JPH0613662B2 - Sealing material or undercoat material for steel plates coated with cationic electrodeposition paint - Google Patents

Description

TECHNICAL FIELD The present invention relates to a vinyl chloride plastisol composition. More specifically, it adheres well to a metal cationic electrodeposition coated surface by heat treatment at a relatively low temperature for a short time, and has good storage stability.
The present invention relates to a plastisol composition of a vinyl chloride polymer or copolymer, which has excellent adhesiveness even after storage.

[Conventional technology and problems]

In recent years, in the automobile industry, in order to increase the corrosion resistance of vehicles, anion type electrodeposition coating has been changed to cation type electrodeposition coating having good corrosion resistance. Further, in the automobile assembly line, from the viewpoint of energy saving, the temperature and time of the baking furnace for paints and the like tend to shift from the conventional temperature of 150 ° C. and 30 minutes to 140 ° C. and 30 minutes or less.

However, vinyl chloride-based plastisols that have been conventionally used adhere to the anion-type electrodeposition coated surface, but do not have sufficient adhesiveness and physical properties on the cation-type electrodeposition coated surface, and further have a low temperature of 130 ° C or lower. At temperature, the adhesiveness tended to deteriorate. Therefore, it is strongly desired that vinyl chloride plastisol adheres well to the cationic electrodeposition coated surface even under the low temperature baking condition, has sufficient physical properties, and has good storage stability.

Conventionally, various studies have been conducted to improve the adhesiveness and physical properties of vinyl chloride plastisol, but examples include (1) acrylic monomers, (2) liquid epoxy resin and curing agent, (3) polyamide and block. Urethane prepolymer (Japanese Patent Publication Sho 59
No. 52901), (4) polyamide and / or polyamine and carboxylic acid (JP-A-59-120651) and the like are known, but sufficient adhesion force is not obtained for cationic electrodeposition coating. It was not possible to satisfy the above-mentioned demand because of the drawbacks such as not being obtained and the storage stability of vinyl chloride plastisol being poor.

The present inventors have conducted extensive studies to improve these drawbacks, and as a result, vinyl chloride plastisol containing an adhesion-imparting agent composed of a diene rubber-added polyamidoamine was subjected to a cationic electrodeposition coated surface by a heat treatment at a relatively low temperature and a short time. The inventors have found that they adhere very strongly to, have good hot water resistance, good heat resistance, and good storage stability, and have reached the present invention.

[Means for solving problems]

That is, the sealing material or the undercoat material for the steel sheet coated with the cationic electrodeposition coating composition of the present invention has a vinyl chloride polymer and / or a copolymer as an essential constituent component.
It is characterized by containing (I), a plasticizer (II), and an adhesion-imparting agent (III) comprising a diene rubber-added polyamidoamine.

The adhesion-imparting agent (III) of the present invention includes, for example, polyamidoamines (III- having an average of one or more amide groups per molecule).
It can be obtained by reacting 1) with a diene-based modified liquid rubber (III-2).

Vinyl chloride polymer and / or copolymer used in the present invention
As the (I), a commonly used one can be used. Examples thereof include copolymers of vinyl chloride and other vinyl monomers copolymerizable with vinyl chloride, such as vinyl acetate maleic anhydride or maleic acid ester, and vinyl ether.

Polymerization degree of vinyl chloride polymer or copolymer is usually 1000
~ 1700. Commercially available vinyl chloride polymers or copolymers include ZEON 121 and ZEON 135J (manufactured by Nippon Zeon), Denka Vinyl PA-100, and Denka Vinyl ME18.
0 (all manufactured by Denki Kagaku Kogyo), Kanevinyl PSL-10, Kanevinyl PSH-10, Kanevinyl PSM-30, and Kanevinyl PCH-
112 (above manufactured by Kanebuchi Chemical Industry) is mentioned. These are 2
It is also possible to use a mixture of two or more species.

In the present invention, as the plasticizer (II), those usually used for vinyl chloride plastisols can be used. For example, phthalates such as diethyl phthalate, dibutyl phthalate, dioctyl phthalate, dilauryl phthalate, and distearyl phthalate, adipates such as dioctyl adipate, sebacates such as dioctyl sebacate, and phosphorus such as tricresyl phosphate. Ester-type plasticizers such as acid esters, and mixtures of two or more thereof.

Of these, preferred are phthalates, especially dioctyl phthalate.

Polyamidoamines (I) having one or more amide groups per molecule on average used in the production of the adhesion-imparting agent (III) of the present invention (I
Preferred as II-1) are polyamines and fatty acids, 2
It is obtained from a basic acid or a derivative thereof.

The polyamide amines (III-1) of the present invention also include an imidazoline ring-containing amidoamine compound obtained by reacting a polyamine having an imidazoline ring-forming ability under a reaction condition in which an imidazoline ring is formed.

Polyamine used here for the production of polyamidoamines (III-1), diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, heptaethyleneoctamine, nonaethylenedecamine, Di-1,2
-Propanetriamine and the like, and other diamines such as aminoethylethanolamine and aminoethylpropanolamine can be used within the scope of the present invention. In addition to the above, ethylenediamine,
N-aminoethylpiperazine or the like can be used.

Further, aromatic polyamines (phenylenediamine, tolylenediamine, xylylenediamine, etc.) and alicyclic polyamines (cyclohexylenediamine, isophoronediamine, etc.) can also be used. And mixtures of two or more of these.

On the other hand, as the fatty acid or its derivative, butyric acid, valeric acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid,
Saturated fatty acids having 4 or more carbon atoms such as behenic acid and their esters, tohsuccinic acid, linderic acid, lauroic acid, tzunic acid, fusetoleic acid, myristoleic acid, zomarinic acid, petroselinic acid, oleic acid, elaidic acid, linole. Acid, linoelaidic acid, eleostearic acid, linoleic acid, valinaric acid, arachidonic acid and their esters, acrylic acid, methacrylic acid, maleic acid and their esters, tall oil fatty acid and its ester obtained from pulp manufacturing waste liquor, Drying oil, semi-drying oil,
Alternatively, polymerized fatty acids such as dimer acid and trimer acid obtained by polymerizing these free fatty acids, and esters thereof may be mentioned. Here, the above-mentioned drying oil or semi-drying oil, linoleic acid, soybean oil containing a highly unsaturated fatty acid such as linolenic acid, linseed oil, tung oil, eno oil, cottonseed oil, sunflower oil, safflower oil, and dehydrated castor oil. Examples include oil. Further, a polymer of acrylic acid and linoleic acid, adipic acid, sebacic acid, saturated dibasic acid such as azelaic acid,
These esters, unsaturated straight-chain dibasic acids, unsaturated branched dibasic acids, these esters can also be used, for example, DAICID-550 (manufactured by Harima Kasei Co., Ltd., trade name), OSK-
DAUL-16 (trade name of Okamura Oil Co., Ltd.), OSK-DA UB-20
(The same) can also be used.

Under known pressure, these polyamines and fatty acids can be formed at a known molar ratio by a known method, for example, when forming an imidazoline ring under normal pressure.
170 to 320 ° C., preferably 250 to 290 ° C., and particularly under normal pressure 120 to 200 ° C. when not intended to form an imidazoline ring,
It is preferable to carry out the reaction at 140 to 180 ° C., and any reaction can be carried out by reducing the reaction temperature by reducing the pressure.

As the fatty acid and / or its derivative, it is preferable to use polymerized fatty acid or dibasic acid alone or a mixture thereof with a saturated fatty acid or an unsaturated fatty acid. In the reaction with the above polyamine, the reaction temperature and the reaction time are appropriately set. The compound containing a desired amide bond can be obtained by adjusting to.

Examples of the diene liquid rubber modified product (III-2) used for the production of the adhesion-imparting agent (III) of the present invention include epoxidized polybutadiene obtained by epoxidizing liquid polybutadiene, polyisoprene, or polypentadiene, and epoxidation. Epoxidized dienes such as polyisoprene or epoxidized polypentadiene, liquid polybutadiene containing a carxyl group, or carboxyl group-containing dienes such as a butadiene-acrylonitrile copolymer and a nitrile-butadiene copolymer can be used.

The average molecular weight of the epoxidized dienes is preferably from 500 to 10,000, particularly preferably from 500 to 5,000. If it is less than 500, the adhesiveness becomes insufficient, and if it exceeds 10,000, the viscosity becomes high, which is not preferable. The microstructure of these dienes is not particularly limited.

The liquid polybutadiene or liquid polyisoprene or liquid polypentadiene is not only a homopolymer of butadiene or isoprene or pentadiene, but also butadiene or isoprene or a pentadiene unit having 70% or more of the units of all monomers, or Isbrene or pentadiene and acrylonitrile, styrene, (meth)
Includes copolymers with acrylic acid esters, vinyl acetate, maleic anhydride and the like. It also includes a copolymer of butadiene or isoprene with butadiene, a copolymer of butadiene or pentadiene with isoprene, and a copolymer of butadiene or isoprene with pentadiene.

Further, liquid polybutadiene, polyisoprene or polypentadiene may have a hydroxyl group, a carboxyl group or other functional group at the terminal.

The epoxidized dienes of the present invention, that is, epoxidized polybutadiene, epoxidized polyisoprene, epoxidized polypentadiene, etc., are the liquid polybutadiene, liquid polyisoprene, liquid polypentadiene, etc. and hydrogen peroxide solution and formic acid, acetic acid, etc. It is produced by subjecting an aliphatic lower carboxylic acid to an epoxidation reaction at 30 to 80 ° C. for several hours in an organic solvent or without being dissolved.

In this reaction, the amount of hydrogen peroxide used is 0. hydrogen peroxide per 1 double bond contained in the liquid polybutadiene, liquid polyisoprene, liquid polypentadiene or the like.
An amount of 05 to 3 molecules, particularly 0.3 to 0.7 molecules is preferable, and the amount of lower carboxylic acid used is one double bond contained in the liquid polybutadiene, liquid polyisoprene, liquid polypentadiene, or the like. On the other hand, the amount is preferably 0.05 to 1.5 molecules of the lower carboxylic acid, particularly 0.1 to 0.8 molecule.

The solvent that can be used in the above reaction is preferably a chlorinated hydrocarbon solvent such as chloroform or carbon tetrachloride, or an aromatic hydrocarbon solvent such as benzene, toluene or xylene, and its addition amount is 80 It is up to 50% by weight, preferably 50 to 70% by weight.

In the above reaction, the use of a catalyst is not always necessary, but for example sulfuric acid, phosphoric acid, paratoluenesulfonic acid,
The reaction can be promoted by using an acid catalyst such as a cation type ion exchange resin.

The present invention is not limited to the method described in detail above. (1) In advance, hydrogen peroxide and a lower carboxylic acid such as formic acid and acetic acid are reacted to produce a percarboxylic acid. A method in which an acid is added to the reaction system of the present invention to react with liquid polybutadiene, liquid polyisoprene, liquid polypentadiene, or the like in the presence or absence of the solvent as described above (2) The presence of acetaldehyde in the presence of ozone or another catalyst Below, acetaldehyde monoperoxyacetate produced by autoxidation at low temperature is treated with liquid polybutadiene or liquid polyisoprene or liquid polyisoprene while evaporating acetaldehyde produced in the presence of a solvent such as acetone or ethyl acetate. Method of reacting with pentadiene, etc. (3) Hydrogen peroxide, such as osmic acid, tungsten A method of reacting with liquid polybutadiene or liquid polyisoprene or liquid polypentadiene or the like in the presence of a catalyst and an insoluble solvent such as (4) aromatic percarboxylic acid such as perbenzoic acid or monoperoxyphthalic acid, chloroform, ether By reacting with liquid polybutadiene or liquid polyisoprene or liquid polypentadiene or the like in the presence of an inert solvent such as benzene, etc., to react liquid polybutadiene or liquid polyisoprene or liquid polypentadiene or the like with an epoxidizing agent be able to.

The epoxidation degree and the hydroxylation degree in the epoxidized polybutadiene, epoxidized polyisobrene, epoxidized pentadiene and the like of the present invention can be adjusted by appropriately changing the kind of the epoxidizing agent, the reaction ratio and the like.

It is preferable to set reaction conditions such that the epoxy equivalent of the epoxidized polybutadiene, epoxidized polyisoprene or epoxidized polypentadiene of the present invention is 150 to 1500 and the hydroxyl equivalent is 400 to 1500.

Carboxyl group-containing liquid polybutadiene of the present invention or butadiene-acrylonitrile copolymer or nitrile
As the butadiene copolymer, those having a molecular weight of 1000 to 4000 and having an average of two or more carboxyl groups in one molecule at both ends of the molecule or in the molecule are preferable.

As commercial products, NISSOPB, C-1000, C-2000 manufactured by Nippon Soda Co., which has carboxyl groups at both ends of the molecule, and Hycar CTBN1300 × 8, CTBN1300 × 9, CTBN1300 manufactured by BF Guddleitchi.
X13, CTBN1300x15, Nippon Zeon DN-601 having a carboxyl group in the molecule, and the like.

An essential component of the composition of the present invention, an adhesion promoter (III)
Is a polyamidoamine (III-1) having one or more amide groups per average molecule, and a diene-based liquid rubber modified product.
It can be obtained by subjecting (III-2) to an adduct reaction at 50 to 200 ° C. for several hours.

In the above reaction, the polyamidoamines (III-1) and the diene liquid rubber modified product (III-2) are polyamidoamines.
(III-1) relative to 99-65% by weight (preferably 95-70% by weight), a diene liquid rubber modified product (III-2) 1-3.
It is preferable to react 5% by weight (particularly preferably 5 to 30% by weight).

Further, these adhesion-imparting agents (III) can be used after being diluted in advance with the plasticizer (II) used in the present invention.

The diene rubber-added polyamide polyamine of the present invention preferably has an amine value of 100 to 450.

Further, as another production method of the adhesion-imparting agent (III) of the present invention, the same adduct reaction as the above reaction conditions of polyamine and epoxidized polybutadiene or epoxidized polyisoprene or epoxidized polypentadiene before forming polyamides It is also possible to carry out a polyamidation reaction by reacting a fatty acid or the like after forming an adduct product.

Further, at the time of producing poiamidoamine from fatty acid and polyamine, liquid polybutadiene containing a carboxyl group or butadiene-acrylonitrile copolymer can be reacted at the same time to produce the adhesion promoter (III).

In the composition of the present invention, the addition of the blocked polyurethane prepolymer (IV) has an effect of imparting adhesiveness and an effect of preventing burn coloration.

Polyether polyols as the polyols used in the production of the blocked urethane prepolymer (IV),
Examples thereof include polyester polyols, hydroxyl-terminated diene-based liquid rubbers, and hydroxyl-terminated urethane prepolymers obtained from these and organic diisocyanates. Examples of the polyether polyol include a polyfunctional low-molecular active hydrogen-containing compound, for example, a low-molecular polyol having 2 to 3 functional groups, a low-molecular amine or a phenol obtained by adding an alkylene oxide.

Examples of the low molecular weight polyol having 2 to 3 functional groups include ethylene glycol, propylene glycol, butylene glycol, 1,4-butanediol, 1,6-hexanediol,
Examples include trimethylolpropane, glycerin, castor oil and mixtures thereof. Of these, preferred are ethylene glycol, propylene glycol, glycerin and trimethylolpropane.

Alkanolamines (mono-, di- or triethanolamine etc.) as low molecular weight amines having 2 to 3 functional groups;
Aliphatic or aromatic polyamines (ethylenediamine,
N-alkyl or aryl substituents of tolylenediamine, etc.) having 2-3 functional groups; heterocyclic polyamines having 2-3 functional groups, such as piperazine, N-aminoethylpiperazine, and mixtures thereof.

Examples of the phenols having 2 to 3 functional groups include catechol, resorcin, hydroquinone and bisphenol (bisphenol A etc.).

Among the above-mentioned low molecular weight active hydrogen-containing compounds, low molecular weight polyols are preferable.

Examples of the alkylene oxide include ethylene oxide (EO), propylene oxide (PO), butylene oxide, styrene oxide, and one or more of these. Preferred is propylene oxide or a combination of propylene oxide and ethylene oxide (the content of propylene oxide is usually 50% by weight or more based on the total amount of ethylene oxide). When two or more kinds of alkylene oxides are used, they can be randomly or block-wise added to the low molecular weight polyol or the like.

Further, polytetramethylene ether glycol obtained by ring-opening polymerization of tetrahydrofuran can be used.

As the polyester polyol, dicarboxylic acid,
Polylactone polyol obtained by ring-opening polymerization of polyester polyol or lactone (eg, ε-caprolactone) obtained by polycondensing the ester or halide and low molecular weight polyol in the presence of low molecular weight polyol (eg ethylene glycol). Esters can be mentioned.

The above dicarboxylic acids include aliphatic dicarboxylic acids (adipic acid, sebacic acid, maleic acid, dimer acid, etc.),
Examples thereof include aromatic dicarboxylic acids (terephthalic acid, isophthalic acid, etc.) and their anhydrides. Of these, preferred are aliphatic dicarboxylic acids, and particularly preferred is adipic acid.

Examples of the above-mentioned low molecular weight polyol include the low molecular weight polyol having 2 to 3 functional groups and the alkylene oxide adduct thereof (low molecular weight) described in the section of the polyether polyol. Of these, preferred are ethylene glycol and diethylene glycol.

The hydroxyl group terminated diene liquid rubber is particularly preferably hydroxyl group terminated liquid polybutadiene. The microstructure is not particularly limited. As commercial products, R-45HT made by Idemitsu Petrochemical, NISSO PB G-1 made by Nippon Soda
For example, 000-2000.

The molecular weight of the polyols used in the polyurethane prepolymer of the present invention is 100 to 4000, preferably 200 to 3000.

As the organic diisocyanate, conventionally known ones are used and are not particularly limited. For example, aliphatic diisocyanates (hexamethylene diisocyanate, lysine diisocyanate, etc.), alicyclic diisocyanates (hydrogenated diphenylmethane diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, etc.),
Aromatic diisocyanate [(tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI),
Naphthylene diisocyanate, xylylene diisocyanate, etc.)]. Of these, aromatic diisocyanates are preferable, and hydrogenated diphenylmethane diisocyanate and isophorone diisocyanate are particularly preferable.

Examples of the blocking agent used to obtain the blocked urethane prepolymer (IV) include active methylene compounds such as malonic acid diesters (such as diethyl malonate), acetylacetone, acetoacetic acid esters (such as ethyl acetoacetate); oxime compounds such as acetone. Examples include oximes, methylethylketoxime (MEK oxime), methylisobutylketoxime (MIBK oxime), phenols such as phenol and m-cresol; lactams such as ε-caprolactam.

Among them, suitable blocking agents are isocyanates,
Or, the dissociation temperature for regenerating the isocyanate group is generally 100 to 160 depending on the baking temperature when the blastisol is applied.
It is in the range of ° C.

Particularly preferred blocking agents are oxy compounds (especially ketoxime). Ketoxime is particularly advantageous because it easily reacts with isocyanate, and the dissociation temperature of the block is relatively low as compared with other compounds.

When obtaining the urethane prepolymer, the molar ratio of the isocyanate group to the hydroxyl group is usually 1.2 to 2.0, preferably 1.
3 to 1.8. The isocyanate group equivalent of the prepolymer is usually 200 to 2000, preferably 300 to 1500. When the isocyanate equivalent is less than 200, the resin becomes hard and brittle, which adversely affects the physical properties of the burned plastisol, and when it exceeds 2000, good adhesion cannot be obtained.

The NCO% of the prepolymer is usually 1 to 20%, preferably 2 to 15%.

The urethane prepolymer can be obtained by a usual method. When carrying out the urethane prepolymer formation reaction, the reaction temperature is usually 40 to 110 ° C, preferably 50 to 100 ° C.
In carrying out the urethane prepolymer formation reaction, known urethane polymerization catalysts for promoting the reaction, for example, organometallic compounds such as dibutyltin dilaurate, stannous octoate and stannas octoate, and tertiary amines such as triethylenediamine and triethylamine It is also possible to use amine compounds.

The blocking agent can be added and reacted at any stage of the above reaction to obtain a blocked urethane prepolymer (IV). The amount added is usually 1 equivalent or more and less than 2 equivalents, preferably 1.05 to 1.5 equivalents, relative to the free isocyanate group. The addition method may be such that it is added at the end of a predetermined weight, or it is added at the beginning of the polymerization, or it is partially added at the beginning of the polymerization and the rest is added at the end of the polymerization. A method of adding at the end of the polymerization is preferred.
In this case, the isocyanate percentage (for example, "polyurethane", which can be measured by the method described in Maki Shoten, 1980, page 21) may be used as a standard at the end of the predetermined polymerization. The reaction temperature when adding a blocking agent is usually 60 to
100 ° C. During the reaction, a known urethane polymerization catalyst may be added to accelerate the reaction. Further, the plasticizer of the present invention may be added in any amount.

The composition of the present invention may also contain various additives other than the above-mentioned component (I), (II), (III) or (IV), such as a filler or a stabilizer. Examples of the filler include inorganic fillers (calcium carbonate, talc, diatomaceous earth, kaolin, etc.) and organic fillers (cellulose powder, powdered rubber, recycled rubber, etc.). Examples of stabilizers include metallic soaps (calcium stearate, aluminum stearate, etc.), inorganic acid salts (dibasic phosphite, dibasic sulfate, etc.), and organometallic compounds (dibutyltin dilaurate, dibutyltin sulfonate). Rate etc.). or,
A coloring agent such as a pigment may be added optionally.

The ratio of each component in the vinyl chloride plastisol composition for cationic electrodeposition coating of the present invention (in the composition) is 20 to 40% by weight of vinyl chloride polymer and / or copolymer (I), plasticizer (II). 20 to 40% by weight, 0.2 to 5% by weight of an adhesion-imparting agent (III) consisting of a diamine rubber-added polyamidoamine,
When the blocked polyurethane prepolymer (IV) is added, its compounding ratio is 0.1 to 20% by weight. Particularly, if the adhesion-imparting agent (III), which is a characteristic component of the present invention, is less than 0.2% by weight, the desired effect cannot be obtained, and if it exceeds 5% by weight, the phenomenon of thickening of plastisol occurs, which is not preferable. Further, the filler is 70% by weight or less (preferably 10 to 60% by weight),
The stabilizer is used in the range of 3% by weight or less (preferably 0.1 to 2% by weight).

The vinyl chloride plastisol composition for cationic electrodeposition coating of the present invention can be produced by kneading the above-mentioned components by a usual method.

The composition of the present invention can be applied to various metal surfaces and various undercoat coated surfaces of metals, and is particularly useful for cationic type electrodeposition coated surfaces. For cationic type electrodeposition coating, normal electrodeposition coating,
For example, there may be mentioned a method in which an adduct of an epoxy resin and a primary or secondary amine is neutralized with an acid to solubilize it in water, and the metal surface of the cathode is coated with direct current by applying a direct current together with the blocked isocyanate.

The coating amount of the vinyl chloride plastisol composition of the present invention on the coated surface is usually 1000 to 5000 g / unit, and the film thickness is 0.3 to
It is 2 mm. After coating, it is heated and cured at 120 to 150 ° C. for 20 to 40 minutes. The application method may be an ordinary method, for example, a method of supplying from a pressure feed pump and discharging and applying with a flow gun, an airless spray, or the like.

〔The invention's effect〕

As described in detail above, the vinyl chloride plastisol composition of the present invention firmly adheres to a cationic electrodeposition coated surface at a temperature of 120 to 140 ° C. under a baking condition of 30 minutes or less, and is immersed in warm water and then heated. It has excellent adhesion after treatment, and also has excellent storage stability of the vinyl chloride plastisol composition, and can be used as a body sealer or undercoat paint for automobile bodies. But excellent.

〔Example〕

Hereinafter, the effects of the present invention will be specifically shown in Examples and Comparative Examples, but these do not limit the present invention.

Reference Example-1 Production of Polyamidoamine A dimer acid 580 g, tall oil fatty acid 580 g and triethylene tetramine 584 g were dehydrated at 200 ° C. for 5 hours in a 4-necked flask equipped with a stirrer, a thermometer and a nitrogen inlet tube. By reaction, a polyamidoamine (A) having an amine value of 340 was obtained.

Reference Example-2 Production of Epoxidized Polybutadiene 1,4-cis 60%, 1,4-trans 20%, 1,2-vinyl 20%
500 parts of liquid polybutadiene having a molecular weight of 2800 and an OH equivalent of 1200 having the structure of is added to 1300 parts of benzene, 1500 parts of a 30% hydrogen peroxide aqueous solution is added, and 132 parts of formic acid is added to the obtained suspension with stirring. It was added dropwise at 20 ° C. for about 30 minutes. After that, the reaction is performed at about 35 ° C. for 5 hours, and after the reaction is completed, the reaction solution is washed with water,
Benzene was removed by vacuum distillation to give an epoxy equivalent of 20
Epoxidized polybutadiene (B) having a viscosity of 360 P / 45 ° C. was obtained.

Reference Example-3 Production of Epoxidized Polyisoprene Liquid polyisoprene 6 having a molecular weight of 2280 and a hydroxyl equivalent of 960.6
Dissolve 7 parts in 134 parts of chloroform and add 80% formic acid 5.7.
After adding 5 parts and 0.067 part of phosphoric acid and raising the temperature to 60 ° C., 6
39.7 parts of 0% hydrogen peroxide solution was added dropwise for 30 minutes. After the completion of the dropping, the reaction was continued at the same temperature for 1 hour, then the aqueous layer was separated, the oil layer was washed with water, and the solvent was removed to obtain epoxidized polyisoprene (C) having an epoxy equivalent of 350 as a product. .

Reference Example-4 Production of Epoxidized Polypentadiene 67 parts of liquid polypentadiene having a molecular weight of 2300, 134 parts of chloroform, 5.75 parts of 80% formic acid, 0.067 parts of phosphoric acid, and 39.7 parts of hydrogen peroxide solution were used as Reference Example-3. Epoxidized polypentadiene with an epoxy equivalent of 340
(D) was obtained.

Reference Example-5 Production of Blocked Urethane Prepolymer (1) 1000 parts of glycerin-based polypropylene triol (molecular weight 1000) and hydrogenated diphenylmethane were placed in a four-necked flask equipped with a stirrer, thermometer and nitrogen gas inlet tube. Charge 865 parts of diisocyanate (molecular weight 262), 1652 parts of dioctyl phthalate, 0.21 part of dibutyltin dilaurate, react at 60 ° C for 12 hours under nitrogen gas blowing,
Urethane prepolymer with a CO content of 3.4% (NCO equivalent 123
5) got. Further, 310 parts of MEK oxime (MEK oxime / NCO equivalent ratio = 1.25) was gradually added, and the temperature was kept at 60 ° C. for 2 hours.
After reacting for a time, a blocked urethane prepolymer (IV-1) in which the NCO group was completely blocked was obtained.

(2) R-45HT (molecular weight 2800) 1205 parts and isophorone diisocyanate (molecular weight 222) 222 parts, dibutyltin dilaurate 0.05 part, DOP 85.7 parts, MEK oxime 29.2 parts are reacted in the same manner as in (1). A blocked urethane prepolymer (IV-2) was obtained.

Example-1 100 parts of the polyamidoamine (A) of Reference example-1 and Reference example-2
15 parts of the epoxidized polybutadiene (B) of 3 was reacted at 100 ° C. for 3 hours to obtain an epoxidized polybutadiene-added polyamidoamine (1) having an amine value of 290 and a viscosity of 50,000 cps (30 ° C.). A vinyl chloride plastisol composition containing this was obtained as follows.

Polyvinyl chloride powder (a) (Zeon 12 manufactured by Nippon Zeon Co., Ltd.)
1) 60 parts, polyvinyl chloride copolymer powder (b) (ZEON 130ZX manufactured by Nippon Zeon Co., Ltd.) 20 parts, dioctyl phthalate (DOP) 100 parts, calcium carbonate (a) (shiraishi calcium
Co., Ltd., 80 parts of Shirahama CC, calcium carbonate (b) (manufactured by Shiraishi Calcium Co., Ltd., Whiten SB) 20 parts, titanium oxide (manufactured by Titanium Industry Co., Ltd., KR-380) 3 parts, anti-aging agent A vinyl chloride plastisol composition was prepared by kneading 1.5 parts, 0.5 part of a flow control agent, and 2 parts of epoxidized polybutadiene-added polyamidoamine. The adhesiveness of this composition was evaluated. The results are shown in Table-1.

Example-2 100 parts of the polyamidoamine (A) of Reference example-1 and Reference example-2
20 parts of epoxidized polybutadiene (B) is reacted at 100 ° C. for 3 hours to obtain epoxidized polybutadiene-added polyamidoamine, 70 parts of the epoxidized polybutadiene-added polyamidoamine is diluted with 30 parts of DoD, and DOP diluted epoxidation is carried out. Polybutadiene-added polyamidoamine (amine value 190) (2) was obtained.

A vinyl chloride plastisol composition was prepared in the same manner as in Example 1, and the test results are shown in Table 1.

Example-3 100 parts of the polyamidoamine (A) of Reference Example-1 and Reference Example-3
15 parts of epoxidized polyisoprene (C) were reacted in the same manner as in Example 1 to obtain epoxidized polyisoprene-added polyamidoamine (3).

After that, a vinyl chloride plastisol composition was prepared with the same composition as in Example-1, and the test results are shown in Table-1.

Example-4 100 parts of the polyamidoamine (A) of Reference Example-1 and Reference Example-4
Example 15 with 15 parts of epoxidized polypentadiene (D)
The reaction was performed in the same manner as in 1 to obtain epoxidized polypentadiene-added polyamidoamine (4).

A vinyl chloride plastisol composition was prepared in the same manner as in Example 1, and the test results are shown in Table 1.

Comparative Example-1 In the same PVC plastisol composition as in Example 1, the polyamidoamine (A) of Reference Example-1 was used instead of the epoxidized polybutadiene-added polyamidoamine (1). The test results are shown in Table 1.

Example-5 100 parts of the polyamidoamine (A) of Reference Example-1 and NISSOPB C-1
Polybutadiene-added polyamidoamine (5) having an amine value of 300 and a viscosity of 40,000 cps / 25 ° C was obtained by dehydration reaction with 10 parts of 000 (manufactured by Nippon Soda Co., Ltd.) at 200 ° C for 3 hours. A vinyl chloride plastisol composition to which this was added was produced as follows.

100 parts of polyvinyl chloride powder (a), 150 parts of DOP, 100 parts of calcium carbonate (a), 200 parts of calcium carbonate (b), 30 parts of titanium oxide, 6 parts of polybutadiene-added polyamidoamine (5) are kneaded into vinyl chloride. A plastisol composition was prepared.
The test results are shown in Table-2.

Example-6 Versadim 216 (Henkel Hakusui Co., Ltd., dimer acid)
50 parts and tall oil fatty acid 35 parts and Hycar CTBN 1300 × 9 1
Polyamideamine having an amine value of 180 by reacting 5 parts with 52 parts of isophoronediamine while dehydrating at 200 ° C. for 5 hours (6)
Got A vinyl chloride plastisol composition was prepared in the same manner as in Example-5, and the test results are shown in Table-2.

Comparative Example-2 Polybutadiene-added polyamidoamine (5) of Example-5
ACR Hardener H-270 (Polymerized fatty acid polyamide made by AC R, amine value 300) is added and created instead of
Comparative tests were conducted and the results are shown in Table-2.

Examples-7-11, Comparative Examples-3-5 60 parts of polyvinyl chloride powder (a) (Zeon 121), 20 parts of polyvinyl chloride copolymer powder (b) (Zeon 103ZX), D
OP 100 parts, calcium carbonate (a) (white luster CCR) 80
Parts, calcium carbonate (b) (whiten SB) 20 parts, polyamidoamine or noamide 215X shown in Table 3, 3 parts of ACR Hardener H-260, and 9 parts of blocked urethane prepolymer were kneaded in the same manner as in Example-1. The results of the tests conducted are shown in Table-3.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Akira Baba 7-1 Akita-cho, Takatsuki-shi, Osaka Sunstar Giken Co., Ltd. (56) Reference JP-A-60-106871 (JP, A))

Claims (7)

[Claims] 1. Vinyl chloride polymer and / or copolymer (I) 20 to 40% by weight and plasticizer (II) as essential constituents.
A sealing material or undercoat material for a steel sheet coated with a cationic electrodeposition coating composition, which comprises 20 to 40% by weight and 0.2 to 5% by weight of an adhesion promoter (III) consisting of a diamine-based polyamide-added polyamidoamine. 2. A diamine rubber-added polyamidoamine having a polyamidoamine having one or more amide groups per molecule on average (III-1) and a diene liquid rubber modified product (III-2).
The sealing material or undercoat material according to claim 1, which is a reaction product of 3. A diene liquid rubber modified product (III-2) is epoxidized polybutadiene, epoxidized polyisoprene or epoxidized polypentadiene obtained by epoxidizing liquid polybutadiene, polyisoprene or polypentadiene. The sealing material or undercoat material according to claim 2. 4. The sealing material or undercoat according to claim 3, wherein the epoxidized polybutadiene, the epoxidized polyisoprene, or the epoxidized polypentadiene has a molecular weight of 500 to 10,000 and an epoxy equivalent of 150 to 1500. Material. 5. The sealing material or undercoat material according to claim 2, wherein the diene-based liquid rubber modified product (III-2) is a carboxyl group-containing liquid polybutadiene or a butadiene-acrymenitrile copolymer. . 6. The sealing according to claim 5, wherein the carboxyl group-containing liquid polybutadiene or butadiene-acrymenitrile copolymer has two or more carboxyl groups and a molecular weight of 1,000 to 4,000. Material or undercoat material. 7. Vinyl chloride polymer and / or copolymer (I) 20 to 40% by weight and plasticizer (II) as essential constituents.
A cation-type electrode containing 20 to 40% by weight, 0.2 to 5% by weight of an adhesion-imparting agent (III) comprising a polyamine amine with a diene rubber and 0.1 to 20% by weight of a blocked polyurethane prepolymer (IV). Sealing material or undercoat material for steel plates coated with coating material.