JPS6254768A - Heat-resistant paint - Google Patents

Abstract

PURPOSE:To obtain heat-resistant paint which has a high baking residue ratio in air and can be baked in air, by dispersing or dissolving a polymetallocarbosilane, a silicone resin and an inorg. filler in an org. solvent. CONSTITUTION:The titled heat-resistant paint is obtd. by dispersing or dissolving a polymetallocarbosilane, a silicone resin and an inorg. filler in an org. solvent. The polymetallocarbosilane contains a carbosilane linkage unit of formula I and a metalloxane linkage unit of formula II, comprises a polymer wherein the units of formulas I, II are randomly bonded in the skeleton of its main chain and/or a polymer wherein at least part of Si atoms in the unit of formula I is bonded to each element in the unit of formula II through an O atom so that the polycarbosilane moiety formed by the chains in the unit of formula I is crosslinked by the unit of formula II, and is an organo-metallic polymer having a number-average MW of 400-50,000 and a ratio of the unit of formula I to the unit of formula II of 1:1-10:1.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel heat-resistant coatings containing polymetallocarbosilanes. More specifically, the present invention relates to a novel heat-resistant paint containing a polymetallocarbosilane, a filler, and a silicone resin.

(Prior Art) Paints containing polyorganosiloxane as a vehicle and various pigments added thereto are known as heat-resistant paints that prevent corrosion and deterioration of metal and non-metallic base materials at high temperatures. This polyorganosiloxane paint has excellent heat resistance when compared with conventional W1 commercial molecular paints such as polyester and polyimide. It peels off from the material.

Furthermore, with the development of industry, coatings that can prevent oxidation and corrosion of metal or non-metallic base materials that are exposed to high temperatures exceeding 1000°C, such as aircraft parts, ironworks, or the furnace body and surrounding parts of metal smelting furnaces, are becoming increasingly popular. Demand for materials is increasing.

Japanese Patent Publication No. 159-12746 discloses that polycarbosilane containing carbon and silicon as skeleton components and a small amount of metal elements is coated on a metal material and then heated to 800-200% in a non-oxidizing atmosphere.
A method for producing a heat-resistant metal material is described in which polycarbosilane is converted to silicon carbide by heating and firing at 000°C. Japanese Patent Application Laid-open No. 55-84370 discloses that a coating composition prepared by adding ceramic or metal powder to a semi-black iso compound containing polycarbonane is applied to a metal or non-metallic material, and then heated for 400 minutes in a non-oxidizing atmosphere. ~2
A method for obtaining a heat-resistant coating film by heating to 000° C. and baking is described.

However, the temperature of this polycarbonate at 1000℃ (in air)
Since the residual rate after firing is about 30% (w weight equivalent), large volumetric shrinkage occurs due to thermal decomposition of polycarbosilane during baking.

For this reason, the baking property of the coating film to the substrate becomes insufficient. When baking is performed in an oxidizing atmosphere such as air, most of the coating film peels off from the base material.

Furthermore, the heat resistance of the produced coating film is about 400° C. in air, which is not much different than the heat resistance temperature of conventional polyorganosiloxane paints.

(Problems to be Solved by the Invention) The present invention provides a heat-resistant paint that has a high firing survival rate in air, can be baked in and baked in air, and has a high heat resistance temperature in air. By providing this, it is intended to prevent oxidation and corrosion of metal or non-metallic substrates under high temperature conditions.

(Means for Solving the Problems) The present invention is a heat-resistant paint comprising polymetallocarbosilane, silicon 1[1, and an inorganic filler dissolved or dispersed in an organic solvent.

The polymetallocarbosilane used in the present invention has the following (A) carbosilane bonding unit and at least one of the following (B) methylocarbosilane R+ joy (A): -+S 1-CH2 Imaichi (however, %R1 and R2 may be the same or different and independently represent a lower furkyl group, a phenyl group or a hydrogen atom) (B'): -+M -0? (However, M represents at least one element selected from the group consisting of Ti, ZrMo, and Cr, and in some cases, at least one part of each of the above elements has at least a lower alkoxy group or a phenoxy group as a gA chain group. A polymer in which each of the bonding units of (A) and (B) are randomly bonded in the main chain skeleton, and/or a polymer in which the bonding units of (A) have a small number of silicon atoms (in both cases, a portion of the bonding units are The polycarbosilane moiety obtained by the chaining of the bonding units of (A) is bonded to each of the above elements of the bonding unit of (B) via an oxygen atom, and the polycarbosilane moiety obtained by the chaining of the bonding units of (A) is It is a combination, old man? 1A1f% story Δ Degome A noodles song F
/ Q Itha story 4 The ratio of the total number of us is in the range of 1:1 to 10:1 and the number average molecular weight is 400 to 50.0
It is an organometallic polymer consisting of 00.

The main chain skeleton of the polymetallocarbosilane is mainly →S
It is a polymer copolymer derived from polycarbosilane consisting of i CH2+- structural units and metal alkoxide having 1+M-〇'+- bonding units, and the spun fiber made from this is different from conventional polycarbosilane. It is shown in Japanese Patent Application No. 54-149977 that the heat resistance is superior to that of the resulting fibers.

After applying this paint consisting of polymetallocarbosilane, silicone resin, and inorganic filler to metal/nonmetal substrates,
200-2000℃ in oxidizing or non-oxidizing atmosphere
It has been discovered that the coating film obtained by heating and baking the above-mentioned polycarbosilane has better adhesion to the underlying metal/non-metal substrate and has better heat resistance than the coating film made of polycarbosilane. reached.

The polymetallocarbosilane used in the present invention can be used in an air atmosphere of UH.
Even after heat treatment at 1000°C for 10 hours or more under The thus formed coating film after baking is IIk dense.

In addition, since polymetallocarbosilane contains metal,
When this is baked onto the surface of a metal substrate, the ultrafine particles of metallization or metal oxide form a strong bond between the coating and the saw substrate, creating a dense bond that will not peel off even in the air at temperatures above 1,000°C. i11! form a layer. Similarly, on ceramic and glass surfaces, the ultrafine particles also have the function of binder, forming a strongly bonded coating film.

Furthermore, this coating film made of polymetallocarbosilane, silicone resin, and inorganic filler adheres more firmly to the base material than a coating film made of polymetallocarbosilane alone, and further improves heat resistance and flexibility. Also excellent.

10 to 900 parts by weight of silicone resin per 100iii parts of polymetallocarbosilane or 1 ILP or 50 to 500 parts by weight
Add part by weight. If the amount of silicone resin added is less than 10 parts, the flexibility of the baked coating film will be poor, and if the amount of silicone resin added is more than 900 parts by weight, the heat resistance at high temperatures above the decomposition temperature of the silicone resin will be impaired. The silicone resin used in the present invention is at least 1111 selected from the group consisting of polyorganosiloxane, zircon oil, silicone rubber, and silicone rubber.

Further, an inorganic filler is added in an amount of 10 to 900 parts by weight, preferably 50 to 500 parts by weight per 100 parts by weight of the polymetallocarbosilane. If the amount of the inorganic filler added is less than 10 parts, the adhesion of the baked coating film to the substrate will be poor, and if it exceeds 900 parts by weight, the flexibility of the coating film will be reduced.

The inorganic fillers used in the present invention are known additives such as boron, magnesium, aluminum, silicon, calcium, titanium, vanadium, chromium, manganese, zinc, zirconium, molybdenum, cadmium, sulfur χ, antimony, barium, tungsten, and lead. , bismuth oxides, their carbides, their nitrides, borates, phosphates, silicates of lithium, sodium, potassium, magnesium, calcium, zinc, etc.

These may be used alone or in combination.

Polymetallocarbosilane, silicone resin and inorganic light JI
A paint is obtained by dissolving or dispersing Eu in a suitable solvent such as benzene, toluene, or xylene.

This paint is applied to a metal base material or a non-metal base material such as glass or ceramic refractory brick by brushing, roll coater, spray gun, dipping, or the like, and then dried and baked.

A coating amount of 20 to 100 g/w+' is generally desirable.

If it is less than 20 g/m'', pin ice will occur and the setting property will be reduced. On the other hand, if it is more than 100 g/w'', the coating film is likely to crack during baking, which is not preferable.

The baking temperature is preferably 150°C or higher, but if the object to be coated is placed in an environment of 150°C or higher after painting, there is no need to carry out a baking process. It is not preferable because it has low hardness and poor 1HwJ impact resistance.

The baked paint film obtained from the one-heat paint of the present invention has excellent heat resistance and at the same time exhibits good corrosion resistance, impact resistance, and flexibility.

A more specific explanation will be given below with reference to Examples. In the Reference Examples and Examples, % and parts indicate weight % and parts by weight unless otherwise specified.

(Reference Example 1) 2.51 g of anhydrous xylene and 400 g of sodium were put in a 3-lough flask, heated to the boiling point of xylene under a nitrogen gas stream, and trimethyldichlorosilane IIl was added dropwise over 1 hour. After the completion of the 0 dropwise addition, The mixture was heated under reflux for 10 hours to form a precipitate. This precipitate was filtered and washed first with methanol and then with water to obtain a white powder of polymethylsilane 4.
20. I got it.

400 g of the above polydimethylsilane was charged into 31 three-necked flasks equipped with a gamma gas inlet tube, a stirrer, a condenser, and a distillation tube.
A colorless, transparent, slightly viscous liquid of 3508 was obtained in the distillation vessel by heat treatment at 420°C. The number average molecular weight of this liquid was determined to be 470 by vapor pressure osmosis (VPO method).

Furthermore, measurements of far-infrared absorption of this material revealed that mainly →Si
It was confirmed that it was an organosilicon polymer consisting of CH2+- bond units and →5iSi+ bond units and having hydrogen atoms and methyl groups in the silicon side chains.

(Reference Example 2) Next, 40 g of this organosilicon polymer and 20 g of titanium tetraisopropoxide were weighed, and 400 mff1 of xylene was added to this mixture to make a mixed solution consisting of a homogeneous phase.
A reflux reaction was carried out under a nitrogen gas atmosphere at 130°C for 1 hour with stirring. After the completion of the 3il flow reaction, the temperature was further raised to distill out the solvent xylene, and then
Polymerization was carried out at .degree. C. for 10 hours to obtain an organometallic cross-linked III polymer containing silicon and titanium. The number average molecular weight of this polymer was 1165''Ch as measured by the vpo method.

The polymer obtained here from the infrared absorption spectrum of the Del Permeability 5-in chromatograph 7 shows that the 5i-H bond in the organosilicon polymer has disappeared -W6, and the silicon atom in this part is combined with the titanium atom of titanium tetraisopropoxide and oxygen. bonded through atoms, whereby some organosilicon polymers have -077i(OC3)(?)3 groups in the 11 chain, and some organosilicon polymers have →Ti-0+
It is a polytitanocarbosilane crosslinked with - bonds, and the reaction rate and/or crosslinking rate at the Si H binding moiety in this polymer is 44.5%. One tithe of the organosilicon polymer of this polymer + S i -, CHd "" bonding units - + S i - Si - total number of bonding units - 〇 -T
It was confirmed that the ratio of the total number of i(OC4H,) and -Ti-0- bonding units was approximately 6:1.

The above reaction product was dissolved in xylene and the solid content was 50%.
% solution.

(@4 Example 3) In place of titanium tetraisopropoxide, one of the starting materials in Reference Example 2, zirconium tetraisopropoxide, chromium trimethoxide, or molybdenum triphenoxide was used to prepare polyzirco/IJ.
) Levosilane, polychronocarbosilane or bolimolypdecarbosilane were obtained. The reaction conditions and operation method are substantially the same as those in Reference Example 2.

[Example 1] Oxygen 9250% 1 of polytitanocarbosilane of Reference Example 2
30 parts of llli, 50 parts of methylphenyl silicone oil
% xylene solution (TSR-116 manufactured by Toshiba Silicon Corporation) 3
A heat-resistant paint was obtained by mixing 0 parts of titanium dioxide and 10 parts of titanium dioxide. Apply this paint to a 1m111 thick stainless steel plate (SUS).
304) to a thickness of approximately 50 μm using a percoater and baked at 200°C in an oven that was open for 1 hour. After heating this baked-on coated steel plate in a 1000°C oven for 96 hours, it was removed from the oven and removed in air. It got cold.

In order to evaluate the adhesion of this coating film to the substrate, two
Use a cutter knife to make 11 vertical and 11 horizontal cuts into the base material with a width of 1 Ifi, making a total of 100 gobans, paste adhesive cellophane tape on the surface, and peel it off rapidly. When the number of remaining coating films on the eyes was examined, it was found to be 95/100, indicating very good adhesion.

[Example 2] 250% polyzyl core carbosilane solution 4 of Example 3
0 parts dimethyl silicone oil (next summer') Near 7 companies lTsF431) 40n and (/, 1%' Potassium heptaate 2
0 parts by weight were mixed, and 50 parts by weight of xylene was added per 100 parts by weight of this composition to obtain a heat-resistant paint. 0 for this paint
, After dipping and coating a 5 arm thick titanium plate, 2
It was baked for 1 hour in the open at 00°C.

Heat cycle test (
1 hour at room temperature - 1 000℃ audio - 10
Although the coating was repeated several times, there was no change in the appearance of the coating film, and no peeling of the coating film from the base material was observed.

[Example 3] Xylene 50 of polysilipude 7 carbosilane of Reference Example 3
A heat-resistant paint was obtained by mixing 20 parts of methylphenyl silicone oil (TSF-451, manufactured by Next Summer Silicon Co., Ltd.) and 20 parts of talc. After applying this paint to a 1-thick stainless steel plate (SUS304) with a brush,
Bake in the oven for 1 hour at °C.

This baked-coated steel plate was heated at 1000°C for 96 hours in the open air, then slowly cooled in the air, and the adhesion of the paint film was evaluated using the same method as in the examples.The result was a very good result of 92/100. Obtained.

[Example 4] 50% xylene of Boric a-Simosilane of Reference Example 3
fif150m, methylphenyl silicon festival 50
% xylene solution (next summer silicon company WTSR-1 1 6
)208% and 30 parts of boron oxide were mixed to obtain a heat-resistant paint. This paint was applied to a 1 m thick nickel plate using a percoater to a thickness of 40 μm, and then baked in an oven at 200° C. for 1 hour.

This baked-coated nickel plate was heated in an open environment at 1000° C. for 3 hours, then slowly cooled in air, and the adhesion of the coating film was evaluated in the same manner as in Example 1 and found to be 95/100.

[Example 5] 80 parts of a 50% xylene solution of the polytitanocarbosilane of Reference Example 2, a 50% xylene solution to methylphenyl silicone face (next summer Silicon Company!!!TSR-1 1 6
) and 10 parts of tin dioxide were mixed to obtain a heat-resistant paint. This paint was roller coated on a titanium plate with a thickness of 0.5 mm and baked at 200° C. for 1 hour in an open environment.

Heat cycle test (
Although the treatment was repeated 5 times at room temperature for 1 hour to 1000° C. for 1 hour, no change in the appearance of the coating film or peeling from the substrate was observed.

[Comparative Example 1] Polycarbosilane obtained in Reference Example 1 xylene 50%ff
[30? i, 30 parts of 50% xylene solution of methylphenyl silicon face (TSR116 manufactured by Next Summer Silicon Co., Ltd.),
A paint was prepared by mixing 40glS of aluminum oxide powder. This paint was applied to a thickness of about 50 μm on a Q1 mm thick stainless steel plate using a bar coater, and then baked at 200° C. for 1 hour in an open environment.

This baking-painted steel plate was heated at 600° C. for 10 hours in the open air, then slowly cooled in air, and the adhesion of the coating film was evaluated in the same manner as in Example 1 and found to be 58/100.

[Comparative Example 2] 50 parts of 50% xylene solution of polytitanocarbosilane of Reference Example 2, 50% xylene solution of notylphenyl silicon face 8! (Next Summer Silicon Company%tTRS-116) 5
A paint was obtained by mixing 0 parts. This paint was applied to a thickness of about 50 μm on a stainless steel plate with a thickness of 1 using a Wopercoater, and then baked at 200° C. in an IEL open-circuit.

This baking-painted steel plate was heated at 1'000°C in an open room for 1 hour, then taken out and left to cool in the air, and the adhesion of the coating film was evaluated in the same manner as in Example 1, and it was found to be 62/100. .

[Comparative Example 3] A coating material was obtained by mixing 30 parts of a 50% xylene solution of the polycarbosilane obtained in Reference Example 1 and 70 parts of carborundum powder. A titanium plate with a thickness of 0.5 ms was immersed in this paint.
After coating, it was baked in an oven at 200°C for 1 hour.

This baked-on titanium plate was subjected to a heat cycle test (1 hour at room temperature - 1000℃ open and 1vP dark) for 10 minutes.
When I went over it several times, I found that some of the paint had peeled off and cracks were visible.

Patent applicant Ube 9! Sansan Co., Ltd. Agent Patent Attorney Taira Odajima and one other person Procedural Amendment (Chief) January 1985! 9th Japan Patent Office Commissioner Michibe Uga 1, Indication of the case 1985 Patent No. 193786 2, Name of the invention Heat-resistant paint 3, Person making the amendment Relationship to the case Patent applicant name (We Ube) Kosan Co., Ltd. 4, Agent 107 Telephone: 585-2256 5, Date of amendment order None 6, Subject of amendment 7, Contents of amendment (1) The scope of claims stated in the specification of the present application is corrected as follows. .

R2, *Request for permission@dish (1) A heat-resistant paint characterized in that Volime, po carbosilane, silicone resin, and inorganic filler are dispersed or dissolved in an organic solvent.

(2) Volume L locarbosilane consists of the following (A) carbosilane bonding unit and at least one metalloxane bonding unit of the following (13), (A): 1S i -CH2← (However, R and R1 are the same - or (B): fM-0+- (However, M is at least one selected from the group consisting of Ti, Zr, Mo and C. In some cases, at least a portion of each of the above elements is a low t &
Full': A polymer in which the bonding units of (A) and (B) are randomly bonded in the main chain skeleton, and/or the bonding unit of (A). At least 1 of the silicon atoms of the bonding unit of (B) are bonded to each of the elements of the bonding unit of (B) via an oxygen atom, so that the polycarbosilane moiety obtained by the chain of the bonding units of (A) is ) is a polymer crosslinked by the bonding units of (A) to the total number of bonding units of (B).
The heat-resistant paint according to claim 1, wherein the ratio of the total number of bonding units is in the range of 1:1 to 10:1, and the number average molecular weight is 400 to so, ooo.

(3) The heat-resistant paint according to claim 1, wherein the silicone resin is selected from the group consisting of polyorganosiloxane, silicone oil, silicone oil, and silicone rubber.

(4)! 'a Isochang materials are oxides, borates, phosphates,
The heat-resistant paint according to claim 1, which is at least one selected from the group consisting of t-salts, silicon cutlery, nitride borides, and carbides.

(5) The silicone resin is 10 to 900 parts by weight with respect to 100 parts by weight of the polycarbosilane.
900 parts by weight of the heat-resistant paint according to item 1 of the patent. (2) Specification 1 of the present application
! This is what is written in the 12th line of the 5th line. " is changed to "is something that attempts to do." Correction 11:.

(3) 1 METHYROKI J written on page 5, line 19 is corrected to "Metalloki".

(4) 41 directly below No. 6? 1. Correct "by these" to "by this."

Claims (5)

[Claims] (1) A heat-resistant paint characterized in that polymethylocarbosilane, silicone resin, and inorganic filler are dispersed or dissolved in an organic solvent. (2) Polymethylocarbosilane consists of the following (A) carbosilane bonding unit and at least one type of the following (B) metalloxane bonding unit, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, R_1 and R_2 are the same or (B): -(M-O)- (However, M is selected from the group consisting of Ti, Zr, Mo and Cr) at least one element, and in some cases, at least a portion of each element has at least one lower alkoxy group or phenoxy group as a side chain group) Each of the bonding units (A) and (B) has a main chain skeleton. and/or at least a portion of the silicon atoms of the bonding unit of (A) are bonded to each of the elements of the bonding unit of (B) via oxygen atoms, and thus the A polymer in which the polycarbosilane moiety obtained by chaining the bonding units of (A) is crosslinked by the bonding units of (B), and the total number of bonding units of (A) is
2. The heat-resistant paint according to claim 1, wherein the ratio of the total number of bonding units in ) is in the range of 1:1 to 10:1 and the number average molecular weight is 400 to 50,000. (3) The heat-resistant paint according to claim 1, wherein the silicone resin is selected from the group consisting of polyorganosiloxane, silicone oil, silicone varnish, and silicone rubber. (4) Claim 1, wherein the inorganic filler is at least one selected from the group consisting of oxides, borates, phosphates, silicates, silicates, nitrides, borides, and carbides.
Heat-resistant paint as described in section. (5) 10 to 900 parts by weight of the silicone resin and 10 parts by weight of the inorganic filler per 100 parts by weight of the polycarbosilane.
The heat-resistant paint according to claim 1, characterized in that the amount is 900 parts by weight.