JPS5865764A - Composition for protection of vehicle - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a composition that is applied to a vehicle to protect the vehicle from scratches caused by gravel, rock salt, and the like.

Coal tar, bituminous materials such as asphalt, modifiers for bituminous materials, fillers such as asbestos, etc. have been used as protective compositions for the purpose of rust prevention, soundproofing, etc. on the underside of vehicle bodies or wheelhouses, etc. Compositions containing fibrous fillers, powder fillers, and organic solvents have been used.

However, there is a problem that the bituminous substances, asbestos, etc. used in this type of paint are carcinogenic, and improvements to this problem have been desired.

On the other hand, there is a strong demand for improved durability for vehicles, especially automobiles, and in North America, Northern Europe, etc., rock salt is widely sprinkled on roads during the winter, and these rock salts are scattered by high-speed vehicles. Scratches caused by dirt, gravel, and flying stones, and the occurrence of rust in the scratched areas, have become a major problem. Therefore, it has chipping resistance against rock salt, gravel, and flying stones, especially in low temperature ranges.

The underside of the car body has excellent adhesion and bendability.

It has been desired to develop a composition for the foil housing section. However, since conventional bituminous protective compositions have poor chipping resistance in normal flow, vinyl chloride has been developed as a protective composition with excellent chipping resistance. Sol-type resin spray materials and synthetic rubber latex-based spray agents are already available. However, vinyl chloride sol-type spraying agents and synthetic rubber latex-based spraying agents are not effective enough in terms of chipping resistance unless they are coated with a coating thickness of 600 to 700 mm or more, and chipping resistance, especially at low humidity, is insufficient. Adhesion and bending workability were insufficient and improvements were desired. As a means to solve these problems, JP-A-52-51
418. As in JP-A-55-34219, spraying agents using nitrile rubber, polyphtadiene rubber, petroleum resin, etc. as protective compositions have been proposed. However, even when these resins are used, it is necessary to have sufficient chipping resistance, cold adhesion resistance, and rust prevention.
A coating film thickness of about 0 μm to 1000 μm was required.

On the other hand, from the standpoint of energy conservation, there is a strong desire to reduce the weight of vehicles, and in the field of vehicle painting, it is also necessary to make the film as thin as possible. The same is true.

In view of the current situation, the inventors of the present invention have conducted extensive research and have found that a coating film thickness of 500μ or less can be used as a protective composition for the underfloor and wheelhouse areas of vehicles, and has excellent chipping resistance, rust prevention, adhesion, and We have now invented a vehicle protection composition that has excellent adhesion at low humidity, bending T-ability, and chipping resistance. This product improves the problems of conventional protective compositions used for the underside of vehicle floors and wheel wells, and allows for thinner coatings than before in order to meet the needs of the times in terms of energy conservation. It is a protective composition and is a new technology that has never existed before.

That is, the present invention provides a composition for protecting a vehicle containing an inorganic pigment, an organic pigment, a filler, an additive, and an organic solvent, which includes: (1) a polyol having a hydroxyl value of 30 or higher) and 3 or lower; Resin (A) However, if the effective isocyanate group content is 1% or more, 15
Blocked isocyanate-containing resin (E
) (e) 1 block isocyanate dissociation catalyst (0)
(A), CB) Solid content ratio to resin: 0.
01 market weight% or more -L, 5wt% or less (6) and a mixture in which the blending ratio of effective incyanate groups to hydroxyl groups is (A): (B) -50: 100 to 100 to 50 in equivalent ratio. The present invention provides a composition for protecting a vehicle, characterized in that the composition contains:

Furthermore, if the composition of the present invention is applied to the underside of a vehicle's floor, wheelhouse area, and surrounding area to form a coating film with a thickness in the range of 50 μm to 1-1500 μm, it becomes a practically useful protective film.

Hydroxyl value melting in the present invention, polyol resin 1
The number of milligrams of potassium hydroxide equivalent to neutralizing g. In general, polyol resin (A) refers to a resin having a hydroxyl group with a hydroxyl value of 30 or more and 300 or less, such as polyester polyol, polyether polyol, epoxy polyol, and acrylic polyol.

Examples include alkyd resins, oils and fats, and these can be used alone or in combination of two or more.

Among these, the most preferred are polyester polyols,
It is a polyether polyol. The reason for this is that, as a required performance of the protective composition of the present invention, it is preferable that the non-volatile content of the painted surface be as high as possible. This type of composition has chipping resistance, chipping resistance after water resistance deterioration,
Cold resistance, bendability, adhesion, impact resistance, etc. are required, and epoxy polyols tend to have poor cold resistance and bendability, and acryl polyols have low non-volatile content on the painted surface and poor chipping resistance. Also, alkyd resins and oils and fats tend to have slightly worse chipping resistance after deterioration of water resistance.

The polyester polyol referred to in the present invention refers to polyhydric carboxylic acids and polyhydric alcohols in an equivalent proportion of hydroxyl groups to carboxyl groups at 150°C to 250°C.
Refers to a resin obtained by thermal condensation at a temperature of °C.

Polycarboxylic acids include compounds having at least one carboxyl group in one molecule, including aromatic polycarboxylic acids, saturated or unsaturated aliphatic polycarboxylic acids, and alicyclic polycarboxylic acids. etc., and any of them can be used. Examples of aromatic polycarboxylic acids include 7-talic acid, isophthalic acid, and terephthalic acid. Tridylic acid etc. can be used. Examples of saturated or unsaturated aliphatic polycarboxylic acids include succinic acid, azelaic acid, adipic acid, pimelic acid, sepacic acid, maleic acid, and fumaric acid. Examples of saturated or unsaturated alicyclic polycarboxylic acids include hexahydrophthalic acid 1. Methylhexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, etc. can be preferably used. It can also be used as an oxycarboxylic acid having one or more -F carboxyl groups in one molecule and at least one -L or more hydroxyl groups in the same molecule.

As the oxycarboxylic acid, for example, hydroxybenzoic acid,
Examples include hydroxystearic acid and tartaric acid.

Examples of polyhydric alcohols include compounds having at least two or more F hydroxyl groups in one molecule, such as ethylene glycol, propylene glycol, butanediol,
Neopentyl glycol, -trimethylbentanediol, diethylene glycol, dipropylene glycol,
Hydrogenated bisphenol A, glycerin, tree retardant.

-ruethane, trimethylolpropane, pentaesthritol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, and the like.

The polyether polyol referred to in the present invention includes, for example, polyoxyethylene glycol, polyoxypropylene glycol, polyoxybutylene glycol, polyoxypropylene triol, orioxybu-propylene quadrol, ethylene or propylene blocks, or random covalent polyols. Polyether polyols, or polymer polyols obtained by partially grafting acrylic to these polyols, etc., can be mentioned.

Hydroxyl value of polyol resin (A) of the present invention: 30
Therefore, it is 400 or less, but more preferably 50 or more E+
200 or less. When the hydroxyl value is lower than 30, the amount of hydroxyl groups that react with the effective isocyanate is small, so the crosslinking density is insufficient, resulting in poor chipping resistance, chipping resistance after water resistance deterioration, adhesion, etc. Also, if the hydroxyl number is more than 300, the cured coating will have poor impact resistance and cold bending properties, so it should be used as a protective coating.

It cannot be used as a food composition.

The polyol resin (A) referred to in the present invention desirably has a number average molecular weight usually in the range of 1,000 to 200,001 degrees, with those in the range of 1,500 to 10,000 being particularly optimal.

Next, the Boutique isocyanate-containing resin (B) having an effective isocyanate group content of 1*% by weight or more and 15% by weight or less as used in the present invention includes, for example, tolylene diisocyanate, metaphenylene diisocyanate, and naphthylene diisocyanate.

Aromatic, aliphatic or alicyclic polyvalent isocyanates such as xylylene diisocyanate, hexa, methylene diisocyanate, isophorone diisocyanate, dicyclohegycylmethane diisocyanate, dicyclohexyl propaldi isocyanate, trimethylpentane diisocyanate, and these polyvalent isocyanates Active hydrogen is added to polyvalent isocyanate groups such as polymers or adducts of these polyvalent isocyanates and polyhydric alcohols (adducts obtained by reacting polyvalent isocyanates with excess equivalents of polyhydric alcohols). It is synthesized by reacting with a compound that has an active iso-cyanate group and causing the active iso-cyanate group to disappear at room temperature. Examples of the polyhydric alcohols include polyester polyols, polyether polyols, acrylic polyols, resins such as epoxy resins, diols such as ethylene glycol, propylene glycol, and butanediol, trizotyrolpropane, trinotyrollethane, glycerin, and pentaerythritol. Triol, Fordroll, etc. Examples of compounds having an active hydrogen include aliphatic alcohols such as alcohol and ethanol, phenol, hengeal alcohol, cyclohexane, alcohols such as alcohol, and oximes such as methyl ethyl ketoxime and methyl isobutyl ketoxime. kind.

- Refers to lactams such as caprolactam and β-propiolactam, active methylenes such as diethyl malonate, ethyl acetoacetate, and ethyl acetoacetate. These active hydrogen-containing compounds have an equivalent ratio of 1.
It is preferable to carry out the reaction in a state of excess active hydrogen at a ratio of 0 to 1.1.

In the present invention, the effective isocyanate group content % (B) refers to the above-mentioned aromatic, aliphatic or alicyclic polyvalent isocyanates, polymers of these polyvalent isocyanates, or additions of these polyvalent isocyanates and polyhydric alcohols. I isocyanate polymer containing isocyanate group
It is the percentage value divided by the total weight of the Jn product plus the weight of the active hydrogen-containing compound reacted with the Jn product. In the present invention, the effective isocyanate group content is 1% by weight.
The above is 15% by weight or less, and more preferably L< is 3% by weight or more and 12% by weight or less. When the effective isocyanate group content is lower than 1% by weight, crosslinking is insufficient and chipping resistance is poor and the composition cannot be used as a protective composition. When the effective isocyanate group content is higher than 115% by weight, the cured coating film becomes hard and has poor impact resistance, bendability at low temperatures, etc., and cannot be used as a protective composition.

Blocked isocyanate dissociation catalyst (0) according to the present invention
refers to commonly used organic or inorganic compounds of various metals such as tin compounds, bismuth compounds, titanium compounds, and 6th-class amines. Examples of organic and inorganic compounds of various metals include tin octoate, tin chloride, butyl tin oxide, dibutyltin diacetate, dibutyltin silaurylate, bis(2-ethylhexyl)tin oxide, dibutyldibutoxytin, bismuth trichloride, and octenoic acid. Bismuth, tetraxy(2-ethylhexyl)
Examples include titanate, tetrabutoxytitanium, and the like. Examples of the tertiary amine compound include triethylenediamine, pentamethyldiethylenetriamine, and 1°4-diazabicyclo(2,2,2)octane.

N,N-dimethylcyclohexylamine, N-methyldicyclohexylamine, N,N,N''.

N'-tetrazotylpropylene diamine, N, NNl
, Nl-tetrazotylhexyldiamine, 1,8-diaza-bicyclo(5,4,0)undecene-7 and their phenol salts, higher fatty acid salts such as oleic acid, octylic acid, 2-ethylhexanoic acid, etc. grade amine compound,
Examples include morpholine compounds such as N-ethylmorpholine and N-methylmorpholine, and alkanolamine compounds such as N,N-dimethylethylamine, N,N-diethylethyl-4-nolamine, and the like. In the present invention, organic or inorganic tin compounds, 1,8-diaza-bicyclo(5,4,0)undecene-7 or their phenol salts, oleic acid, 2-ethylhexane are added to the L formulation among organic or inorganic compounds. Acid, higher fatty acid salts such as octylic acid are particularly preferred, and the above compounds can be used alone or in combination.

Blocked isocyanate dissociation catalyst in the present invention (0
) is used in an amount of 0.01% by weight or more and 5% by weight or more in terms of solid content ratio with respect to the above resins (A) and (B), but
A particularly preferable range is 0.2% or more, 4%
It is as follows. When the weight of the M-free catalyst (0) is less than 0601% by weight, the reaction between isocyanate groups and hydroxyl groups is insufficient, and chipping resistance, chipping resistance after water resistance deterioration, adhesion, etc. tend to deteriorate. When the dissociation catalyst (C) is more than 5% by weight, it cannot be used as a protective composition because it becomes expensive and the storage stability of the protective composition deteriorates.

Next, in the present invention, the blending ratio of effective isocyanate groups to hydroxyl groups is (A):(B)-
50: 100=I Do: 50, particularly preferably L< is (A):(B)-70: 100-100:
It is 70. In the present invention (A): (B> −
When the ratio of (A) is less than 50:100, the cured coating film tends to be hard and has poor bending workability at low humidity. Also (A
):(B)-100: When the amount of (A) is more than 50, curing and crosslinking is insufficient, resulting in poor chipping resistance.

Reduces chipping after water resistance deteriorates.

In the protective composition of the present invention, (A) and (E)
In addition to component (0), for example, organic pigments such as titanium oxide, carbon black, red iron oxide, oxide yellow F-, phthalocyanine blue, phthalocyanine green, clay, charcoal calcium, mica, vermiculite, white 1-. As additives and diluting solvents such as fillers such as Palite and Niichi Stone, leveling agents, anti-cissing IL agents, pigment dispersants, anti-sagging agents, etc., aromatic solvents, aliphatic solvents, ketones, etc. , esters, alcohols, etc. using a known stirrer such as a disper, a ball mill,
It may be blended using a known dispersing machine such as a sand grinder or a roll mill. In addition to the components listed above in the present invention, other cellulose derivatives 9 petroleum resins, epoxy resins, noramine resins, urea resins, phenol resins 9 may be used as a vehicle protection composition within the range that does not impede the effects of the present invention.
Synthetic resins such as synthetic rubber and rosin, and natural resins can also be used in addition.

The vehicle protection composition made of the above component composition has extremely stable storage stability, and the coating film formed by applying it to the vehicle body has chipping resistance, water resistance, chipping resistance after deterioration, Adhesion.

It is a protective composition with excellent impact resistance, cold bending resistance, corrosion resistance, etc.

The protective composition of the present invention is most suitable for applying to a vehicle to protect the vehicle from scratches caused by gravel, rock salt, etc. Application areas and LL include the underside of the floor, the wheel house portion such as the inner surface of the wheel house, the rocker panel portion, a portion of the sill outer, the lower portion around the vehicle such as the front and rear apron portions, and the suspension fuel tank.

The coating method is to adjust the viscosity of the protective composition to 1000p8-2.
Airless spray painting and hot airless spray painting with paint adjusted to about 0,000 cps are common, but brush painting, roller painting, or spatula painting are used for repairs such as painting or when applying without masking to complex areas. I can do it. .

In the case of vehicles, these protective compositions can be used in all kinds of applications, such as on the coating film after electrodeposition and curing of the undercoat electrodeposition paint, on the cured intermediate coating film, and on the cured coating film of the paint. It can be used. Usually, it is mainly used on the underside of the vehicle floor and wheel wells, and therefore it is commonly applied to electrodeposited coatings. The protective film formed by coating is approximately 100°
It can be baked and hardened for 10 minutes to 40 minutes at a temperature of 170°C to 170°C. In the present invention, the coating film thickness is 50μ or more and 50077 or less. When the coating film thickness is less than 50 units, the chipping resistance and chipping resistance after deterioration of water resistance are insufficient and the composition cannot be used as a protective composition. In addition, when the coating thickness is thicker than 500μ, there is no possibility of improving the quality of the vehicle, which is one of the objectives of the present invention, and the thick coating of expensive urethane resin becomes a problem in terms of cost and cannot be used. It becomes difficult.

Here, the present invention will be explained in more detail with reference to Examples and Comparative Examples. It goes without saying that the present invention is not limited only to the embodiments described above. In Examples and Comparative Examples, parts are heavy weight parts, and % is heavy wall %.

Example 1 190 parts of phthalic anhydride, 384 parts of adipic acid, 5260 parts of triditylolpro, 445 parts of neopentyl glycol, and 0.5 parts of dibutyltin oxide were placed in a four-ringed flask equipped with a stirrer and a thermometer, and while passing an inert gas. The dehydration reaction was carried out at a reaction temperature of 180°C to 240°C, and the reaction was terminated when the market price reached 1.5. The reaction was diluted with 125 parts of Kijirole and 125 parts of cellosolve acetate to obtain polyester polyol (A). the law of nature. The resulting resin (A) had a hydroxyl value of 80 (calculated as solid content) and a number average molecular weight of 1,900. Note that this number average molecular weight is a polystyrene equivalent value determined by gel perfusion chromatography. (The number average molecular weight of the examples described below was also measured in the same manner.) Next, a four-eye flask equipped with a stirrer, a thermometer, and an inert gas inlet tube was charged with polypropylene glycol (ppo-100).
0, diol with number average molecular weight 1000) 1000 parts, trizotyrolbroban 134 parts, 2.4-80 TD
After preparing 870 parts of l, 429 parts of Kijirole, and 429 parts of cellosolve acetate and introducing an inert gas,
The reaction was carried out at .degree. C. to 80.degree. C., and the reaction was stopped when the percentage of isocyanate groups reached 10% in terms of solid content. (
Hereinafter, the isocyanate base 0-% hydroxyl value will be expressed in terms of solid content. ) Next, take 1000 parts of this resin into another four-eye flask and pour it through the dropping funnel! 150 parts of thylethyl ketoxime was gradually added dropwise to carry out the reaction at 60°C to 80°C. After the dropwise addition was completed, the temperature was raised to 80°C and the reaction was carried out for about 1 hour, and then diluted with Kijirol to a solid content of 60%, and the blocked isocyanate resin (
B) was obtained. The effective isocyanate % of this resin (B) was 8.2%.

A protective composition was produced using this resin with the following formulation.

Polyester polyol (A) A 1
00 parts Blocked isocyanate (B)
97.4 parts Catalyst 5A-106 (4) 2
．． 5 parts Calcium carbonate 208 parts Carbon black 2 parts 100:10Cl blending ratio of hydroxyl groups and isocyanate groups 1,8-diaza-bicyclo(5,4,0) undecene-7 oleate, manufactured by San Abbott Co., Ltd. Product The protective composition thus prepared was diluted to a B viscosity of 4500 cps/20°C with a thinner having a ratio of kijirol and cyclohexane 7 to 1:1. Next, the above-mentioned protective composition was applied with an airless coating machine to the steel plate H, which had been electrodeposited with an epoxy-based cationic electrodeposition paint and cured by baking to form an undercoat film.
Painted to a thickness of 50μ and placed in a cloud atmosphere at 140°C.
Bake harden for 0 minutes. The results of the performance tests for this coating showed very good results as shown in Table 3.

Example 2 111,133 parts of reed fin, 10 parts of trimethylolpropane
9 MS, 206 parts of neopentyl glycol, 210 parts of diethylene glycol, 0 parts of dibutyltin oxide
．． 5 parts were placed in a four-eye flask equipped with a stirrer, a thermometer, and an inert gas introduction tube, and the same method as in Example 1 was carried out to obtain polyester polyol (0). The resulting resin (C) had a hydroxyl value of 100, a number average molecular weight of 2000, and a nonvolatile content of 80%.

Next, in a four-eye flask equipped with a stirrer, an fA meter, and an inert gas inlet tube, Olestar P49-753 (a product manufactured by Mitsui Toatsu Chemical Co., Ltd., a prepolymer prepared by reacting toluene diisocyanate with trimethylolpropane, non-volatile content of 75 %, isocyanate group-containing electric current % is 16%) was taken, and 260 parts of methyl ethyl ketoxime was gradually added dropwise from the dropping funnel in the same manner as in Example 1 to carry out a reaction to obtain a blocked isocyanate resin (D). This resin (D) had an isocyanate group content of 11.9% and a solid content of 60%.

A protective composition was manufactured using these resins with the following formulation.

Polyester polyol (c) 100 parts Blocked isocyanate (D) 85.9
Part catalyst 5A-102 Note 2.6 parts Comparative example 1
．． 2.3, 4.5 In a four-eye flask equipped with a stirrer, a thermometer, and an inert gas inlet tube, add MDl-OR-200 (a product manufactured by Mikata 11 Sodium Urethane Co., Ltd., isocyanate group content % is 31% N0OO parts, 558 parts of kijirole was charged, and 674 parts of methyl ethyl ketoxime was added dropwise from the dropping funnel, and the same reaction as in Example 1 was carried out to obtain a blocked isocyanate resin.

The effective isocyanate group% of this resin (F) is 18.5%
, solid content was 60%. Table 2 using these resins
A protective composition was manufactured using the formulation shown in the following. The performance test results of the coating film are shown in Table 3.

Table-2 0) Mitsui Nichiden urethane product, hydroxyl value 4
20 average molecular weight 5t400 Paint film test method Adhesion (burlap test); 10 cuts were made in each direction at 2rIIm intervals vertically and horizontally on a sample coated with a specified film thickness on a 70x150x0.8M electrodeposited plate until it reached the metal surface. Place cellophane tape on the cut part and peel it off to check whether the paint film has peeled off or not.

The table shows the number of adhesion after peeling and trial i. Normal test is 2
The drought deterioration test was performed in a 0°C atmosphere after 10 days of immersion in 4000°C warm water, and the heat deterioration test was performed in a 20°0 atmosphere after being held in a 70°0 atmosphere for 10 days.

Cold resistance bending test: A sample coated with a predetermined film thickness on a 70 x 150 x O, 8-stroke electrodeposition coated plate was kept in a -30°C low temperature chamber for 3 hours, and after taking it out, the sample was quickly coated on the coated surface. Turn it outward and bend it uniformly 180° along a mandrel with a diameter of 25 mm. Remove the tape from this bent surface to clean the paint film.

Check for cracks, cracks, etc.

Impact resistance: A sample coated with a predetermined film thickness on a 70 x 150 x 0.8 mm electrodeposited plate was subjected to one impact from a 90° angle using an impact tester shown in J.S. K-6830-26. Check for cracks and peeling of the paint film. Immediately after holding for 3 hours in an atmosphere of 20°C under normal conditions and -30°C in low temperatures.

Salt water spray resistance test: A sample coated with a predetermined film thickness on a 70X 150X 0.8rrrn electrodeposited plate was cut in the center of the sample until it reached the metal, held in a salt spray tester for 240 hours, and then cut. Displays the maximum peeling width when the surface is covered with sellotape.

Chipping resistance test: A sample coated with a predetermined film thickness on a 70 x 150 x 0.8 mm electrodeposited plate was subjected to Type 6-M- specified in J Engineering 5B1181.
4-shaped brass hexagonal nuts from a height of 3 m to a pipe diameter of 40 m.
The nut was dropped through the same cylinder of 300 mm onto each sample board at an angle of 30° to the direction of the brass drop, and the weight of the falling nut until the scratches on the paint film reached the metal surface was indicated. The water immersion deterioration test shows the test results after being immersed in 40°C warm water for 10 hours.

Paint stability test: Spraying is carried out by applying B at a temperature of 20°C to the protective composition during painting.
H-type viscometer (rotation speed 2 OR, P, M rotor N05~
7) is the initial viscosity V. Measure. Refuse composition at 45°C
After storage for 10 days in an atmosphere of , the viscosity V, is measured at a measurement temperature of 20°C. The viscosity increase rate was determined by the following formula: v, -V.

Thickening rate (%) -- The company provides compositions with

patent applicant Aisin Chemical Co., Ltd. Representative Seiji Kurimoto Toyota Motor Corporation Representative Yutaka 1) Part of the chapter Mitsui Toatsu Chemical Co., Ltd. Representative Makoto Matsubakama 557-

Claims (1)

[Scope of Claims] A composition for protecting a vehicle containing at least a hairs resin and a catalyst (1) having a hydroxyl value of 30 or more; 1. ,300F or more
Polyol resin (A) (1) Effective isocyanate group content is 1% or more, 1
Blocked isocyanate-containing resin with a weight of 5% or less (
B) (E) The solid content ratio of the dissociation catalyst (C) for blocked isocyanate to the above (A) and (B) resin is 0.0.
1% by weight or more and 5% or less (3) and the blending ratio of if-effective incyanate groups to hydroxyl groups in equivalent ratio (A): (B) - 50 =
The underfloor of a vehicle and/or is characterized by containing a mixture of 100-100:50
or a protective composition around it.