JPS6119660A - Room temperature drying silicone composition - Google Patents

Abstract

PURPOSE:The titled composition which has a high drying rate, gives a uniform coating of suitable hardness, and consists of a silanol-terminated polyorganosiloxane compound, a silyl isocyanate compound, a specified acid compound, and an organic solvent. CONSTITUTION:5-50wt% silanol-terminated polyorganosiloxane compound (A) (e.g. alpha.omega-dihydroxydimethylpolysiloxane) having a molecular weight of 1,000- 20,000 and a viscosity of 50-2,000cSt; 1-50wt% silyl isocyanate compound (B) containing 2 or more Si-NCO groups (e.g. tetrasilyl isocyanate); 0.01-0.5wt% of one or more acid compounds (C) selected from a carboxylic acid (anhydride), a trivalent or pentavalent phosphoric acid (derivative), an alkylsulfonic acid, and an arylsulfonic acid; and 20-80wt% organic solvent (D) which will dissolve components A-C and will not react with component B (e.g. ethyl acetate) are mixed.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a novel room-temperature-drying silicone composition, particularly a room-temperature-drying silicone composition containing a silanol-terminated polyorganosiloxane compound and a silyl incyanate compound as main components and suitable for use as a surface treatment agent. It is related to.

Silanol-terminated polyorganosiloxane compounds and silyl incyanate compounds (incyanate silane compounds)
Several room-temperature curable compositions containing as main components have been proposed in the past, for example, Japanese Patent Publication No. 3-3277 and Japanese Patent Publication Akihiro! The invention described in Publication No. 6 proposes a composition in which amines, organic acid metal salts, and organic tin derivatives are added as curing catalysts or curing accelerators in addition to both compounds or their combination with silicone resin. There is. Also, Japanese Patent Application Laid-open No. 111976/1987 (U.S. Patent No. 1) developed by the present inventors
．． ≠33. / Corresponding to the Core Specification), a composition is proposed in which a titanium phosphate organic compound having a Ti-0-P bond is blended as a curing agent in addition to both compounds. It is used as a sealant and is often used to bond or seal joints between concrete and window frames, and joints between stubs and walls in bathrooms. In this case, elasticity is required as well as adhesion, and therefore a terminal silanol polyorganosiloxane compound having a relatively small number of terminal silanol groups and therefore having a relatively large molecular weight, and which is curable and has a relatively large viscosity is used. For example, in the former invention, 3. ooo ~ 3,100 centipoise,
The latter invention uses polyorganosiloxanes with /J, 600 to 2θ, 000 centistokes, which are approximately 2o, oi:ro -aθ, 0
A polyorganosiloxane compound having a relatively large molecular weight corresponding to a molecular weight of 0.00 is used.

Curable compositions containing such silanol-terminated silicon compounds have excellent heat resistance, water repellency, scratch resistance, stain resistance, etc., and are therefore suitable for metals, plastics, stones, ceramic materials (e.g. ceramic tiles), etc. However, in this case, the comparatively thick silanol-terminated silicon compound with a relatively large molecular weight as mentioned above is too soft to be used, so it is recommended to use a similar silicon compound with a low molecular weight valve. It becomes necessary. However, with this compound, even if the above-mentioned curing agent is used, it is not possible to obtain a composition that has a practical drying rate, such as drying and curing within about one hour, and that can form a homogeneous coating film. Although the reason for this is not clear, it is thought that the curing agents used in the prior art as described above either have insufficient stability and solubility or do not have sufficient reactivity with low molecular weight silanol-terminated silicon compounds.

Thus, the present invention provides a room-temperature-drying silicone composition that uses a low molecular weight silanol-terminated silicone compound, provides a homogeneous coating film with a practical drying rate, and can be effectively used for surface treatment of solid materials. The purpose is to

According to the research and experiments of Nagisa et al. in the present invention, these purposes are to add carminic acid or its anhydride, trivalent or At least one acidic compound among phosphoric acid or a derivative thereof and an alkylsulfonic acid or an arylsulfonic acid is dissolved in each compound of stiffness, but before? It has been found that this can be achieved when adding a silyl isocyanate compound that does not react with the silyl isocyanate compound.

Therefore, the present invention provides a) a silanol-terminated polyorganosiloxane compound), a silyl isocyanate compound having two or more Si-NCO groups, and c) carminic acid or its anhydride, trivalent or pentavalent phosphoric acid, or At least one compound among its derivatives and alkylsulfonic acids or arylsulfonic acids 2) An organic solvent that dissolves the compounds in a), 7), and 3) above and does not react with the compounds in 7). The present invention provides a room temperature drying silicone composition containing:

To describe the present invention in more detail, the silanol-terminated polyorganosiloxane compound used is a silicon compound having a 7-ranol group at the end, that is, having two or more hydroxy groups in the molecule, such as α
, ω-dihyProxydimethylpolysiloxane, α, ω-
Examples include dihydroxymethylphenylpolysiloxane. Of course, this compound is not limited to those exemplified here, but it is assumed that a compound with a low viscosity in the range of 3ON2,000 centistokes and a low molecular weight in the range of i, ooo-2o, ooo is used.

Further, as the silyl isocyanate compound, a compound having two or more 5i-NCO groups, that is, 5i(Ne
o), or RnS 1(NCO)4 (in this formula, n R is an alkyl, phenyl, vinyl, alkoxy, phenoxy group or a group derived therefrom, n=/or, 2) or a compound or partially hydrolyzed A silyl isocyanate compound obtained by condensation is used. Examples include tetrasilyl isocyanate, methylsilyltriisocyanate, butylsilyltriisocyanate, octylsilyltriisocyanate, octadecylsilyltriisocyanate, methoxysilyltriisocyanate, ethoxysilyltriisocyanate, phenyldylyltriisocyanate, vinylsilyltriisocyanate, Examples include isocyanate, dimetersilyl diisocyanate, methylphenylsilyl diisocyanate, dimethoxysilyl diisocyanate, dimethoxysilyl diisocyanate, silicon incyanate containing dimethylpolysiloxane, and seven or more types of these are used.

Optionally, it can then be used to act as a crosslinking reaction modifier or storage stabilizer. For example, acetic acid, acetic anhydride, phthalic acid, phthalic anhydride, maleic acid, maleic anhydride, pyromellitic acid, pyromellitic anhydride, barfluorooctanoic acid, -70 lolauric acid, -fluoroalkyl chain. Examples include aromatic carboxylic acids (trade name: 7 tercients).

Next, trivalent or pentavalent phosphoric acid or its derivatives are also optional as long as they do not impair the stability of the composition and are compatible with the organic solvent used, the silanol-terminated silicon compound, and the silyl isocyanate compound. It can be used for. For example, when R represents alkyl, phenyl, polyoxyalkyl, alkoxyacyl, etc., and n represents 1 or 2, a compound represented by the formula (RO)P(OH) or n ++ '' -n its P -0 -P condensate, RP(OH)s-n'nI+ RP(OH) A phosphoric acid compound represented by □ is used.
sn, such as dibutyl acid phosphate, dioctyl acid phosphate, ethoxyethyl acid phosphate,! -Acryloxyethel acidic phosphoric acid ester, phenylphosphonic acid, butylphosphinic acid, etc. can be exemplified.

Next, as the alkylsulfonic acid or arylsulfonic acid, laurylsulfonic acid, nomuradolenesulfonic acid,
Dodecylbenzenesulfonic acid and the like can be used.

Seven types of the above organic or inorganic acidic compounds may be used, or two or more types may be used in any combination.

Next, as organic solvent 1, an organic solvent that dissolves each of the above compounds and does not react with the silyl isocyanate is used.Since alcohols and amines lack stability of the composition, esters, ethers, and hydrogen carbonates are used. , ketones other than acetone, etc. can be used. For example, acetic acid esters such as ethyl acetate and butyl acetate, dibutyl ether, tetrahydro-7rane, ethylene glycol dimethyl ether, ethylene glycol cyphthyl ether, ethyl cellosolve acetate, diethylene glycol diacetate, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, etc. The following fluorine W powders can be used singly or in combination.

When blending the above component compounds to form a room temperature drying silicone composition, the blending ratio is such that the silanol-terminated polyorganosiloxane compound is j to 50 g, preferably 10 to 30 g, and the silyl isocyanate is silyl isocyanate. The compound is /-30%, preferably lI-:to%, the acidic compound is 0.0/-0,j, preferably o, or to 0.
3, the organic solvent is J~go%, preferably t/-0~7
It is preferable to set it in the range of 0%. Each component compound or its blending ratio is appropriately selected depending on the material to be surface treated, the purpose, etc.

The composition according to the present invention essentially consists of the compounds listed in a) to 2) above, but in order to improve the physical properties such as external resistance or heat resistance, acrylic, urethane, Various synthetic resins such as imide, vinyl acetate, and polyester can be added. It is appropriate that the amount added be up to 30% of the total weight of the above 911 composition.

In the present invention, when the above-mentioned component compounds are combined in a predetermined ratio and coated on the surface of various solid substances and dried at room temperature, it has excellent heat resistance, water repellency, etc., a practical drying speed, and a moderate drying rate. The present invention can provide a room-temperature-drying silicone composition that can provide a uniform coating with hardness and is effective as a surface treatment agent.

Examples are given below.

Examples/~3 Three types of compositions were prepared by blending a silanol-terminated polyorganosiloxane, a silyl isocyanate, an acidic compound, and an organic solvent in the ratios shown in Table 9 shown in weight percent.

These compositions were spray applied to ceramic tiles, dried at room temperature, and the surface condition was observed. The water repellency was examined at room temperature/after being left in the evening moon, and the state of the coating film was examined after continuous heating for 100 hours.

The results are shown in Table 2, and were good in all cases.

Table 1 Composition Magaji O7 Tashijime 2 Magamodgu 13//
B # /j
Silyl isocyanate xp s
stj
0. / Par 70 Loocta Clear 0.
J monobutyl acidic acid 4
0.3 Butyl acetate HiroO≠0 30 Toluene 27 HiroOgθ Cellosolzoacetate 10
10 (viscosity 1000 centistokes) X = tetrasilyl isocyanate (81 (Woo)
& ) IY= Methylsilyltriisocyanate (C Xin 5i (Neo), )
Table 2 Kettle 1/ Smoke l12 Kettle 13 Example 4 15 parts (by weight) of silanol-terminated dimethylpolyorganosiloxane with viscosity Fli, ooo centistokes,
5 parts of tetrasilyl isocyanate.

097 parts of para-toluenesulfonic acid, W parts of butyl acetate, and W parts of toluene were mixed to prepare a dissolved composition. When this was sprayed onto a ceramic tile at 5°C, it dried in about ic minutes, forming a transparent film showing water repellency. This tile is 21
) Even after treatment with O''Q for ioo hours, there was no change in appearance and the water repellency was further significantly improved.

Claims (1)

[Scope of Claims] a) Silanol-terminated polyorganosiloxane compound b) Silyl isocyanate compound having two or more Si-NCO groups c) Carboxylic acid or its anhydride, trivalent or pentavalent phosphoric acid or its At least one compound among derivatives and alkylsulfonic acids or arylsulfonic acids d) A room temperature containing an organic solvent that dissolves the compounds in a), b), and c) above and does not react with the compound in b) above. Drying silicone composition.