour, and cure at 40 ℃ for 10 days,
A test piece in which a cured product of a sample is adhered to a steel plate is prepared. Then, in accordance with the Ministry of Construction Architectural Research Institute type adhesion test method, the tester attachment is bonded with an epoxy resin adhesive,
The adhesive force (kg / cm ² ) was measured from the load (P) when the adhesive surface between the adherend and the test solidified material was peeled off by pulling it upward with the hydraulic pressure of the tester to determine the bondability. .. The display is kg / cm
A value of ² was used.

[0150]

As a result of the above, the liquid organosiloxane composition of the present invention was blended with various fillers, and the composite blend was heat-cured to form a composite hardened body consisting of a coating film, a paint and an adhesive, These composite cured products have heat resistance,
It is well understood that it is a material excellent in nonflammability, alkali resistance, weather resistance, adhesiveness, and the like.

V. Application as a structure The liquid organosiloxane composition of this example shown in Table 9 was mixed with a powdery filler (activator, filler, pigment, colorant, etc.) of 200 μm or less. Select 3 kinds from the mixture prepared in the form of paint or paste,
100 parts by weight (parts by weight) shown in Table 11 below is mixed with materials such as reinforcing materials, aggregates, and moldings with a size of 200 microns or more shown in Table 10 below, and then left at 40 ° C for 24 hours. A structure of a composite cured body integrated with a polymer having a siloxane bond as a main chain was prepared by heat curing. The structure of this example was evaluated by the following test methods. The above results are also shown in Table 11.

Materials such as a reinforcing material, an aggregate and a molded body used in this example are shown in Table 10. These reinforcing materials, aggregates, molded bodies, etc. were dried in advance at about 200 ° C. and thoroughly dehydrated before use.

Test methods for each item : Heat resistance: Same as in the case of transparent film test method Non-combustibility: Same as in case of transparent film test method Compressive strength: In accordance with the method described in JIS A 1108, the structure of the present invention The composition was prepared in a rectangular mold (2 × 2 × 8 cm), left at room temperature for 7 days, then demolded, using a compression tester in accordance with the method described in JIS A 1132. Compressive strength (kg /
cm ² ) was calculated. In addition, the value was displayed in kg / cm ² .

[0155]

As a result of the above, the mixture of the liquid organosiloxane composition of the present invention and the filler was mixed with various reinforcing materials, aggregates, and
When integrated with materials such as molded bodies and applied to a structure of composite cured body, it quickly forms a structure by heat curing, and this structure has excellent heat resistance, noncombustibility, compressive strength, etc. Is well understood.

Claims (13)

[Claims] 1. A precursor (A) comprising an organosiloxane.
In a two-part liquid mixture composition of a resin and a crosslinking agent (B); a precursor
R ¹・ Si group (R ¹ is a monovalent hydrocarbon group) in which (A) is an organosilicon group and OR ² group (R ² is a hydrogen atom or a C ₁ to C ₅ alkyl group) which is a functional side chain Or a combination of two or more liquid organosiloxanes composed of an acyl group), wherein the cross-linking agent (B) has a functional group consisting of at least one alkoxy group, acyloxy group or oxime group, and liquid silicon or titanium. Or a compound of one or more organic compounds of zirconium,
And a metal element component to which the two parties mixture composition contains MO ₂
A heating-type solvent-free catalyst-free organosiloxane composition, characterized by containing 40% by weight or more on an oxide basis (M is an element of silicon, titanium or zirconium). 2. The precursor (A) is represented by the following general formula (1) (In the formula, R ² is a hydrogen atom or a C ₁ to C ₅ alkyl group or an acyl group; R ³ to R ⁷ are each a hydrogen atom, O
A low molecular weight poly-organic composed of one or a combination of two or more liquid organopolysiloxanes represented by R ² groups or the same or different groups selected from monovalent hydrocarbon groups and n is a number smaller than 15). The heating-type solventless catalyst-free organosiloxane composition according to claim 1, which is a group of compounds containing siloxane in an amount of 10% by weight or more. 3. The precursor (A) contains an organic silicon group.
It has an R ¹ · Si group (R ¹ is a monovalent hydrocarbon group) and an OR ² group that is a functional side chain (R ² is a hydrogen atom, a C ₁ to C ₅ alkyl group or an acyl group). The heating type solventless catalystless organosiloxane composition according to claim 1 or 2, which is a group of compounds in which a silicone resin is dissolved and blended in an amount of 10% by weight or more. 4. The thermoplastic resin of a linear organic polymer compound having a carboxyl group is dissolved in the liquid organosiloxane of the precursor (A) in an amount of 30% by weight or less. The solvent-free, catalyst-free organosiloxane composition of the above. 5. The cross-linking agent (B) is represented by the following general formula (2) R ⁸ _mM · (OR ² ) _4-m (2) (wherein M is silicon, titanium or zirconium). element;
R ² is a hydrogen atom or a C ₁ to C ₅ alkyl group, an acyl group or an oxime group; R ⁸ is a hydrogen atom, a group selected from an OR ¹ group or a monovalent hydrocarbon group, and m is an integer of 3 or less) The solventless non-catalyst organosiloxane composition according to claim 1, which is one or a combination of two or more organic compounds of liquid silicon, titanium or zirconium represented by 6. The cross-linking agent (B) contains one or two kinds selected from the group consisting of a β-keto acid ester, a β-diketone compound, and a malonate ester optionally having an alkyl group or a trifluoro group. The heating-type solventless catalyst-free organosiloxane composition according to claim 1, wherein the reaction blocking agent comprising the above-mentioned combination keto-enol type tautomeric compound is blended in an amount of 80% by weight or less. 7. The crosslinking agent (B) is blended in an amount of 100 parts by weight or less based on 100 parts by weight of the precursor (A).
7. A heating type solvent-free catalyst-free organosiloxane composition as described in 6 above. 8. A precursor or a cross-linking agent of the precursor (A).
8. The heating mold according to claim 1, wherein the mixture with (B) has been previously subjected to a curing step in the absence of water at a temperature of 100 ° C. or lower for 10 minutes or longer to be storable as one liquid. A solvent-free catalyst-free organosiloxane composition. 9. The main chain is a polysiloxane bond produced by heating the heating-type solventless catalyst-free organosiloxane composition according to claim 1 to 40 ° C. or higher. A transparent film made of a polymer. 10. The heating type solvent-free catalyst-free organosiloxane composition according to any one of claims 1 to 8.
A coating mixture containing 400 parts by weight or less of 1 or 2 or more kinds of combination fillers selected from the group of activators, fillers, pigments and colorants per 00 parts by weight, 40 ° C
A coating material comprising a composite cured product formed from a polymer having a polysiloxane bond as a main chain, which is produced by heating above. 11. The above-mentioned filler is blended with a precursor (A) consisting of an organosiloxane alone or in a mixture with a cross-linking agent (B), and then treated in advance in the absence of water at 100 ° C. for 10 minutes or more. 11. The coating material according to claim 10, which is a stabilized coating liquid mixture which is subjected to a curing step and can be stored as one liquid. 12. The heating type solvent-free catalyst-free organosiloxane composition according to any one of claims 1 to 8.
A fluid or plastic mixture prepared by pre-blending one or more kinds of combination fillers selected from the group of activators, fillers, pigments and colorants in an amount of 500 parts by weight or less with respect to 00 parts by weight is prepared. A binder comprising a composite cured product formed of a polymer having a polysiloxane bond as a main chain, which is produced by heating at 40 ° C. or higher. 13. 100 parts by weight of the fluid or plastic mixture according to claim 12, and 100 or more of one or more combination materials selected from the group consisting of a reinforcing material, an aggregate or a molded body in advance. A structure characterized by comprising a composite cured product formed by using as a binder a polymer having a polysiloxane bond as a main chain, which is produced by heating a composite compounded and combined in a range of 2000 parts by weight to 40 ° C. or more. body.