JPS58168658A - Curable composition containing organopolysiloxane - Google Patents

Abstract

PURPOSE:To provide the titled compsn. which is curable at room temp. and suitable for use as an impregnant, etc., by blending a metal salt of an org. acid such as Mn, Fe, Co, Ni or Cu salt with a mixture of a polysiloxane contg. SH- group and a polysiloxane contg. epoxy group, etc. CONSTITUTION:An org. compd. having at least two hydrocarbon groups substituted with a mercapto group of formulaI(wherein n is 1-4) or II per molecule, such as organopolysiloxane, and an org. compd. having at least two groups selected from epoxy, isocyanato and carboxyl groups per molecule, such as organo-polysiloxane, are blended together with the proviso that one of them is organopolysiloxane. 0.001-5pts.wt. Mn, Fe, Co, Ni or Cu salt of an org. acid such as iron octenoate and 0-300pts.wt. filler such as silica are blended with 100pts.wt. above compsn. to obtain the titled compsn.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention can be applied to liquids at room temperature or by heating. 1- This relates to a tri-curable composition that cures, and (2) a composition containing an organopolysiloxane that has no reaction by-products that can be easily cured at room temperature and is free of catalyst poisons. 42. RTV silicone rubber is a widely known method for curing silicone polymers at room temperature.

Due to its curing mechanism, this RTV silicone rubber is of the so-called condensation reaction type, in which silanol groups in the polymer are reacted with hydrolyzable functional groups and a metal fatty acid salt catalyst, typically tin, and vinyl in the polymer. It is called an addition reaction type in which a group containing an aliphatic unsaturated bond such as a group, an allyl group, and 5t-H in a hydrogen polysiloxane are reacted using a trace amount of a Pt-based catalyst. Broadly classified.

Furthermore, in recent years, techniques for curing mercapto group-containing silicone polymers with organic peroxides (Japanese Unexamined Patent Publication No. 1853-12958) or iron carbonyl compounds (TRY HOME 56-501407) have been disclosed, and the techniques have become increasingly diversified.

Many of the condensation reaction types mentioned above have the disadvantage of producing irritating or corrosive gases such as acetic acid, alcohol, amines, or amides as by-products during curing, and also cause poor curing or cracking due to heating when kept in a closed environment. It also has some disadvantages, such as:

However, if a catalyst or crosslinking agent is added during use,
It is widely used because it can easily block not only liquid droplets but also air leakage, and it has a relatively good adhesion to various substrates.

On the other hand, the addition reaction type does not produce reaction by-products during 6'X curing, so it does not have the disadvantages of the condensation reaction type, but it is easy to use a small amount of Pt catalyst. This has the drawback of being poisoned and causing poor curing, and its use is severely limited. In addition, PT catalysts are bulky and expensive, so when rapid curing is required, such as in release paper coatings, it is necessary to increase the amount of catalyst used (this is also a major problem). It is considered one.

As mentioned above, currently known RTV silicone compositions each have their advantages and disadvantages, and at present no one has been found that is fully satisfactory in all aspects.

On the other hand, in recent years, attention has been focused on the reactivity of mercapto groups, and new types of curing systems that utilize this reactivity are being developed, and a series of techniques such as those described above have been disclosed.

Although this curing system has problems with the odor and corrosivity of Mercap) 41, it can be said that the disadvantages and drawbacks in the curing process seen in the condensation reaction type and addition reaction type are being improved to some extent.

The present inventors have conducted intensive research on the problem of curing haze of silicone polymers containing mercapto groups, and found that EG
G! Mn, Fe, Co, Ni or Cua
) This discovery of a new composition that can be easily cured at room temperature using a catalyst called an organic acid salt, which is extremely inexpensive compared to Pt-based catalysts, led to the completion of the present invention.

That is, the present invention provides (a) (a) in which a mercapto group-substituted hydrocarbon group represented by the formula H8CnH,n- (where n is an integer from 1 to 4) or a mercapto group-substituted hydrocarbon group is present in the molecule.
and (b) an organic compound having a small number (2 groups) selected from epoxy groups, incyanato groups, and carbonyl groups in the molecule, and one of the organic compounds is an organopolysiloxane. 100 parts by weight of a certain composition, (o) Mn, Fe%Co1N1 4$cu(7
) 1111tJ [0,001 to 5 parts by weight, (c) filler 0 to 300 parts by weight.

Hereinafter, the composition according to the present invention will be explained in detail.

The main component of the composition of the present invention is (a)
The components are (a) - (a) component and (a) - (b)
It consists of ingredients.

Component (a) in the present invention is an organic compound having a small number (both 2) of mercabuto-substituted hydrocarbon groups in the molecule, an epoxy group (\n), and an isocyanato group (-N-) in the molecule. C-0), carbonyl group (C-0), and in the present invention, at least one of these organic compounds is an organopolysiloxane. is required.

That is, each of the above organic compounds includes both organopolysiloxane and compounds other than organopolysiloxane.

This (a) -(organic compound containing a mercapto group-substituted hydrocarbon group constituting the Ml component (i) -(a) is
Other than having at least two mercapto group-substituted hydrocarbon groups in the molecule, there are no limitations on the type, molecular structure, viscosity, etc. of atoms or groups other than the mercapto group-substituted hydrocarbon single group.

As this mercapto group-substituted hydrocarbon group, the formula) 18C
n) 12n- (where n is the number of ships from 1 to 4) or groups such as the following can be mentioned. The bonding position of this mercapto group-substituted hydrocarbon group may be within the molecular chain, at the end of the molecular chain, or both).

Examples of atoms or groups other than the mercapto group-substituted hydrocarbon groups described above include alkyl groups such as methyl, ethyl, and propyl groups; cycloalkylphenyl groups such as cyclohexyl and cyclopentyl groups; and aryl groups such as xylyl groups. groups, aralkyl groups such as benzyl groups and phenylethyl groups, alkaryl groups such as ethylphenyl groups and tolyl groups, hydrogen atoms of these groups partially /''i rogen atoms,
Groups substituted with amino groups or cyano groups, hydroxyl groups, methoxy groups, ethoxy groups, propoxy groups, butoxy groups
Examples include alkoxy groups such as a 9-methyl group, and acyloxy groups such as an acetoxy group. .

Examples of organic compounds other than siloxane in this (a)-(a) component include H8+CHg (m; integer), H8CH,
tCOO+CH,)-00CCH, 8H.

H8CH,OH,OCH2CH,8H, thiocol (
A variety of organic compounds can be used, including those commercially available under trade names such as (manufactured by Torre Thiokol).
The organopolysiloxanes used here include those synthesized by various known methods,
For example, a hydrolyzable organosilane having a mercapto group and a hydrocarbon group in its molecule is subjected to a (co)hydrolytic reaction with any hydrolyzable organosilane, and then neutralized to synthesize siloxane. Then, in the presence of a suitable catalyst, polymerization is carried out to give a desired molecular weight of 41. body, for example ((CH,)2810)
,,((C,H,),8 Todoroki O),,((CH, )
(C,H, ) 8 10) , ((CH3)(OF
, CH, CH,)8i0), (z: integer)11 in the presence of a catalyst.

Hydrolyzable organosilanes with mercapto-substituted hydrocarbon groups that can be used here include:
18cH, 81C13, (H8CH2) (CH3)8
s C l m, ()18C)l,), 8401□, (
H80H,),8iC1,)180)1,C)1,OH
28 Todoroki C13, (H8CH, CH2CH,), 8
iC 凰、、H8CH、8i(OCH3)、、(H8CH
2), 8i(OCHs), (H2O)1,CH,OH
,)(CH,)81(OCR,),,H2O)1. C)
i,C)1,8i(OCR,), and as an optional organosilane, CH8iC13,C,H,8iC13,C,)1,8i
C13,C3H,8iC1,,CH,8i(OCH,)
,,C,H,84(QC)13),,0F3C)l,e
)118101. , (OH,),8iC12, (C,H
,)! 8iC1,,(CH,),81(UC'll,)
,,(C,H,)! 8iC1,,(CH,)(C,H,
)8iC1,, (OH,)(CF,OR,OH,)81C1,,(CH
s), 8iC1.

(C,)i,),8tCt, (CsH,)s8iC1,
(CH,)s8i00H,, (c2n,), smQC)
l, etc. can be given.

Next, organic compounds other than organopolysiloxanes having two or more groups selected from epoxy groups, isocyanato groups, and carbonyl groups in the molecule in component (a) -(b) and - include, for example, (an , 5-), cnccooc, n, , also (a)
The organopolysiloxane in the organic compound that is component (b) can be synthesized by various methods, such as CH, -CHCH20CO
A method of addition reaction between C(CH3)=CH2,\1 group and silane or siloxane having 81-H, CH,"=C(CH,)CONa and X(-OH,9,
-81= (X; halogen atom, p-1 to 4), oxidation of OH, -CHCH, 81iii,
Examples of methods include reacting HO+CH*h8sE (P F 1-4) with diisocyanate and thiopropylene acid.

Components (II) and (b) in component (a) must be present in small amounts (and one of them must be an organopolysiloxane). This is because the results will be significantly improved.

The ratio of the components (a) to (b) to the components (a) to (b) is not particularly limited, but generally the ratio of mercapto group to epoxy group, incyanato group, or carbonyl group is 0. It is preferable to set the temperature to .5 to 2.54 degrees.

The components constituting the composition of the present invention are the features of the present invention, and are characterized by the reaction between the functional groups of the components (a) and (a) and (a) and (b) described above. In the present invention, it is essential to use an organic acid salt of Mn, Fe, Co1N1 or Cu. Examples of organic acids that can be used include stearic acid, oleic acid, lauric acid, 2-ethylhexonic acid, naphthenic acid, and benzoic acid.
- Those having compatibility with component (b) are more suitable.

Among the organic acid salts mentioned above, F@also 61C
The organic acid salts of U have an advantageous effect from the viewpoint of achieving the purpose, and the organic acid salts of Fe have the effect of acting as an antioxidant and can also be expected to improve heat resistance, so they are more preferable. 'This component is required to be used in a range of 0.001 to 5 parts by weight per 100 parts by weight of the above component, but this is because the amount used when coughing is 0.
．． If the amount is less than 0.001 parts by weight, sufficient catalytic ability will not be obtained, and curing will take a long time, making it impractical (on the contrary, if the amount exceeds 5 parts by weight, it will become difficult to obtain the catalyst). This is because a proportional curing speed cannot be obtained, and instead, the cured physical properties deteriorate.

The filler as component (c) is an optional component, but is essential for applications requiring reinforcement.

All substances that are normally blended into silicone rubber can be used for this purpose, and among these, reinforcing silica such as all silica, precipitated silica, and silica aerogel, and semi-reinforcing silica such as quartz powder and celite are the most preferable. Although it is a filler, other materials such as aluminum silicate, magnesium silicate, calcium silicate, calcium carbonate, carbon black, iron oxide, titanium dioxide, aluminum hydride, and aluminum oxide can also be used. Ethylene powder, BN% 8i, N4.8iC, carbon fiber, glass fiber, Tetron fiber, etc. may also be added and used depending on the purpose.

Furthermore, depending on the type of filler, the amount used, etc., there is no problem in using a small amount of various silanes called wetters, low molecular weight siloxanes, or carbon functional silanes effective as adhesion improvers.

Examples of the carbon functional silane include vinyltrimethoxysilane, methacryloxypropyltrimethoxysilane, glycidyloxypropyltrimethoxysilane, mercaptopropyltrimethoxysilane, and 3-aminopropyltriethoxysilane.

Note that it is optional to use additives such as uneven coloring agents, heat resistance improvers, and flame release agents.

Above (/→The amount of filler used as an acid component is shown in (a) above.
The amount is 300 parts by weight or less per 100 parts by weight of the components.

The composition of the present invention can be applied to both rubber-like (Iil-like) and resin-like (branched) forms, and its application range is floor desks. In addition to curing at room temperature, the curing speed can be significantly increased by heating, so it can be applied to a wide range of usage conditions.
It can also be applied as an impregnating agent〇Also, in advance, (a) - (a) component and (a) - (b)
The components may be partially reacted and used as intermediates for applications such as those described above.

The composition according to the present invention does not require curing due to poisoning that occurs in conventional addition reactions using Pt catalysts, does not require curing due to high temperature heating G that occurs in condensation reactions, does not require sealing heat resistance,
It cures using an excellent curing mechanism that does not cause surface uncuring, which is seen in peroxide atmospheric pressure vulcanization, and therefore can be expected to be applied in an extremely wide range of fields.

Next, examples of the present invention will be described, but the present invention 5i11 is not limited thereto.

In the following description, Me 42 CHs- and Ph are C, H
, -, and all parts indicate parts by weight. Using Example 1 and M e a 8 i 08 i Me s, a mercapto group-containing polysiloxane with an average degree of polymerization of 800 as shown below was prepared. Obtained ((Il-(a)).

After synthesizing methylhydrodiene polysiloxane with an average degree of polymerization of 100 using HMe s 8108 i Ma s H and addition reaction in the presence of chloroplatinic acid, !Origin<1)-(a) 6011S
After mixing 40 parts of (a) and (b), 0.5 parts of iron octenoate (F@8 steamed rice) and 100 parts of toluene were added and homogeneously mixed and dissolved. Laminated kraft paper heat coated at a rate of 1.511 parts m'' at 120'C.
When heated for 5 minutes, a glossy silicone rubber coating with no surface tack was obtained, and this coating adhered well to the polyethylene.The coating showed excellent mold release properties and no residual adhesion. At a ratio of 9596 or higher, there was almost no silicone migration.

Example 2 A sponge-like cured product was obtained by thermally reacting 90 parts of components (a) and (a) obtained in Example 1 with 10 parts of toluene diisocyanate and Freon-1. This cured product had no surface tack. No such defects were observed at all, indicating excellent rubber elasticity.

Example 3 Dimethylpolysiloxane in which both ends of the molecular chain represented by the formula were blocked with mercaptopropyl groups was obtained ((a)-(1))
).

Sota, Me Ph8mu (-081-H).

was reacted with Me in the presence of a Pt catalyst to obtain an epoxy group-containing siloxysilane represented by the formula ((
b)-(b)).

Obtained above (a) - (1) 96 parts G (a) - (b) 4
After mixing, add 50% of quartz powder with an average particle size of 5μ bait.
part, 3 parts of ferric oxide and the surface with Me s 8 s O
□7. Reinforcing silica treated with (specific surface area 100 m”)
/ Jil, Aerosm 1200 processing goods) was added and a paste was obtained by passing it through a three-roll jar 2ruJ. When a certain amount of curing catalyst was added and blended and these were left to stand at room temperature, they were cured after a period of time as shown in the same table.

When the physical properties of the rubber were examined for the cure obtained above, the following results were obtained.

Example 4 After dissolving 5 parts of 1 ((I) - (Jl), crosslinking agent) and 95 parts of υ in 100 parts of tetrahydrofuran, 2 parts of iron octenoate were added and mixed therein, and this was mixed with glassine paper. Applied directly.

Next, heating was carried out at 170°C for 20 seconds (the silicone was adhered at a ratio of 11/-). A commercially available rubber adhesive tape was pasted onto the silicone-coated surface, and 201/10R. ? Crimp, 70"C't
' Leave it for 1 day @ This item has a peeling force of 20II/inch and a residual adhesion rate of 96-
showed that. These properties were sufficient as a release agent for paper.

Example 5 An epoxy group-containing siloxysilane represented by the following formula was obtained by addition-reacting Danzu in the presence of a Pi catalyst ((I)-(
b)').

In addition, after hydrolyzing e, this and this were copolymerized at a molar ratio of 1:3, and the average degree of polymerization was 5.
A mercapto group-containing polysiloxane ((a)-
(a) ).

65 parts of (a)-(a) obtained above and 35 parts of (()-(b)
20 parts of Aerosil 130 (fumed silica, manufactured by Nippon Aerosil Co., Ltd.) were added to this mixture, passed through a three-roll mill twice, and then 0.5 part of iron octate was added. The mixture was placed in a 10-sized glass petri dish, and an aluminum square piece and an iron panel were embedded inside the dish and left at room temperature. After 10 days, the mixture hardened uniformly to the inside and took on a resin-like appearance. When observing the state of adhesion to the glass petri dish, aluminum square piece, and iron panel, it was found that all of them were in close contact with Natsumeko f.

Claims (1)

[Scope of Claims] t(a) (1) The molecule contains at least two mercapto group-substituted hydrocarbon groups represented by 2H8CnH,n- (where n is an integer of 1 to 4) or
and (b) an organic compound having at least two groups selected from epoxy groups, incyanato groups, and carbonyl groups in the molecule, and one of the organic compounds is an organopolysiloxane. (a) 0.001 to 5 parts by weight of organic acid salts of Mn, Fa%Co, Nl or Cu, (c)
Organopolysiloxane-containing curable composition consisting of 0 to goo parts by weight of filler