JPS62138574A - Binding agent composition - Google Patents

Abstract

PURPOSE:A binding agent composition, containing a polymetallocarbosilane and silicone resin, capable of joining even at low temperatures without deteriorating the strength in an atmosphere at high temperatures and capable of joining metallic members and nonmetallic members in a severe atmosphere. CONSTITUTION:The title composition obtained by blending (A) a polymetallocarbosilane, preferably a polymer, consisting of carbosilane linking units expressed by the formula (R1 and R2 are lower alkyl, phenyl or H) and siloxane linking units expressed by the formula -(M-O)- (M is Ti, Zr, Mo or Cr which may have alkoxy or phenoxy group at the side chain group thereof) in which the above-mentioned linking units are randomly linked in the backbone skeleton, etc., at 1:1-10:1 ratio of the total number of the above-mentioned linking units and having 400-50,000 number-average molecular weight with (B) a silicone resin, preferably at 100:10-900 weight ratio.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel adhesive compositions containing polymetallocarbosilanes. More specifically, the present invention relates to a novel adhesive composition containing a metallocarbosilane and a silicone resin.

(Prior art) Mechanical joining such as bolts and rivets have traditionally been used for joining applications that require heat-resistant plastic or chemical durability, but with recent technological innovations, mechanical joining has been used in a wide variety of fields. Bonding using adhesives has begun to be implemented in the industry, and various types of fasteners have been used as fasteners accordingly.

Among these, organic adhesives such as polyimide and polybenzimidazole have a heat resistance temperature of 200 to 400° C. At higher temperatures, adhesive strength decreases and durability becomes poor.

On the other hand, many types of inorganic adhesives using inorganic compounds as binders are known.

Among these, as a type that hardens due to the formation of hydrates,
There are Portland cement, gypsum, etc.

However, these cured products have insufficient heat resistance, as they lose their cohesive strength when reheated, and are also inferior in water resistance and acid resistance.

Further, as types that harden due to evaporation of water, those containing water-soluble silicate such as water glass have drawbacks such as low adhesive water resistance and generation of alkaline stain.

Another type is low-melting glass, which is melt-bonded.
There is solder. Naturally, these do not have adhesive properties at temperatures above the melting point, and in order to satisfy the high heat resistance temperature, a high melting point composition must be used (problem to be solved by the invention). In particular, by providing an adhesive composition that can be bonded at relatively low temperatures, exhibits very little deterioration in adhesive strength in high-temperature atmospheres, is durable, and has excellent water resistance, it can withstand harsh conditions. The purpose of this invention is to enable the joining of metal and non-metallic members that can withstand practical use under a harsh atmosphere.

(Means for Solving the Problems) The present invention is an adhesive composition formed by mixing a polymetallocarbosilane and a silicone resin.

, the polymetallocarbosilane used in the present invention has the following (A) carbosilane binding tendency and at least if! Consisting of the following (B) metalloxane bonding unit of i, R1 (A): →5i-CH2← R7 (However, R1 and R2 may be the same or different and each independently represents a lower alkyl group, a phenyl group, or a hydrogen atom. (B): →M-O)- (where M represents at least one element selected from the group consisting of Ti, Zr, Mo, and Cr, and in some cases, at least a portion of each of the above elements has at least one lower alkoxy group or phenoxy group as a side chain group) A polymer in which each of the bonding units of (A) and (B) are bonded randomly in the main chain skeleton, and/or a bond of (A) At least a part of the silicon atoms of the unit are bonded to each of the elements of the bonding unit of (B) via an oxygen atom, whereby the polycarbosilane moiety found in the chain of bonding units of (A) is formed. A polymer crosslinked by the bonding units of (B), wherein the ratio of the total number of bonding units of -(A) to the total number of bonding units of (B) is in the range of 1:1 to 10=1. It is an organometallic polymer having a number average molecular weight of 400 to so, ooo.

This adhesive composition consisting of polymetallocarbosilane and silicone resin is applied to the surface of a metal or non-metallic adherend, and after the adherends are bonded together, the adhesive composition is placed in an oxidizing or non-oxidizing atmosphere. It was discovered that metal and non-metallic adherends are firmly bonded together when heated in a temperature range of 200 to 2000°C, and the present invention has been achieved based on this discovery.

Even if the polymetallocarbosilane used in the present invention is heat-treated at 1000°C for 10 hours or more in an air atmosphere, the weight loss on heating is only 10 to 15% by weight, so shrinkage and cracking due to weight loss of the baked coating film are avoided.・Hard to bow 9. Therefore, the dimensional change of the formed adhesive layer due to heating is small and the adhesive layer is dense.

In addition, since polymetallocarbosilane contains a gold plate,
When this is especially applied to the surface of the gold 1 base material and heated, the ultrafine metallized particles or gold scrap oxide form a strong bond between the adhesive layer and the metal base material.
An adhesive layer is formed that exhibits little decrease in adhesive strength even when heated to a higher temperature. Because the ultrafine particles function as a binder on ceramic and glass surfaces,
Forms an adhesive layer that firmly adheres to the adherend.

Furthermore, this adhesive composition composed of polymetallocarbosilane and silicone resin adheres more firmly to the adherend than an adhesive composed of polymetallocarbosilane alone, and also has improved heat resistance and flexibility.・It was discovered that it has a remarkable effect of being superior. That is, the adhesive layer consisting of polymetallocarbosilane alone is flexible and chipped.
It does not show good adhesion to peeling force that involves bending like T-peel. Furthermore, although polymetallocarbosilane loses a small amount of heat due to high-temperature heat treatment, its existence causes volumetric shrinkage. Therefore, in order to compensate for the disadvantages of 4'lJ metallocarbosilane and to obtain an even better adhesive composition, we have made extensive research efforts.As a result, we found that when polymetallocarbosilane is used in combination with silicone resin, flexibility and The inventors have discovered that an adhesive composition with excellent film-forming properties and heat resistance can be obtained, and have arrived at the present invention.

10 to 900 heavy blue parts, preferably 50 to 200 parts by weight, of silicon w fat t-holimetallocarbosila, 7100 parts by weight
Add part by weight.

If the amount of silicone resin added is less than 10 parts, the resulting adhesive layer will have poor flexibility, while if it exceeds 900 parts, the excellent heat resistance of polymetallocarbosilane will not be exhibited, and it will not be possible to obtain the adhesive layer after high-temperature heating. The adhesion of the product is extremely reduced.

The silicone resin used in the present invention is at least one selected from the group consisting of polyorganosiloxane, zircon oil, silicone rubber, and silicone rubber.

Furthermore, an inorganic filler may be added in an amount of 10 to 500 parts by weight per 1.0 parts by weight of the polymetallocarbosilane. Adding an inorganic filler is desirable in that it improves the softening properties of the adhesive layer at high temperatures, but adding too much is not preferable because it reduces mechanical strength.

The inorganic fillers used in the present invention include known additives such as boron, magnesium, aluminum, silicon, calcium, titanium, vanadium, chromium, manganese, zinc, zirconium, molybdenum, cadmium, soot, antimony, barium, tungsten, lead, and 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.

A powder adhesive composition is obtained by mixing and pulverizing polymetallocarbosilane, silicone resin, and inorganic filler. Alternatively, a liquid adhesive composition may be obtained by dissolving or dispersing it in a suitable solvent such as benzene, toluene, or xylene.

In the case of a powdered adhesive, sprinkle this adhesive composition evenly on one or both sides of a pre-cleaned metal adherend or non-metallic adherend such as glass, ceramic, firebrick, etc. If necessary, apply by brushing, spraying, roller, dipping, etc., bond the adhered surfaces together, and heat while applying pressure from the outside as necessary.

The heating temperature is preferably 200° C. or higher, but if the object to be coated is placed in a usage environment of 200° C. or higher after painting, there is no need to provide a particular heating step. If the heating temperature is 200° C. or lower, the drying and curing of the adhesive layer will be insufficient and sufficient adhesive strength will not be obtained.

By this heating, the adhesive layer is completely cured and firmly adheres to the adherend. The thickness of the adhesive layer after drying and curing may be from 0.1 to 100 .mu.m, most preferably from 1 to 10 .mu.m, and can be appropriately selected depending on the need (/i:).

A more specific explanation will be given below based on the implementation sequence.

In the examples, % and parts indicate weight % and parts by weight, unless otherwise indicated by i4M.

(Reference Example 1) 2.5 t of anhydrous xylene and sodium 4009 were placed in a 5 t three-lough flask, heated to the boiling point of xylene under a nitrogen gas stream, and 1 t of dimethyldichlorosilane was added dropwise over 1 hour. After the dropwise addition was completed, 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 polydimethylsilane 42.
(I got l.

The above polydimethylsilane 400f was charged into a 3t three-neck flask equipped with a gas inlet tube, a stirrer, a condenser, and a distillation tube, and was poured under a nitrogen stream (50 ml/ml) while stirring.
By heating at 420° C., a colorless and transparent slightly viscous liquid of 3502 was obtained in a distillation vessel. The number average molecular weight of this liquid is determined by vapor pressure osmosis method (VPO method)
When measured, it was 470.

Furthermore, by measuring the far-infrared absorption of this substance, mainly →8i
It was confirmed that it was an organosilicon polymer having a hydrogen atom and a methyl group in the silicon side chain from the -CH2← bond position and the →5i-8i← bond position.

(Reference Example 2) Next, this organosilicon polymer 401P and titanium tetraisopropoxide 202 were weighed, and xylene 400-7 was added to this mixture to make a mixed solution consisting of a homogeneous phase. The reflux reaction was carried out while stirring at ℃ for 1 hour. After the reflux reaction was completed, the temperature was further raised to distill out the dissolved xylene A, and then polymerization was carried out at 300° C. for 10 hours to obtain a metal-crosslinked polymer containing silicon and titanium. The number average molecular weight of this polymer is v
When measured (by pO method), it was 1165. Gel permeation chromatography and infrared absorption spectroscopy showed that the polymer obtained here has some Si-H bonds in the organosilicon polymer disappeared, and the silicon atoms in this part are the titanium atoms of titanium tetraisopropoxide. The organosilicon polymer has 3 20-Ti (OC3H7) groups in its side chain, and some of the organosilicon polymer has →Ti-(t)- bonds. The reaction rate and/or crosslinking rate at the S 1-Hi bonding moiety in this polymer is 44.5%. -48'1-CH2→bond degree -(Si
−8i←゛1 Total number pair of Yoshiai units −〇−T i (QC,
It was confirmed that the total ratio of H, ), and -Ti-〇- bonding units was about 6:1.

(Reference Example 3) Polyzirconocarbosilane was obtained using zirconium tetraisopropoxide instead of titanium tetraisopropoxide, which is one of the starting materials in Reference Example 2.

The reaction conditions and operating method are substantially the same as in Reference Example 2.

[Example 1] 100 parts of the polytitanocarbosilane obtained in Reference Example 2 and 200 parts of a 50% xylene solution of methylphenyl silicon face (TSR-116 manufactured by Toshiba Silicon Corporation) were mixed to obtain a slurry composition. . This composition was sandblasted and degreased with acetone. 50 x 50 (1 m) 8
US 304f! Apply the coating to a thickness of about 5) to 4 plates, and place another similarly treated steel plate on top of it and fix it for 20 minutes.
It was left in an air oven at 0° C. for 1 hour to dry and harden.

Next, the bonded sample was heated in an air oven under the conditions shown in the table below, and after being left to cool in the oven, the bond strength (rl) was evaluated by tensile shear stress. The results of the first measurement are shown in Table 1.

Table 1 Here, for example, (B) is 20
This indicates that a further heat treatment was performed from 0°C to 350°C at a rate of 10°C/min. The following applies to (C) to (F').

Q2>, <Q3> [Example 2] 80% polyzirconocarbosilane obtained in Reference Example 3, 60 parts of xylene solution, and 20 parts of dimethyl silicone oil (TSP 431 manufactured by Toshiba Silicon Co., Ltd.) were mixed to form a paste. It was used as an adhesive. Two commercially available silicon carbide plates (density 3.0
The above paste was applied to one side of each of the samples (f/cyn3) and then stacked on top of each other. 2001: After being left in the air for 1 hour to dry and harden, the tensile shear strength was 200k.
An adhesion of g/α2 was achieved. This adhesive piece was left in an open air environment at 800° C. for 1 hour, and then allowed to cool in the oven. It was found that the tensile shear strength after cooling was 50 kg/Crn', and that the paste adhesive had excellent heat resistance.

[Comparative Example 1] Polytitanocarbosilane 80% xylene solution was prepared from Example 1.
When dried and cured at 200° C. in the same manner as above, the tensile shear strength was 10 kg/cm 2 , and this low adhesion was thought to be due to the poor flexibility of the adhesive layer.

〔Effect of the invention〕

As is clear from the above description, the adhesive composition of the present invention can be bonded at relatively low temperatures, has little strength loss in high-temperature atmospheres, and can bond metal and non-metallic members in harsh environments. This is what makes it possible. Furthermore, in the adhesive composition of the present invention, when a highly insulating metal oxide is used as an inorganic filler, K is excellent as a heat-resistant insulating adhesive. This makes it possible to provide adhesives having various properties.

Claims (5)

[Claims] (1) An adhesive composition formed by mixing polymetallocarbosilane and silicone resin. (2) Polymetallocarbosilane consists of the following (A) carbosilane bonding unit and at least one of the following (B) metalloxane bonding units, (A): ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, R_1 and R_2 may be the same or different and independently represent a lower alkyl group, a phenyl group, or a hydrogen atom) (B): -(M-O)- (However, M is from the group consisting of Ti, Zr, Mo and Cr. At least one selected element, and in some cases, at least one portion of each element has at least one lower alkoxy group or phenoxy group as a side chain group) (A) and (B) each bonding unit is a polymer randomly bonded in the main chain skeleton, and/or at least a portion of the silicon atoms of the bonding unit of (A) bonding to each of the elements of the bonding unit of (B) via an oxygen atom; As a result, the polycarbosilane moiety obtained by the chaining of the bonding units of (A) is a polymer crosslinked by the bonding units of (B), and the total number of the bonding units of (A) is equal to the total number of bonding units of (B).
The adhesive composition 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) Claim 1, wherein the silicone resin is at least one selected from the group consisting of polyorganosiloxane, silicone oil, silicone varnish, and silicone rubber.
The adhesive composition described in . (4) The adhesive composition according to claim 1, wherein the silicone resin is contained in an amount of 10 to 900 parts by weight based on 100 parts by weight of the polycarbosilane. (5) Claim 1, wherein the adhesive composition is in powder form or in liquid form dissolved or dispersed in a solvent.
The adhesive composition described in .