JPH083016B2 - Plastisol composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a plastisol composition, and more particularly to a vinyl chloride plastisol composition.

[Prior Art] Conventionally, as a vinyl chloride plastisol composition, an adhesiveness-imparting agent composed of a blocked urethane prepolymer using an organic polyisocyanate such as tolylene diisocyanate and an active amino group-containing mono- or polyamide-based compound is blended. Vinyl chloride plastisol compositions are known. (For example, Japanese Examined Patent Publication No. 59-52901) [Problems to be Solved by the Invention] However, the above composition does not have sufficient adhesion when heat-treated at a relatively low temperature for a short time (for example, 120 ° C., 20 minutes). Not obtained, and various plated steel sheets (for example, tin plated steel sheet, lead-tin alloy plated steel sheet, aluminum plated steel sheet, nickel plated steel sheet and other various plated steel sheets)
However, there is a problem that sufficient adhesiveness cannot be obtained.

[Means for Solving the Problems] As a result of intensive studies to solve the above problems, the present inventors have sufficient adhesiveness to various plated steel sheets by heat treatment at a relatively low temperature for a short time, Further, the inventors have found a vinyl chloride plastisol composition having excellent storage stability of plastisol, and arrived at the present invention. That is, the present invention relates to a plastisol composition comprising a vinyl chloride polymer or copolymer (A), a plasticizer (B) and an adhesiveness-imparting agent (C) as essential components. Blocked product (y) of a complete adduct (x) of an aliphatic diisocyanate of methylolpropane with a ketoxime and a ketoxime of a prepolymer from α, α, α ', α'-tetramethylxylylene diisocyanate and an active hydrogen-containing compound Or blocked product with lactam (z)
An active amino group-containing mono- or polyamide-based compound; an organotitanium and / or an organotitanium polymer; and a urethane compound having a hydrolyzable silyl group at its terminal;
It is a plastisol composition comprising:

As the vinyl chloride polymer or copolymer (A), those usually used can be used. Examples of the vinyl chloride copolymer include copolymers of vinyl chloride with other vinyl monomers copolymerizable therewith, such as vinyl acetate, maleic anhydride or maleic ester, and vinyl ether. The vinyl chloride polymer or copolymer polymer is usually 1,000 to 1,700. Commercial products of vinyl chloride polymer or copolymer include Kanevinyl PSL-10, Kanevinyl PSH-10, Kanevinyl PCH-12.
(Above manufactured by Kanegafuchi Chemical Industry), ZEON 121 and ZEON 135J
(Nippon Zeon), Denka Vinyl PA-100, and Denka Vinyl ME-180 (all Denki Kagaku Kogyo). These may be used as a mixture of two or more.

Examples of the plasticizer (B) include phthalic acid esters such as diethyl phthalate, dibutyl phthalate, dioctyl phthalate, dilauryl phthalate, distearyl phthalate and diisononyl phthalate, adipic acid esters such as dioctyl adipate, and sebacic acid such as dioctyl sebacate. Ester, phosphate ester such as tricresyl phosphate, 2,2,4-trimethyl 1,3-
Mention may be made of ester type plasticizers such as pentanediol diisobutyrate and mixtures of two or more thereof. Of these, preferred are phthalates, especially dioctyl phthalate and diisononyl phthalate.

In the present invention, the aliphatic diisocyanate of the blocked product (y) of the complete adduct of the aliphatic diisocyanate of trimethylolpropane (x) with the ketoxime has 2 to 12 carbon atoms (excluding carbon in the NCO group). Examples thereof include aliphatic diisocyanates, alicyclic diisocyanates having 4 to 15 carbon atoms, and araliphatic diisocyanates having 8 to 12 carbon atoms. Hexamethylene diisocyanate (HDI) and lysine diisocyanate are used as the aliphatic diisocyanate, and hydrogenated diphenylmethane diisocyanate (hydrogenated MD is used as the alicyclic diisocyanate.
I), isophorone diisocyanate (IPDI), cyclohexane diisocyanate (CHDI), hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate, and the like, and the araliphatic diisocyanate includes xylylene diisocyanate, etc. Mixtures of can also be used. Among these, preferred are aliphatic diisocyanates and alicyclic diisocyanates, and particularly preferred are HDI and IPDI.

As the complete adduct (x) of the aliphatic diisocyanate of trimethylolpropane, one partially modified with a low molecular weight alcohol can be used. As the low molecular weight alcohol, primary alcohols (methyl alcohol, ethyl alcohol, n-butyl alcohol, oleyl alcohol, stearyl alcohol, etc.), secondary alcohols (isopropyl alcohol, sec-butyl alcohol, s)
ec-amyl alcohol, etc., tertiary alcohol (t-
Butyl alcohol, t-amyl alcohol, etc.), glycol ether (ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, etc.), halo alcohol (ethylene chlorohydrin, 2,2-difluoroethyl alcohol, etc.) and two or more of these. A mixture may be mentioned. The most desirable of these is primary alcohol.

In the present invention, a blocked product (y) of a complete adduct (x) of an aliphatic diisocyanate of trimethylolpropane with a ketoxime and α, α, α ′, α′-
Blocked products (z) of a prepolymer from tetramethylxylylene diisocyanate and an active hydrogen-containing compound with a ketoxime or a lactam are methylethylketoxime (MEK oxime), methylisobutylketoxime (such as MIBK oxime), and the like. There are two or more types. Of these, the preferred is the MEK oxime.

As the lactam compound, ε-caprolactam, δ-
Examples thereof include valerolactam and γ-butyrolactam. Of these, preferred is ε-caprolactam.

The amount of the ketoxime and the lactam to be added when producing the blocked product of the ketoxime and the lactam is usually 1 equivalent or more with respect to the free isocyanate group, 2
It is less than equivalent, preferably 1.05 to 1.5 equivalent. When the ketoxime is added, the reaction temperature is usually 50 to 150 ° C.

It is possible to accelerate the reaction by adding a known urethane polymerization catalyst (such as dibutyltin dilaurate) during the reaction.

The reaction can usually be carried out in the presence of a solvent or a plasticizer. Examples of the solvent include aromatic hydrocarbons (toluene, xylene, trimethylbenzene, etc.), ester systems (ethyl acetate, butyl acetate, etc.), ether systems (dioxane, cellosolve acetate, etc.), ketone systems (acetone, methyl ethyl ketone, etc.) and A mixed solvent of two or more of these may be mentioned.

As the plasticizer, the same as those exemplified as the plasticizer (B) can be used. The same applies to the preferred ones.

The NCO / OH equivalent ratio of the aliphatic diisocyanate and trimethylolpropane is usually 3.0 or more, preferably 3.0 to 3.3.
Is.

In carrying out the prepolymer formation reaction, known polymerization catalysts for promoting the reaction, for example, dibutyltin dilaurate, stannous octoate, organometallic compounds such as stannas octoate, triethylenediamine, triethylamine, 1,8-diazabicyclo [ 5,4,0] Undecen-
It is also possible to use a tertiary amine compound such as 7.

The reaction temperature is usually 40 to 140 ° C, preferably 60 to 120 ° C. The reaction time is usually 3 to 10 hours, preferably 4 to 8 hours.

In the present invention, the blocked compound (z) with the ketoxime or lactam is α, α, α ′, α′-
Tetramethylxylylene diisocyanate, [hereinafter TMXD
Also called I. ] And, if necessary, other organic polyisocyanate, a high molecular weight polyol, and optionally a polyol having an average number of functional groups of 2.01 or more consisting of low molecular weight alcohols and having an isocyanate group at the end blocked with a ketoxime or lactam. Is mentioned.

TMXDI includes o-, m-, p-forms and mixtures thereof. Preferably, it is m-TMXDI.

Other organic polyisocyanates other than the above include aliphatic polyisocyanates [hexamethylene diisocyanate (HDI), hexamethylene isocyanurate, lysine diisocyanate, etc.], alicyclic polyisocyanates [hydrogenated diphenylmethane diisocyanate (hydrogenated MD
I), isophorone diisocyanate (IPDI), isophorone isocyanurate, cyclohexane diisocyanate (CHDI), hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate, etc.], araliphatic polyisocyanate [xylylene diisocyanate] and two or more of these A mixture of

 Of these, hydrogenated MDI and IPDI are preferable.

The amount of TMXDI in the organic polyisocyanate is usually at least 50% by weight, preferably at least 60%.

The molecular weight per hydroxyl group of polymer polyol is usually 500-
It is 3,000.

As the polymer polyol, polyether polyol, polyester polyol, polymer polyol,
Examples include polycarbonate polyols and mixtures of two or more of these.

Examples of the polyether polyol include polytetramethylene glycol (PTMG) which can be obtained by ring-opening polymerization of tetrahydrofuran. Also, alkylene oxide adducts of low molecular weight alcohols can be used. As low molecular weight alcohols, the molecular weight per hydroxyl group is usually 30-
500, preferably 30 to 400 diols such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol and 3-methyl-1,5-pentanediol; the molecular weight per hydroxyl group is usually 30-600. ,
Preferable examples include low molecular weight triols of 40 to 500, such as glycerin, trimethylolpropane, and a mixture of two or more thereof. As the alkylene oxide, ethylene oxide, propylene oxide,
Examples thereof include 1,2-, 1,3- or 2,3-butylene oxide, tetrahydrofuran, styrene oxide, epichlorohydrin, and a mixture of two or more thereof.

Examples of the polyester polyol include a polyester polyol obtained by polycondensing a dicarboxylic acid, an ester or a halide thereof, and a low-molecular-weight polyol. Examples of the dicarboxylic acid include aliphatic dicarboxylic acids (adipic acid, sebacic acid, maleic acid, dimer acid, etc.), aromatic dicarboxylic acids (terephthalic acid, isophthalic acid, etc.) and their anhydrides. Among the dicarboxylic acids, preferred are the aliphatic dicarboxylic acids, and particularly preferred is adipic acid. Examples of the low molecular polyol include those described in the section of polyether polyol, and preferable ones are ethylene glycol and 1,4-butanediol. Further, polylactone polyols obtained by ring-opening polymerization of lactones (ε-caprolactane etc.) in the presence of low molecular weight alcohols (ethylene glycol etc.) such as polycaprolactone diol (PCL) can also be used.

As the polymer polyol, those described in JP-A-55-118948 can be used.

As the polycarbonate polyol, low molecular weight alcohols (dihydric alcohols) and carbonic acid diesters (dimethyl carbonate, diethyl carbonate, etc.)
Those obtained can be mentioned.

Among the high molecular polyols, preferred are polytetramethylene glycol and polyester polyols (especially polyethylene adipate diol and polycaprolactone polyol). Examples of the low molecular weight alcohols include those described in the section of polyether polyol, low molar addition products of alkylene oxides (low molecular weight ones), and mixtures of two or more kinds thereof. Of these, preferred are ethylene glycol and trimethylolpropane.

Blocking (y) of a complete adduct (x) of an aliphatic diisocyanate of trimethylolpropane with a ketoxime and a prepolymer of α, α, α ', α'-tetramethylxylylene diisocyanate and an active hydrogen-containing compound The weight ratio of (y) to (z) in the case of combining the blocked product (z) with a ketoxime or lactam is usually 1:99 to 99: 1, preferably 10:90 to 90:10, particularly preferably 80:20. ~ 20: 80.

In the present invention, as the active amino group-containing mono- or polyamide-based compound, for example, a polyamide-based compound obtained by reacting polymerized fatty acid and optionally at least one selected from the group of aromatic and / or aliphatic dicarboxylic acids with polyamines A compound (polyamide resin) may be mentioned.

The content of dimer acid in the polymerized fatty acid is 80% or more, preferably 90% or more, particularly preferably 94% or more.

Polyamines are disclosed in JP-B-53-41121 and JP-B-5.
Those described in 3-41122 can be used. Specific examples of the polyamides include aliphatic polyamine [alkylene (C2-C4) diamine (ethylenediamine,
Propylenediamine, etc.)], polyalkylenepolyamines (diethylenetriamine, dipropylenetriamine,
Triethylenetetramine), aromatic polyamines (phenylenediamine, tolylenediamine, xylylenediamine, etc.), alicyclic polyamines (cyclohexylenediamine, isophoronediamine, diaminodicyclohexylmethane, dimethyldiaminodicyclohexylmethane, etc.), heterocyclic polyamines [Piperazine, aminoalkyl-substituted piperazine (such as aminoethylpiperazine) and the like] and mixtures of two or more thereof. Preferred among the polyamines are polyalkylene polyamines.

The amine value of the mono- or polyamide-based compound is usually 90.
Or more, preferably 100 to 450, particularly preferably 150 to 400
Is. Since those having an amine value of less than 90 generally have a high molecular weight, the compatibility with plastisol decreases.

The molecular weight of the mono- or polyamide-based compound is usually 200.
~ 5,000, preferably 500-4,000. The mono- or polyamide-based compound is a partially modified product thereof, for example, one containing an imidazoline ring in the molecule, and the mono- or polyamide-based compound is modified with a compound such as a vinyl compound having an electron-withdrawing group (acrylonitrile, acrylic acid epoxy, etc.). Modified compound having an active amino group (for example, Japanese Patent Publication
51-23560 and JP-B-525554) and ketimine which is a modified compound with a ketone compound (methyl ethyl ketone, methyl isobutyl ketone, etc.).

The mono- or polyamide-based compound may also contain free polyamines.

In the present invention, the organic titanium and / or the organic titanium polymer has a general formula (In the formula, R represents an alkyl group having 1 to 4 carbon atoms, and X represents 1 to 10). Specific examples thereof include tetramethoxy titanium, tetraethoxy titanium, tetrapropoxy titanium, and tetrabutoxy titanium. These compounds can be used as a mixture of two or more kinds. Of these, tetrapropoxytitanium and tetrabutoxytitanium are preferable, and tetrabutoxytitanium is particularly preferable.

In the present invention, examples of the polyurethane compound having a hydrolyzable silyl group at a terminal include a compound composed of an organic aminosilane compound and a urethane prepolymer (e). Examples of the organic aminosilane compound include hydrocarbon group-containing aminosilane compounds, silazanes, and carbonyl group-containing aminosilane compounds.

The hydrocarbon group-containing aminosilane compound has the general formula [In the formula, R is an alkyl group having 1 to 4 carbon atoms, X is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, A is an alkylene group,
m is 0 or 1, n is 0, 1 or 2, Z is a hydrogen atom, a hydrocarbon group or a formula And a plurality of A's may be the same or different. ] The compound shown by these is mentioned.

Specifically, [N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-
Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, bis (3- (triethoxysilyl) propyl) amine, bis (3- (trimethoxysilyl) propyl) ethylenediamine, N -Methylaminopropyltriethoxysilane, 1-trimethoxysilyl-2- (p
-(Aminomethyl) phenyl) ethane, 1-trimethoxysilyl-2- (m- (aminomethyl) phenyl) ethane, trimethoxysilylpropylallylamine, trimethoxysilylpropylethylenetriamine, p-aminophenyltrimethoxysilane, amino Examples thereof include ethylaminomethylphenethyl trimethoxysilane.

Examples of silazanes include 1.3-divinyltetramethyldisilazane and hexamethyldisilazane.

Examples of the carbonyl group-containing aminosilane compound include methyl-3- (2- (3-trimethoxysilylpropylamino) ethylamino) -3-propionate, triethoxysilylpropylethylcarbamate and N- (triethoxysilylpropyl) urea. To be

These organic aminosilane compounds can also be used as a mixture of two or more kinds.

Also preferred among these are N- (2-aminoethyl) -3-aminopropyltrimethoxysilane,
3-aminopropyltrimethoxysilane, and N-
(2-aminoethyl) -3-aminopropylmethyldimethoxylane, and particularly preferred is N- (2-
Aminoethyl) -3-aminopropyltrimethoxysilane and 3-aminopropyltrimethoxysilane.

Examples of the polyisocyanate and polymer polyol used in the urethane prepolymer (e) include the same as those described in the section of the ketoxime or lactam block compound (z) described above. The same applies to the preferred ones.

The amount of the organic aminosilane compound added to the urethane prepolymer (e) is usually 1 equivalent or more and less than 2 equivalents, preferably 1.05 to 1.5 equivalents, relative to the free isocyanate groups of the urethane prepolymer (e). The reaction temperature when the organic aminosilane compound is added is usually 50 to 150.
° C. The reaction is usually performed in the presence of a solvent or a plasticizer. Examples of the solvent and the plasticizer include the same ones as described above. The same is preferable.

The composition of the present invention includes the above (A), (B) and (C).
In addition to the components, various other additives such as fillers and stabilizers can be incorporated. Examples of the filler include inorganic fillers (calcium carbonate, talc, diatomaceous earth, kaolin, etc.) and organic fillers (cellulose powder, powder rubber, recycled rubber, etc.). As the stabilizer, metal soaps (calcium stearate, aluminum stearate, etc.), inorganic acid salts (dibasic phosphite, dibasic sulfate, etc.) and organic metal compounds (dibutyltin dilaurate, dibutyltin malate, etc.) are used. Can be mentioned. Further, a colorant such as a pigment can be added optionally.

In the plastisol composition of the present invention, the content of each component is not particularly limited, but an example of the formulation is as follows. (% Is weight%) When using fillers as additives, usually 10-70
% (Preferably 20 to 60%), and when a stabilizer is used, it is usually 0 to 3% (preferably 0.1 to 2%).

The plastisol composition of the present invention can be produced using a commonly used dispersion kneader. The plastisol composition of the present invention can be applied to various metal substrates and various undercoating surfaces applied to metal (especially steel) surfaces,
In particular, it can be advantageously applied to various plated steel sheets (for example, tin-plated steel sheet, lead-tin alloy-plated steel sheet, aluminum-plated steel sheet, nickel-plated steel sheet and other various plated steel sheets), cationic electrodeposition coated surface, and acrylic resin coated surface. As the cationic electrodeposition coating, the ordinary electrodeposition coating such as polyamine resin (epoxy resin having an amino group in the molecule) as a film forming component is neutralized with a lower organic acid or the like to prepare an aqueous solution or water dispersion. A coating method in which the body fluid is used as a coating (existing as cations), and the object to be coated (metal) is used as a cathode to direct current to deposit the coating on the surface of the object to be coated is mentioned.

Acrylic resin paints used for acrylic resin coating include thermoplastic type and thermosetting type. The thermoplastic type is mainly used for room temperature drying by using an acrylic (co) polymer together with a fibrin derivative (nitrocellulose, cellulose acetate butyrate, etc.), a plasticizer and the like. The thermosetting type has a functional group in an acrylic (co) polymer and forms a three-dimensional network structure by heating by itself or by reacting with a crosslinking agent. Examples of the coating method include brush coating, spray coating, electrostatic coating, flow coating, dip coating, powder coating and roller coating. The coating amount of the plastisol composition of the present invention on the coated surface is usually 500.
~ 3,000g / m ² and coating thickness is usually 0.2 ~ 2mm.

Examples of the coating method include brush coating, roller coating, airless spray coating and the like.

Further, heat treatment is performed after coating, and the temperature in this case is usually 120 to 140 ° C. and the time is usually 20 to 40 minutes.

[Examples] The present invention will be further described below with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In the examples, "part" or "%" is based on weight.

Production Example 1 (1) Production of blocked product (y) of ketoxime of complete adduct of aliphatic diisocyanate of trimethylolpropane (x) Production of stirrer, thermometer and nitrogen introduction tube of 1 L volume 4
A full-length Kolben was charged with a complete adduct of hexamethylene diisocyanate of trimethylolpropane (Nippon Polyurethane Industry Co., Ltd., trade name: Coronate EL NCO% = 18.0), 516 parts, ethyl acetate, 83 parts, and MEK oxime, 201 parts, under a nitrogen stream 70 After reacting at ℃ for 1 hour, it was confirmed by infrared absorption spectrum that the absorption of isocyanate group (2250 cm-1) was completely extinguished, and at room temperature, low viscosity liquid trimethylolpropane aliphatic diisocyanate A block product of the complete adduct with the ketoxime was obtained.

(2) Production of blocked product (z) of prepolymer from α, α, α ′, α′-tetramethylxylylene diisocyanate and active hydrogen-containing compound with ketoxime or lactam Reaction similar to Production Example 1 (1) 163 parts of polycaprolactone diol (PCL) (hydroxyl value 140, molecular weight 800) in the device,
27 parts of trimethylolpropane (molecular weight 134), α, α,
Charge 248 parts of α ', α'-tetramethylxylylene diisocyanate (TMXDI) (molecular weight 244) and 360 parts of xylene, react under nitrogen stream at 90 to 95 ° C for 3 hours, and then add 0.03 parts of dibutyltin dilaurate and further 2 The reaction was carried out at the same temperature for the same time, and the active isocyanate content was 5.2%.
A urethane polymer of was obtained. Furthermore, 87 parts of MEK oxime (molecular weight 87) was charged into this product, and the mixture was reacted at 70 ° C for 1 hour in a nitrogen stream, and it was confirmed by infrared absorption spectrum that the absorption of isocyanate groups (2250 cm-1) had completely disappeared. Then, a blocked product (z) of a prepolymer of α, α, α ', α'-tetramethylxylylene diisocyanate and an active hydrogen-containing compound, which is a low-viscosity liquid at room temperature, with a ketoxime was obtained.

(3) Production of polyamide compound.

Attached stirrer, thermometer, cooler and nitrogen inlet pipe
After charging 500 parts of polymerized fatty acid (made by Henkel Shiramizu, Versadym 288, dimer acid content 94%) and 15 parts of adipic acid into a 4-liter Kolben with a volume of 1 L and heating to 90 ° C under a nitrogen stream, 250 parts of tetraethylenepentamine. Add 200-250
A condensation reaction was performed at ℃ to obtain a polyamide compound having a total amine value of 300.

(4) Production of a urethane compound having a hydrolyzable silyl group at the terminal.

In the same reactor as in Production Example 1 (1), 120 parts of polycaprolactone diol (PCL) (hydroxyl value 140, molecular weight 800),
20 parts of trimethylolpropane (molecular weight 134), α, α,
α ′, α′-Tetramethylxylylenediamine (TMXD
I) (Molecular weight 244) 183 parts and xylene 265 parts were charged and reacted under a nitrogen stream at 90 to 95 ° C. for 3 hours, then dibutyltin dilaurate 0.03 parts was added and further reacted for 2 hours at the same temperature, and the active isocyanate content was 5.3% urethane prepolymer was obtained. This urethane prepolymer was charged with 212 parts of 3-aminopropyltriethoxysilane (manufactured by Shin-Etsu Silicone Co., Ltd., KBE-903, molecular weight 221),
After reacting for 1 hour at 70 ° C under nitrogen flow, it was confirmed by infrared absorption spectrum that absorption of isocyanate group (2250cm-1) was completely extinguished, and hydrolyzable silyl group was added to the end of low viscosity liquid at room temperature. A urethane compound containing was obtained.

(5) Production of plastisol composition.

Kanevinyl PSL-10 (Kanebuchi Chemical Industry Straight Resin) 70 parts, Kanevinyl PCH-12 (Kanebuchi Chemical Industry Copolymerization Resin) 30 parts, Dioctylphthalate (DOP) 110 parts, NC
C-110 (Nippon Shokuhin Kogyo Co., Ltd., calcium carbonate) 150 parts, dibasic lead phosphite 3 parts, 3.5 parts of a complete adduct of an aliphatic diisocyanate of trimethylolpropane blocked with ketoxime (y), α, α, α ', α'
3.5 parts of a block product (z) of a prepolymer from tetramethylxylylene diisocyanate and an active hydrogen-containing compound with a ketoxime, polyamide-based compound 10.0
Part, organic titanium polymer (TBT-200, manufactured by Nippon Soda Co., Ltd.) 3.
A plastisol composition was prepared by uniformly kneading 5 parts and 10.0 parts of a urethane compound having a hydrolyzable silyl group at the end and defoaming.

(6) Properties of plastisol composition The initial viscosity of the plastisol is 610 (PS / 25 ° C).
The viscosity after storage at ℃ for 10 days was 770 (PS / 25 ℃). When the plastisol composition was applied to a lead-tin alloy-plated steel sheet to a coating thickness of 0.5 mm and heat-treated at 120 ° C. for 20 minutes, a coating film with excellent elasticity and excellent adhesion was obtained. Was given. Furthermore, the adhesiveness of this product after being immersed in warm water at 40 ° C. for 10 days hardly changed.

Production Example 2 (1) Production of blocked compound (z) of lactam of prepolymer from α, α, α ′, α′-tetramethylxylylene diisocyanate and active hydrogen-containing compound.

The MEK oxime used in Production Example 1 (1) was replaced with 201 parts of ε-caprolactam and 261 parts of the MEK oxime, and charged under a nitrogen stream.
After reacting at ℃ for 3 hours, it was confirmed by infrared absorption spectrum that the absorption of isocyanate group (2250 cm-1) was completely extinguished, and α, α, α ', a low viscosity liquid at room temperature,
A lactam-blocked product (z) of a prepolymer from α'-tetramethylxylylene diisocyanate and an active hydrogen-containing compound was obtained.

(2) Blocked product (z) of a prepolymer of α, α, α ', α'-tetramethylxylylene diisocyanate and an active hydrogen-containing compound of Preparation Example 1- (5) with a ketoxime (z) instead of 3.5 parts. The same procedure as in Preparation Example 1- (5) except that 3.5 parts of a lactam-blocked product of a prepolymer of α, α, α ′, α′-tetramethylxylylene diisocyanate and an active hydrogen-containing compound is used. To produce a plastisol composition.

Production Example 3 A blocked product of a complete adduct of an aliphatic diisocyanate of trimethylolpropane (x) with a ketoxime produced by replacing 201 parts of MEK oxime of Production Example 1- (1) with 26.5 parts of isopropyl alcohol and 161.5 parts of MEK oxime. A plastisol composition was prepared in the same manner as in Production Example 1- (5) except that (y) was used.

The properties of the compositions obtained in Production Examples 1 to 3 are shown in Table 1.

Production Comparative Example 1 In Production Example 1- (5), a plastisol composition was prepared without using the polyamide compound.

Production Comparative Example 2 In Production Example 1- (5), a plastisol composition was prepared without using the organotitanium polymer.

Production Comparative Example 3 In Production Example 1- (5), a plastisol composition was prepared without using the urethane compound having a hydrolyzable silyl group at the terminal.

The properties of the compositions obtained in Production Comparative Examples 1 to 3 are shown in Table 1.

[Effects of the Invention] The vinyl chloride plastisol composition of the present invention can be applied not only to lead-tin alloy plated steel sheets used for automobile fuel tanks but also to many other substrates such as cationic electrodeposition coated surface as well as acrylic coated surface. On the other hand, even if the heat treatment temperature is lowered by about 10 to 20 ° C. as compared with the conventional one, the effect of firmly adhering is exhibited. In addition to the above-mentioned effects, it has excellent storage stability. For example, the storage stability is fairly stable even under the severe condition of 45 ° C. × 10 days, and the viscosity increase is small. Therefore, the thermal energy at the time of applying these rust preventive agents is greatly reduced, and the industrial merit is very large.

The plastisol composition of the present invention comprises an adhesive, a sealant,
It can be applied to various industrial applications such as paints, but in addition to lead-tin alloy-plated steel sheets used in the automobile industry, especially in fuel tanks, many other substrates such as body sealers and undercoats for car bodies with cationic electrodeposition coating are used. Particularly excellent as a coating material for coats.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location C08L 75:04 77:00 85:00 (56) References JP-A-1-170633 (JP, A) JP 56-24435 (JP, A) JP 55-118948 (JP, A) JP 63-183913 (JP, A) JP 63-86715 (JP, A) JP 63 -10615 (JP, A)

Claims (1)

[Claims] 1. A plastisol composition comprising a vinyl chloride polymer or copolymer (A), a plasticizer (B) and an adhesion-imparting agent (C) as essential components, wherein the adhesion-imparting agent (C) is a triad. Blocked product (y) of a complete adduct (x) of an aliphatic diisocyanate of methylolpropane with a ketoxime and a ketoxime of a prepolymer from α, α, α ', α'-tetramethylxylylene diisocyanate and an active hydrogen-containing compound Or a blocked product with a lactam (z); an active amino group-containing mono- or polyamide-based compound; an organotitanium and / or an organotitanium polymer; and a urethane compound having a hydrolyzable silyl group at the terminal;
A plastisol composition comprising: