JP3325962B2 - Plastisol 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 plastisol composition comprising a polyvinyl chloride resin and a polyester plasticizer for a sealant having excellent paintability, gelling properties, and properties after baking. Specific polyhydric alcohol component, specific terminal termination component and polybasic acid component as plasticizer
The present invention relates to a plastisol composition using a polyester plasticizer obtained from adipic acid .

[0002]

2. Description of the Related Art A sealant is applied to a sheet metal fitting portion of an automobile in order to prevent rust, prevent rain leakage and improve airtightness. Chipping primer is applied to the lower part of the vehicle body to prevent damage.

[0003] Polyvinyl chloride resin is excellent in heat resistance and weather resistance, and has appropriate elasticity, flexibility and adhesiveness by adjusting the amount of plasticizer. Therefore, plastisol used in sealants and chipping primers is used. It has been utilized in compositions. However, when a polyvinyl chloride resin is used for these applications, it is used as a composition containing a monomeric plasticizer such as di-2-ethylhexyl phthalate phthalate as a plasticizer. When a top coat and a top coat are applied, there is a problem that the plasticizer migrates into the paint and the coating film sticks or the paint repels.

In order to solve these problems, Japanese Patent Laid-Open No.
JP-A-2-246982, JP-A-63-43969, JP-A-63-193967, JP-A-63-2
JP-A-51445, JP-A-2-255749, JP-A-3-79651, JP-A-3-277644, JP-A-4-146986, etc. disclose a polyester plasticizer to a plastisol of a polyvinyl chloride resin. The use of polyester plasticizers described in these publications has been proposed in many cases, but when the polyester plasticizers described therein are used, the effect of improving the coatability is very small.

[0005] Further, by increasing the molecular weight of the polyester plasticizer used in the plastisol, it is possible to improve its coatability to some extent. However, in such a case, the viscosity of the plastisol increases, and the viscosity preservability and the gel stability are increased. This has the disadvantage of adversely affecting the chemical properties and further reducing the physical properties after baking.

Accordingly, it is an object of the present invention to provide a plastisol composition for a sealant having excellent paintability, gelling properties, and physical properties after baking.

[0007]

The present inventors have SUMMARY OF THE INVENTION, in intensive result of extensive investigations, the plastisol composition comprising a polyvinyl chloride resin and polyester-based plasticizers, as the polyester resin is a plasticizer, 1 , 4-butane
By using a polyester polyol obtained from adipic acid as a polyhydric alcohol component which is a diol (linear) -branched mixed glycol, a linear alcohol or / and a linear fatty acid as a terminal terminating component, and a polybasic acid component, It has been found that the above object can be achieved.

The present invention has been made on the basis of the above findings, and comprises 100 parts by weight of a polyvinyl chloride resin and 80 to 300 parts by weight of a polyester plasticizer, wherein the polyester plasticizer is (a) 1,4 - butane diol 20
A polyhydric alcohol component comprising 80% by weight and 80 to 20% by weight of a branched glycol; (b) a terminal terminating component comprising a linear alcohol having 4 to 18 carbon atoms and / or a linear fatty acid; and (c) an adipic acid. It is an object of the present invention to provide a plastisol composition.

Hereinafter, the plastisol composition of the present invention will be described in detail.

Examples of the polyvinyl chloride resin used in the present invention include polyvinyl chloride, pentachlorinated polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, and 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 arylmaleimide copolymer, vinyl chloride-styrene-acrylonitrile copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer, vinyl chloride-chlorinated propylene copolymer, vinyl chloride-vinylidene chloride-acetic acid Vinyl terpolymer, vinyl chloride-acrylate copolymer, chloride Cycloalkenyl - maleic acid ester copolymer, vinyl chloride - methacrylic acid ester copolymers, vinyl chloride - acrylonitrile copolymer, vinyl chloride - urethane copolymer and the like, can also be used commercially available products. When used, they can be used alone or as a mixture.

The polyester plasticizer used in the present invention comprises (a) a polyhydric alcohol component comprising 20 to 80% by weight of 1,4-butanediol and 80 to 20% by weight of a branched glycol, and (b) a polyhydric alcohol component having 4 to 18 carbon atoms. Straight-chain alcohol or /
And terminal stop component made of linear fatty acids, and (c) azide
It is obtained from pinic acid . The upper Symbol branched glycol, 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-hexane Diol, 3-methyl-1,
5-pentanediol, 2-ethyl-1,3-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, and the like. When used, they can be used alone or as a mixture. In addition,
A small proportion of polyhydric alcohols such as glycerin, trimethylolpropane, trimethylolethane, and pentaerythritol can be used in combination as long as the effects of the present invention are not impaired.

The amount of the 1,4-butanediol used is:
80 to 20% by weight of the total used linear or branched glycol, and the amount of the above-mentioned branched glycol used is 1,4-butanediene.
20-80% by weight in all (linear) or branched glycol
It is. Here, 1,4-butanediol is used for all 1,
80 in 4-butanediol (linear) or branched glycol
If the amount exceeds 10% by weight, the freezing point increases, or the viscosity increases, causing an increase in the viscosity of the plastisol, thereby reducing the gelling property. The branch glycols full use 1,4 Bed
80% by weight in tandiol (linear) or branched glycol
If it exceeds, the paintability will decrease.

The straight chain alcohol having 4 to 18 carbon atoms used as the terminal terminating component includes butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol. Examples thereof include phenol, hexadecanol, heptadecanol, and octadecanol, and a mixed alcohol thereof. In addition, as a linear fatty acid having 4 to 18 carbon atoms,
Butyric, valeric, caproic, heptanoic, caprylic,
Examples include pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, and stearic acid. Among them, straight-chain alcohols or fatty acids having 6 to 10 carbon atoms are particularly preferred. Among the above straight-chain alcohols and straight-chain fatty acids, those having less than 4 carbon atoms are inferior in storage stability of plastisols, and those having more than 18 carbon atoms have increased sol viscosity and are inferior in gelling properties. When used, they can be used alone or as a mixture.

A part (30% by weight or less) of the terminal terminating component may be another monohydric alcohol and / or monobasic acid. Examples of the monohydric alcohol include methanol, ethanol, propanol,
Isopropanol, isobutanol, isohexanol, isoheptanol, isooctanol, 2-ethylhexanol, isononanol, isodecanol, isoundecanol, isotridecanol, cellosolve, carbitol, phenol, nonylphenol, benzyl alcohol, etc .; Examples of the monobasic acid include monobasic acids such as acetic acid, propionic acid, isobutyric acid, pivalic acid, 2-ethylhexylic acid, and benzoic acid. When used, they can be used alone or as a mixture.

In addition to the adipic acid (polyacid component) ,
A small proportion of phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, aromatic polybasic acids such as pyromellitic acid, or butanetricarboxylic acid, butanetetracarboxylic acid,
An aliphatic polybasic acid such as tricarballylic acid and citric acid may be used in combination.

In the polyester plasticizer, a part of the adipic acid and / or the polyhydric alcohol component can be replaced with 12-hydroxystearic acid, caprolactone, or the like.

The above-mentioned polyester plasticizer can be prepared using the above-mentioned components by a well-known method. For example, each component is reacted in the presence of a catalyst such as dibutyltin oxide or tetraalkyl titanate. By doing so, it can be easily manufactured.

The ratio of each component used in the production of the polyester-based plasticizer varies depending on the type of the component used, the characteristics and the molecular weight of the target polyester-based plasticizer, and generally, 10 to 80% by weight of adipic acid. %, Polyhydric alcohol component 10 to 80% by weight, terminal end component 10 to 50
Used in percentages by weight.

The number average molecular weight of the polyester plasticizer used in the present invention is preferably from 500 to 3000, more preferably from 500 to 1500. The polyester-based plasticizer has an acid value of 1 or less;
The hydroxyl value is preferably 30 or less.

The amount of the above-mentioned polyester plasticizer is 80 to 300 parts by weight per 100 parts by weight of the polyvinyl chloride resin.
Parts by weight, preferably 100 to 200 parts by weight.

A plasticizer used in a general polyvinyl chloride resin can be used together with the above-mentioned polyester plasticizer, if necessary. As these plasticizers, any plasticizers used for ordinary vinyl chloride resins can be used.For example, diheptyl phthalate, dioctyl phthalate, phthalate plasticizers such as diisononyl phthalate, dioctyl adipate, diisononyl adipate, Examples include adipate plasticizers such as di (butyldiglycol) adipate, phosphate plasticizers, chlorinated paraffin plasticizers, trimellitate plasticizers, and epoxidized vegetable oils. The added amount of these plasticizers is preferably 80 to 300 parts by weight, more preferably 100 to 200 parts by weight, based on 100 parts by weight of the polyvinyl chloride resin.

Further, the plastisol composition of the present invention comprises:
Fillers such as calcium carbonate, talc, titanium oxide, clay and silica can be added. The amount of these fillers is preferably 80 to 800 parts by weight, more preferably 1 to 100 parts by weight, based on 100 parts by weight of the polyvinyl chloride resin.
It is 00 to 600 parts by weight.

Also, the plastisol composition of the present invention comprises:
Elastic agents such as nitrile rubber, chloroprene rubber, acrylic rubber, hydrin rubber, urethane rubber, polysulfide rubber, chlorinated polyethylene, and chlorosulfonated polyethylene can be added. The addition amount of these elastic agents is preferably from 0 to 3 based on 100 parts by weight of the polyvinyl chloride resin.
00 parts by weight, more preferably 10 to 200 parts by weight.

The composition of the present invention may contain an adhesion-imparting agent such as an epoxy resin, an acrylic resin, and an amino resin.

The composition of the present invention may contain perchloric acid and its metal salts, organic ammonium salts, or hydrotalcite or silicate perchloric acid-treated products. Adhesion and weather resistance of the film can be improved.

The composition of the present invention may contain stabilizers used in ordinary vinyl chloride resins, such as Pb-based, organic Sn-based, and metallic soap-based stabilizers.

The composition of the present invention may further contain various additives usually used as additives for polyvinyl chloride resins, for example, amines, phenols, sulfurs, and the like.
A phosphite-based antioxidant, a hindered amine-based light stabilizer or an epoxy compound can be added, and, if necessary, a crosslinking agent, a filler, an antistatic agent, a plate-out preventing agent, and a surface treatment. Agents, lubricants, flame retardants, fluorescent agents, fungicides, fungicides, metal deactivators, pigments, processing aids,
Antioxidants, light stabilizers and the like can be added.

[0028]

EXAMPLES The present invention will be described in more detail with reference to Synthesis Examples and Examples of the polyester plasticizer used in the present invention, but the present invention is not limited thereto.

Synthesis Example <Synthesis of Sample No. 1 Plasticizer (Table 1 below)> 438.5 g of adipic acid, 124.4 g of 1,3-butanediol and 1,4-butanediol in a flask.
9 g, 235.0 g of n-hexanol and 0.132 g of titanium tetraisopropoxide were charged, the temperature was increased to 220 ° C. under a nitrogen stream, and a dehydration reaction was performed for 10 hours. The end point of the reaction was the time when the acid value became 1 or less. Next, the reaction was performed at 210 ° C. for 2 hours under reduced pressure. The reduced pressure reaction was terminated when the viscosity increased to 150 cps. Then, the product was obtained by celite filtration.

The acid value and hydroxyl value of the obtained product were measured by a titration method. Further, the number average molecular weight was determined by gel permeation chromatography (GPC), and the weight% of the terminal termination component was determined by gas chromatography (GC). I asked.
The results are shown in Table 1 below.

Other synthetic samples (No. 2 to No. 10) shown in the following [Table 1] and [Table 2] were synthesized in the same manner. Finally, the viscosity was set so as to be in the range of 150 to 200 cps, and the terminal terminating component was empirically charged and synthesized so as to be introduced in an amount of 10 to 30% by weight. Sample Nos. 2 to N obtained
For o.10, the average molecular weight, oxidation, hydroxyl value, and% by weight were determined in the same manner as in Sample No. 1 described above. The results are shown in [Table 1] and [Table 2] below.

[0032]

[Table 1]

[0033]

[Table 2]

Example 1 The following ingredients were kneaded in a kneader for 30 minutes, and defoamed and stirred 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 aging at 40 ° C. for 168 hours, and the rate of change with time was determined from the ratio. Separately, the paintability was evaluated as follows, and a test piece was prepared from the coating film after baking, and the test was conducted according to JIS.
A tensile test was performed according to K 7113 to measure tensile strength and elongation [physical properties after baking (mechanical physical properties)]. The results are shown in Table 4 below. Here, the quality of the gelling property was determined by evaluating the physical properties of the gelled product.

<Evaluation of Coating Property> After applying the plastisol composition, an alkyd melamine resin-based intermediate coating white paint and an acrylic melamine resin-based top coating black coating were applied and baked at 140 ° C. for 30 minutes. Was evaluated on a 5-point scale from the following viewpoints for three points: reversal, scale, and gloss. The larger the value, the better. (Reversed) Is the intermediate paint exposed on the surface? 1: Reversal over the whole (intermediate paint is exposed on the surface
Part) is recognized. 5: Inverted (the intermediate coating is exposed on the surface)
No part is recognized. * 5 steps based on 1 and 5 criteria depending on the rate of inversion
Rated on the floor. (Scaling) Is the intermediate paint visible through? 1: Scaling throughout (intermediate paint is visible)
Part is recognized. 5: Skew (intermediate paint is seen through) is all
Not accepted. * Five levels based on the criteria of 1 and 5 depending on the ratio of skew
Was evaluated. (Gloss) Is the coating surface glossy? 1: Comparative Example 1-1 where no gloss was observed on the coating film surface
The standard of 1 was used. 5: Example 1-1 in which the coating film surface is excellent in gloss is based on 5 criteria.
did. * Gloss by visual inspection in 5 levels based on 1 and 5 standards
evaluated.

The compounds shown in Table 3 below were used as comparative compounds.

[0037]

[Table 3]

(Combination) parts by weight Zeon-121 (polyvinyl chloride resin manufactured by Zeon Corporation) 70 Zeon-51 (polyvinyl chloride resin manufactured by Zeon Corporation) 30 CML # 41 (calcium oxide manufactured by Omi Chemical Industry Co., Ltd.) 2) Calcium carbonate (SB) 120 Calcium carbonate (CCR) 50 Test plasticizer 150

[0039]

[Table 4]

Example 2 The following components were kneaded in a kneader for 30 minutes, and defoamed and stirred for 60 minutes to prepare a plastisol composition. The paintability of the plastisol composition in both cases with and without calcining was evaluated. The results are shown in the following [Table 5].
Regarding the evaluation of paintability, after coating with plastisol, 120
After pre-baking at 10 ° C. for 10 minutes or without baking, after applying an alkyd melamine resin-based intermediate coating white paint and an acrylic melamine resin-based top coating black coating,
Baking was performed at 140 ° C. for 30 minutes, and the paintability was evaluated according to the same evaluation criteria as in Example 1.

(Combination) parts by weight Zeon-38J (PVC-vinyl acetate resin manufactured by Zeon Corporation) 70 Zeon-51 (PVC blend resin manufactured by Zeon Corporation) 30 Surface-treated ultrafine calcium carbonate 50 Heavy Calcium carbonate 150 Test plasticizer 120

[0042]

[Table 5]

As is clear from the examples, when a monomeric plasticizer such as di-2-ethylhexyl phthalate is used, the coatability is remarkably poor. In addition, other than the above-mentioned polyester plasticizers, that is, when a glycol component is a branched glycol only or a terminal-stopping component is a branched one such as 2-ethylhexyl, a monomeric plasticizer is used especially when its molecular weight is large. The paintability is somewhat improved compared to the case, but the improvement effect is still not enough, and the physical properties after baking,
On the contrary, it decreased with the improvement of the paintability.

On the other hand, as in the present invention, 1,4-butyl
A plastisol composition containing a tandiol (straight chain) -polyester polyol having a branched mixed glycol as a polyhydric alcohol component and a linear alcohol having 4 to 18 carbon atoms or a straight chain fatty acid as a terminal terminating component has a coatability. Was particularly excellent even when pre-baking was not performed, the gelling property was good, and the sol viscosity did not increase.

[0045]

EFFECT OF THE INVENTION The plastisol composition of the present invention is for a sealant having excellent paintability, gelling properties and physical properties after baking.

────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Tadashi Sengoku 5-2-13-1 Shirahata, Urawa-shi, Saitama Asahi Denka Kogyo Co., Ltd. (56) References JP-A-2-158649 (JP, A) JP JP-A-60-199049 (JP, A) JP-A-6-287384 (JP, A) JP-A-6-271731 (JP, A) JP-A-3-111441 (JP, A) JP-A-2-150416 (JP) JP-A-1-284520 (JP, A) JP-A-62-273244 (JP, A) JP-A-50-92394 (JP, A) JP-A-3-277644 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) C08L 27/06 C08L 67/00-67/08

Claims (1)

(57) [Claims] 1. A plasticizer comprising 100 parts by weight of a polyvinyl chloride resin and 80 to 300 parts by weight of a polyester plasticizer, wherein the polyester plasticizer is (a) 1,4-butanediene.
A polyhydric alcohol component consisting of 20 to 80% by weight of all and 80 to 20% by weight of branched glycol, (b) a carbon number of 4 to 1
A plastisol composition obtained from a terminal terminating component comprising a straight-chain alcohol or / and a straight-chain fatty acid of No. 8 and (c) adipic acid .