JPH0423865A - Adhesive organopolysiloxane composition and method for curing the same and its cured product - Google Patents

Abstract

PURPOSE:To provide a composition capable of being adhered and cured by a high frequency wave heating method by compounding an alkenyl group- containing organopolysiloxane, an organo hydrogen polysiloxane, a platinic catalyst, an organic silicon compound, iron oxide powder and ferrite powder. CONSTITUTION:A composition comprises (A) 100 pts.wt. of an organopolysiloxane having two or more alkenyl groups and a viscosity of 100-200000CS (25 deg.C), (B) an organo hydrogen polysiloxane having two or more Si-bonded hydrogen atoms, the number of the hydrogen atoms being 0.6-6 per the alkenyl group of the component A, (C) a platinic catalyst, (D) 0.5-20 pts.wt. of an organic silicon compound having a Si-bonded H and a Si-bonded alkoxy group and/or an organic silicon compound having an oxirane group bonded to the Si through a carbon atom(s) and (E) 10-200 pts.wt. of the powder of an iron oxide of formula I ((x) is 0.5-1; (y) is 0-0.5; (x+y)=1) or the powder of a ferrite of formula II (M is a divalent metal such as Mn or Fe).

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention is an adhesive organopolysiloxane composition, which can be cured and bonded using an ultra-high frequency heating method, and is therefore applicable to insulating double-glazed glass for buildings, machinery, The present invention relates to an adhesive organopolysiloxane composition that is useful for safety laminated glass used for observation windows of chemical equipment, etc., a method for curing the same, and a cured product thereof.

[Prior Art] Addition-curing adhesive compositions based on organopolysiloxanes having vinyl groups bonded to silicon atoms are conventionally known. It has also been proposed to use an adhesion promoter (Japanese Patent Publication No. 53-13508, Japanese Patent Publication No. 53-2102)
No. 6, Special Public Showa 5! (See Publication No. 1-5219).

[Problems to be Solved by the Invention] However, since addition-curing adhesive compositions are generally cured by heating, when the adherend has a large heat capacity, the adhesive composition A large amount of energy is required to heat the adherend compared to heating, and there is a disadvantage that adhesiveness deteriorates when the temperature at the bonding interface is insufficiently raised.

[Means for Solving the Problems] The present invention relates to an adhesive organopolysiloxane composition that solves the above-mentioned disadvantages, a method for curing the same, and a cured product thereof. has an alkenyl group, and has a viscosity of 10 at 25°C.
100 parts by weight of an organopolysiloxane having a molecular weight of 0 to 200,0OOcS, (B) having two or more hydrogen atoms bonded to a silicon atom in one molecule, and containing 0 hydrogen atoms per alkenyl group of the organopolysiloxane. .6 to 6.0 organohydrodiene polysiloxanes, (
C) a catalytic amount of platinum or a platinum compound catalyst; (D) one or more hydrogen atoms bonded to a silicon atom in one molecule;
0.5 to 20 parts by weight of an organosilicon compound having an alkoxy group directly bonded to a silicon atom and/or an oxirane group bonded to a silicon atom via a carbon bond;
(E) General formula (Fe20) x (Fezes) y
(Here, x and y are each positive numbers, and 0.5≦X≦
1.0≦y≦0.5, x+y=f) or iron oxide powder with the general formula MO4ez03 (where M is Mn,
Fe, Cu.

The present invention is characterized in that it consists of ferrite powders 10 to 20 (1 part by weight) represented by divalent metal atoms selected from Ni, Mg, Co, and Zn.

That is, the present inventors developed a high-frequency heating method (Llltra
As a result of various studies aimed at developing an adhesive organopolysiloxane composition that can be adhesively cured by high frequency heating (hereinafter abbreviated as UHF heating), we added iron oxide powder and ferrite powder to a conventionally known addition-curing organopolysiloxane composition. It was discovered that the microwave absorption properties of this substance were improved by adding it, so that this composition could be adhesively cured by UHF heating. The present invention was completed by conducting research on the relationship between hardenability.

This will be explained in further detail below.

[Function] The present invention relates to an adhesive organopolysiloxane composition that is adhesively cured by UHF heating by adding iron oxide powder and ferrite powder, a method for curing the same, and a cured product thereof.

The organopolysiloxane as component (A) constituting the composition of the present invention has at least two alkenyl groups in one molecule, and has a viscosity of 10 at 25°C.
It is in the range of 0 to 200,000 cS. In this case, the alkenyl group includes vinyl group, allyl group,
Examples include abrasive alkenyl groups such as methallyl group and hexenyl group, and as organic groups other than alkenyl groups,
Alkyl groups such as methyl group, ethyl group, propyl group, butyl group, substituted alkyl groups such as 3.3.3-trifluoropropyl group, aryl groups such as phenyl group, etc. having 1 to 1O carbon atoms
5. It may contain an unsubstituted or substituted monovalent hydrocarbon group, preferably having 1 to 8 carbon atoms.

Specific examples of such organopolysiloxanes include the following.

C84 (In the above formula, p is 2 or 3, S, U, and W are positive integers, and t, v, and X are 0 or positive integers.) The above-mentioned organopolysiloxane may be used alone or in combination of two or more It may be a mixture, and its structure is preferably a linear diorganopolysiloxane, but it may also have a partially branched structure.

The organohydrodiene polysiloxane as the component (B) constituting the composition of the present invention acts as a crosslinking agent for the alkenyl group-containing organopolysiloxane as the component (A) described above, and is Those having two or more hydrogen atoms in one molecule are used.

This organohydrodiene polysiloxane may have a linear, branched, or cyclic structure, or may be a mixture thereof, and these organohydrodiene polysiloxanes have a polymerization degree of 300 or less. Although it is preferable, specifically, the following can be exemplified.

(In the above formula, b, c, d, e, f, g, i represent 0 or a positive integer, and h represents an integer of 2 or more.) (In the above formula, R4 is a hydrogen atom, a methyl group, (Does not represent a propyl group or a trimethylsiloxy group.) This organohydrodiene polysiloxane as component (B) has a bond to a silicon atom per alkenyl group contained in the organopolysiloxane as component (A) described above. an amount sufficient to supply 0.6 to 6.0 hydrogen atoms, preferably a molar ratio of 5t-H groups to alkenyl groups of 1.2 to 6.0.
4.0.

Further, the platinum or platinum compound catalyst with component (C) constituting the composition of the present invention is a catalyst for addition reaction and acts as a curing accelerator. Examples of such catalysts include, but are not limited to, solid platinum supported on a carrier such as platinum black, alumina, or silica, chloroplatinic acid, alcohol-modified chloroplatinic acid, chloroplatinic acid and olefins. Examples include a complex with platinum and a complex with vinylsiloxane.

When using these catalysts, if they are solid catalysts, it is sometimes preferable to crush them finely in order to improve their dispersibility, or to use a carrier with a small particle size and a large specific surface area. Furthermore, it is desirable to use chloroplatinic acid or a complex of chloroplatinic acid and an olefin by dissolving it in a solvent such as alcohol, ketone, ether or hydrocarbon.

A desired curing rate can be obtained by adjusting the amount of these catalysts used, but from an economic standpoint or to obtain a good cured product, it is preferable to use them in the following proportions. That is, for substances compatible with the siloxane component such as chloroplatinic acid, the amount is 0.1 to 110% relative to the total amount of the sulganopolysiloxane of the components (^) and (B).
0 ppm (in terms of platinum), and for solid catalysts such as platinum black, it is preferably in the range of 20 to 500 ppm (in terms of platinum).

Next, the organosilicon compound as component (D) constituting the composition of the present invention acts as an adhesive agent, and this compound has one hydrogen atom bonded to a silicon atom in one molecule. or more, and has an alkoxy group directly bonded to a silicon atom and/or an oxirane group bonded to a silicon atom via a carbon atom. This organosilicon compound itself is well known, and those having an alkoxysiloxy group (Japanese Patent Publication No. 53-21
026 Publication), those having an epoxy-containing hydrocarbon group (see Japanese Patent Publication No. 13508/1983), those having an alkoxysiloxy group and an epoxy-containing hydrocarbon group (
(see Japanese Patent Publication No. 59-5219) and the like are preferably used. The following organic silicon compounds are exemplified, but these can be used by increasing the degree of polymerization as appropriate depending on the application.

)l If this organosilicon compound is less than 0.5 parts by weight with respect to 100 parts by weight of the organopolysiloxane as the above-mentioned component (^), the self-adhesive strength will be poor, and if the amount is more than 20 parts by weight, this composition will Since this impairs the physical properties and is economically disadvantageous, it is necessary to use it in the range of 0.5 to 20 parts by weight, but this preferable range is 1 to 1 part by weight.
0 parts by weight.

Further, iron oxide powder or ferrite powder as component (E) constituting the composition of the present invention is added to improve the microwave absorption properties of this composition and make it suitable for UHF heating. This is - Membrane composition formula (Fe20)
Indicated by
<o, s iron oxide powder, or - film composition formula MO4
e20. where M is Mn or Fe.

The ferrite powder is one or more divalent metal atoms selected from Cu, Ni, Mg, Go, and In. However, regarding this iron oxide powder, Fe20s, which is generally called red red iron oxide, has a poor microwave absorption heat generation effect, so it has an X value of 0.5 at Fe0 minutes.
It should be more than that. Examples of ferrite include (MnO) O, B (ZnO) O, 5Feao
s, (Nip) o, 5(ZnO) o, BF
e20m, (MgO) o, a (MnO) o
, 5Fez03. (MnO) 6. g.

(FeO)o, 5FezOs, (MnO)o, 3
2 (ZnO)o, +4. (FeO)o, 04(
Fezos). Examples include S, and the iron oxide powder and ferrite powder may have a particle size in the range of 0.01 to 15 μm, preferably 0.1 to 5 μm. In addition, the blending amount of this iron oxide powder and ferrite powder is 10% of the organopolysiloxane as the component (^) described above.
If it is less than 10 parts by weight relative to 0 parts by weight, the microwave absorption will be low, and if it is more than 200 parts by weight, the physical properties will deteriorate, so it is necessary to keep it in the range of 10 to 200 parts by weight, but this is preferable. The range is 30 to 150 parts by weight.

The adhesive organopolysiloxane composition of the present invention can be obtained by uniformly mixing predetermined amounts of the components (A) to (E) described above. Compounding agents may be added.

For example, as fillers, all those commonly used for addition-type silicone rubber compositions can be used, and specifically, fumed silica, precipitated silica, hydrophobized silica, carbon black, titanium dioxide, Ferric oxide, aluminum oxide, zinc oxide, quartz powder, diatomaceous earth, calcium silicate, talc, bentonite, asbestos, glass fiber, organic fiber, etc. are used alone or in combination of two or more. The blending amount of such filler is arbitrary as long as it does not impair the purpose of the present invention, but -
For boat fishing, the amount is 600 parts by weight or less per 100 parts by weight of organopolysiloxane (A). Among these, the amount of fumed silica is preferably 25 parts by weight or less, and in the case of alumina, etc., the amount is preferably in the range of 300 to 500 parts by weight. The amount added varies.

In addition, in order to reinforce the strength of the cured product,
6771, 5i02 unit disclosed in Japanese Patent Publication No. 45-9476, etc., CH2-CH(R')2-5jOo,
An organopolysiloxane having a resin structure containing s units and R'3-5iO05 units (R' is a monovalent hydrocarbon group not containing an unsaturated aliphatic group) can be added, and the curing speed of the composition can be further increased. For the purpose of controlling
0947, an organopolysiloxane containing CM, -CHR''SiO units (R'' is the same as R° above), an acetylene compound disclosed in U.S. Pat. No. 3,445.420, and a U.S. Pat. Patent! 3,532,6
The ionic compounds of heavy metals disclosed in No. 49 can be blended, and non-functional organosiloxanes can also be blended to improve the thermal shock resistance, flexibility, etc. of the cured product.

Additionally, heat resistance improvers such as cerium oxide,
Flame retardant agents such as carbon, titanium oxide, benzotriazole, zinc carbonate and manganese carbonate, addition reaction control agents such as vinyl group-containing siloxane and acetylene compounds, and blowing agents may also be appropriately blended.

The adhesive organopolysiloxane composition of the present invention produced in this way contains iron oxide powder or ferrite powder as component (E), and is therefore treated with ultra-high frequency (usually referred to as UHF). When irradiated with microwaves in the so-called frequency range, the composition absorbs the microwaves well and generates heat, so even if the adherend has a large heat capacity, the composition easily adheres and hardens. It has the advantage that it can be used even with materials such as glass and engineering plastics with low properties.

For this UHF heating, a generally known UHF vulcanizer may be used, and usually after the adhesive organopolysiloxane composition of the present invention is coated or sealed on the adherend, the adhesive organopolysiloxane composition of the present invention is applied to this type of heating device. 2,450 allocated
All you have to do is send it to a UHF heating section equipped with a high frequency oscillator of ±50 MHz or 915 ±25 MHz and irradiate it with high frequency. Accordingly, this composition will be uniformly heated to around 150°C. Curing progresses uniformly and the temperature rises uniformly on the adhesive surface, reducing internal stress strain during curing and increasing adhesive stability, but this product also stabilizes the physical properties and adhesive properties of the cured product. It may be post-heated for this purpose.

[Example] Next, Examples and Comparative Examples of the present invention will be given. In the examples, parts are parts by weight, and viscosity is a value measured at 25°C.

Example 1 An octatool solution of chloroplatinic acid (platinum) was added to 100 parts of dimethylpolysiloxane having an average composition formula of content 2% by weight) 0.1 part, 0.01 part of 3-methyl-3-hydroxy-1-butyne as a control agent,
50 parts of heavy silica and triiron tetroxide Fe504 (Fe”
After adding 50 parts of "Fe2"'04) powder and mixing uniformly, an organosilicon compound as an adhesion promoter represented by organohydrodiene polysiloxa having an average compositional formula of 3.0 1 and kneaded uniformly to prepare adhesive composition-1.

Next, using this composition-1, a glass adhesive sample as shown in Figure 1 was made, and this was heated to a frequency of 2,450.
50cm UHF transmitting ±50MHz microwave
When I put it in the launcher and irradiated it with waves for 15 minutes,
A cured silicone rubber was obtained, and its shear adhesive strength was measured, and the results shown in Table 1 below were obtained.

Example 2 Instead of 50 parts of triiron tetroxide powder in Example 1, average composition formula (MnO)4(ZnO), (FeO), .Fe
Adhesive composition-II was prepared in the same manner as in Example 1, except that 50 parts of ferrite powder Ferrotop BSF400 [trade name, manufactured by Toda Kogyo ■] was used. When this was treated in the same manner as in Example 1 and its shear adhesive strength was measured, the results were obtained as shown in Table 1 below.

Comparative Example A Comparative Composition-8 was prepared in the same manner as in Example 1, except that 50 parts of the triiron tetroxide powder in Example 1 was not added. I irradiated it, but it did not harden, so I heated it to 120℃ for 15 minutes.
The adhesive was cured by heating for 60 minutes, and the shear adhesive strength of this product was measured, and the results shown in Table m1 were obtained.

Example 3 Both ends of the molecular chain were blocked with dimethylvinylsilyl groups,
Dimethylpolysiloxane 10 with a viscosity of 10.500 cS
0 parts of octatool solution of chloroplatinic acid (platinum content 2
% by weight) 0.15 parts, 3-methyl-3 as control agent
-Hydroxy-1-butyne 0.02 part, surface hydrophobized with hexamethyldisilazane, specific surface area is 200a+2/
15 parts of fumed silica of g, and formula MnO.Zn
50 parts of ferrite powder Ferrotop BSF400 (mentioned above) represented by O.Fe2O3 was added and mixed uniformly, and 1.3 parts of methylhydrodiene polysiloxane represented by the average compositional formula was added.
Organosilicon compound as adhesion promoter represented by part and formula 3.0
1.0 parts and mixed uniformly to prepare adhesive composition-Summer 11.

Then, this composition-■ was subjected to the same UH treatment as in Example 1.
The material was cured by irradiating F for 10 minutes and then heated to 120°C in a conventionally known drying amount, and the physical properties of the obtained cured product were examined, and the results are shown in Table 2. was gotten.

In addition, regarding this composition -
-5758, the glass H-shaped block adhesive sample shown in Figure 2 was prepared using a Teflon spacer, and the material was cured by irradiating it with UHF for 15 minutes. The results are shown in the table below.

Table 2 [Effects of the Invention] The present invention relates to a heat-adhesive organopolysiloxane composition, which, as described above, comprises (^) an alkenyl group-containing organopolysiloxane, (B) an organohydrodiene polysiloxane, ( C) platinum-based catalyst, (D) organosilicon compound as an adhesion imparting agent, (E) iron oxide powder,
However, since this composition is a known addition-curing adhesive composition to which iron oxide powder or ferrite powder is added as component (E), it is a microwave absorbing composition. The properties of the adherend are improved, and the adhesive can be cured by heating when ultra-high frequency heating (UHF heating) is applied. It has the advantage of being easy to cure adhesives even when made of poorly conductive glass or engineering plastics, so it is particularly useful for peripheral seal adhesives on laminated glass. For example, it has the industrial advantage of being particularly useful for adhesion of safety laminated glass (glass-polycarbonate, glass-polyacrylate) used for insulating double-glazed glass for buildings, or for observation windows of machinery, chemical equipment, etc. Become a thing.

[Brief explanation of drawings]

FIG. 1 is a perspective view of the glass adhesive sample used in Example 1, and FIG. 2 is a perspective view of the glass H-shaped block adhesive sample used in Example 3. Figure 2

Claims (1)

[Claims] 1. (A) has at least two alkenyl groups in one molecule and has a viscosity of 100 to 200,000 c at 25°C;
100 parts by weight of organopolysiloxane that is S, (B)
An organohydrodiene polysiloxane having two or more hydrogen atoms bonded to a silicon atom in one molecule, in an amount that provides 0.6 to 6.0 hydrogen atoms per alkenyl group of the organopolysiloxane. (C) Catalyst amount of platinum or platinum compound catalyst (D) One molecule has one or more hydrogen atoms bonded to a silicon atom, and has an alkoxy group and/or a carbon atom directly bonded to a silicon atom. an organosilicon compound having an oxirane group bonded to a silicon atom through 0.5 to 2
0 parts by weight, (E) General formula (Fe_2O)_x(Fe_2O_3)_
y (here x and y are each positive numbers, 0.5≦x≦
1, 0≦y≦0.5 and x+y=1) or the general formula MO・Fe_2O_3 (here M is Mn
, 10 to 200 parts by weight of ferrite powder represented by a divalent metal atom selected from Fe, Cu, Ni, Mg, Co, and Zn. 2. A method for curing adhesive organopolysiloxane, which comprises curing the composition according to claim 1 by irradiating the composition with microwaves of 900 to 5,000 MHz. 3. A cured product obtained by curing the composition according to claim 1.