JPS603341B2 - Room temperature curable organopolysiloxane composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a room temperature curable organopolysiloxane composition comprising:
In particular, it is an object to provide a composition having excellent adhesive properties.

Conventionally, various room-temperature-curable organopolysiloxane compositions, particularly compositions containing aminoxy group-containing organopolysiloxane as a crosslinking agent, are known. A composition consisting of an organic poppy, an elementary compound having at least two SIR(OY)- bonds, and an organic poppy, an elementary compound having at least three Si-○-Y bonds in one molecule (Kosho Hakama 43-24545 (see publication), there is, is (2'
A composition consisting of a diorganopolysiloxane with a hydroxyl group-blocked molecular chain end and a cyclic organopolysiloxane having an alkoxy group and an aminoxy group (Japanese Patent Publication No. 47-139574)
(Refer to the name Koboko) is considered to be publicly known.

However, when each of the entrusted compositions is used as a sealant, the former is subjected to undercoating treatment (primer treatment).
The latter has the disadvantage of not adhering sufficiently to untreated substrate surfaces, and although the latter has no problems with adhesion, the rubber elastic material obtained from this has high modulus, low elongation, and poor durability. It has the disadvantage of being inferior.

The present invention relates to a room-temperature curable organopolysiloxane composition which eliminates the above-mentioned drawbacks of the conventional organopolysiloxane composition. part, '0) General formula [wherein RI is a -valent hydrocarbon group, R2 is a divalent hydrocarbon group, R3 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms, Y is the formula or ( Here, R5 and R6 are a hydrogen atom or a monovalent hydrocarbon group, R7 is a divalent organic group), A is a monovalent hydrocarbon group or an alkoxy group, a is 1 or 2, and b is 2 to 8, c is 0 to 6, provided that a+b+c is 23 to 10]. Each group is selected from the same range as above, d is 2 to 10, e is 0 to 6, but d+
0 to 2 parts by weight of a cyclic organopolysiloxane (e=3 to 10), and 1 to 40 parts by weight of a filler.

To explain this, the present inventor has conducted extensive research into room-temperature-curable organopolysiloxane compositions that have excellent adhesion to various substrates, and has found that they contain a predetermined amount of '' as described above. }~ The present invention was completed by confirming that a composition consisting of one component is extremely effective.

In fact, the composition can be applied to various substrates that have not been subjected to an undercoating treatment using a primer or the like, such as float glass, sun-cut glass, reflex light glass, and JIS Japan 4000.
Painted aluminum with sulfuric acid methacrylate glaze, F
It exhibits extremely high adhesion to molded products made of RP resin, epoxy resin, etc.

In other words, when performing on-site construction using a room-temperature curable composition that requires an undercoat treatment, there is a risk that the undercoat may leak in some areas, and in such cases,
Although peeling is expected to occur, the composition of the present invention does not have the above-mentioned problems and can omit the complicated work step of undercoating.

Furthermore, the composition of the present invention can be well applied to a substrate surface that has been subjected to an undercoat treatment, and in this case exhibits extremely superior adhesion compared to conventional compositions of this type.

Next, to explain the present invention in more detail, firstly, the diorganopolysiloxane in which both ends of the molecular chain are blocked with hydroxyl groups as the {i' component used as the main component in the present invention is conventionally known as a raw material for silicone rubber. This is, for example, represented by the general formula.

Here, R4 represents a monovalent hydrocarbon group, including an alkyl group such as a methyl group, an ethyl group, a propyl group, an alkenyl group such as a vinyl group or an allyl group, an aryl group such as a phenyl group, or a carbonized group thereof. Examples include groups in which a hydrogen atom of a hydrogen group is partially substituted with a halogen atom.

n represents a positive integer, and the value of n is preferably such that the diorganopolysiloxane exhibits a viscosity of 100 to 1,000,000 centistokes, preferably 3,000 to 20,000 centistokes at 25°C. ,. This is because if the diorganopolysiloxane has a viscosity of 100 centistokes (290) or less, a cured rubber elastic body with excellent physical strength cannot be obtained; This is because, in some cases, the viscosity of the composition of the present invention containing it becomes too high, resulting in poor workability during use of the composition. Next used in the present invention'.

The cyclic organopolysiloxane as the component is represented by the above general formula (i). In this formula, the monovalent hydrocarbon group represented by RI includes an alkyl group such as a methyl group, an ethyl group, and a propyl group, an alkenyl group such as a vinyl group and an allyl group, an aryl group such as a phenyl group, or a hydrocarbon group thereof. Examples include groups in which hydrogen atoms are partially substituted with halogen atoms, etc., and examples of divalent hydrocarbon groups represented by R2 include methylene groups, ethylene groups,
Examples include alkylene groups such as propylene groups and butylene groups, and arylene groups such as phenylene groups. moreover,
The monovalent hydrocarbon group having 1 to 12 carbon atoms represented by R3 includes methyl group, ethyl group, propyl group, butyl group,
Examples include vinyl group and phenyl group. The amino group represented by Y is, for example, a group represented by the formula or the formula (where R5 and R6 represent a hydrogen atom or a monovalent hydrocarbon group, and R7 represents a divalent organic group), specifically, Examples include --NH2, , -N(Cmelon)2, -N(C2 ratio)2, -N(C3day7)2, and the like.

In addition, as the monovalent hydrocarbon group represented by A, the above-mentioned R
The same groups as I are exemplified, and examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, butoxy group, etc., but in the present invention, this alkoxy group has 1 to 4 carbon atoms. I wish there was something.

The cyclic organopolysiloxane as the {o-component is, for example, a polysiloxane having at least three \Si bonds in one molecule, and a polysiloxane having the general formula (where R3 has the same meaning as above, R8 has 3 carbon atoms). -5 alkenyl group, R9 represents a monovalent hydrocarbon group having 1 to 12 carbon atoms) in the presence of chloroplatinic acid at a temperature of 20 to 150°C.
(preferably 40 to 100 qo), and then the reactant obtained here and hydroxylamine represented by the general formula YOH (Y has the same meaning as above) at a temperature of -20 to 15,000 (preferably can be synthesized by deaminoxytrialyl-resilane and dehydrogenation reaction in the range of 0 to 80 qo).

This reaction formula is shown below. (In the above, a and b represent the same meanings as above.) Specific examples of the cyclic organopolysiloxane as the raw component include those shown below.

It is essential that the amount of this component used be in the range of 0.01 to 2 parts by weight based on 100 parts by weight of component ``a'' above. If it is less than 2 parts by weight, it will not be possible to improve the adhesive strength, which is the objective of the present invention. On the other hand, if it exceeds 2 parts by weight, the curing speed will be slow, a good cured rubber product will not be obtained, and it will not be economical. This is because it will be disadvantageous.

Note that the 'o} component is not necessarily limited to one type, and two or more types may be used in combination.

Next, the cyclic organopolysiloxane used as a component in the present invention is represented by the above general formula (ii), and R1, Y and A in the formula are exemplified by the same groups as above. be done.

When the group represented by A in the formula in this one component is an alkoxy group, it is preferable that the number of carbon atoms is 1 to 4, as in the case of the above {rho component. Specific examples of such internal components include the compounds shown below. Such a W component can be easily synthesized by a conventionally known method (see Japanese Patent Publication No. 43-24 Nezumi No. 5, Japanese Patent Publication No. 47-26200, etc.).

The amount of this component to be used is 2 parts by weight or less relative to the 10 parts by weight of component {i} above, but this is because even if it is used in excess of 2 parts by weight, no particularly significant effect will be obtained. This is because it would be economically disadvantageous.

In addition, one of the ingredients is the above.

}As with the components, they may be used as a mixture of two or more. In addition, when a cyclic organopolysiloxane in which b in the formula has a value of 2 is used as the above [o} component, it is necessary to use a cyclic organopolysiloxane in which d in the formula has a value of 3 or more as the first component. It is.

Further, fillers as single components used in the present invention include, for example, fumed silica, makuraden silica, quartz powder, quartzite, titanium oxide, aluminum oxide, lead oxide, iron oxide, carbon black, and bentonite. , graphite, calcium carbonate, myriki, clay, glass beads, glass micro balloon, shirasu balloon, glass fiber,
Examples include polyvinyl chloride beads, polystyrene beads, and acrylic beads.

The amount of these eight components to be used is in the range of 1 to 40 parts by weight, preferably 50 to 15 parts by weight, based on 100 parts by weight of the component [A].

This is because if the amount used is less than 1 part by weight, the rubber elastic body obtained from the composition of the present invention will have poor mechanical strength, whereas if it exceeds 400 parts by weight, a good quality rubber elastic body will not be obtained. That's because there isn't. The composition of the present invention is as described above.
The composition of the present invention prepared in this manner can be prepared by uniformly kneading a predetermined amount of the nine components of B-9 using a conventionally known strainer. By doing so, it is easily cured by the action of atmospheric moisture to become a silicone rubber elastic body.

In addition, the composition of the present invention may contain metal salts of organic acids such as dibutyltin dilaurate, dioctene tin, iron stearate, lead octylate, pigments, heat resistance improvers,
A flame retardant imparting agent, an antibacterial/antifungal agent, a dehydrating agent, etc. may be added and blended, and these additives are optional as long as they do not impair the purpose of the present invention.

Next, Examples of the present invention will be given, and all parts in each example indicate parts by weight.

However, the cyclic organopolysiloxane used in each example was synthesized as follows.

o Synthesis 1 4 parts of dehydrated xylene, 48 parts of 1,3,5,7-tetramethyl-1,3,5,7-tetrahydrodienecyclotetrasiloxane, and 0.005 part of chloroplatinic acid were mixed, and the mixture was heated with nitrogen gas. After heating to 90 to 95 qo in an atmosphere, 2 parts of dehydrated xylene and 19.4 parts of N-(trimethylsilyl)allylamine were added dropwise over 2 wells, and reaction was carried out at 95 to 105°C for 1 hour. went.

After the reaction was completed, stripping was carried out under a reduced pressure of less than 5 pi, and 49.6 parts of a pale yellow transparent liquid was obtained. This product was confirmed to be a cyclic organopolysiloxane represented by the formula from the analysis results below.

Theoretical value Actual value Si daily amount (meq no. 9) 8.13 7.94N
Analysis (Son) 38 3.7 Next, 36.9 parts of the cyclic organopolysiloxazole obtained above was added to 44.5 parts of diethylhydroxylamine at room temperature under a nitrogen gas atmosphere for 3 minutes. After the dropwise addition was completed, the temperature was gradually raised and the reaction was carried out at 6-0 for 1 hour.

The reaction product was then stripped under reduced pressure at a temperature below 60°C, yielding a pale yellow, low viscosity liquid. From the analysis results below, it was confirmed that this was a cyclic organopolysiloxane represented by the formula (hereinafter referred to as cyclic organopolysiloxane-1).

Theoretical value Value SiMH amount (meq-9) Trace amount N analysis (multiple) 10.0 9.8o Synthesis 2 Dehydrated xylene 4 Base part "113,5,7-tetramethyl-1-butyl-3,5,7-trihydrogencyclo Tetrasiloxane 59. Mix Moribe and 0.005 part of chloroplatinic acid,
After heating this to 90 to 9y0 in a nitrogen gas atmosphere, 2 parts of dehydrated xyreso and 19.4 parts of N-(trimethylsilyl)allylamine were added dropwise over 20 minutes.
The reaction was carried out at 95-105°C for 1 hour.

After the reaction was completed, vacuum stripping was carried out at 50°C, and a pale yellow transparent liquid was obtained. Ikaribe was obtained. This product was confirmed to be a cyclic organopolysiloxane represented by the formula from the analysis results below.

Theoretical value Actual value Si-daily amount (meq no. 9) 4.69 4.52N
Analysis (multiple) 3.3 3.3 Next, 42.6 parts of the cyclic organopolysiloxane obtained above was added to 35.6 parts of diethylhydroxylamine* at room temperature under a nitrogen gas atmosphere for 30 minutes. After the dropwise addition was completed, the temperature was gradually raised and the reaction was carried out at 60°C for 1 hour.

The reaction product was then stripped under reduced pressure below 60 qo to obtain a pale yellow, low viscosity liquid. From the analysis results below, it was confirmed that this was a cyclic organopolysiloxane represented by the formula (hereinafter referred to as cyclic organopolysiloxane). Theoretical value Actual value Si-daily amount (meq no. 9) Trace amount N analysis (multiple) 8.1 8.0 Example Compositions i~ were prepared as follows.

◎ Preparation of composition i (product of the present invention) 67 parts of precipitated calcium carbonate was added to 10 parts of dimethylpolysiloxane, which had a viscosity of 5,000 centistokes at 25:00 and was capped at both ends of the molecular chain with hydroxyl groups. This was uniformly kneaded using three rolls to obtain a non-flowable base mixture.

Next, 1 part of the mixture 10 obtained above and 2.5 parts of the mixture of cyclic organopolysiloxanes 1 and 0 obtained above (mixing ratio (weight %) 5:95) were added and mixed.

◎Preparation of Compositions B to V (all products of the present invention) To 100 parts of a base mixture having the same composition as the above composition i, a moat of cyclic organopolysiloxane of the type shown in Table 1 below was added. 5 parts were added.

◎Preparation of composition (control product) Base mixture 10 having the same composition as the above composition 2.5 parts of a mixture consisting of

Next, the rubber physical properties and adhesive properties of the compositions i to W prepared above were examined.

{11 Rubber physical properties A sheet with a thickness of 2 mm was formed using the compositions i~ prepared above, and this was left to cure at room temperature for 7 days. When the tensile strength and hardness were examined, the results shown in Table 2 below were obtained.

Table 2 '2} Adhesion The compositions i to h prepared above were placed in parallel on two various substrates without surface treatment (float glass, refrite glass, sulfuric acid alumite manufactured by Nippon Test Panel Co., Ltd.). Painted aluminum with methacrylate scales (JIS Japan)
4000, A5052P) and Asada color (amber color) manufactured by Showa Koki Co., Ltd., to prepare a cross-sectional date-shaped test specimen (according to JISA 5757), and this was heated at a temperature of 20°C and a relative humidity of 55%. After being allowed to stand for 7 days under these conditions, the sample was further left in an atmosphere at a temperature of 50° C. for 7 days to obtain a test specimen.

Next, using an Instron tensile testing machine, tension was applied to the H-shaped block at a speed of 5 yen/min until it broke, and the maximum tensile strength until breakage was measured at 150% elongation. The strength, elongation at break, and cohesive failure rate were examined and the results are shown in Tables 3 to 6 below, respectively.

Further, the test specimen obtained above was immersed in hot water at a temperature of 50 qo for 7 days, and various physical properties of the test specimen after immersion were investigated, and the results are shown in the same table.

The cohesive failure rate is defined as 0% when the surfaces of the cured rubber elastic body of the composition and the base material are completely separated, and 100% when the cured rubber elastic body is cut. .

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Claims (1)

[Claims] 1 (a) 100 parts by weight of diorganopolysiloxane whose molecular chain ends are blocked with hydroxyl groups, (b) General formula▲There are numerical formulas, chemical formulas, tables, etc.▼ [In the formula, R^1 is a monovalent hydrocarbon group, R^2 is a divalent hydrocarbon group, R^3 is a monovalent hydrocarbon group having 1 to 12 hydrogen atoms,
Y is a formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (Here, R^5, R^6 are hydrogen atoms or monovalent hydrocarbon groups, R^7 is divalent A is a monovalent hydrocarbon group or an alkoxy group, and a is 1 or 2.
, b is 2 to 8, c is 0 to 6, but a+b+c is 3 to 1
A cyclic organopolysiloxane represented by 0.
01 to 20 parts by weight, (c) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R^1, Y and A are each a group selected from the same range as above, d is 2 to 10, e is 0 to 6, but d
+e=3-10) 0-20 parts by weight of a cyclic organopolysiloxane and (d) filler 1-4
00 parts by weight of a room temperature curable organopolysiloxane composition.