JP3394635B2 - Vehicle coating composition - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a vehicle coating composition having excellent paintability and gelling property, and more specifically, it comprises a polyvinyl chloride resin, a filler and a polyester plasticizer, and the polyester plasticizer is A coating composition for a vehicle, which comprises a plastisol composition having an excellent coating property, characterized in that a long-chain 1,2-alkanediol or 1,2-epoxyalkane is used as an essential reaction component It is a thing.

[0002]

2. Description of the Related Art Sealant is applied to a sheet metal joining portion of an automobile to prevent rust, prevent rain leaks, and improve airtightness. A chipping primer is applied to the lower part of the vehicle body to prevent damage.

In addition, polyvinyl chloride resin has heat resistance,
It has been used for the plastisol composition used for the sealant and the chipping primer because it has excellent weather resistance and has appropriate elasticity, flexibility and adhesion by adjusting the amount of plasticizer. However, when a monomeric plasticizer such as di-2-ethylhexyl phthalate is used as a plasticizer for these purposes, when the intermediate coating and the top coating are applied thereon, the plasticizer is a paint. There is a problem that the particles migrate to the inside and the coating film becomes sticky or the coating material is repelled.

In order to solve these problems, Japanese Patent Laid-Open No.
No. 2-246982, JP-A-63-43969, JP-A-63-193967, JP-A-63-2.
No. 51445, Japanese Unexamined Patent Publication No. 2-255749, Japanese Unexamined Patent Publication No. 3-79651, Japanese Unexamined Patent Publication No. 3-277644, Japanese Unexamined Patent Publication No. 4-146986 discloses a plastisol of polyvinyl chloride resin containing a polyester plasticizer. Many proposals have been made to use them, but when any of the polyester plasticizers described therein was used, the effect of improving the paintability was very small.

Further, it is possible to improve the paintability to some extent by increasing the molecular weight of the polyester plasticizer used in the plastisol, but in such a case, the viscosity of the plastisol increases and the viscosity stability or gel is improved. The chemical conversion is adversely affected and the physical properties after baking are deteriorated.

[0006] Therefore, the object of the present invention is excellent in coatability,
In addition, another object of the present invention is to provide a vehicle coating composition having a low sol viscosity, excellent viscosity stability, and excellent physical properties after baking.

[0007]

Means for Solving the Problems As a result of intensive investigations, the present inventors have found that in a plastisol composition comprising a polyvinyl chloride resin, a filler and a polyester plasticizer, the polyester plasticizer causes a specific reaction. It was found that a coating composition using a plastisol composition characterized by being formed from the components can achieve the above object.

The present invention has been made on the basis of the above findings. (A) 100 parts by weight of polyvinyl chloride resin, (b)
A plastisol composition comprising 80 to 300 parts by weight of a filler and 80 to 300 parts by weight of a polyester plasticizer (c), wherein the component (c) is a 1,2-alkanediol having 6 to 18 carbon atoms as a reaction component or It is intended to provide a vehicle coating composition using a plastisol composition, which is a polyester plasticizer using 1,2-epoxyalkane.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The vehicle coating composition of the present invention will be described in detail below.

Examples of the polyvinyl chloride resin of component (a) used in the present invention include polyvinyl chloride, post-chlorinated polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer. , Vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-styrene-maleic anhydride terpolymer, vinyl chloride -Alkyl, cycloalkyl or aryl maleimide copolymer, vinyl chloride-styrene-acrylonitrile copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer, vinyl chloride-chlorinated propylene copolymer, vinyl chloride -Vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-acrylic acid ester copolymer Coalescence, vinyl chloride - maleic acid ester copolymer, vinyl chloride - methacrylic acid ester copolymers, vinyl chloride - acrylonitrile copolymer, vinyl chloride - and the like urethane copolymer.

As the filler of the component (b) used in the present invention, a filler used in ordinary polyvinyl chloride resins can be used, and the filler includes calcium carbonate, talc, and oxidation. Examples include titanium, clay, silica and the like. These fillers can be used alone or in combination.

The amount of the filler added is 80 to 300 parts by weight, preferably 100 to 200 parts by weight, based on 100 parts by weight of the polyvinyl chloride resin. The above addition amount is 8
If the amount is less than 0 parts by weight, proper thixotropic properties cannot be obtained in work,
If it exceeds 300 parts by weight, the sol viscosity becomes too high.

The polyester plasticizer as the component (c) used in the present invention is a polyhydric alcohol component as a reaction component,
It is formed from a polybasic acid component and, if necessary, a terminal terminating component, and the polyhydric alcohol component is a 1,2-alkanediol having 1 to 6 carbon atoms or 1,2
-Similar to conventional polyester plasticizers except that epoxy alkanes are used. The number of carbon atoms is 6
If it is less than the above range, the effect of improving the coatability is insufficient, and if the number of carbon atoms exceeds 18, the compatibility decreases. The amount of the 1,2-alkanediol or 1,2-epoxyalkane used is preferably 20% by weight or more based on the whole polyhydric alcohol component. The amount used is 2
If it is less than 0% by weight, the effect of improving the coatability may be insufficient, which is not preferable.

Here, the 1,2-epoxyalkane is capable of easily reacting with an acid to form an ester bond, and is substantially the same as one using a 1,2-alkanediol having the same number of carbon atoms. It forms an equivalent polyester plasticizer, and the 1,2-epoxyalkane is also included in the polyhydric alcohol component.

Examples of the polyhydric alcohol component, which is a component for forming the polyester plasticizer of the component (c), include ethylene glycol, diethylene glycol, in addition to the 1,2-alkanediol or 1,2-epoxyalkane. Linear glycols such as 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol and 1,6-hexanediol; 1,2-propanediol, 2-methyl-1,3-propanediol , 2,
2-dimethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,5-hexanediol, 3-methyl-1 , 5-pentanediol, 2-
Examples include branched alcohols such as ethyl-1,3-hexanediol and 2,2,4-trimethyl-1,3-pentanediol. In addition, a small proportion of glycerin,
Polyhydric alcohols such as trimethylolpropane, trimethylolethane and pentaerythritol can also be used.

The polybasic acid component which is a component for forming the polyester plasticizer of the component (c) is, for example,
It is mainly composed of an aliphatic dibasic acid such as malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, azelaic acid and dodecanedicarboxylic acid. In addition to these, a small proportion of an aromatic polybasic acid such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, and pyromellitic acid, or butanetricarboxylic acid, butanetetracarboxylic acid, tricarballylic acid, Aliphatic polybasic acids such as citric acid can also be used.

Further, as the above-mentioned end-stopping component, methanol, ethanol, propanol, propanol, isopropanol, butanol, 2-butanol, 2-methyl-1-propanol, tert-butanol, pentanol, 2-pentanol, 3- Pentanol, 2-methyl-1-butanol, 3-methyl-1-butanol,
tert-amyl alcohol, hexanol, 2-hexanol, 3-hexanol, 4-methyl-2-pentanol, 2-methyl-1-pentanol, 3-methyl-
1-pentanol, 4-methyl-1-pentanol, heptanol, 2-heptanol, 3-heptanol, 4
-Heptanol, 2-methyl-1-hexanol, 3-
Methyl-1-hexanol, 4-methyl-1-hexanol, 5-methyl-1-hexanol, octanol,
2-ethylhexanol, nonanol, isononanol, decanol, isodecanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol,
Monohydric alcohols such as octadecanol, cellosolve, carbitol, phenol, nonylphenol, benzyl alcohol, and acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, pivalic acid, caproic acid, 2-
Methylpentanoic acid, 2-ethylbutyric acid, heptanoic acid, caprylic acid, 2-ethylhexylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid,
Examples thereof include monobasic acids such as heptadecanoic acid, stearic acid, oleic acid, linoleic acid, linoleic acid and benzoic acid.

The ratio of each component of the polyhydric alcohol component, the polybasic acid component and the end-terminating component varies depending on the type of each component used, the characteristics of the intended polyester plasticizer, the molecular weight, etc. The polyhydric alcohol component is used in a proportion of 10 to 80% by weight, the polybasic acid component is used in a proportion of 10 to 80% by weight, and the end-terminating component is used in a proportion of 10 to 50% by weight.

The polyester plasticizer as the component (c) is
Its number average molecular weight is 500 to 3000, especially 500 to 1.
It is preferably 500, and preferably has an acid value of 1 or less and a hydroxyl value of 30 or less.

It is well known to produce the polyester plasticizer of the component (c) using the polyhydric alcohol component, the polybasic acid component and the end-terminating component.
For example, it can be easily produced by reacting in the presence of a catalyst such as dibutyltin oxide or tetraalkyl titanate.

Examples of the polyester plasticizer as the component (c) include polyester plasticizers obtained by using the components shown in Table 1 below (number average molecular weight of each polyester plasticizer, oxidation and The hydroxyl value is shown in [Table 1]).

[0022]

[Table 1]

The amount of the polyester plasticizer added is 80 to 30 with respect to 100 parts by weight of the polyvinyl chloride resin.
It is 0 part by weight, preferably 100 to 200 parts by weight. When the amount added is less than 80 parts by weight, the sol viscosity becomes too high, and when it exceeds 300 parts by weight, thixotropic properties suitable for work cannot be obtained.

The composition of the present invention is a vehicle coating composition using a plastisol composition comprising the above-mentioned components (a), (b) and (c) as essential components.

In the composition of the present invention, other plasticizers used for ordinary polyvinyl chloride resins can be used in combination with the polyester plasticizer as the component (c), if necessary. As the other plasticizer, any plasticizer used for ordinary polyvinyl chloride resins can be used, and examples thereof include phthalate plasticizers such as diheptyl phthalate, dioctyl phthalate and diisononyl phthalate, dioctyl adipate, Diisononyl adipate,
Examples include adipate plasticizers such as di (butyldiglycol) adipate, phosphate plasticizers, polyester plasticizers, chlorinated paraffin plasticizers, trimellitate plasticizers, and epoxidized vegetable oils.

The addition amount of the other plasticizer is preferably 80 to 300 with respect to 100 parts by weight of the polyvinyl chloride resin.
Parts by weight, more preferably 100 to 200 parts by weight.

The composition of the present invention also contains nitrile rubber, chloroprene rubber, acrylic rubber, hydrin rubber,
Elastic agents such as urethane rubber, polysulfide rubber, chlorinated polyethylene, and chlorosulfonated polyethylene can be used in combination.

The amount of the elastic agent added is preferably 300 parts by weight or less, more preferably 10 to 200 parts by weight, based on 100 parts by weight of the polyvinyl chloride resin.

Further, the composition of the present invention can be used in combination with an adhesion-imparting agent such as an epoxy resin, an acrylic resin or an amino resin.

Further, by adding perchloric acid and its metal salt, organic ammonium salt, hydrotalcite or silicate perchloric acid-treated product to the composition of the present invention together, the adhesiveness and weather resistance of the coating film can be improved. It is possible to improve the sex.

In the composition of the present invention, stabilizers such as Pb-based, organic Sn-based and metallic soap-based resins which are commonly used in polyvinyl chloride resins can be used.

Further, the composition of the present invention further comprises various additives which are usually used as additives for polyvinyl chloride resins, such as amine-based, phenol-based, sulfur-based and phosphite-based additives. An antioxidant, a hindered amine-based light stabilizer, an epoxy compound, or the like can also be added.

In addition, if necessary, the composition of the present invention may contain additives such as a cross-linking agent, a filler, an antistatic agent, an anti-plate-out agent and a surface treatment agent, which are usually used in polyvinyl chloride resins. Lubricants, flame retardants, fluorescent agents, antifungal agents, bactericides, metal deactivators, pigments, processing aids, antioxidants and light stabilizers can be added.

The composition of the present invention is applied to the sheet metal fittings of automobiles for the purpose of preventing rust, preventing leakage of leaks, and preventing airtightness of the sealant, and to prevent damage to steel plates and coatings by flying stones during running. It is a coating composition used for vehicle applications such as a chipping primer used in the lower part of a vehicle body.

[0035]

EXAMPLES The present invention will now be described in more detail with reference to examples, but the present invention is not limited to the following examples.

Example 1 The following formulation was kneaded with a kneader for 30 minutes and defoamed with stirring for 60 minutes to prepare a plastisol composition. The sol viscosity at 20 rpm was measured immediately after preparation of the plastisol composition and after deterioration (after acceleration) at 40 ° C. for 168 hours,
Furthermore, the rate of change over time was determined from the ratio. In addition, the paintability was evaluated by the method described below.

The coating property was evaluated by applying plastisol, then applying an alkyd melamine resin-based intermediate coating white paint and an acrylic melamine resin-based top coating black paint, and then applying 14
After baking at 0 ° C for 30 minutes, the paintability of the intermediate coating is not exposed on the surface (reversal), the intermediate coating cannot be seen through (transparent), or the gloss of the coating surface ( The three points of (gloss) are evaluated on a scale of 5, and the larger the value, the better.

Further, a test piece was prepared by baking without coating, and a tensile test was conducted according to JIS K 7113 to measure the tensile strength and elongation. Here, the quality of the gelation property was judged by evaluating the physical properties of the gelled product.

The results are shown in Table 3 below. still,
Compounds (ratio 1 to ratio 3) obtained by using the components shown in [Table 2] below were used as comparative compounds (the number average molecular weight, acid value and hydroxyl value of each compound are shown in [Table 2]). .

[0040]

[Table 2]

[0041]   (Combined) Weight part Zeon-121 [Polyvinyl chloride resin manufactured by Nippon Zeon Co., Ltd.] 70 ZEON-51 [PVC blend blend resin manufactured by ZEON CORPORATION] 30 CML # 41 (calcium oxide manufactured by Omi Chemical Industry) 2 Calcium carbonate (SB) 120 Calcium carbonate (CCR) 50 Test compound (see Table 3 below) 150

[0042]

[Table 3]

In the table, the test compounds No. 1 to No. 7 and the ratios 1 and 2 indicate the samples of [Table 1] and [Table 2] (hereinafter the same).

Example 2 The following formulation was kneaded in a kneader for 30 minutes and defoamed for 60 minutes to prepare a plastisol composition. The coatability of the plastisol composition was evaluated both with and without calcination.

The evaluation of the above coatability was performed as follows. That is, after applying plastisol, after performing 10 minutes at 120 ° C. (prebaking) or without prebaking,
After applying an alkyd melamine resin-based intermediate coating white paint and an acrylic melamine resin-based top coating black paint, 1
After baking at 40 ° C. for 30 minutes, its coatability was evaluated in Example 1
It evaluated by the same evaluation criteria as.

The results are shown in Table 4 below.

[0047]   (Combined) Weight part Zeon-38J [Nippon Zeon Co., Ltd. vinyl chloride-vinyl acetate resin] 70 ZEON-51 [PVC blend blend resin manufactured by ZEON CORPORATION] 30 CML # 41 (calcium oxide manufactured by Omi Chemical Industry) 2 Surface treatment ultrafine calcium carbonate 50 Ground calcium carbonate 150 Test compound (see [Table 4] below) 120

[0048]

[Table 4]

As is clear from the results of [Table 3] and [Table 4], when a monomeric plasticizer such as di-2-ethylhexyl phthalate was used (Comparative Examples 1-1, 2-1).
Is extremely inferior in paintability. Further, when a polyester plasticizer other than the component (c) according to the present invention, that is, a polyhydric alcohol component having a low molecular weight (having less than 6 carbon atoms) is used (Comparative Examples 1-2, 1-3, 2-2, 2-3), the paintability is slightly improved compared to the case where the above-mentioned monomeric plasticizer is used, but the improvement effect is not yet sufficient. Is, on the contrary, decreases as the paintability is improved.

Further, even when a polyhydric alcohol component having a long chain (having 6 to 18 carbon atoms), which does not have a branch such as 1,8-octanediol, is used (sample ratio 3). Is a compound that solidifies and cannot be used as a plasticizer, or increases the sol viscosity, thereby deteriorating the physical properties of the coating film.

On the other hand, 1, which has 6 to 18 carbon atoms,
A composition of the present invention comprising a plastisol composition containing a polyester plasticizer formed by using 2-alkanediol or 1,2-epoxyalkane as a polyhydric alcohol component (Examples 1-1 to 1-1). -7, 2-1 to 2-7)
The coating property is remarkably excellent even when calcination is not performed, the gelation property is good, and the sol viscosity does not increase.

[0052]

The vehicle coating composition of the present invention comprises a plastisol composition comprising a polyvinyl chloride resin, a filler and a specific polyester plasticizer, and has excellent coating properties and physical properties after baking. It is a thing.

─────────────────────────────────────────────────── ─── Continuation of front page (58) Fields surveyed (Int.Cl. ⁷ , DB name) C09D 127/06

Claims (2)

(57) [Claims] 1. A plastisol composition comprising (a) 100 parts by weight of a polyvinyl chloride resin, (b) 80 to 300 parts by weight of a filler, and (c) 80 to 300 parts by weight of a polyester plasticizer, wherein A vehicle paint composition using a plastisol composition, wherein the component is a polyester plasticizer using a 1,2-alkanediol or 1,2-epoxyalkane having 6 to 18 carbon atoms as a reaction component. object. 2. The (c) component is formed from a polyhydric alcohol component and a polybasic acid component, and the 1,2-alkanediol or 1,2-epoxyalkane is added to the polyhydric alcohol component in an amount of 20% by weight. % Of the polyester plasticizer used, the coating composition for vehicle according to claim 1.