JPS59131668A - Plastisol composition of vinyl chloride resin - Google Patents

Abstract

PURPOSE:To provide the titled composition containing a compound having plural allyl groups and a polyamide having active amino groups, having self-penetrability and adhesivity of the gap at the weld part of the electrodeposited steel plates, and useful as an adhesive, sealant, paint, etc. CONSTITUTION:The objective composition is prepared by compounding (A) 100pts.wt. of a vinyl chloride resin with (B) preferably 5-30pts.wt. of a compound having >=2 allyl groups (preferably diallyl phthalate) and (C) preferably 5-20pts.wt. of a polyamide having active amino groups [preferably a polyamide having an amine value of 200-300 and obtained by condensing a polybasic acid with a polyamine at a ratio (-NH2/-COOH) of 1.2-3]. Usually, a plasticizer such as dioctyl phthalate, etc. is added to the composition. USE:Useful in the automobile industry, especially excellent as a body sealer and an under-coating paint of automobile body coated with cationic electrodeposition coating as a substrate.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a vinyl chloride resin-based plastisol composition that has self-penetration and adhesive properties in the gaps between electrodeposition coated steel sheets.

Electrodeposition coating is rapidly progressing as one of the coating methods and is particularly employed in the automobile industry for the purpose of rust prevention. In the case of automobiles, intermediate and top coats are applied on top of this electrodeposited coating, but a body sealer is also applied to the openings and joints of automobile steel plates to maintain watertightness and airtightness. Rust prevention is achieved by A vinyl chloride V resin-based plastisol composition is used as a body sealer for joints and joints.

Such a body sealer is required not only to have adhesion to a one-coat coated steel plate, but also to have properties that prevent it from sagging during storage after application or during heating and drying of the paint film in the next intermediate coating or top coating process. There is.

For this reason, conventional vinyl chloride thread plastisol compositions have a high viscosity, and even when applied to narrow joints and joints, it is difficult to penetrate into the gaps, making it difficult to achieve the purpose of water retention and airtightness in such areas. There was a problem with workability in that the coating had to be applied by pushing it into the gap.

As a result of intensive research on vinyl chloride resin-based plastisol compositions, the present inventors found that when a compound having at least two allyl groups, such as diallyl phthalate, and a polyamide containing active amino groups are combined with vinyl chloride-based Mu resin, the gap narrows. It has been discovered that a plastisol composition can be obtained that sufficiently penetrates the electrodeposition coating and has excellent adhesion to the electrodeposition coating.
Based on this knowledge, we have completed the present invention.

That is, the present invention is a vinyl chloride IL/resin plastisol composition containing a compound having at least two allyl groups and an active amino group-containing polyamide.

Examples of the compound having at least two allyl groups used in the present invention include diallyl phthalate, diallyl carbonate, diallyl remaleate, diethylene glycol bis(allyl carbonate), and triallyl isocyanurate, with diallyl phthalate being particularly preferred.

The amount of the compound having at least two allyl groups used is approximately 5 to 30 parts by weight per 100 parts by weight of the vinyl chloride resin. If the amount used is less than 5 parts by weight, the effect of improving physical properties due to polymerization of the above compound may not be observed. on the other hand,
If it exceeds 30 parts by weight, the cured product may become hard and brittle.

In the present invention, a portion of the compound having at least two allyl groups, that is, a urethane prepolymer having an isocyanate group at the end, which is made of a relatively low molecular weight polyold organic diisocyanate in the range of 10% to 50% by weight. For example, acrylic urethane obtained by reacting with an acrylic compound having a hydroxyl group such as hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxyethyl acrylate, and hydroxypropyl acrylate can also be used.

Examples of relatively low molecular weight polyols include low molecular weight glycols such as ethylene glycol and propylene glycol, and triols such as trimethylolpropane and glycerin.
Polypropylene polyol to which alkylene oxide such as propylene oxide is added, polyethylene polyol, polyethylene propylene polyol with 1 hydroxyl group
Examples include polyols having a molecular weight per unit of about 50 to 2,00.0, preferably about 500 to 2,000. If the molecular weight per hydroxyl group exceeds 2,000, the concentration of acrylic or methacrylic groups may be low and the improvement of reactivity and adhesiveness may not be effective.

Examples of organic diisocyanates include aromatic diisocyanates such as tolylene diisocyanate and diphenylmethane diisocyanate; alicyclic diisocyanates such as isophorone diisocyanate, hydrogenated tolylene diisocyanate, and hydrogenated diphenylmethane diisocyanate; Examples include aliphatic diisocyanates such as methylene diisocyanate and lysine diisocyanate, and aromatic aliphatic diisocyanates such as xylylene diisocyanate.

Acrylic urethane is produced according to a normal urethanization reaction, and in some cases, a urethanization catalyst such as stannous octoate or dibutyltin dilaurate may be used.

The active amino group-containing polyamide used in the present invention contains a polybasic acid and a polyamine in an excess ratio of amino groups to carboxyl groups (-NH2/-COOH=1.2 to 3.0
) and has some amino groups and/or secondary amino groups in the molecule.

Examples of polyamines include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, xylylenediamine, hexamethylenediamine, 4,4'
Examples include -methylenebis(cyclohexylamine), 3-aminomethyl-3,5,5-trimethylcyclohexylamine, bis(aminomethy/l/)cyclohexane, and 1-methy/L'-2,4-diaminocyclohexane.

Examples of polybasic acids include adipic acid, azelaic acid, sepacic acid, and dodecane2+'E? , polymerized vegetable oil fatty acids (dimer acids), etc. Among the above, particularly desirable polybasic acids include polymerized vegetable oil fatty acids.

The reaction between the polyamine and the polybasic acid is carried out by mixing the two and heating the mixture to about 150 to 22 liters while removing the produced water. If necessary, a catalyst such as an organic acid may be used.

The active amino group-containing polyamide may be used as it is, but it can also be used as a so-called ketimine or enamine by reacting it with ketones.

The amine value of the active amino group-containing polyamide used in the present invention is about 90 to 450. Preferably, about 200 to 300 is used. Those having an amine value of less than 90 may have poor compatibility with plastisol compositions due to their high molecular weight.

If the amine value exceeds 450, adhesion to electrodeposition coatings may be poor. The amount used is 10% of the vinyl chloride resin described below.
The culmness is about 5 to 20 parts by weight to 0 parts by weight. If the amount used is less than 5 layers, the adhesion to the electrodeposited coating may decrease. On the other hand, if the amount exceeds 20 parts by weight, the cured product may become colored.

The plastisol composition of the present invention contains a vinyl chloride resin and a non-polymerizable plasticizer in addition to the above components.

As the vinyl chloride resin used in the present invention, conventionally known resins for plastisols are used, but vinyl chloride copolymers for plastisols containing vinyl chloride as the main (14 components) are also used. Examples of copolymers include copolymers with one or more comonomers such as vinyl acetate, vinylidene chloride, and acrylic/I/e esters.

Examples of non-polymerizable plasticizers that can be used include phthalate esters, bicyclic M acid esters, acid esters, polyester plasticizers, etc., which are commonly used in vinyl chloride V resins. L/acid esters, especially dioctyl phthalate, are preferred.

Usage: Approximately 1 star per 100 parts by weight of vinyl chloride resin
However, if the amount is 100 parts by weight, the viscosity of the sol will be high and the desired sol may not be obtained. On the other hand, if the amount exceeds 250 parts by weight, the adhesiveness and physical properties of the cured product may deteriorate, which may be undesirable.

In addition to the above ingredients, for example, fillers and stabilizers.

An organic radical polymerization agent, a viscosity control agent, etc. may be added.

Examples of fillers include inorganic fillers (eg, calcium carbonate, talc, kaolin, etc.). Among these fillers, calcium carbonate is particularly preferred. In particular, if the average particle diameter is about 2 to 5 μm, 1. Tl5K5
Dioctyl phthalate (D.

P) It is preferable that the oil absorption amount is 10 to 35 CC/100 g. If the particle size of calcium carbonate is less than 2 μm, the viscosity of the plastisol composition will be high, and the amount added must be extremely small, which may cause problems such as deterioration of adhesion. When the particle size exceeds 5μ, dispersibility and adhesion are improved, but thixotropic properties may become extremely poor.

If the DOP oil absorption is less than 10CC/100g, the dispersibility will be good, but the thixotropic properties will be poor! J:
6ru. If the DOP oil absorption exceeds 75f35CC/100 g, the viscosity of the plastisol composition will be high and the amount added will be extremely small, making it impossible to obtain the desired plastisol composition.

The amount of filler used is about 100 to 300 parts by weight, preferably about 150 to 25 parts by weight, per 100 parts by weight of vinyl chloride resin.
It is approximately 0 parts by weight. If the amount of filler is less than 100 parts by weight, problems may occur in terms of adhesiveness and cost. 30
If it exceeds 0 parts by weight, the viscosity becomes high and self-penetration into gaps may be lost.

Stabilizers include those commonly used in the processing of vinyl chloride/I/resins, such as inorganic acid lead salts, gold 11 μs soap, organic 7 ide compounds, and organic 7 osphites. The amount used is approximately 1 to 5 parts by weight per 100 parts by weight of the vinyl chloride resin.

If it is less than 1 layer, it has no effect as a stabilizer;
If the amount exceeds parts by weight, the thermal stabilization effect may not be improved.

The organic radical polymerization agent is preferably a high temperature radical generator, such as dialkyl peroxide or peroxy ester. The amount of organic radical polymerization agent used is approximately 0 for a compound having at least two allyl groups.
．． The amount is approximately 5 to 5% by weight, and if it is less than 0.5% by weight, polymerization may be incomplete and the physical properties of the cured product may deteriorate. On the other hand, if it exceeds 5% by weight, the plastisol composition may become unstable.

As the viscosity modifier, for example, a thixotropic agent such as fumed silica or an organic thixotropic agent, or a viscosity reducing agent such as a titanate coupling agent can be used in an amount of about 0 to 10 parts by weight.

The plastisol composition of the present invention can be produced using a commonly used dispersion kneader or the like.

The viscosity of the plastisol composition obtained in this way is
Although the components can be selected arbitrarily by changing the type and amount of the components, the apparent viscosity at 20°C is considered to be a practically acceptable viscosity range due to poor permeability into gaps and low fluidity (sag). is about 5,000 to 50,000 centipoise, particularly preferably 10,000 to 40,000 centipoise. If the apparent viscosity is less than 5,000 centipoise, the fluidity is too high and it is not practical. On the other hand, if it exceeds 50,000 centipoise, it may not be possible to penetrate into narrow gaps.

The plastisol composition of the present invention can sufficiently penetrate into narrow gaps, and can be used at a relatively low temperature of 120°C for a short period of time (e.g.
It firmly adheres to cationic electrodeposited coatings by heat treatment for 0 minutes). Moreover, the storage stability is also good.

The plastisol composition of the present invention can be applied to various industrial applications as adhesives, sealants, paints, etc., but it can also be used as a body sealer and undercoat paint for automobile bodies that have been subjected to cationic electrodeposition coating as an undercoat. It is excellent.

EXAMPLES The present invention will be explained in more detail by giving Examples and Comparative Examples below. In Examples and Comparative Examples, parts indicate parts by weight.

Example/ (1) Production of acrylic urethane Polypropylene glycol) L/(hydroxyl value 55.0) 1
2 moles of malt toluylene diisocyanate at 80°C, 5
After reacting for an hour, 2 moles of hydroxyethyl methacrylate were added, and the reaction was further carried out at 60°C for 4 hours.
It was confirmed that 2250 cm ) had disappeared, and acrylic urethane which was a viscous liquid at room temperature was obtained.

(2) Production of plastisol composition Vinyl chloride polymer (PVC121i Nippon Zeon (oil))
80 parts, 120 parts of diallyl phthalate, 150 parts of dioctyl phthalate, 200 parts of calcium carbonate (manufactured by M-White Kyuubi Riki μsium 41), 7 parts of Dimer 1 finished polyamide* (amine value 1236), tertiary Glyyl perbenzoate 0. A plastisol composition was prepared by uniformly mixing 2 parts of PbSO, 43 parts of PbSO, and 5 parts of Aeroge A/4200.

*Dimer acid polyamide was obtained by the following method.

520 g of diethylenetriamine was slowly added to 1728 g of free vegetable oil fatty acids (Henkel Nipponsha +4j!! + Versaguim 288), and while removing the water produced with nitrogen gas, the mixture was heated to 180 to 185 °C until no water came out. A brown viscous polyamide with an amine value of 236 was obtained.

(3) Characteristics of Plastisol Composition (a) Measurement of Viscosity The viscosity of Plastisol P was measured using a Pruckhui pFBH type viscometer, and the initial viscosity was 18,000 centipoise (cps).

(b) Penetration of plastisol composition into 0.2x gap between cationically coated steel plates Two 25x150x0.8x steel plates coated with cationic electrodeposition are placed in the long side direction by 0.2% gap. 10 yen - Stack them one on top of the other, apply the plastisol composition to the opening using a paste applicator, and after 10 minutes, heat it in a curing oven at 140℃ for 30 minutes.
Allow to cure for minutes. After curing, the two coated steel plates were peeled off and the degree of penetration (χ) of the plastisol composition was read, and it was found that it had penetrated up to 8χ.

(c) Fluidity (sag) test using a cationic electrodeposition coated plate, JIS K6830
(Testing method for sealing materials for automobiles) As a result of the flow test (according to the previous method (2), sol thickness was 3 tons), the fluidity in 10 minutes at room temperature (25°C) was In addition, the fluidity of 14C1 after curing for 30 minutes was 12χ horizontally and 25χ vertically, and it had good penetration into steel plate joints, and when applied to vertical surfaces, it remained at room temperature. The plastisol composition did not run off even after being left for a long time.

2) Measurement of shear strength using a cationic electrodeposition coated plate as the adherend J-K5K6830 (
According to the automotive sealant test method)
The shear adhesive strength was measured (at a thickness of 3') and found to be 22.1 kg/cm.

Example λ and Comparative Examples/~3 Plastisol compositions were produced in the same manner as in Example/, and their properties were measured. The composition and properties are listed in Table-1.

(Margin below) Table-1 ) Gap permeability 1986100 (10 minutes) (z):' □□□□□To□□□Bow□１□

Claims (1)

[Claims] A vinyl chloride V resin plastisol composition comprising a compound having at least two allyl groups and an active amino group-containing polyamide.