JPH04178428A - Non-reactive silicone resin, production thereof and polishing agent - Google Patents

Abstract

PURPOSE:To obtain the title liquid or solid resin useful for polishing agent of car wax, etc., excellent in safety and water repellent property, etc., composed of a specific unit and having specific properties by silylating a partial condensate of an organosilane with an organosilicon compound. CONSTITUTION:(A) A partial condensate of one or more kind of organosilane consisting of 0-50mol.% of the formula SiY4 (Y is hydrolyzable group), 30-100mol.% of the formula RSiY3 (R is unsubstituted monovalent hydrocarbon and/or polyfluoroalkyl) and 0-80mol.% of the formula R2SiY2 is silylated with a compound expressed by the formula (a is 1 or 2; Z is H, halogen, etc., when a is 1 and Z is O, S etc., when a is 2) to provide the objective resin composed of 30-99%, RSiO3/2 unit, 0-80% R2SiO unit, 1-20%, R3SiO1/2 unit and 0-50% SiO2, having >=500 average molecular weight and <=0.5% silanol. Furthermore, the resin is blended with waxs to

Description

[Detailed Description of the Invention] [Technical Field of the Invention] The present invention relates to non-reactive silicone resins, and more specifically, non-reactive silicone resins, in particular liquid to solid silicone resins that have excellent water repellency, antifoaming properties, heat resistance, and mold release properties. This invention relates to a non-reactive silicone resin and a polishing agent containing the same as an active ingredient.

[Technical background of the invention and its problems]

Diorganopolysiloxane has long been well known as a non-reactive silicone, and is used as a water repellent, antifoaming agent, heat resistant agent,
It is used as a mold release agent, polishing agent, and additive for modifying plastic molded bodies. Furthermore, diorganopolysiloxanes range from liquid to semi-solid, and at present, either liquid or semi-solid (raw rubber) is used depending on the purpose. However, depending on the application, water repellency, antifoaming properties, heat resistance, mold releasability, polishing properties, etc. may not be sufficient, or more performance than ever before is required.

It is well known that dimethylpolyorganosiloxane, also known as silicone oil, is used as a water repellent material for car waxes and other products that require water repellency. However, liquid dimethylpolysiloxane does not have durable water repellency and requires frequent wax treatment to maintain water repellency.

In addition, semi-solid (raw rubber) polymeric dimethylpolysiloxane is sometimes used to improve durability, but the water-repellent surface is easily stained, and since it is a polymer, it has a high viscosity and is difficult to handle, and it is difficult to emulsify. There were also some problems, such as difficulty.

In addition, when modifying plastic molded products using dimethylpolysiloxane, dimethylpolyorganosiloxane as a modifier is generally used for the purpose of improving the moisture resistance of the plastic molded product. However, low-molecular dimethylpolysiloxane has problems with bleeding from plastic molded products, and high-molecular dimethylpolysiloxane has problems with poor dispersion in plastic molded products or mold contamination due to bleeding.

In addition, thermosetting silicone resins containing silanol groups mainly composed of organosilsesquioxane units can be used as heat-resistant panels for electrical insulation, as vehicles for heat-resistant and weather-resistant paints, or as water-repellent and mold-release materials. It is widely used as. Most of this thermosetting silicone resin is solid, but it has a lower molecular weight than the semi-solid polymer dimethylpolysiloxane, has a low solution viscosity, is easy to handle, and has excellent stain resistance and durability. It is. However, such thermosetting silicone resins have a major problem in stability because the dehydration condensation reaction due to silanol groups progresses gradually.

Examples of silicone resins containing organosilsesquioxane units include the organopolysiloxanes described in claims (A) and (b) of JP-A-53-43171, and the patent of JP-A-60-106890. The general formula in claim 3, (R'3StOo, s)w(R'zSiO)x(R'
Those represented by SiO, , )v(SiO,)2 are known.

However, since silicone resins produced by these methods are obtained by cohydrolytic condensation of corresponding hydrolyzable silane compounds, silanol groups remain in the resins.

Furthermore, when l-functional siloxane units are included, there are problems such as easy formation of low-molecular products, difficulty in increasing the molecular weight, and difficulty in obtaining a uniform high-molecular weight product during cohydrolytic condensation. Ta.

[Purpose of the invention]

The object of the present invention is to solve the above-mentioned problems by providing a liquid to solid non-reactive silicone resin that imparts water repellency, antifoaming properties, heat resistance, and mold release properties, and furthermore, a non-reactive silicone resin containing this non-reactive silicone resin. Our objective is to provide a polishing agent consisting of:

[Summary of the invention]

That is, the present invention provides R31O:L units 30 to 99 mol% R, SiO
Unit: 0 to 80 mol% R35iO□ unit
1 to 20 mol% and 5i02 units 0 to 50 mol% (wherein R represents an unsubstituted monovalent hydrocarbon group and/or polyfluoroalkyl group), and has an average molecular weight of 500 or more, and A non-reactive silicone resin characterized by a silanol group content of 0.5% or less, and a polishing agent containing this as an active ingredient.

The silicone resin of the present invention is produced by hydrolyzing a silane compound [compounds (1) to (3)] represented by the general formula R, 5iYn-(-=0.1.2)" as a first step.
Perform condensation.

(1) General formula 5iY40-50 mol% (2) General formula
R51Ys, 30 to 100 mol% (3) General 2 RzSiYz 0 to 80 mol% (wherein R represents an unsubstituted monovalent hydrocarbon group and/or polyfluoroalkyl group, and Y represents a hydrolyzable group ) In the formula R, SiY, of component (A), the unsubstituted monovalent hydrocarbon group of R is a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, Alkyl groups such as octyl, nonyl, decyl, and dodecyl; cycloalkyl groups such as cyclopentyl and cyclohexyl; aralkyl groups such as 2-phenylethyl and 2-phenylpropyl; phenyl, tolyl Examples thereof include aryl groups such as C1-C4 alkyl groups or phenyl groups from the viewpoint of ease of synthesis or availability.

Examples of silanes corresponding to the units of (1), (2), and (3) include tetrachlorosilane, tetramethoxysilane, tetraethoxysilane, and tetraisopropoxysilane, and (2), Methylchlorosilane, phenyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisoprokoxysilane, phenyltrimethoxysilane,
Examples include phenyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, etc. (3)
Examples include dimethylchlorosilane, diphenylchlorosilane, methylchlorosilane, dimethyldimethoxysilane, dimethyljethoxysilane, diphenyldimethoxysilane, diphenyldimethoxysilane, and methylphenyldimethoxysilane.

The partial condensates produced from (102) and (3) can be prepared using conventional methods such as Japanese Patent Publication No. 5
Although a condensate of any molecular weight can be obtained by cohydrolytic condensation using the method shown in No. B-27808, even if a hydrolyzable group other than a hydroxyl group remains in this condensate, it is still within the scope of the present invention. It does not exceed.

Here, as the molar ratio of silane, (2) is 30 to 10
The content is 0 mol %, and 50 to 100 mol % when considering the effects as a water repellent and a mold release agent. Moreover, if (3) exceeds 50 mol%, water repellency, mold release properties, antifoaming properties, etc. will be poor, which is not preferable.

The resin composition obtained by this method is basically a known silicone resin having the composition described in claim 1, and is, for example, a resin used in the grease of Japanese Patent Publication No. 63-40471. The non-reactive silicone resin of the present invention, which has the above-mentioned problem in that a large amount of silanol groups remain in the resin, is produced by surface-treating the above partial condensate (A) with the organic compound (B) to significantly remove the silanol groups. It is characterized by decreasing

(B) The unsubstituted monovalent hydrocarbon group of R in the organosilicon compound is the same as above, and includes a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group,
Alkyl groups such as octyl group, nonyl group, decyl group, dodecyl group; cycloalkyl group such as cyclopentyl group, cyclohexyl group; aralkyl group such as 2-phenylethyl group, 2-phenylpropyl group; phenyl group,
Examples include aryl groups such as tolyl groups; however, alkyl groups having 1 to 4 carbon atoms or phenyl groups are preferred from the viewpoint of ease of synthesis or availability.

Further, a polyfluoroalkyl group is an unsubstituted monovalent hydrocarbon group in which at least a portion of the hydrogen atoms are replaced with fluorine atoms. Such a polyfluoroalkyl group has the formula P"Q- (wherein, R" represents a perfluoroalkyl group having 1 to 20 carbon atoms, and Q represents a divalent unsubstituted alkylene group having 2 to 6 carbon atoms.

Examples of the organosilicon compound of component (B) include trimethylsilane, triethylsilane, trimethylchlorosilane, trimethylsilanol, trimethylmethoxysilane, trimethylethoxysilane, hexamethyldisilazane, (CL)ssiNHcHs, (CH3)5siNH(
CHs)t.

(CH3) 5siN (CzHs)a, (CHI)3
SiON(CtHs)z 5(CH3)ssiOcOc
Hz, CH.

CF3 (CF,) z (CHz) t-Si -0C
H3CH.

C8゜CFx (CFz) 4 (CJ) z-Si-OCH
:1CH.

CH3 CFs (Ch)? (CHz)z-Si-OCH3■ CH.

For example,

Note that, among the above, silazane or chlorosilane are preferable because unreacted substances can be easily removed after the silylation reaction, and they may be used alone or in combination.

The silylation reaction of component (A) with component (B) proceeds easily by simply mixing or mixing and heating, so there is no particular operational problem.The mixing ratio of component (A) and component (B) is:
Theoretically, it is sufficient to make R in (B) equal to the hydroxyl group in (A), but the progress of the silylation reaction may be slow depending on the degree of crosslinking of the partial condensate of (A). In addition, in order to facilitate the removal of component (B) after silylation, R in B) is preferably used in a molar amount of 1 to 10 times that of the hydroxyl group in (A).

In addition, although this reaction may be carried out in a solvent-free system, in order to suppress side reactions such as condensation reactions between the components (A) during the silylation reaction,
It may be carried out in a solvent, such as toluene,
Hydrocarbon solvents such as xylene and hexane; ether solvents such as tetrahydrofuran and dioxane; and chlorinated hydrocarbon solvents such as dichloromethane and dichloroethane. There is no particular restriction on this reaction temperature, but since the reactivity changes depending on the type of organosilicon compound (B), the temperature range is from room temperature to 200°C depending on the type of organosilicon compound. You can decide accordingly.

Next, the non-reactive silicone resin thus obtained has a molecular weight of 500 or more and a silanol group content of 0.5.
It is a liquid to solid silicone resin with excellent stability and water repellency, and the present invention also provides a polishing agent containing this non-reactive silicone resin as an active ingredient.

The polishing agent according to claim 3 of the present application is characterized in that it contains the above-mentioned non-reactive silicone resin, and other components that are blended include wax, a solvent, a surfactant, and a thickening agent. , abrasives, colorants, fragrances, detergent-resistant agents, and other additives commonly incorporated into polishes.

Examples of the above-mentioned waxes include animal waxes such as beeswax, wool wax, spermaceti wax, vegetable waxes such as carnauba wax and cotton wax, montan wax, celite wax, ceresin wax,
Mineral waxes such as paraffin wax and petrolatum, synthetic waxes such as hydrogenated castor oil and polyethylene wax, etc. are used as solvents, toluene, kerosene, naphtha, mineral spirits, etc. are used as thickeners, soybean lecithin, methylcellulose, etc. are used as abrasive agents. is aluminum silicate, diatomaceous earth,
Bentonite, silica, hydrated calcium silicate, magnesium oxide, iron oxide, tin oxide, etc., and surfactants include alkyl sulfate, alkyl sulfonate, polyoxyethylene alkylphenyl ether sodium sulfate, polyoxyethylene alkylphenyl ether, polyoxy Ethylene alkyl ether, sorbitan monoester, benzyl ammonium salt, etc., and examples of detergent resistance agents include silanes or siloxanes having an amino group such as -MHz or -(CHz)-NHZ in the molecule.

The polishing agent of the present invention can be applied in any form including solvent-based, water-based, and pasty.

Furthermore, the polishing agent of the present invention has -1γ2 (where Rt is the same as above, - is 3.4 or 5).
A cyclic siloxane or a siloxane-oxyalkylene copolymer represented by the above may be blended as necessary.

[Effects of the Invention] The non-reactive silicone resin of the present invention is a liquid to solid non-reactive silicone resin that has excellent stability over time, water repellency, antifoaming properties, heat resistance, and mold release properties. This non-reactive silicone resin can be added to synthetic resins to greatly improve its water repellency, and can also be used in polishing agents such as car wax to create a gloss with excellent water repellency and durability. You can get a pickle.

〔Example〕

The present invention will be described below with reference to Examples. In addition, all "parts" in Examples represent "parts by weight."

Here, the silanol group content is 30
The amount of moisture generated during heating at 0° C. for 2 hours was measured using a coulometric titration moisture measuring device model CA-06 manufactured by Mitsubishi Kasei ■, and calculated using the following formula.

Silanol group content (%) In addition, the thermal softening point is determined by the ring and ball softening point measurement method (JISC210
Measurement was performed according to 4).

Reference Example-1 Weigh out a mixed solution of 1 mole of methylisoprokoxysilane and 150 parts of toluene into a flask, and add 10 parts of a 1% aqueous hydrochloric acid solution.
8 parts were added dropwise to the above mixture over 20 minutes to hydrolyze methyltriisopropoxysilane. After 40 minutes of addition, stirring was stopped and the mixture was separated into two layers, the lower layer containing water containing a small amount of hydrochloric acid and isopropyl alcohol. is removed under reduced pressure, and the softening point is 1.
A methylpolysiloxane (s-1) having a temperature of 10 to 120°C and a silanol group content of 1.2% was prepared.

Example 1 100 parts of the silanol group-containing methylpolysiloxane prepared in Reference Example 1, 20011 toluene, 10 parts of trimethylchlorosilane, and 50 parts of hexamethyldisilazane were weighed into a flask and heated and stirred. After heating and stirring for 2 hours under reflux of toluene, etc., the toluene and the like were removed by heating at 130'C under a reduced pressure of 20° Hg, and trimethylsilyl group-containing methylpolysiloxane (S -1) was prepared. Furthermore, S-
The silanol group content of No. 1 was 0.3%.

Reference Example-2 A mixed solution of 0.5 mol of methylisopropoxysilane, 0.5 mol of dimethyldichlorosilane, and 150 parts of toluene was weighed into a flask, and 108 parts of a 1% aqueous hydrochloric acid solution was added dropwise to the above mixture over 20 minutes. Methyltriisopropoxysilane was hydrolyzed.

After 40 minutes of dropping, the stirring was stopped, and the mixture of water and isopropyl alcohol in the lower layer containing a small amount of hydrochloric acid was separated into two layers, and then the hydrochloric acid in the remaining toluene resin solution was removed by water washing, and then Toluene was removed under reduced pressure and the viscosity was 4 at 25°C.
A methylpolysiloxane (S-2) of 00 cP and a silanol group content of 1.5% was prepared.

Example 2 200 parts of toluene and 100 parts of hexamethyldisilazane were weighed into a flask and heated and stirred.

While toluene was refluxing, 100 parts of the silanol group-containing methylpolysiloxane (s-2) prepared in Reference Example-2 was added dropwise. After continuing to stir under reflux for 5 hours, under a reduced pressure of 20 mHg,
Toluene and the like were removed by heating at 30'C, and a trimethylsilyl group-containing methylpolysiloxane (S-2) having a viscosity of 50 cP was prepared at 25C. Furthermore, S-2
The silanol group content of was 0.1%.

Reference example-3 Weigh out 1000 parts of water and 50 parts of acetone in a flask,
A solution of 0.3 mol of methyltrichlorosilane, 0.3 mol of dimethyldichlorosilane, and 0.4 mol of phenyltrichlorosilane dissolved in 200 parts of toluene was added dropwise to the mixed solution. 40 minutes after the addition, stirring was stopped and two layers were added. The hydrochloric acid water in the lower layer separated is removed, and the water remaining in the toluene solution of organopolysiloxane in the upper layer and the hydrochloric acid are removed under reduced pressure together with excess toluene, and the softening point is 50 to 60°C.
An organopolysiloxane (s-3) having a silanol group content of 3.5% was prepared.

Example 3 200 parts of toluene and 100 parts of hexamethylene disilazane were weighed into a flask and heated and stirred. While toluene was refluxing, 100 parts of the silanol group-containing organopolysiloxane (S-3) prepared in Reference Example-3 was added dropwise. 5
After continuing to reflux and stir for an hour, 130° under a reduced pressure of 20 mHg.
Remove toluene etc. by heating at 25°C.
A trimethylsilyl group-containing methylpolysiloxane (S-3) with a viscosity of cP was prepared. Incidentally, the silanol group content of S-3 was 0.1%.

Reference example-4 Weigh out 1000 parts of water and 50 parts of acetone in a flask,
A solution of 1 mole of phenyltrichlorosilane dissolved in 200 parts of toluene was added dropwise to the mixed solution, and 40 minutes after the addition, stirring was stopped, and the lower layer of hydrochloric acid water separated into two layers was removed.
Furthermore, water and hydrochloric acid remaining in the toluene solution of the organopolysiloxane in the upper layer were removed together with excess toluene under reduced pressure, and organopolysiloxane (S-4) with a softening point of 150 to 160°C and a silanol group content of 3.0% was prepared. ) was prepared.

Example 4 200 parts of toluene and 100 parts of hexamethylene disilazane were weighed into a flask and heated and stirred. While toluene was refluxing, 100 parts of the silanol group-containing organopolysiloxane (S-4) prepared in Reference Example-4 was added dropwise. 5
After continuing to stir under reflux for an hour, under a reduced pressure of 20 ttg,
Non-reactive silicone resin (S-4) with a softening point of 120-130°C by removing toluene etc. by heating at ℃
was prepared. In addition, the silanol group content of S-4 is 0.4
%Met.

Hiroshi 1 Mashi'' 1.5 For the purpose of observing the stability over time of the siloxane resin of the present invention, the siloxane resins (S-1, S-2, S-3, S-4,
Dissolve 2 parts of 5-Ls-2, s-3, 5-4) in 10 parts of chloroform, weigh this into an aluminum petri dish, and add 15
It was left at 0°C for 10 hours. After that, the aluminum Petri dishes were taken out, 10 parts of chloroform was added to each one again, and it was observed whether or not it dissolved. The results are shown in Table 1.

In addition, stability is passed when redissolved in chloroform (O
), and cases where the sample was not redissolved in chloroform were judged as failed (x).

Table 1 The above siloxane resins (S-1, S-2, S-3, S-4
, s-1, s-2, s-3, 5-4), viscosity 100cS
t polydimethylsiloxane or viscosity 1 million cS
10 parts of polydimethylsiloxane of t and 90 parts of xylene were uniformly mixed to prepare solvent type polishing agents (P-1, P-2, P-3, P-4, p-1, p
-2, P-3, P-4, p-s, p-6).

After soaking a cotton cloth in these polishes, the cotton cloth was taken out and lightly wrung, and was used to lightly wipe the aluminum panel.

The water contact angle and water repellency of each aluminum panel after being left for 1 hour were evaluated.

In the water repellency test, one drop of water was dropped onto each aluminum panel using a pipette, the water was angled at a speed of 10°/1w1n, and the water was judged based on the angle at which the water fell.

The results are shown in Table 2.

Claims (1)

[Claims] 1 RSiO_3_/_2 units 30 to 99 mol% R_2
SiO units 0-80 mol% R_3SiO_1_/_2 units 1-20 mol% and S
It is composed of 0 to 50 mol% of iO_2 units (in the formula, R represents an unsubstituted monovalent hydrocarbon group and/or a polyfluoroalkyl group), has an average molecular weight of 500 or more, and has a silanol group of 0.5 % or less. 2 (A) One or more partial condensates of organosilanes represented by the following (1) to (3) (1) General formula SiY_40 to 50 mol% (2) General formula RSiY_330 to 100 mol% (3) General formula R_2SiY_20-80 mol% (in the formula,
(R represents an unsubstituted monovalent hydrocarbon group and/or a polyfluoroalkyl group, and Y represents a hydrolyzable group) (B) General formula: (R_3Si)_aZ (wherein, R represents an unsubstituted monovalent represents a hydrocarbon group and/or a polyfluoroalkyl group, a represents 1 or 2, and Z represents a hydrogen atom, a halogen atom, a hydroxyl group, -
OR', -NR'X, -ONR'_2 or -OCOR
', and when a is 2, it represents -O-, -N(X)- or -S-. However, R' represents an alkyl group having 1 to 4 carbon atoms, and X represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. The method for producing a non-reactive silicone resin according to claim 1. 3. A polishing agent comprising the non-reactive silicone resin according to claim 1.