JP2604498B2 - Non-reactive silicone resin and polishing agent - Google Patents

Description

Description: TECHNICAL FIELD OF THE INVENTION The present invention relates to a non-reactive silicone resin,
The present invention relates to a liquid to solid non-reactive silicone resin excellent in imparting water repellency, defoaming property, heat resistance, and mold release property, and to a polishing agent containing the same as an active ingredient.

[Technical background of the invention and its problems]

Diorganopolysiloxane has been well known as a non-reactive silicone, and is used as a water repellent, defoamer, heat-resistant agent, mold release agent, polishing agent, or additive for modifying plastic molded products. Have been. In addition, diorganopolysiloxanes range from liquid to semi-solid, and at present, liquid or semi-solid (raw rubber) substances are used depending on the application. However, depending on the use, water repellency, defoaming agent, heat resistance, mold release properties, glazing properties, etc. are not sufficient, or higher performance than ever is required.

It is well known that dimethylpolyorganosiloxane, which is a so-called silicone oil, is used as a wax material as a water repellent such as car wax which requires water repellency. However, liquid dimethylpolysiloxane is not durable in water repellency, and it is necessary to increase the frequency of wax treatment in order to maintain water repellency. In some cases, semi-solid (raw rubber) -like high molecular dimethylpolysiloxane is used for the purpose of improving 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. There were also difficult problems.

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

Further, a thermosetting silicone resin containing a silanol group mainly composed of an organosilsesquioxane unit,
It is widely used as a heat-resistant varnish for electrical insulation, as a vehicle for heat-resistant and weather-resistant paint, or for water repellency and mold release. The thermosetting silicone resin is mostly solid, but has a lower molecular weight than the semi-solid high molecular dimethylpolysiloxane, and has a low solution viscosity and is easy to handle. Further, it is excellent in stain resistance or durability.
However, such a thermosetting silicone resin has a serious problem in stability because a dehydration condensation reaction caused by a silanol group gradually proceeds.

Examples of the silicone resin containing an organosilsesquioxane unit include the organopolysiloxanes described in claims (A) and (B) of Japanese Patent Application No. 53-43171 and the patents of Japanese Patent Application Laid-Open No. Sho 60-106890. formula claim ^{_{3, (R 1 3 SiO 0.5)}} W (R 1 2 SiO) X (R 1 SiO 1.5) Y (SiO 2)
_Z and the like are known.

However, since the silicone resin is obtained by co-hydrolyzing and condensing the corresponding hydrolyzable silane compound by these methods, silanol groups remain in the resin. Furthermore, when a monofunctional siloxane unit is contained, there is a problem that a low molecular weight product is liable to be formed, a high molecular weight is hardly obtained, and it is difficult to obtain a uniform high molecular weight product during cohydrolysis condensation. .

[Object of the invention]

The object of the present invention is to solve the above problems, water-repellent, defoaming, heat-resistant, liquid to solid non-reactive silicone resin imparting mold release properties, further includes this non-reactive silicone resin And a glazing agent comprising:

[Summary of the Invention]

That is, the present invention Wherein R represents an unsubstituted monovalent hydrocarbon group and / or a polyfluoroalkyl group, and has an average molecular weight of 500 or more and a silanol group of 0.5% or less. It is a non-reactive silicone resin and a polishing agent containing the same as an active ingredient.

The silicone resin of the present invention, first silane compound represented by the general formula _{R a SiY 4-a (a} = 0,1,2) [Compound (1) to (3)] to hydrolysis as a first step, condensation Do what you want.

(1) General formula SiY _{40 to} 50 mol% (2) General formula RSiY ₃ 30 to 100 mol% (3) General formula R ₂ SiY ₂ 0 to 80 mol% (where R is unsubstituted monovalent carbonized In the formula _Ra SiY _4-a of the component (A), the unsubstituted monovalent hydrocarbon group represented by R is _a methyl group or a polyfluoroalkyl group, and Y represents a hydrolyzable group. An alkyl group such as a group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group or a dodecyl group; a cycloalkyl group such as a cyclopentyl group or a cyclohexyl group; -Phenylethyl group, 2-
An aralkyl group such as a phenylpropyl group; an aryl group such as a phenyl group and a tolyl group; and the like. Examples thereof include an alkyl group having 1 to 4 carbon atoms or a phenyl group because of ease of synthesis or availability. Groups are preferred.

(1) Examples of the silane corresponding to the units of (2) and (3) include (1) tetrachlorosilane, tetramethoxysilane, tetraethoxysilane, and tetraisopropoxysilane. (2) Examples include methylchlorosilane, phenyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, and the like. , (3)
Examples thereof include dimethylchlorosilane, diphenylchlorosilane, methylchlorosilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldimethoxysilane, and methylphenyldimethoxysilane.

(1) The partial condensate resulting from (2) and (3) is
The corresponding silanes can be co-hydrolyzed and condensed by a conventionally known method, for example, the method shown in JP-B-58-27808, to obtain a condensate of any molecular weight. Even when the decomposable group remains,
It is not beyond the scope of the present invention.

Here, as the silane molar ratio, (2) is 30 to 100
In consideration of the effects as a water repellent and a release agent, the content is 50 to 100 mol%. On the other hand, if (1) exceeds 50 mol%, the water repellency, the releasability, the defoaming property and the like are inferior.

The resin composition thus obtained is basically defined in claim 1
It is a known silicone resin having the composition described, for example, a resin used for grease and the like in JP-B-63-40471.However, if this method is used as it is, a large amount of silanol groups remains in the resin, which has the above-mentioned problems. . The non-reactive silicone resin of the present application is characterized in that the partial condensate (A) is surface-treated with the organic compound (B) to thereby significantly reduce silanol groups.

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

Further, the polyfluoroalkyl group is obtained by replacing a hydrogen atom of at least a part of an unsubstituted monovalent hydrocarbon group with a fluorine atom. As such a polyfluoroalkyl group, a compound represented by the formula R′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 as the component (B) include trimethylsilane, triethylsilane, trimethylchlorosilane, trimethylsilanol, trimethylmethoxysilane, trimethylethoxysilane, hexamethyldisilazane, (CH ₃ ) ₃ SiNHCH ₃ , and (CH ₃ ) ₃ SiNH (CH ₃ ) ₂ , (C
_{H 3) 3 SiN (C 2} H 5) 2, (CH 3) 3 SiON (C 2 H 5) 2, (C
H ₃ ) ₃ SiOCOCH ₃ , And the like.

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

Since the silylation reaction of the component (A) by the component (B) easily proceeds only by mixing or heating, there is no particular problem in operation. The mixing ratio of the component (A) and the component (B) can theoretically be such that R in (B) is equal to the hydroxyl group in (A). Depending on the degree of crosslinking of the condensate, in addition to the fact that the progress of the silylation reaction may be slow, the component (B) after the silylation is easily removed.
R in the above is preferably a 1 to 10-fold molar amount.

The reaction may be solvent-free, but may be carried out in a solvent in order to suppress side reactions such as a condensation reaction between the components (A) during the silylation reaction. Examples of the solvent include toluene, xylene, and the like. Hydrocarbon solvents such as hexane; ether solvents such as tetrahydrofuran and dioxane;
Chlorinated hydrocarbon solvents such as dichloromethane and dichloroethane are exemplified. The reaction temperature is not particularly limited, but the reactivity varies depending on the type of the organosilicon compound (B). Therefore, this temperature range is from room temperature to 200 ° C. depending on the type of the organosilicon compound. May be determined.

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

The glazing agent according to claim 3 of the present application is characterized by containing the above-mentioned non-reactive silicone resin. Other components to be blended include wax, solvent, surfactant, and thickener. All conventionally known substances selected from abrasives, coloring agents, fragrances, detergent resistance agents, and other additives usually blended in polishing agents are included.

Examples of the above wax include animal waxes such as beeswax, wool wax, whale wax, carnauba wax, vegetable waxes such as cotton wax, montan wax, celite wax, ceresin wax, paraffin wax, mineral wax such as petrolatum, hardened castor oil, polyethylene wax and the like. Synthetic wax, etc., as solvents, toluene, kerosene, naphtha, mineral spirits, etc., as thickeners, soybean lecithin, methylcellulose, etc., as abrasives, aluminum silicate, diatomaceous earth, bentonite, silica, hydrated silica Calcium, magnesium oxide, iron oxide, tin oxide, etc., as surfactants alkyl sulfate, alkyl sulfonate,
Polyoxyethylene alkyl phenyl ether sodium sulfate, polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl ethers, sorbitan esters, benzylammonium salts. Examples of the detergent resistance agent -NH ₂ and in the molecule - (CH ₂₎ - Examples thereof include silane or siloxane having an amino group such as NH ₂ .

The polishing agent of the present invention can be applied to all forms including a solvent base, a water base, and a paste form.

Further, in the polishing agent of the present invention, (Where R ² is the same as described above, and m is 3, 4, or 5), and a cyclic siloxane or a siloxane-oxyalkylene copolymer represented by the formula (1) can be blended as required.

〔The invention's effect〕

The non-reactive silicone resin of the present invention is a liquid to solid non-reactive silicone resin having excellent stability over time, water repellency, defoaming property, heat resistance, and release property. This non-reactive silicone resin can greatly improve its water repellency by being compounded with synthetic resin and the like, and has excellent water repellency and durability by being used as a polishing agent such as car wax. A dispensing agent can be obtained.

〔Example〕

Hereinafter, an embodiment of the present invention will be described. In the examples, "parts" all mean "parts by weight".

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

The thermal softening point is determined by the ring and ball softening point measurement method (JIS C 2104).
It measured according to.

Reference Example-1 A mixed solution of 1 mol of methylisoprokoxysilane and 150 parts of toluene was weighed and placed in a flask, and a 1% aqueous solution of hydrochloric acid 108
The mixture was added dropwise to the above mixture in 20 minutes to hydrolyze methyltriisopropoxysilane. Stop stirring 40 minutes after dropping,
The lower layer of water containing a small amount of hydrochloric acid separated into two layers, a mixed solution of isopropyl alcohol was removed under reduced pressure, and the softening point was 110 to 120.
A methylpolysiloxane (s-1) having a silanol group content of 1.2% at a temperature of ° C was prepared.

Example-1 100 parts of the silanol group-containing methylpolysiloxane prepared in Reference Example-1, 200 parts of toluene, 10 parts of trimethylchlorosilane, and 50 parts of hexamethyldisilazane were weighed into a flask, and heated and stirred. Under reflux of toluene etc.
After continuing heating and stirring for 2 hours, toluene and the like were removed by heating at 130 ° C. under a reduced pressure of 20 mmHg, and the softening point was 80 to 90.
Trimethylsilyl group-containing methylpolysiloxane (S
-1) was prepared. In addition, the silanol group content of S-1 is
0.3%.

Reference Example-2 A mixture of 0.5 mol of methyl isopropoxysilane, 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 to the mixture.
In minutes, the methyltriisopropoxysilane was hydrolyzed. After 40 minutes from the dropping, the stirring was stopped, the lower layer of water containing a small amount of hydrochloric acid separated into two layers, a mixed solution of isopropyl alcohol was separated, and then the remaining hydrochloric acid of the resin solution of toluene was removed by washing with water. Toluene was removed under reduced pressure to prepare methylpolysiloxane (s-2) having a silanol group content of 1.5% and a viscosity of 400 cP at 25 ° C.

Example 2 A flask of 200 parts of toluene and 100 parts of hexamethyldisilazane was weighed and heated and stirred. Under reflux of toluene, 100 parts of the silanol group-containing methylpolysiloxane (s-2) prepared in Reference Example-2 was added dropwise. After continuing reflux stirring for 5 hours, toluene and the like were removed by heating at 130 ° C. under a reduced pressure of 20 mmHg to prepare a methylpolysiloxane containing trimethylsilyl group (S-2) having a viscosity of 50 cP at 25 ° C. In addition, the silanol group content of S-2 was 0.1%.

Reference Example-3 1000 parts of water and 50 parts of acetone were weighed in a flask, and a solution obtained by dissolving 0.3 mol of methyltrichlorosilane, 0.3 mol of dimethyldichlorosilane, and 0.4 mol of phenyltrichlorosilane in 200 parts of toluene was dropped into the mixed solution. , Dripping
After 40 minutes, the stirring was stopped, the lower hydrochloric acid aqueous solution separated into two layers was removed, and the water and hydrochloric acid remaining in the toluene solution of the organopolysiloxane in the upper layer were removed under reduced pressure together with excess toluene, and the softening point was reduced to 50. Silanol group content at ~ 60 ° C 3.
A 5% organopolysiloxane (s-3) was prepared.

Example 3 200 parts of toluene and 100 parts of hexamethylene disilazane were weighed into a flask, and heated and stirred. Under reflux of toluene, 100 parts of the silanol group-containing organopolysiloxane (s-3) prepared in Reference Example-3 was added dropwise. After continuing reflux stirring for 5 hours, toluene and the like are removed by heating at 130 ° C. under a reduced pressure of 20 mmHg, and trimethylsilyl group-containing methylpolysiloxane (S-3) having a viscosity of 120,000 cP at 25 ° C.
Was prepared. In addition, the silanol group content of S-3 is 0.1%.
Met.

Reference Example-4 1000 parts of water and 50 parts of acetone were weighed and placed in a flask, and a solution obtained by dissolving 1 mol of phenyltrichlorosilane in 200 parts of toluene was dropped into the mixed solution. The separated lower layer of hydrochloric acid aqueous solution was removed, and water remaining in the toluene solution of the upper layer organopolysiloxane, and hydrochloric acid were removed under reduced pressure together with excess toluene,
An organopolysiloxane (s-4) having a softening point of 150 to 160 ° C and a silanol group content of 3.0% was prepared.

Example-4 200 parts of toluene and 100 parts of hexamethylene disilazane were weighed into a flask, and heated and stirred. Under reflux of toluene, 100 parts of the silanol group-containing organopolysiloxane (s-4) prepared in Reference Example-4 was added dropwise. After continuing stirring under reflux for 5 hours, toluene and the like were removed by heating at 130 ° C under a reduced pressure of 20 mmHg to prepare a non-reactive silicone resin (S-4) having a softening point of 120 to 130 ° C. In addition, S-4
Had a silanol group content of 0.4%.

For the purpose of observing the stability over time of the siloxane resin of the present invention,
The siloxane resin (S-1, S-2, S-3, S-
4, 2 parts of s-1, s-2, s-3, s-4) are dissolved in 10 parts of chloroform and weighed on an aluminum Petri dish.
It was left at 150 ° C. for 10 hours. Thereafter, the aluminum petri dishes were taken out, and 10 parts of chloroform was added again to each of them, and it was observed whether or not they were dissolved. The results are shown in Table 1.

The stability was evaluated as pass (合格) when redissolved in chloroform, and failed (x) when not redissolved in chloroform.

Evaluation of water repellency The siloxane resin (S-1, S-2, S-3, S-
4, s-1, s-2, s-3, s-4), 10 parts of polydimethylsiloxane having a viscosity of 100 cSt or polydimethylsiloxane having a viscosity of 1,000,000 cSt and 90 parts of xylene are uniformly mixed, and a solvent is prepared. Type polish was prepared (P-
1, P-2, P-3, P-4, p-1, p-2, p-
3, p-4, p-5, p-6).

After immersing the cotton cloth in these polishes, the cotton cloth was taken out and squeezed lightly, and the aluminum panel was gently wiped with this. The water contact angle and water repellency of each aluminum panel left for 1 hour were evaluated.

In the test of water repellency, one drop of water was dropped on each aluminum panel using a pipette, the angle was formed at a speed of 10 ° / 1 min, and the angle at which water flowed down was determined.

 The results are shown in Table 2.

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location C09G 1/00 C09G 1/00 A

Claims (2)

(57) [Claims] (A) One or two or more partial condensates of an organosilane represented by the following (1) to (3): (1) 0 to 50 mol% of the general formula SiY ₄₀ (2) Formula RSiY ₃ 30 to 100 mol% (3) General formula R ₂ SiY ₂ 0 to 80 mol% (wherein R represents an unsubstituted monovalent hydrocarbon group and / or a polyfluoroalkyl group, and Y represents hydrolysis (B) General formula: (R ₃ Si) _a Z (wherein, R has an unsubstituted monovalent hydrocarbon group and / or a polyfluoroalkyl group, and a represents 1 or 2) ,
Z is a hydrogen atom, a halogen atom, a hydroxyl group, when a is 1;
OR ', -NR'X, -ONR' ₂ or -OCOR ',
Represents -O-, -N (X)-or -S- when is 2.
Here, 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). RSiO _3/2 unit 30-99 mol% R ₂ SiO unit 0-80 mol% R ₃ SiO _1/2 unit 1-20 mol% and SiO ₂ unit 0-50 mol% (where R is an unsubstituted A monovalent hydrocarbon group and / or a polyfluoroalkyl group), a solid having an average molecular weight of 500 or more, and a silanol group of 0.5% or less. 2. A polishing agent comprising the non-reactive silicone resin according to claim 1.