JPH08886B2 - Adhesive organopolysiloxane composition, curing method thereof and cured product thereof - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention relates to an adhesive organopolysiloxane composition, in particular, because it can be cured and adhered by a super high frequency heating method, it can be used as an insulating double glazing for construction, a machine, The present invention relates to an adhesive organopolysiloxane composition that is useful for safety laminated glass used for a peep window of a chemical device, a method for curing the same, and a cured product thereof.

[Prior Art] An addition-curable adhesive composition containing an organopolysiloxane having a vinyl group bonded to a silicon atom as a main component has been conventionally known. It is also proposed to use an adhesion promoter together (Japanese Patent Publication No. 53-13508, Japanese Patent Publication No. 53-21026, Japanese Patent Publication No.
59-5219).

[Problems to be Solved by the Invention] However, since the addition-curable adhesive composition is generally cured by heating, when the adherend has a large heat capacity, the adhesive composition A large amount of energy is required for heating the adherend rather than heating, and there is a disadvantage that the adhesiveness decreases when the temperature rise at the adhesive interface is insufficient.

[Means for Solving the Problems] The present invention relates to an adhesive organopolysiloxane composition which has solved such disadvantages, a method for curing the same, and a cured product thereof, which comprises at least two (A) molecules in one molecule. With an alkenyl group of 100 ° C and a viscosity at 25 ° C of 100
100 parts by weight of organopolysiloxane which is ~ 200,000 cS,
(B) An organohydrogenpolysiloxane having two or more hydrogen atoms bonded to a silicon atom in one molecule and supplying 0.6 to 6.0 hydrogen atoms per alkenyl group of the organopolysiloxane, (C) a catalytic amount of platinum or a platinum compound catalyst, (D) an alkoxy group and / or carbon atom having one or more hydrogen atoms bonded to a silicon atom in one molecule and directly bonded to a silicon atom. 0.5 to 20 parts by weight of an organic silicon compound having an oxirane group bonded to a silicon atom via a (E) general formula (Fe ₂ O) _x
(Fe ₂ O ₃ ) _y (where x and y are positive numbers, and 0.5 ≦
Iron oxide powder represented by x ≦ y, 0 ≦ y ≦ 0.5 and x + y = 1) or the general formula MO · Fe ₂ O ₃ (where M is Mn, Fe, Cu, Ni, M)
10 to 200 parts by weight of a ferrite powder represented by a divalent metal atom selected from g, Co and Zn).

That is, the present inventors have used a high frequency heating method (Ultra High
As a result of various studies to develop an adhesive organopolysiloxane composition that is adhesively cured by frequency heating (hereinafter abbreviated as LHF heating), iron oxide powder and ferrite powder were added to a conventionally known addition-curing organopolysiloxane composition. It was found that if this is done, the microwave absorptivity of this product will be improved, so that this composition will be adhesively cured by UHF heating, and the type, addition amount and adhesiveness of the iron oxide powder and ferrite powder used here The present invention has been completed by conducting research on the relationship of curability.

 This is further detailed 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 the component (A) constituting the composition of the present invention has at least two alkenyl groups in one molecule and has a viscosity at 25 ° C. of 100.
It is in the range of up to 200,000 cS. In this case, as the alkenyl group, a vinyl group, an allyl group, a methallyl group,
A lower alkenyl group such as a hexenyl group can be mentioned, and as an organic group other than the alkenyl group, a methyl group,
Alkyl groups such as ethyl, propyl and butyl, 3,3,
A substituted alkyl group such as a 3-trifluoropropyl group, an aryl group such as a phenyl group, or the like, which contains an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms. Good.

As such an organopolysiloxane, the following can be specifically exemplified.

(In the above formula, p is 2 or 3, s, u and w are positive integers,
t, v and x represent 0 or a positive integer. The above-mentioned organopolysiloxane may be a single kind or a mixture of two or more kinds, and its structure is preferably a linear diorganopolysiloxane, but this is a partially branched structure. May be.

The organohydrogenpolysiloxane as the component (B) constituting the composition of the present invention acts as a cross-linking agent for the alkenyl group-containing organopolysiloxane as the component (A), and is bonded to the silicon atom. Those having two or more hydrogen atoms in one molecule are used. This organohydrogenpolysiloxane may have a linear, branched or cyclic structure, or may be a mixture thereof, and these organohydrogenpolysiloxanes have a degree of polymerization of 300 or less. Although the following are preferred, specific examples include those shown below.

(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, R ⁴ represents a hydrogen atom, a methyl group, a propyl group or a trimethylsiloxy group.) The organohydrogenpolysiloxane as the component (B) is the same as the organopolysiloxane as the component (A). An amount sufficient to supply 0.6 to 6.0 hydrogen atoms bonded to silicon atoms, preferably a molar ratio of ≡Si-H groups to alkenyl groups of 1.2 to 4.0 per contained alkenyl group. Used in various proportions.

The platinum or platinum compound-based catalyst with the 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, platinum black, alumina, those obtained by supporting solid platinum on a carrier such as silica, chloroplatinic acid, alcohol-modified chloroplatinic acid, chloroplatinic acid and olefins. Examples thereof include complexes of platinum and vinyl siloxane.

When using these catalysts, when they are solid catalysts, it is preferable to pulverize them in order to improve the dispersibility, or to make the carrier have a small particle size and a large specific surface area. Further, regarding chloroplatinic acid or a complex of chloroplatinic acid and an olefin, it is desirable to dissolve and use these in a solvent such as alcohol, ketone, ether or hydrocarbon.

The amount of these catalysts used is a so-called catalyst amount to obtain a desired curing rate, but from the economical viewpoint or in order to obtain a good cured product, it is preferable to use the following ratios. That is, for those which are compatible with the siloxane component such as chloroplatinic acid, 0.1 to 100 ppm relative to the total amount of the organopolysiloxane of the components (A) and (B).
(Platinum equivalent), or for solid catalysts such as platinum black,
It is recommended to set it in the range of 20 to 500 ppm (converted to platinum).

Next, the organosilicon compound as the component (D) constituting the composition of the present invention operates as an adhesion promoter, and this compound has one hydrogen atom bonded to a silicon atom in one molecule. It has the above, and has an alkoxy group directly bonded to a silicon atom and / or an oxirane group bonded to a silicon atom through a carbon atom. This organic silicon compound itself is a known compound, which has an alexyloxy group (Japanese Examined Patent Publication No. 53-21026).
(See Japanese Patent Publication No. 53-13508), those having an alkoxysiloxy group and an epoxy-containing hydrocarbon group (Japanese Patent Publication No. 59-58).
For example, see Japanese Patent No. 5219). Examples of the organic silicon compound include the following, but these can be used by appropriately increasing the degree of polymerization and the like depending on the application.

This organosilicon compound has poor self-adhesive strength at 0.5 parts by weight to 100 parts by weight of the organopolysiloxane as the above-mentioned component (A), and when the amount is more than 20 parts by weight, the physical properties of this composition are Since it is impaired and economically disadvantageous, it is necessary to use it in the range of 0.5 to 20 parts by weight, but the preferred range is 1 to 10 parts by weight.

Further, the iron oxide powder or the ferrite powder as the component (E) constituting the composition of the present invention is added to improve the microwave absorptivity of this composition and use it for heating UHF. This is a general composition formula (Fe ₂ O)
_x (Fe ₂ O ₃ ) _y , where x and y are positive numbers, and x <y = 1, 0.5 <x ≦ 1, 0 ≦ y <0.5, iron oxide powder, or a general composition formula MO · Fe ₂ O ₃ , M is M
The ferrite powder is one or more divalent metal atoms selected from n, Fe, Cu, Ni, Mg, Co and Zn. However, with respect to this iron oxide powder, Fe ₂ O _3, which is generally called red red iron oxide, is inferior in microwave absorption and heat generation effect, and therefore, the x value in FeO content should be 0.5 or more. For ferrite, for example, (MnO) _0.5 (ZnO)
_0.5 Fe ₂ O ₃ , (NiO) _0.5 (ZnO) _0.5 Fe ₂ O ₃ , (MgO) _0.5 (Mn
O) _0.5 Fe ₂ O ₃ , (MnO) _0.5 (FeO) _0.5 Fe ₂ O ₃ , (MnO) _0.32
(ZnO) _0.14 , (FeO) _0.04 (Fe ₂ O ₃ ) _0.5, etc. are exemplified, but the iron oxide powder and ferrite powder have a particle diameter of 0.01
The thickness may be in the range of ˜15 μm, preferably 0.1 to 5 μm. If the amount of the iron oxide powder or the ferrite powder is less than 10 parts by weight with respect to 100 parts by weight of the organopolysiloxane as the component (A), the microwave absorptivity becomes low, and if it is more than 200 parts by weight. Since the physical properties are deteriorated, it is necessary to set the range of 10 to 200 parts by weight, and the preferable range is 30 to 150 parts by weight.

The adhesive organopolysiloxane composition of the present invention can be obtained by uniformly mixing the predetermined amounts of the above-mentioned components (A) to (E). A compounding agent may be added.

For example, as the filler, any of those usually 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. alone or 2 Used in combination of more than one species. The blending amount of such a filler is arbitrary as long as it does not impair the object of the present invention,
Generally, it is 600 parts by weight or less per 100 parts by weight of the component (A) organopolysiloxane. Further, among these, fumed silica is preferably 25 parts by weight or less, and in the case of alumina or the like, a range of 300 to 500 parts by weight is suitable, depending on the oil absorption amount of the filler, the surface area, the specific gravity, etc. The suitable addition amount is different.

Moreover, in order to reinforce the strength of the cured product, Japanese Patent Publication No. 38-26
771 and Japanese Patent Publication No. 45-9476, the SiO ₂ unit, CH ₂ ═CH (R ′) ₂ —SiO _0.5 unit and R ′ ₃ —SiO.
An organopolysiloxane having a resin structure containing _0.5 units (R 'is a monovalent hydrocarbon group not containing an unsaturated aliphatic group) may be added, and for the purpose of controlling the curing rate of the composition, a special composition may be used. CH ₂ = CH disclosed in JP-A-48-10947
Organopolysiloxanes containing R "SiO units (where R" is the same as R'above), acetylene compounds disclosed in U.S. Pat. No. 3,445,420, and ionicity of heavy metals disclosed in U.S. Pat. No. 3,532,649. A compound or the like can be blended, and a non-functional organosiloxane can be blended in order to improve the heat shock resistance and flexibility of the cured product.

In addition, heat resistance improvers such as cerium oxide, carbon, titanium oxide, benzotriazole, zinc carbonate, flame retardant imparting agents such as manganese carbonate, vinyl group-containing siloxane, addition reaction control agents such as acetylene compounds, A foaming agent and the like can also be appropriately mixed.

The thus-prepared adhesive organopolysiloxane composition of the present invention contains iron oxide powder or ferrite powder as the component (E), so that it is referred to as an ultra high frequency wave (usually called UHF). When irradiated with microwaves in the so-called frequency range, the microwaves are well absorbed and heat is generated, so even when the adherend has a large heat capacity, this composition easily adheres and cures, which means that the adherend does not conduct heat. There is an advantage that it can be used even in the case of glass having low properties and engineering plastics.

Incidentally, in this UHF heating, a generally known UHF vulcanizer may be used, and usually after coating or sealing the adherend organopolysiloxane composition of the present invention on an adherend,
It may be sent to a UHF heating section equipped with a high frequency oscillator of 2,450 ± 50 MHz or 915 ± 25 MHz assigned to this kind of heating device and irradiated with high frequency, according to which the composition is 150 ° C. Since it is uniformly heated up and down, this curing progresses uniformly, and the temperature of the adhesive surface rises evenly, which reduces internal stress strain during curing and increases the stability of adhesion. Further, post-heating may be performed to stabilize the physical properties and adhesiveness of the cured product.

[Examples] Examples and comparative examples of the present invention will be described below. In the examples, parts are parts by weight and viscosity is a value measured at 25 ° C.

Example 1 The average composition formula is In 100 parts of dimethylpolysiloxane having a viscosity of 100,000 cS and having both ends of its molecular chain blocked with trivinylylsilyl groups, 0.1 part of an octanol solution of chloroplatinic acid (platinum content 2% by weight), as a control agent 3-methyl-3
- hydroxy-1-butyne 0.01 parts of heavy silica 50 parts of triiron tetroxide ^{_{Fe 3 O 4 (Fe (II}} ) Fe 2 (III) O 4) After 50 parts of the powder were added and uniformly mixed, which The average composition formula is Organohydrogenpolysiloxane represented by 2.5
Part and formula Adhesive composition-I was prepared by adding 3.0 parts of an organic silicon compound as an adhesion-imparting agent and kneading the mixture uniformly.

Then, using this composition-I, an adhesive sample of glass as shown in FIG. 1 was prepared, and this was used at a frequency of 2,450 ± 5.
When placed in a 50 cm UHF emitting device that emits a microwave of 0 MHz and irradiated with high frequency for 15 minutes, a cured silicone rubber was obtained. The shear adhesive strength of this was measured and shown in Table 1 below. The following results were obtained.

Example 2 Instead of 50 parts of triiron tetraoxide powder in Example 1, an average composition formula (MnO) ₁ (ZnO) _m (FeO) _n · Fe ₂ O ₃ (however, 1
+ M + n = 1) Ferrite powder / ferrotop BSF400 [trade name of Toda Kogyo Co., Ltd.] (50 parts) was used to prepare an adhesive composition-II by the same treatment as in Example 1. Was treated in the same manner as in Example 1 and its shear adhesive strength was measured, and the results shown in Table 1 below were obtained.

Comparative Example Comparative composition A was prepared in the same manner as in Example 1 except that 50 parts of triiron tetraoxide powder in Example 1 was not added, and the composition was used to prepare UHF in the same manner as in Example 1. It was irradiated, but it did not cure, so it was cured by heating it to 120 ° C for 15 minutes and 60 minutes, and the shear adhesive strength of this product was measured, and the results shown in Table 1 were obtained. .

Example 3 To 100 parts of dimethylpolysiloxane having both ends of the molecular chain blocked with dimethylvinylsilyl groups and having a viscosity of 10,500 cS, 0.15 part of an octanol solution of chloroplatinic acid (platinum content 2% by weight) was used as a control agent. 3-methyl-3-hydroxy-1-butyne 0.02 parts, hexamethyldisilazane hydrophobized surface fumed silica having a specific surface area of 200 m ² / g 15
And 50 parts of the ferrite powder represented by the formula MnO / ZnO / Fe ₂ O ₃ / ferrotop BSF400 (described above) were added and uniformly mixed, and the average composition formula was further added. 1.3 parts of methylhydrogen polysiloxane represented by Was added and uniformly mixed to prepare an adhesive composition-III.

Then, for this composition-III, the same U as in Example 1 was used.
When irradiated with HF for 10 minutes to cure and heating it to 120 ° C in a conventionally known dryer to cure it, the physical properties of the obtained cured product were examined, and the results shown in Table 2 were obtained. was gotten.

For this composition-III, JIS A
According to -5758, the glass H-shaped block adhesive sample shown in Fig. 2 was prepared with a Teflon spacer.
When the physical properties of the product cured by irradiation with UHF for 15 minutes were examined, this product showed the same results as shown in Table 2.

[Advantages of the Invention] The present invention relates to a heat-adhesive organopolysiloxane composition, which comprises (A) an alkenyl group-containing organopolysiloxane, (B) an organohydrogenpolysiloxane, and (C) a platinum-based composition. The composition comprises a catalyst, (D) an organic silicon compound as an adhesiveness-imparting agent, (E) iron oxide powder, or ferrite powder. This composition is a known addition-curable adhesive composition ( Since E) component is added with iron oxide powder or ferrite powder, this has an improved microwave absorptivity, so that when it is heated by ultra high frequency (UHF), it is heated and adhesively cured. Therefore, when the adherend has a large heat capacity, or the adherend is made of poorly heat-conductive glass or engineering plastic. It is given the advantage that it can be easily adhesive-cured even when it is an object, and therefore it is specifically used for peripheral sealing adhesion of laminated glass, such as insulating double glazing for construction, or machinery, chemical equipment, etc. It has an industrial advantage that it is particularly useful for bonding safety laminated glass (glass-polycarbonate, glass-polyacrylate) used for a peep window.

[Brief description of drawings]

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

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location C09J 183/07 JGH

Claims (3)

[Claims] 1. (A) 100 parts by weight of an organopolysiloxane having at least two alkenyl groups in one molecule and having a viscosity at 25 ° C. of 100 to 200,000 cS, (B) a silicon atom in one molecule. An organohydrogenpolysiloxane having two or more hydrogen atoms bonded to each other and supplying 0.6 to 6.0 hydrogen atoms per alkenyl group of the organopolysiloxane, (C) platinum or platinum compound catalyst Amount (D) An oxirane having one or more hydrogen atoms bonded to a silicon atom in one molecule and bonded to a silicon atom through an alkoxy group and / or a carbon atom directly bonded to the hydrogen atom. 0.5 to 20 parts by weight of an organic silicon compound having a group, (E) General formula (Fe ₂ O) _x (Fe ₂ O ₃ ) _y (where x and y are positive numbers, and 0.5 ≦ x ≦ 1, When 0 ≦ y ≦ 0.5, x + y =
Iron oxide powder represented by 1) or ferrite powder represented by the general formula MO · Fe ₂ O ₃ (where M is a divalent metal atom selected from Mn, Fe, Cu, Ni, Mg, Co and Zn) An adhesive organopolysiloxane composition comprising 10 to 200 parts by weight of 2. A method for curing an adhesive organopolysiloxane, which comprises irradiating the composition according to claim 1 with a microwave of 900 to 5,000 megahertz to cure the composition. 3. A cured product obtained by curing the composition according to claim 1.