JPH01141964A - Coating composition - Google Patents

Abstract

PURPOSE:To obtain a coating composition improved in flexibility, adhesion, solvent resistance, weather resistance, restorability, etc., by adding a paint modifier based on an organosilicon compound both of whose terminals are blocked with specified groups to a synthetic resin paint. CONSTITUTION:Thus coating composition is prepared by adding a paint modifier based on an organosilicon compound both of whose terminals are blocked with alkoxysilyl groups of formula I (wherein R<1> and R<2> are each a 1-4C alkyl, A is a bivalent organic group, including an ester bond or an ether bond, and n is 1-3), e.g., a compound of formula II or III, to a synthetic resin paint. When said organosilicon compound is added to a synthetic resin paint and the mixture is optionally reacted, the obtained resin paint can show excellent flexibility, adhesion, restorability, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention provides a coating composition that has flexibility, solvent resistance, and adhesion, and is particularly useful for automobiles, architecture, and the like.

The present invention relates to a coating composition with improved weather resistance, re-repairability, etc.

(Prior art) Paints are generally applied to the surface of a molded product and allowed to dry and solidify to form a continuous film with various functions on the surface of the object to be coated, thereby achieving purposes such as improving aesthetics and protecting the product. This requires that the coating film has excellent solvent resistance, adhesion, weather resistance, and re-repairability.

However, there is no commercially available paint that satisfies all of these properties, and synthetic resin paints have the problem of lacking flexibility and becoming brittle when the crosslinking density becomes high. This becomes noticeable during outdoor exposure, cold weather, and heat shock, so there is a need for a paint that does not have these disadvantages.

For this reason, plasticizers and various thermoplastic resins that are non-reactive with the resin component are added to commonly commercially available synthetic resin paints, but this does not mean that they are just a mixture. Because of this, there are disadvantages such as a decrease in coating strength, bleed-out, and deterioration over time.

Therefore, for this type of paint, a method of adding diorganopolysiloxane whose molecular chain ends are blocked with hydroxyl groups has been proposed (see Japanese Patent Publication No. 52-36800); Although it shows the effect of imparting flexibility to paints, it has the disadvantage that it does not have the expected effect on resin paints other than silicone.
A method has also been proposed in which an organosilicon compound having a paraffinic chain whose molecular chain ends are capped with alkoxysilyl groups is added (see Japanese Patent Publication No. 58103/1983).
Although this provides a superior effect to the above-mentioned hydroxyl group-containing organopolysiloxane, it has the disadvantage that its flexibility imparting effect is still insufficient.

(Structure of the Invention) The present invention relates to a coating composition to which a coating modifier is added which solves the above-mentioned disadvantages. an alkyl group, A is a divalent organic group having an ester bond or an ether bond,
It is characterized by adding a paint modifier based on an organosilicon compound whose molecular chain ends are blocked with alkoxysilyl groups (n is an integer from 1 to 3) to a synthetic resin paint. It is something to do.

That is, 1. As a result of various studies on methods for improving the flexibility, adhesion, and re-repairability of various commercially available synthetic resin paints, the present inventors found that synthetic resin paints have the following general formula: It was discovered that by adding an organosilicon compound and reacting as necessary, this resin-based paint can be made to have excellent flexibility, adhesion, and re-repairability. The present invention was completed by conducting research on the following.

The synthetic resin paint as the main material constituting the paint composition of the present invention may be any known one, including alkyd resins, urea resins, melamine resins, polyester resins, epoxy resins, polyurethane resins, xylene resins, and fluororesins. , vinyl acetate resin, vinyl chloride resin, acrylic resin, SBR
Examples include paints made from resins and the like, but they may also be mixtures of these. Since these are paints, colorants are added as necessary, but they also include silica, quartz powder, glass powder, alumina, clay, talc, wollastonite, titanium oxide, magnesium hydroxide, Fillers selected from magnesium oxide etc., triethanolamine, N-β-aminoethyl-γ-
Amine compounds such as aminopropyltrimethoxysilane; carboxylic acid metal salts such as zinc octylate and tin octylate; organic tin compounds such as dibutyltin dilaurate and dibutyltin dioctate; titanate esters such as tetrabutyl titanate and tetrapropyl titanate;
It is optional to add a catalyst selected from aluminum organic compounds such as aluminum acetylacetone, organic solvents such as methanol, ethanol, toluene, and xylene, as well as antioxidants, antiaging agents, and antistatic agents. The filler is preferably one that is reactive with an alkoxysilyl group, and the catalyst is preferably a condensation catalyst of a hydrolyzable silyl group-containing compound.

The coating composition of the present invention is prepared by adding a coating modifier represented by the general formula described above to the various synthetic resin coatings described above. This paint modifier is represented by the general formula as described above, and R1 and R2 are selected from methyl group, ethyl group, propyl group, butyl group, etc. From the viewpoint of reactivity, preferably methyl group or ethyl group. an alkyl group having 1 to 4 carbon atoms, n is an integer of 1 to 3, and A is the formula % -R30-+R''-C-O+-R3- or r (where R1 is the number of carbon atoms 2-1o divalent hydrocarbon group, R4
is a divalent hydrocarbon group having 2 to 6 carbon atoms, and R5 is a divalent hydrocarbon group having 2 to 6 carbon atoms.
R6 is a divalent hydrocarbon group having 3 to 5 carbon atoms, R7 is a divalent hydrocarbon group having 1 to 2 o carbon atoms, Q, m
, p, and P are integers).

Therefore, in this RJ Ni”)1.N, -CH2CR2-
.

-CH2CH2CH2-.

CH3CI(s-CH, -CH-CR2-, -CR2-C-CR2-
.

CH.

CH3 -CH,CH,CH2-@-1-CH2CH2CH2-
@- etc., and for R4 -CH2CH2-2 CH.

-CH2CH, CH, +, -CH-CH2-.

-CH2-CH-CH2-, -CH2-C-CH, -C
H.

CH.

-CH2~C-CH,CH,- CH.

Examples include -CT(2CR2-) for R5.

-CR2CH2CH,-, -@-.

-CH2CH, CH, CH2CH, CH2CH2CH,
-, etc., when applied to R6 are -CH, CH2CR2-.

CH3 -CH2-CH-CH2-, -CH2CH2CH2CH
,-.

-CH2CH2CH2CH, CH, - etc., but R7 is -CH2-1-CH2CR2-1-CH,CH2
CH-1-CH, CH2CR2CR2-, -CH2CH
Examples include 2CH2CH2CH2CH2CR2CH, -1→D-, and the molecular weight of A is preferably 1,000 or less in order to make this organosilicon compound solvent resistant. If it exceeds 4,000, the flexibility will be insufficient and the strength of the coating will decrease, so this may be selected arbitrarily depending on the physical properties required of the intended coating composition.

The organosilicon compound represented by the above general formula (1) can be produced by a known method, for example, the formula % (R8 is a divalent carbon hydrogen group having 8 or less carbon atoms, p ,
m is the same as above).

(R4, R5, Ra, Q are the same as above), aliphatic unsaturated bonding groups ( For example, by carrying out an addition reaction between 1 mole of an organic compound having a vinyl group and 2 moles of an alkoxymonohydrodiene silane represented by the formula (wherein R2 and n are the same as above) in the presence of a platinum-based catalyst. Examples of these organic metal silicides include those shown by the following formula.

<CHJO)3SiCII□C, H2C1l□(ocx
H4) 3 D oco□CHz (lJlz Sl
(OCI(3)3, (C1+30)3SiCH,CH2
C) 12 (QC2S t's ) 4゜0CH2CH2C
H2Si (QC)+3)3,-3i (OCH3)
3, CHl C11゜-C11□C1l□CH2-5i (Civil 89) 2, (C
tl, 0), 5iG(2CI(2CH20(C11,C
H,CI(,CI(2CI(2αυ,,CH,Q(,Q
12SL (OCH3)3, Mu (C1130), 5iCH, CH□CH, (QC, H4
),. OCH,CH2CH25i(OCH,),,(C
I, ■3SiCH2CH, Cll, (QC2,, Hs)
□. 0CH2CH,CH25i(OCH3)3゜The coating composition of the present invention is made by adding the organosilicon compound represented by the general formula (1) to the general commercially available synthetic resin coating described above. If the amount of silicon compound added is less than 1 part by weight per 100 parts by weight of the synthetic resin paint, the expected effect will not be obtained, and if it is added more than 30 parts by weight, no further effect will be obtained. The amount may be in the range of 30 parts by weight, and the preferred range is 2 to 20 parts by weight. The synthetic resin paint containing the organosilicon compound represented by the general formula (1) has an alkoxy group and a polar group in its main chain, so it is difficult to apply this paint. The resulting coating film is flexible,
It has the advantages of improved solvent resistance, adhesion, weather resistance, repairability, and tightness, and is particularly useful for automobiles, construction, etc. In addition, this effect is due to the presence of substituents such as alcohol groups, phenol groups, thiol groups, carboxyl groups, and oxime groups, or alkoxysilyl groups and silanol groups that react with alkoxy groups in synthetic resin paints. It exhibits the greatest effect when it has a hydrolyzable silyl group such as silazane group, isopropenoxysilyl group, etc.

Next, synthesis examples and examples of the organosilicon compound represented by the above general formula (1) used in the present invention will be given, and the various physical property values in the examples are those shown by the following test results.

[Appearance]

The appearance of the coating film was visually observed and peeled off as described below.

◎...Smooth and with good gloss, O...Smooth, Mouth...Slight creases, Δ...Significant creases, X...
・There is severe creasing.

〔Pencil hardness〕

For the purpose of checking the tightness of the coating film, JIS-5,
Pencil hardness was measured by the method of No. 400.

[Solvent resistance]

After placing absorbent cotton soaked in toluene on top of the coating,
Wipe with a soft cloth and check for changes (20℃, 1 hour)
.

○...No change 1 mouthful...Swelling, Δ...Glossy, X
...Complete dissolution [adhesion] The coating film was cut vertically and horizontally at intervals of IIm to form 100 gobbles, and cellophane tape was crimped and peeled off, and the remaining goblets were counted.

[Repairability■]

Apply lacquer paint to a thickness of 2oμ on a dull steel plate,
After drying at 40℃ for 3 days, apply the specified paint to a film thickness of 20℃.
It was coated with a thickness of ±3 μm, dried for 24 hours at 20° C. and 65% RH, and then the changes after the lacquer coating were observed.

0...no change, mouth...minor lifting, Δ...large lifting, complete lifting of the X mountain.

[Repairability■]

After baking a melamine alkyd resin paint on a dull steel plate to a film thickness of 20 μm, apply a compound and blur the specified paint on top of it, then apply a six-curve paint at 2°C and humidity to observe the change.

O: No change, Mouth: Minor lifting, Δ: Large lifting, X: Full lifting [Weather resistance] Change after 1,000 hours of exposure to sunshine weather off-ter compared.

◎...Gloss retention rate 90% or more 1 color difference ΔE<10...
Il 80% 〃 , color difference ΔE<20... 〃
70% 〃 , color difference ΔE<4Δ... 〃 6
0%〃, Color difference ΔE<7×...〃 Less than 60%, Color difference ΔE<7 or more C Color difference display is CIE1976, L
”, A”, B”).

[Bending test]

Temperature 20℃, humidity. Bend using a 3 mm diameter mandrel at 65% RH.

0...Pass, ×...Fail.

[Impact test]

300g at 1/4”φ using DuPont type Wf impact tester
When the weight is dropped, the highest weight position that does not cause any abnormality on the coating film is displayed.

Synthesis Example 1 In an IQ glass reactor equipped with a stirrer, thermometer, reflux condenser and dropping funnel, 2C H2=C H
C H2(O C., H.+τ○C H2C H
= 300 g of diallyl polyether represented by C H2
(0.14 mol) and 300 g of toluene and a solution of chloroplatinic acid in 1-butanol with a platinum concentration of 2% by weight.

After heating to 60'C with stirring, add 37.8 g of trimethoxysilane H5i (OCR,).
(0.31 mol) was added dropwise, and as it was added, heat was generated, so the dropwise addition was adjusted so that the temperature of the reaction system did not exceed 90°C. After completion, reduce the low boiling point content in the reaction solution to 100℃/3
When removed under conditions of mn H g, 328.3 g of a yellow transparent liquid was obtained, which exhibited physical properties such as a viscosity at 25°C of 263 cS, a specific gravity of 1.02, and a refractive index of 1.4511. It was confirmed from the results of absorption spectrum analysis, nuclear magnetic resonance spectrum analysis and elemental analysis that it was a compound represented by the formula % (hereinafter abbreviated as organosilicon compound A).

Synthesis Example 2 The diallyl polyether in Synthesis Example 1 above was converted to 198.5 g of diallyl polyether (0, 14
When treated in the same manner as in Synthesis Example 1 except that mol) was used,
215 g of a compound represented by the formula % (hereinafter abbreviated as organosilicon compound B) was obtained.

Synthesis Example 3 The diallyl polyether in Synthesis Example 1 above was converted to 271.5 g (0,1
4 mol) and trimethoxysilane has the formula H8 i (
Jetoxymethylsilane 4 represented by QC2H,)2
Synthesis Example 1 except that the amount was 1.5 g (0.3 1 mol).
When treated in the same manner as above, 302 g of a compound represented by the formula % (hereinafter abbreviated as organosilicon compound C) was obtained.

Synthesis Example 4 The diallyl polyether in Synthesis Example 1 above is shown by the formula. Diallyl polyester, 254.5g (
0.14 mol) CH□-5 as in Synthesis Example 1
i (OCI+,)3
272 g of a compound represented by '·, D (hereinafter abbreviated as organosilicon compound) was obtained.

Synthesis Example 5 The diallyl polyether in Synthesis Example 1 described above was converted to diallyl polyester represented by the formula % 183.1 g (0,
14 mol) and methoxysilane with the formula)-T S x
Synthesis Example 1 except that 41.5 g (0.31 mol) of jetoxymethylsilane represented by (OC2H3)2 was used.
When treated in the same manner as above, a compound represented by the formula % (hereinafter abbreviated as organosilicon compound E) 2 was obtained.
10 g was obtained.

Synthesis Example 6 442g of diallylpolyether represented by the formula (0°14
mol) and trimethoxysilane to 2CH.

The same procedure as in Synthesis Example 1 was carried out except that 32.9 g (0.13 mol) of dimethoxymethylsilane represented by HS i(OCH3) 2 was used, and a compound represented by the formula (hereinafter abbreviated as organosilicon compound F) 4 was obtained.
53g was obtained.

Synthesis Example 7 332.9 g (0.14 mol) of diallyl polyester represented by diallyl adipate in Synthesis Example 1 above
Process-8j (OCI et al.) 3 in the same manner as in Synthesis Example 1 except that

1. .

359 g of the compound represented by (hereinafter abbreviated as organosilicon compound G) was obtained.

Synthesis Example 8 In the glass reactor used in Synthesis Example 1, 339 g (1.5 mol) of diallyl adipate of the formula and 1.5 g of a 1-butanol solution of chloroplatinic acid with a platinum concentration of 2% by weight were added.
and trimethoxysilane H81 at 60℃ under stirring.
(○CH,) 3402.6 g (3.3 moles) was added dropwise, and the reaction was carried out while adjusting the amount of the drop to prevent the reaction system from heating up to 90°C or higher due to heat generation. After stirring for 2 hours and completing one reaction, low-boiling components in the reaction solution were removed under conditions of 120°C/3 mmHg, and 630.3 g of a pale yellow transparent liquid was obtained.
Viscosity at 5°C: 28.9 cS, specific gravity: 1.114, refractive index: 1.
4410, and from the results of infrared absorption spectrum analysis, nuclear magnetic resonance spectrum analysis, and elemental analysis, the formula CH□CH2-3i (OC113)3
... It was confirmed that the compound was a compound represented by H (hereinafter abbreviated as organosilicon compound H).

Synthesis example 9 Trimethoxysilane CH in Synthesis Example 8 above.

■ is jetoxymethylsilane H-3i (○C2H3).

The same procedure as in Synthesis Example 8 was carried out except that the amount was changed to 442.2 g (3.3 mol), and 665 g of a compound represented by the formula % (hereinafter abbreviated as organosilicon compound 2) was obtained.

Synthesis Example 1゜381g (1゜5 mol) of diallyl adipate expressed by the formula % in Synthesis Example 8 above.
The process was carried out in the same manner as in Synthesis Example 8 except that 671 g of a compound represented by Formula 1 (hereinafter abbreviated as organosilicon compound J) was obtained.

Synthesis Example 11 The same procedure as in Synthesis Example 8 was carried out except that diallyl adipate in Synthesis Example 8 was replaced with 423 g (1.5 mol) of diallyl sebacate represented by the formula. ) 763 g was obtained.

Synthesis Example 12 The serial adipate in Synthesis Example 8 was changed to 369 g (1.5 mol) of diallylphthalate represented by the formula, and the trimethoxysilane was changed to triethoxysilane H8i (QC2
H,) 3541.2 g (3.3 mol) was treated in the same manner as in Synthesis Example 8, and 825 g of a compound represented by the formula % (hereinafter abbreviated as organosilicon compound) was obtained. .

Synthesis Example 13 567 g (1.5 mol) of diallyl adipate in Synthesis Example 8 was converted to diallyl ester represented by the formula %.
The process was carried out in the same manner as in Synthesis Example 8, except that 850 g of a compound represented by the formula % (hereinafter abbreviated as organosilicon compound M) was obtained.

Synthesis Example 14 The diallyl adipate in Synthesis Example 8 is
CH2(QC2H,)i. ○ When treated in the same manner as in Synthesis Example 8 except that 807 g (1-5 mol) of diallyl polyether represented by CH, CH=CH2 was used, the formula (CH,0)3Si-C112CH2CH2-+QC2
114 Mostly CH2CH□CH2-3i (ocu3)i
・・・
1,123 g of a compound represented by N (hereinafter abbreviated as organosilicon compound N) was obtained.

Synthesis Example 15 The diallyl adipate in Synthesis Example 8 was changed to 582 g (1°5 mol) of diallyl polyether represented by the formula %, and the trimethoxysilane was changed to jetoxyCH.

"Methylsilane HSi-+○C2H3) 2442.2
When the same treatment as in Synthesis Example 8 was carried out except that the amount of the compound was changed to 3.3 mol, 970 g of a compound represented by the formula % (hereinafter abbreviated as organosilicon compound P) was obtained.

Examples 1-7. Comparative example 1 Campair Krylic 1,000 type [Kansai Paint■
To 100 parts by weight of the same type of lacquer paint Natconite White (trade name manufactured by Nyco Paint), add organic silicon compounds A-G prepared in Synthesis Examples 1 to 7.
10 parts by weight of each and 1 part by weight of dibutyltin dilaurate were mixed thoroughly, and then applied to a glass plate, dull steel plate, and alkyd melamine plate using a 4 mil applicator, and heated at 20°C and humidity of 65°C. %RH for 7 days, and the physical properties of the thus obtained coating film were examined, and the results shown in Table 1 were obtained.

For comparison, we investigated the physical properties of a coating film obtained by treating a lacquer paint without any organic silicon compounds in the same manner as above, and obtained the results as listed in Table 1. It was done.

Glass plate, dull steel plate: Degreased and dried Melamine alkyd degreased plate: Steel plate coated with melamine alkyd resin.

Baking was done with Comparand afterward Examples 8 to 14, Comparative Example 2 Silicone acrylic resin paint/Natconite White [
Made by Natco Paint ■Product name: 1 to 100 parts by weight Synthesis Example 1
15 parts of each of the organosilicon compounds A to G prepared in Steps 7 to 7 were mixed thoroughly, applied to a glass plate, dull steel plate, and alkyd melamine plate using a 4 mil applicator, and heated at 20°C and humidity 65%. % RH for 7 days and examined the physical properties of the thus obtained coating film, the results shown in Table 2 were obtained. When the physical properties of the coating film obtained using the additive-free material were examined, the results shown in Table 2 were obtained.

Examples 15-22, Comparative Example 3 Campair Krylic 1,000 type [Kansai Paint ■
To 100 parts by weight of the same kind of lacquer paint, Natconite White [product name manufactured by Nyco Paint ■], were added 10 parts by weight of each of the organosilicon compounds H-P prepared in Synthesis Examples 8 to 15 and dibutyltin. After blending 1 part by weight of dilaurate and mixing thoroughly, this was applied to a glass plate, dull steel plate, and alkyd melamine plate using a 4 mil applicator, and dried at 20 ° C. and 65% RH for 7 days.
When we investigated the physical properties of the coating film obtained in this way, we found that
The results shown in the table were obtained.

For comparison, we investigated the physical properties of a coating film obtained by treating a lacquer paint without any organic silicon compounds in the same manner as above, and obtained the results listed in Table 3. Ta.

Examples 23 to 30, Comparative Example 4 Silicone acrylic resin paint/Natococeran White [
Made by Natco Paint ■Product name) 1. Add 15 parts of each of the organosilicon compounds H-P prepared in Synthesis Examples 8 to 15 to the oomffi part, mix thoroughly, and apply this to a glass plate, dull steel plate, and alkyd melamine plate using a 4 mil applicator. When the physical properties of the thus obtained coating film were examined by drying it for 7 days at 20°C and 65% RH, the results shown in Table 4 were obtained. When we investigated the physical properties of the coating film obtained using a coating without any addition of organic silicon compounds, we found that the 4th
The results shown in the table were obtained.

Claims (1)

[Claims] 1. General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (Here, R^1 and R^2 are alkyl groups having 1 to 4 carbon atoms,
A paint modifier based on an organosilicon compound in which both ends of the molecular chain are blocked with alkoxysilyl groups (A is a divalent organic group containing an ester bond or an ether bond, n is an integer of 1 to 3) A paint composition characterized by being added to a synthetic resin paint. 2. The coating composition according to claim 1, wherein the amount of the coating modifier added is 1 to 30 parts by weight per 100 parts by weight of the synthetic resin coating.