JPH0753909A - Plastisol composition - Google Patents

Abstract

PURPOSE:To obtain a plastisol compsn. for a sealant excellent in applicability, gelation properties, and physical properties after being baked. CONSTITUTION:A plastisol compsn. comprises 100 pts.wt. polyvinyl chloride resin and 80-300 pts.wt. polyester plasticizer which is obtd. from a polyhydric alcohol component comprising 20-80wt.% linear glycol and 80-20wt.% branched glycol, a terminal stopper comprising a 7C or lower branched alcohol, and a polybasic acid component.

Description

Detailed Description of the Invention

[0001]

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 coating properties, gelation properties and properties after baking, more specifically, The present invention relates to a plastisol composition using, as a plasticizer, a polyester-based plasticizer obtained from a specific polyhydric alcohol component, a specific end-terminating component and a polybasic acid component.

[0002]

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

Polyvinyl chloride resins are excellent in heat resistance and weather resistance, and by adjusting the amount of plasticizer, moderate elasticity, flexibility, and
Due to its adhesiveness, it has been used in plastisol compositions used for sealants and chipping primers. However, when the polyvinyl chloride resin is used for these purposes, it is used as a composition containing a monomeric plasticizer such as di-2-ethylhexyl phthalate phthalate as a plasticizer. There is a problem in that, when the coating and the top coating are applied, the plasticizer migrates into the coating and the coating becomes sticky or the coating 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, etc., a polyester plasticizer in a plastisol of a polyvinyl chloride resin. Although a lot of proposals have been made to use the above, when the polyester-based plasticizers described therein are used, the effect of improving the coating property is very small.

Further, it is possible to improve the coating property to some extent by increasing the molecular weight of the polyester plasticizer used in the plastisol. In such a case, however, the viscosity of the plastisol increases and the viscosity preservation property and It has a drawback that it adversely affects the gelation property and further deteriorates the physical properties after baking.

Therefore, an object of the present invention is to provide a plastisol composition for a sealant which is excellent in paintability, gelation property and physical properties after baking.

[0007]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that in a plastisol composition comprising a polyvinyl chloride resin and a polyester plasticizer, the polyester resin as a plasticizer is directly It has been found that the above object can be achieved by using a polyester-based plasticizer obtained from a polyhydric alcohol component that is a chain-branched mixed glycol, a terminal terminating component that is a specific branched alcohol, and a polybasic acid component. .

The present invention has been made based on the above findings, and comprises 100 parts by weight of polyvinyl chloride resin and 80 to 300 parts by weight of polyester plasticizer, wherein the polyester plasticizer is (a) linear glycol. A polyhydric alcohol component composed of 20 to 80% by weight and a branched glycol 80 to 20% by weight, (b) an end-terminating component composed of a branched alcohol having 7 or less carbon atoms, and (c) a polybasic acid component. Certain plastisol compositions are provided.

The plastisol composition of the present invention will be described in detail below.

The polyvinyl chloride resin used in the present invention includes, for example, polyvinyl chloride, pentachlorinated 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-acetic acid Vinyl terpolymer, vinyl chloride-acrylic acid ester 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 is (a) a polyhydric alcohol component consisting of 20 to 80% by weight of linear glycol and 80 to 20% by weight of branched glycol, and (b) a branched alcohol having 7 or less carbon atoms. And a (c) polybasic acid component.

As the linear glycol used as the polyhydric alcohol component, ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-
Butanediol, 1,5-pentanediol, 1,6-
Hexanediol and the like can be mentioned. Examples of the branched glycol include 1,2-propanediol and 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-
Examples include 1,5-pentanediol, 2-ethyl-1,3-hexanediol, 2,2,4-trimethyl-1,3-pentanediol and the like. Also, when using,
It can be used alone or as a mixture. In addition, small proportions of polyhydric alcohols such as glycerin, trimethylolpropane, trimethylolethane, and pentaerythritol can be used together within a range that does not impair the effects of the present invention.

The linear glycol is used in an amount of 20 to 80% by weight based on the total linear or branched glycol, and the branched glycol is used in an amount of 80 to 20% by weight based on the total linear or branched glycol used. Here, when the amount of the linear glycol exceeds 80% by weight based on the total amount of the linear or branched glycol used, the freezing point is increased or the viscosity is increased to increase the viscosity of the plastisol, which lowers the gelation property. Also,
All branched glycols used 80 in straight chain or branched glycol
When it exceeds the weight%, the paintability is deteriorated.

As the branched alcohol having a carbon number of 7 or less, which is used as the terminal terminating component, isopropanol,
2-butanol, 2-methyl-1-propanol, te
rt-butanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, 3-methyl-1-butanol, tert-amyl alcohol, 2-hexanol, 3-hexanol, 4-methyl-2-pen Tanol, 2-methyl-1-pentanol, 3-methyl-1-
Pentanol, 4-methyl-1-pentanol, 2-heptanol, 3-heptanol, 4-heptanol, 2
-Methyl-1-hexanol, 3-methyl-1-hexanol, 4-methyl-1-hexanol, 5-methyl-
1-hexanol etc. are mentioned. When the number of carbon atoms in the branched alcohol exceeds 7, the coatability is significantly reduced.

The end-stopping component may be a part (30% by weight or less) of other monohydric alcohol and / or monobasic acid. The above monohydric alcohols include methanol, ethanol, propanol,
Propanol, butanol, pentanol, hexanol, heptanol, octanol, 2-ethylhexanol, nonanol, isononanol, decanol, isodecanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadeca. Nole, cellosolve, carbitol, phenol, nonylphenol, benzyl alcohol and the like; and the monobasic acids include acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, pivalic acid, caproic acid, 2-methyl. Pentanoic 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, heptadecanoic acid,
Examples include stearic acid, oleic acid, linoleic acid, linoleic acid, benzoic acid and the like. Also, when using,
It can be used alone or as a mixture.

The polybasic acid component is, for example, malonic acid,
It is mainly composed of aliphatic dibasic acids such as succinic acid, glutaric acid, adipic acid, sebacic acid, azelaic acid, and dodecanedicarboxylic acid.In addition to these, small proportions of phthalic acid, isophthalic acid, and terephthalic acid are also included. An aromatic polybasic acid such as trimellitic acid or pyromellitic acid, or an aliphatic polybasic acid such as butanetricarboxylic acid, butanetetracarboxylic acid, tricarballylic acid or citric acid can be used in combination.

Further, in the above polyester plasticizer, part of the polybasic 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 produced using the above-mentioned components by a known method. For example, the components are 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 above polyester-based plasticizer varies depending on the type of the components used, the characteristics of the intended polyester-based plasticizer, the molecular weight, etc., but generally, the polybasic acid component 10 is used. -80% by weight, polyhydric alcohol component 10-80% by weight, end-stopping component 10-
Used in a ratio of 50% by weight.

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

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

If desired, a plasticizer used for ordinary polyvinyl chloride resins may be used in combination with the above polyester plasticizer. As these plasticizers, any plasticizer 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 thereof include adipate plasticizers such as di (butyldiglycol) adipate, phosphate plasticizers, chlorinated paraffin plasticizers, trimellitate plasticizers, and epoxidized vegetable oils. The amount of these plasticizers added is
With respect to 100 parts by weight of the polyvinyl chloride resin, preferably 80 to 300 parts by weight, more preferably 100 to 200 parts by weight.
Parts by weight.

The plastisol composition of the present invention also comprises
Fillers such as calcium carbonate, talc, titanium oxide, clay and silica can be added. The amount of these fillers added is 100 parts by weight of the polyvinyl chloride resin,
It is 80 to 800 parts by weight, preferably 100 to 600 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 addition amount of these elastic agents is preferably 0 to 300 parts by weight, and more preferably 10 to 200 parts by weight with respect to 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, perchloric acid and its metal salts, organic ammonium salts, or perchloric acid-treated products of hydrotalcite or silicate can be added to the composition of the present invention. The adhesiveness and weather resistance of the film can be improved.

Further, to the composition of the present invention, stabilizers such as Pb-based, organic Sn-based and metallic soap-based stabilizers, and stabilizers used for ordinary vinyl chloride-based resins can be added.

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,
A phosphite-based antioxidant, a hindered amine-based light stabilizer, an epoxy compound, or the like can be added. In addition, if necessary, a crosslinking agent, a filler, an antistatic agent, a plate-out prevention agent, a surface treatment Agents, lubricants, flame retardants, fluorescent agents, fungicides, bactericides, metal deactivators, pigments, processing aids,
Antioxidants, light stabilizers and the like can be added.

[0029]

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

Synthesis Example <Synthesis of Sample No. 1 Plasticizer (Table 1 below)> Adipic acid 438.5 g, 1,3-butanediol 124.4 g, 1,4-butanediol 82.
9 g, 3-methyl-1-hexanol and 5-methyl-
235.0 g of a 1: 1 mixture of 1-hexanol and 0.132 g of titanium tetraisopropoxide were charged, the temperature was raised to 220 ° C. at the maximum under a nitrogen stream, and a dehydration reaction was carried out for 10 hours. The end point of the reaction was when the acid value became 1 or less. Next, the mixture was reacted under reduced pressure at 210 ° C. for 2 hours. The reduced pressure reaction was terminated when the viscosity increased to 150 cps. Then, the product was obtained by filtration through Celite.

The acid value and hydroxyl value of the obtained product were measured by a titration method, and further the number average molecular weight was determined by gel permeation chromatography (GPC) and the weight percentage of the end-terminating component was determined by gas chromatography (GC). I asked.
The results are shown in [Table 1] below.

Other synthetic samples (No. 2 to No. 7) shown in the following [Table 1] were similarly synthesized. Finally the viscosity is 15
It was set so as to fall within the range of 0 to 200 cps, and the end-terminating component was empirically prepared so as to be introduced in an amount of 10 to 30% by weight. Regarding the obtained samples No. 2 to No. 7,
The average molecular weight, acid value, hydroxyl value and weight% were determined in the same manner as in Sample No. 1 above. The results are shown below [Table 1].
Shown in.

[0033]

[Table 1]

*: 3-methyl-1-hexanol / 3-
Methyl-1-hexanol (1/1) mixture

Example 1 The following formulation was kneaded with a kneader for 30 minutes and defoamed for 60 minutes to prepare a plastisol composition. Immediately after preparation of the plastisol composition and after deterioration at 40 ° C. for 168 hours, the sol viscosity at 20 rpm was measured, and the rate of change with time was determined from the ratio. Separately, the paintability was evaluated as described below, and a test piece was prepared from the coating film after baking.
A tensile test was performed according to SK 7113 to measure the tensile strength and elongation [physical properties after baking (mechanical properties)]. The results are shown in [Chemical Formula 3] below. Here, the quality of the gelation property was judged by evaluating the physical properties of the gelled product.

<Evaluation of coatability> After applying the plastisol composition, after applying an alkyd melamine resin-based intermediate coating white paint and an acrylic melamine resin-based top coating black paint,
Baking was performed at 140 ° C. for 30 minutes, and the coating property was evaluated in five stages from the following viewpoints with respect to three points of reversal, scale and gloss. The larger the value, the better. (Reverse) Is the intermediate coating paint exposed on the surface? (Suke) Isn't the intermediate paint visible? (Gloss) Is the coating surface glossy?

The compound shown in the following [Chemical Formula 2] was used as a comparative compound.

[0038]

[Table 2]

(Distribution) parts by weight ZEON-121 (polyvinyl chloride resin manufactured by ZEON CORPORATION) 70 ZEON-51 (vinyl chloride blend 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 compound 150

[0040]

[Table 3]

Example 2 The following formulation was kneaded with 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 results are shown in [Table 4] below.

Regarding the evaluation of coatability, after applying plastisol, after performing calcination for 10 minutes at 120 ° C., or without baking, an alkyd melamine resin-based intermediate coating white paint and an acrylic melamine resin-based top coating black paint were used. After coating, baking was performed at 140 ° C. for 30 minutes, and the coatability was evaluated according to the same evaluation criteria as in Example 1.

(Distribution) parts by weight ZEON-38J (vinyl chloride vinyl chloride resin manufactured by ZEON Corporation) 70 ZEON-51 (vinyl chloride blend resin manufactured by ZEON CORPORATION) 30 surface-treated ultrafine calcium carbonate 50 heavy Calcium carbonate 150 Test compound 120

[0044]

[Table 4]

As is apparent from the examples, when a monomeric plasticizer such as di-2-ethylhexyl phthalate is used, the coatability is extremely poor. Further, when a substance other than the above polyester plasticizers, that is, a glycol component having only a branched glycol or a long-term chain-terminating component such as 2-ethylhexyl is used, a monomeric plasticizer is used especially when the molecular weight is large. Although its paintability is somewhat improved compared to when it is used, the improvement effect is not yet sufficient, and the physical properties after baking will decrease conversely with the improvement of paintability. .

On the other hand, as in the present invention, a plastisol composition containing a polyester plasticizer containing a linear-branched mixed glycol as a polyhydric alcohol component and a branched alcohol having a carbon number of 7 or less as an end-stopping component. The product has excellent paintability, especially when calcination is not performed.
The gelability was good, and the sol viscosity did not increase.

[0047]

The plastisol composition of the present invention is for use as a sealant having excellent coating properties, gelation properties, and physical properties after baking.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Tadashi Sengoku 5-2-13 Shirahata, Urawa City, Saitama Prefecture Asahi Denka Kogyo Co., Ltd.

Claims (1)

[Claims] 1. A polyvinyl chloride resin 100 parts by weight and a polyester plasticizer 80 to 300 parts by weight, wherein the polyester plasticizer is (a) linear glycol 2
A polyhydric alcohol component composed of 0 to 80% by weight and a branched glycol 80 to 20% by weight, (b) an end-terminating component composed of a branched alcohol having 7 or less carbon atoms, and (c) a polybasic acid component. There is a plastisol composition.