JP2002047477A - Silane compound composition for car polish - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a hydrophilic car polish composition capable of maintaining glossiness and preventing stains. SOLUTION: This composition comprises (A) 99.9-0.1 wt.% of a silane compound denoted by SiRS(ORa)4-S and/or its hydrolytic condensate and (B) 0.1-99.9 wt.% of a silane compound dented by Si(ORb)mRcnXp and/or its hydrolytic condensate (wherein R and Rc are hydrocarbon groups which may be the same of different; Ra and Rb are hydrocarbon groups or alkoxy hydrocarbon groups which may be the same or different; X is a functional group or a hydrocarbon group having a functional group; S is 3-0; (m) is 1-3; (n) is 0-3; (p) is 1-3; and m+n+p=4).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a composition for car polish of a silane compound. In particular, it relates to a silane compound composition for car polish having excellent hydrophilicity.

[0002]

2. Description of the Related Art Conventionally, various waxes, silicone oils, etc. have been proposed as so-called car polish materials as a material which makes it difficult to adhere dirt by applying to a painted surface of an automobile and maintains the gloss of the painted surface. I have. Silicone compounds and / or silane compounds have also been used for car polish, but these have been used primarily for improving water repellency. These conventional car polish materials,
By forming a water-repellent film on the painted surface, it is intended to prevent the adhesion of dirt and maintain the luster, but because of the water-repellency, dust enters the water droplets on the surface,
Even if it is dried, there is a problem that the residue due to the water droplets remains, and that the silicone-based car polish material tends to be dusty. In addition, when the conventional car polish material is applied to the entire surface of the vehicle with a liquid, these materials also adhere to the glass surface and become an oil film, and also become water droplets in rainy weather to impart water repellency to the glass surface. Therefore, there is a disadvantage that the glass is hard to see.

[0003] By using a material that imparts hydrophilicity instead of the car polish material that imparts water repellency, it is possible to impart the effects of preventing the adhesion of stains on both the painted surface and the glass surface of the car and maintaining the gloss. Although it is thought that the effect of being able to be easily washed off with water is obtained even if it is attached,
No suitable material has been found.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a car polish composition which imparts hydrophilicity and good surface gloss to a painted surface of a car to form a durable film. .

[0005]

Means for Solving the Problems The present inventors have solved the above problem by combining a specific silane compound for car polish, and more particularly, by combining two types of alkoxysilane compounds. The present inventors have found that a silane composition for car polish can be provided, and have accomplished the present invention.

That is, the present invention relates to (A) SiR_S(O
R^a)_4-SAnd / or a silane compound represented by
99.9 to 0.1% by weight of the hydrolyzed condensate and (B) S
i (OR^b)_mR^c _nX_pThe silane compound represented by
0.1 to 99.9% by weight
Silane compound composition for car polish comprising
Where R and R^cAre chars which may be different or the same
Hydride group, R^aAnd R^bAre the same even if they are different
A hydrocarbon group and / or an alkoxy hydrocarbon group,
X is a functional group or a hydrocarbon group having a functional group, and S is 3 to
0, m is 1-3, n is 0-3, p is 1-3, m + n + p
= 4. ). Further, the present invention relates to (A) Si
R_S(OR^a)_4-SThe silane compound represented by
And / or 99.8 to 0.1% by weight of a hydrolysis condensate thereof.
(B) Si (OR ^b)_mR^c _nX_pSilanization represented by
0.1 to 99.8 of the compound and / or its hydrolyzed condensate
% By weight, (D) polyether-modified silicone 0.1-1
Silane compound composition for car polish comprising 0% by weight
(However, in the above formula, R and R^cAre the same even if they are different
A hydrocarbon group, R^aAnd R^bAre each different
Or the same hydrocarbon group and / or alkoxy
A hydrocarbon group, X is a functional group or a hydrocarbon having a functional group
Group, S is 3-0, m is 1-3, n is 0-3, p is 1
3, m + n + p = 4. ).

The present invention will be specifically described below.
(A) component in the present invention is ^{_{SiR S (OR a) 4-}} S
And / or a hydrolyzed condensate thereof. In the formula, R is the same or partially the same or different, and is a hydrocarbon group. Specific examples of R represent hydrocarbon groups such as methyl, ethyl, propyl, butyl, cyclohexyl, hexyl, iso-2-ethylhexyl, octyl, phenyl, benzyl, and naphthyl, and these hydrocarbon groups are branched. May also be linear.

In the formula, R ^a is the same or partially the same or different, and is a hydrocarbon group and / or an alkoxy hydrocarbon group. Specific examples of R ^a include methyl,
Ethyl, propyl, butyl, cyclohexyl, hexyl, iso-2-ethylhexyl, octyl, phenyl,
Benzyl, naphthyl, represents a hydrocarbon group having an alkoxyalkyl such as methoxymethyl may be These hydrocarbon groups linear be branched, also, SiR S in one molecule _(OR ^a) ₄ ^{Ra in} _-S may be the same, partially the same, or all different.

In many cases, Ra is more preferably ^a methyl group or an ethyl group from the viewpoint of hydrolysis rate. That is,
A better result tends to be obtained when the hydrolysis rate with the component (B) is adjusted. Further, when the alkoxy group is substituted with another alkyl group or the like as in the component (B), the hydrolysis rate tends to be slow. However, as the number of carbon atoms in the alkoxy group increases, the hydrolysis rate further decreases. Therefore, the component (A) having an appropriate hydrolysis rate can be particularly preferably used in the present invention. Further, it is also effective to use a mixture of two or more compounds in the range of the component (A) described in the present specification as the component (A). (A) _SiR S (OR
^a ) s of _4-S is 3 to 0, preferably 2 to 0, more preferably 1 or 0.

Specific examples of preferred component (A) include tetramethoxysilane, tetraethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, trimethylethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, octyltrisilane. Ethoxysilane, octyltrimethoxysilane, phenyltriethoxysilane and the like can be mentioned.

The component (A) of the present invention comprises SiR _S (O
R ^a ) A hydrolyzed condensate of _4-S may be used. In the case of a hydrolyzed condensate, it is desirably fluid, and the desired viscosity is 0.1 to 10,000,000 cS at 25 ° C.
t, more preferably 0.1 to 1,000,000 cSt
It is. These hydrolysis condensates are hydrolysis reaction residues,
That it is preferably used in a state having a OR ^a residue or OH residues. Note that the hydrolysis-condensation reaction of the silane compound proceeds with the hydrolysis reaction, and the hydrolysis-condensation product in the present invention includes (A)
Both components (B) include those subjected to hydrolysis only, unless otherwise specified.

The component (A) must be added to the composition comprising the components (A) and (B) of the present invention in an amount of 99.9 to 0.1% by weight, more preferably 80 to 2% by weight.
0% by weight, more preferably 70 to 30% by weight.

The component (B) in the present invention is Si (OR)
^b) _m R ^c _n X _p silane compound represented by and / or its hydrolytic condensate. In the formula, R ^b is
Hydrocarbon groups and / or alkoxy hydrocarbon groups which are different or partially or entirely the same, R ^c is different or partially or entirely the same in one molecule, and X is a functional group or a functional group Represents a hydrocarbon group having a group, and m is 1
-3 and n are 0-2, p is 1-3 and m + n + p = 4. In particular, p is preferably 1 to 2, and more preferably p is 1.

Specific examples of R ^b include hydrocarbon groups such as methyl, ethyl, propyl, butyl, cyclohexyl, hexyl, octyl, phenyl, benzyl and naphthyl, and alkoxy hydrocarbon groups such as methoxyethyl.
R in these hydrocarbon groups may be linear be branched, and Si in one molecule _{^{(OR b) m R c n}} X p
Each of ^b and R ^c may be the same, partially the same, or all different. From the ease of production and the rate of hydrolysis and solubility in water, R ^b is methyl, ethyl,
More preferred are methoxymethyl, methoxyethyl, ethoxymethyl and ethoxyethyl. Most preferred are methyl and ethyl. Specific examples of R ^c include those exemplified for R of component (A) described above.

Examples of X include methyl acrylate, acrylate, epoxy (glycidyl), amino, hydroxyamino, vinyl, acetylene, carbonyl, dicarbonyl, polyoxyalkylene, and acid anhydride. Group, aldehyde group, isocyanate group, mercapto group, alkyl mercapto group, chloro group, bromo group, fluoro group, iodo group, formamide group, acetamido group, cyano group, amide group, imide group, hydroxyl group, oxazolyl group, etc. Groups, and substituted alkyl and substituted alkenyl groups in which these groups are substituted with a hydrocarbon group. Examples of the amino group include an aminopropyl group, N-
A (2-aminoethyl) -3-aminopropyl group can be preferably used.

When an amino-based silane is used, it may be used as it is, but it is a preferable method to first neutralize the aminosilane with an organic acid such as acetic acid and then mix it with the component (A). .

M is 1 to 3; n is 0 to 3;
3 and m + n + p = 4. Preferably p is 1-2,
n is 0 to 2, more preferably 0 to 1, preferably m is 2
To 3, more preferably 3. It is also effective to use a mixture of two or more compounds as the component (B) within the range of the component (B) described in this specification.

Further, the component (B) of the present invention comprises Si (OR)
^b) _m R ^c _n X _p may be hydrolyzed condensate of the silane compound represented by. In the case of a hydrolyzed condensate, it is desirably fluid and the desired viscosity is 0.1% at 25 ° C.
-10,000,000 cSt, more preferably 0.1
Ｃ10,000 cSt. These hydrolytic condensate hydrolysis residues, i.e. having a OR ^b residue or OH residue, and a state where the functional group of the hydrocarbon group is not reactive with a functional group or a functional group represented by X It is preferable to use them.

When preparing these hydrolysis condensates,
Hydrolysis and condensation together with the component (A) are preferably performed. At this time, it is important to adjust the hydrolysis rate of the component (A) and the component (B) for hydrolysis, whereby the component ratio, the residual group and the like can be adjusted. Adjustment of the hydrolysis rate
(A), (B) component type selection, pH adjustment, concentration,
(A) / (B) It can be adjusted by the amount ratio or the like.

The component (B) needs to be added to the composition comprising the components (A) and (B) of the present invention in an amount of 99.9 to 0.1% by weight, preferably 80 to 20% by weight. , And 70 to 30% by weight.

In the present invention, the ratio of component (A) to component (B) is not limited, but (A) :( B) = 90: 10.
The ratio is more preferably 10:90, and even more preferably 70:30 to 30:70.

One of the effective uses of the composition of the present invention is to dilute the composition of the present invention with various organic solvents before use. As the organic solvent which is the component (C) in the present invention, a solvent which can dissolve the composition of the present invention is basically preferably used. In this case, by using the composition at a concentration of less than 5%, preferably less than 1%, the composition of the present invention can be used more effectively.

Examples of organic solvents include aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, alcohols, ethers / acetals, ketones / aldehydes, esters, and polyhydric alcohols. And derivatives thereof,
There are carboxylic acid / anhydride type, phenol type, nitrogen-containing compound type, sulfur-containing compound type, fluorine compound type, etc., and details are described in "Solvent Pocket Book" published by Ohmsha on November 20, 1997. ing.

Particularly preferred solvents are alcohols and aliphatic hydrocarbon solvents. Alcohol, one of the preferred solvents, is a hydrocarbon compound containing a hydroxyl group,
Including polyhydric and polyhydric alcohols. The number of carbon atoms of the alcohol is preferably 1 to 6 when the number of hydroxyl groups is one, and more preferably 1 to 3. Preferred alcohols include methanol, propanol, ethanol, butanol, ethylene glycol, phenol, catechol, naphthol, cyclohexanol and the like. These alcohols having a lower water content are desirable from the viewpoint of product stability.

Preferred aliphatic hydrocarbons are aliphatic hydrocarbon solvents, including mixtures. Examples of preferred aliphatic hydrocarbon solvents include hexane, heptane, pentane,
Octane, low aromatic white spirits (LAWS)
And the like.

The polyether-modified silicone as the component (D) in the present invention is a polyether-modified product of polysiloxane, and these modified products, branched products, partially crosslinked products and the like are also within the scope of the present invention. The component (D) is a component that is effective for further increasing the hydrophilicity in the hydrophilic car polish composition of the present invention.

If a specific example of polysiloxane is represented by a chemical formula,
It becomes like the following formula. (R¹R²SiO_2/2)_D・ (R³R⁴R⁵SiO_1/2)_M・ (R⁶Si
O_3/2)_T・ (SiO_4/2) _Q However, D / (M + D + T + Q) = 0.1 to 1, M / (M + D +
T + Q) = 0-0.5, T / (M + D + T + Q) = 0-0.
8, Q / (M + D + T + Q) = 0 to 0.5. Better
More preferably, D / (M + D + T + Q) = 0.5 to 1, M / (M + D
+ T + Q) = 0 to 0.1, T / (M + D + T + Q) = 0 to
0.4, Q / (M + D + T + Q) = 0 to 0.1. This
The preferred viscosity of these polysiloxanes is at 25 ° C.
0.1 to 10,000,000 cSt.

Further, R¹~ R⁶Are the same independently
Or differently selected from the following: This
Methods of their selection are based on identical structural units such as (R¹R²
SiO _2/2)_DIn the structural unit, for example, R¹As
A tyl group such as R²As different at the same time, ie
Simultaneously select three groups, methyl, phenyl, and hydrogen
It does not prevent you from doing things. Also connect each unit
Even if the structure for the unit is different from the unit structure
I do not care.

Examples of R ^{1 to} R ⁶ include linear or branched alkyl or alkenyl groups having 1 to 20 carbon atoms and halogen-substituted cycloalkyl groups or cycloalkenyl groups having 5 to 25 carbon atoms. Group and its halogen-substituted product,
An aralkyl group or an aryl group having 6 to 25 carbon atoms and a halogen-substituted product thereof, hydrogen, a hydroxyl group, an alkoxy group, a halogen group, an acyloxy group, a ketoximate group,
Amino group, amide group, aminoxy group, mercapto group, alkenyloxy group, acid anhydride group, carbonyl group, saccharide,
It can be selected from a cyano group, an oxazolyl group, an isocyanate group, or the like, and / or a hydrocarbon-substituted product of these groups.

Preferred examples of R ^{1 to} R ⁶ include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tertiary butyl group, a pentyl group, an isopentyl group, a neopentyl group and a hexyl group. , An isohexyl group, a heptyl group, an isoheptyl group, an octyl group, an isooctyl group, a nonyl group, a linear or branched alkyl group such as a decyl group, and a halogen-substituted product thereof, an alkenyl group such as a vinyl group, an allyl group, and a homoallyl group. A cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a dicyclopentyl group, a decahydronaphthyl group and a halogen-substituted product thereof, a cyclopentenyl group (1- and 2-, 3-);
Cycloalkenyl groups such as cyclohexenyl groups (1- and 2-, 3-), aralkyl groups and aryl groups such as phenyl group, naphthyl group, tetrahydronaphthyl group, tolyl group and ethylphenyl group and halogen-substituted products thereof, hydrogen , Hydroxyl group, methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, tert-butoxy group, hexyloxy group, isohexyloxy group, 2-hexyloxy group, octyloxy group,
Isooctyloxy group, 2-octyloxy group, fluoro group, chloro group, bromo group, iodo group, acetoxy group, dimethyl ketoxime group, methyl ethyl ketoxime group,
Examples include an amino group, a hydroxyamino group, a dimethylamino group, a diethylamino group, a formamide group, an acetamido group, an aminooxy group, a mercapto group, a methylmercapto group, an ethylmercapto group, and a glycidyl group. The polysiloxane of the present invention is a product of SILICONES.
& INDUSTRY can be manufactured by methods known in the art.

The polyether-modified silicone which is the component (D) in the present invention is a product in which the above-described polysiloxane further contains a polyether bonding group. As the polyether bonding group, an oxyethylene group (—CH
₂ CH ₂ —O—), an oxypropylene group (—O—C ₃ H)
_6- ) and the like. Specific examples include an ethyleneglycoxy group, a diethyleneglycoxy group, a polyethyleneglycoxy group, a propyleneglycoxy group, a dipropyleneglycoxy group, a polypropyleneglycoxy group, a polyoxyethylene-polyoxypropylene copolymer group,
Examples thereof include a methoxyethyleneglycoxy group, an ethoxyethyleneglycoxy group, a methoxydiethyleneglycoxy group, an ethoxydiethyleneglycoxy group, a methoxypropyleneglycoxy group, a methoxydipropyleneglycoxy group, and an ethoxydipropyleneglycoxy group. Among these, a polyethyleneglycoxy group, a polypropyleneglycoxy group, and a polyoxyethylene-polyoxypropylene copolymer group are preferably used. As long as the component (D) is polyether-modified, it may simultaneously contain various groups exemplified as R ^{1 to} R ⁶ described above.

The preferred amount of component (D) is (A),
10 to 0.1% by weight based on the total amount of components (B) and (D)
And preferably 5 to 0.1% by weight.

When the silane composition of the present invention is used as an aqueous solution for car polish, an acid component may be appropriately used, and the acid component may be used alone or in combination with water. Can be added all at once when adding all the components, or simply mix each component with an acid component or water containing an acid component or mix thoroughly with reflux or the like and then mix with other components. It is also possible to combine them. However, the use of strong acids should be avoided to protect the coating.

Any components may be added to the silane compound composition and the composition containing the silane compound in the present invention as long as they do not depart from the gist of the present invention. Examples that may be added include fungicides, antibacterial agents, light, heat stabilizers, flame retardants, pigments, dyes, silicone resins, various waxes, and inorganic fillers.

A preferred example of the present invention is a composition containing an amino silane. In this case, the preferred range of the composition is that component (A) is tetraethoxysilane, tetramethoxysilane, methyltriethoxysilane, dimethyl They are diethoxysilane, methyltrimethoxysilane and dimethyldimethoxysilane, and the component (B) is 3-aminopropyltriethoxysilane and N- (2-aminoethyl) 3-aminopropyltrimethoxysilane. In this case, the ratio of (A) / (B) is 90/10 to 10/9.
0 is preferable, and 70/30 to 30/7 is more preferable.
0, most preferably 65/35 to 35/65.

The hydrolyzed condensate according to the present invention also includes a hydrolyzate. In addition, the car polish in the present invention includes not only a so-called polish having a polishing effect containing a compound but also all chemical products such as a coating agent which widely covers the surface of a car and protects or improves performance.

[0037]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described based on embodiments.

EXAMPLE 1 In a 50 ml beaker, 15 g of tetraethoxysilane (TEOS) as the component (A) and N- as the component (B) were added.
Take 15 g of (2-aminoethyl) 3-aminopropyltrimethoxysilane (AEAPTMS) and sufficiently stir with a magnetic stirrer. 0.1 g of this mixture is taken into 100 g of hexane. This solution is applied to a JIS coated plate. After air drying for 1 hour and visually observing the surface gloss, the contact angle of water is measured with a contact angle meter. Further, water is sprayed on the entire surface every hour, and the contact angle is measured after 3 hours.
As shown in Table 1, the hydrophilicity is maintained even after 3 hours.

Examples 2 to 6 Evaluation was made in the same manner as in Example 1 except that the components described in Table 1 were used in the ratios shown in Table 1.

Example 7 N- (2-aminoethyl) 3-aminopropyltrimethoxysilane (A) as the component (B) was placed in a 50 ml beaker.
15 g of EAPTMS) is neutralized with acetic anhydride while stirring. 15 g of tetraethoxysilane (TEOS) as the component (A) is added thereto and stirred. This mixture was added to 0.
Take 1 g and place in 100 g of hexane. This solution is evaluated as in Example 1. Table 2 shows the results.

Examples 8 to 10 The components shown in Table 2 were blended at the ratios shown in the table and evaluated in the same manner as in Example 7.

Comparative Example 1 For comparison, a JIS coated plate is evaluated as it is. Table 1 shows the results.

Example 11 Example 11 was carried out in the same manner as in Example 1 except that a hydrolyzed condensate of TEOS (viscosity at 25 ° C., 120 cSt) was used as the component (A). The contact angle was 19 degrees and the contact angle after 3 hours was 22 degrees.

[0043]

[Table 1]

[Table 2]

[0044]

According to the present invention, a silane compound composition having good surface gloss, hydrophilicity and durability can be obtained.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) C09D 183/02 C09D 183/02 183/04 183/04 183/12 183/12 C09G 1/00 C09G 1/00 A F Term (Reference) 4J002 CP02W CP03W CP05W CP05X CP08X CP09X CP10X CP14X CP16X CP18Y GH00 HA05 4J038 DF042 DL021 DL022 DL031 DL032 DL051 DL052 DL071 DL072 DL081 DL082 DL091 DL092 DL101 DL102 DL151 DL152 KA06 MA06

Claims (3)

[Claims] (A) SiR_S(OR^a)_4-SOh
Silane compounds and / or hydrolyzed condensates thereof
99.9-0.1% by weight and (B) Si (OR ^b)_mR^c _nX
_pA silane compound represented by
Car polish consisting of 0.1 to 99.9% by weight of decondensate
Silane compound composition for use. (However, in the above formula, R and R^c
Is a hydrocarbon group which may be different or the same, R^aYou
And R^bIs a hydrocarbon group which may be different or the same
And / or an alkoxy hydrocarbon group, X is a functional group or
A hydrocarbon group having a functional group, S is 3 to 0, m is 1 to 3, n
Is 0 to 3, p is 1 to 3, and m + n + p = 4. ) 2. (A) SiR_S(OR^a)_4-SOh
Silane compounds and / or hydrolyzed condensates thereof
99.8-0.1% by weight and (B) Si (OR ^b)_mR^c _nX
_pA silane compound represented by
0.1 to 99.8% by weight of decondensate, (D) polyether
Car policy comprising 0.1 to 10% by weight of modified silicone
Silane compound composition (However, in the above formula, R and R
^cIs a hydrocarbon group which may be different or the same, R^aYou
And R^bIs a hydrocarbon group which may be different or the same
And / or an alkoxy hydrocarbon group, X is a functional group or
A hydrocarbon group having a functional group, S is 3 to 0, m is 1 to 3, n
Is 0 to 3, p is 1 to 3, and m + n + p = 4. ) 3. 0.01 to 10% by weight of an organic solvent (C)
The silane compound composition for car polish according to claim 1 or 2, which is diluted to a concentration of: