JPH04126783A - Vinyl chloride plastisol composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition, containing vinyl chloride (co)polymer, a plasticizer and a specific adhesion imparter, capable of firmly bonding by heat treatment in a short time, good in storage stability and excellent in hot water adhesion resistance without fading even after heat treatment at high temperatures and deteriorating the adhesion. CONSTITUTION:The objective composition containing (A) vinyl chloride (co)polymer, (B) a plasticizer composed of preferably dioctyl phthalate, etc., and (C) a mixture of (i) a blocked isocyanate compound prepared by polymerizing an aliphatic and/or an alicyclic diisocyanate and reacting the resultant isocyanurate ring-containing containing polymer with a blocking agent with (ii) a carboxyl group-containing butadiene/acrylonitrile copolymer-modified polyamidoamine as an adhesion imparter.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to vinyl chloride plastisol compositions. Specifically, the present invention provides strong adhesion to various metal surfaces or various undercoated metal surfaces by short-time heat treatment at 110 to 200°C.
No fading after heat treatment at high temperatures, good storage stability,
The present invention relates to a vinyl chloride plastisol composition that has excellent adhesion even after storage and has excellent hot water resistant adhesion.

[Prior Art and Problems to be Solved by the Invention] Various studies have been made to improve the adhesion of vinyl chloride plastisol compositions to various metal surfaces (particularly bare metal) and various undercoated metal surfaces.

For example, (a) Special Publication No. 59-52901 includes (1)
Acrylic monomer, (2) liquid epoxy resin and curing agent,
(3) A method of blending polyamide and blocked urethane prepolymer is disclosed, (b) JP-A-59-1206
No. 51 discloses a method of blending (1) an acrylic monomer, (2) a liquid epoxy resin and a curing agent, (3) a polyamide and a blocked urethane prepolymer, and (4) a polyamide and/or polyamine and a carboxylic acid. , (c) In JP-A-1-272653, a long-chain alkylphenol block of a diisocyanate polymer was added as an adhesion promoter, and a powder curing agent for epoxy resin with a melting point of 50 to 150°C was used as a curing agent. (d) JP-A-1-272652 discloses an aromatic diisocyanate randomly blocked with two or more alkylphenol blocking agents selected from the group consisting of mono- and dialkylphenols as an adhesion improver. A method of adding a polymer is disclosed, (e) JP-A-1-25
No. 6555 discloses a method of adding a dialkylphenol block of an aromatic diisocyanate polymer as an adhesion promoter, and Japanese Patent Publication No. 63-25515 discloses a method of adding a dialkylphenol block of an aromatic diisocyanate polymer as an adhesion promoter. A method of adding a benzoin acid ester or an alkylphenol block is disclosed, and (g) JP-A-1-225650 discloses a method of adding an epoxy resin, a blocked isocyanate compound, and a latent curing agent for epoxy resin as an adhesion imparting agent. (h) JP-A No. 1-252650 discloses the addition of a modified epoxy resin containing vinyl and hydroxyl groups obtained by reacting an epoxy resin with an α,β-unsaturated carboxylic acid as an adhesion imparting agent. A method is disclosed.

However, each of these methods has problems in terms of sufficient adhesion when heat treated at relatively low temperatures, discoloration of vinyl chloride plastisol due to heat treatment at high temperatures, and storage stability. It was not something that could be done.

[Means for Solving the Problems] As a result of intensive studies to improve these drawbacks, the present inventors have found that a vinyl chloride plastisol composition containing a specific adhesion promoter can be applied to various metal surfaces or metal surfaces. It adheres very strongly to various undercoated surfaces with short heat treatment at 110 to 200°C, and does not fade after heat treatment at high temperatures, meaning it has a wide temperature range from relatively low to high temperatures (ii0 to 200°C).
It was discovered that the heat treatment in step C) improved adhesion, foamability, fading resistance, and hot water resistance, and also had good storage stability, leading to the completion of the present invention.

The vinyl chloride plastisol composition of the present invention comprises (i) a vinyl chloride polymer and/or copolymer, (ii) a plasticizer, and (iii) an aliphatic and/or alicyclic diisocyanate as an adhesion promoter. A blocked isocyanate compound (i) obtained by blocking the isocyanurate ring-containing polymer (ii-1-1) obtained by
ii-1) and carboxyl group-containing butadiene-acrylonitrile copolymer-modified polyamide amine (iii-2)
), and (i)
A vinyl chloride polymer and/or copolymer, (ii) a plasticizer, and (iii) an isocyanurate ring-containing polymer (iii- 1-1), and a urethane prepolymer compound (iii-1-2) obtained by reacting the isocyanurate ring-containing polymerized Th (iii-1-1) with a polyhydroxy compound and blocking it with a blocking agent. blocked isocyanate compound (iii-
1) and a carboxyl group-containing butadiene-acrylonitrile copolymer-modified polyamide amine (in-2), and (i) a vinyl chloride polymer and/or copolymer, ( ii) An isocyanurate ring-containing polymer (iii-1-1) obtained by polymerizing an aliphatic and/or alicyclic diisocyanate as a plasticizer and (iii) an adhesion promoter, the isocyanurate ring-containing polymer Urethane prepolymer compound (i) obtained by reacting (ii-1-1) with a polyhydroxy compound
ii to 1-2), and a blocked isocyanate compound 'Ih obtained by blocking a urethane prepolymer compound (iii-1-3) obtained by reacting a polyhydroxy compound and a polyisocyanate with a blocking agent.
(iii-1), a carboxyl base modified with a butadiene-acrylonitrile copolymer (iii
-2) It is characterized by containing the following.

As the vinyl chloride polymer and/or copolymer (i) used in the present invention, commonly used ones can be used. Examples include copolymers of vinyl chloride and other vinyl monomers that can be copolymerized with vinyl chloride, such as vinyl acetate, maleic anhydride or maleic acid ester, and vinyl ether.

The degree of polymerization of vinyl chloride polymer or copolymer is usually 100.
It is 0-1700. Commercially available vinyl chloride polymers or copolymers include Zeon 121, Zeon 135J, and Zeon 103ZX (manufactured by Nippon Zeon), Denkavinyl PA-100, Denkavinyl ME-180 (manufactured by Denka Kagaku Kogyo), and Kanevinyl PSL-10. , Kanevinyl P
Examples include SI (-10), Kanevinyl PSM-30, and Kanevinyl PCI-12 (manufactured by Kanebuchi Chemical Industries).

These can also be used in combination of two or more types.

As the plasticizer (ii) in the present invention, those commonly used for vinyl chloride plastisol can be used. for example,
Phthalate esters such as diethyl phthalate, dibutyl phthalate, dioctyl phthalate, dilauryl phthalate, distearyl phthalate, adipic esters such as dioctyl adipate, sepatic esters such as dioctyl sebacate, phosphoric esters such as tricresyl phosphate, etc. Examples include ester type stabilizers and mixtures of two or more thereof. Preferred among these are phthalate esters, especially dioctyl phthalate.

Blocked isocyanate compound used in the present invention (
Preferred aliphatic and/or alicyclic diisocyanates used in the production of iii-1) are propane-
1,2-diisocyanate, 2,3-dimethylbutane-
2,3-diisocyanate, 2-methylpentane-2,
4-diisocyanate, octane-3,6-diisocyanate, 3.3-dinitropenkune-1,5-diisocyanate, octane-1,6-diisocyanate, 1°6-hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine Diisocyanate, xylylene diisocyanate, inphorone diisocyanate, isophorone diisocyanate (3-isocyanatomethyl-3,5,5-)limethylcyclohexylisocyanate), l,3- or 1,4-bis(isocyanatemethyl)cyclohexane, dicyclohexylmethane- Examples include 4,4°-diisocyanate, hydrogenated tolylene diisocyanate, and mixtures thereof.

Isocyanurate ring-containing polymers obtained by polymerizing these aliphatic and/or alicyclic diisocyanates (Mountain-1)
-1), for example, in an inert solvent such as methyl acetate, ethyl acetate, butyl acetate, methyl ethyl ketone, dioxane, etc. Fucric acid esters such as mixed alkyl phthalates, butylbenzyl phthalate, hexanolhensyl phthalate, etc. (hereinafter referred to as C1 to C1+),
In plasticizers such as phosphoric acid esters such as triskresyl phosphate and trisphenyl phosphate, adipic acid esters such as di-2-ethylhexyl adipate, or trimellitic acid esters such as mixed alkyl trimellitates of 07 to CI+, It can be obtained by polymerization using a known method using a catalyst such as a tertiary amine, a quaternary ammonium compound, a mannin base, an alkali metal of a fatty acid, or an alcoholade. Polymerization reactions under highly volatile solvents are
Finally, it is desirable to carry out a solvent replacement treatment with a suitable high boiling point solvent, such as a plasticizer.

In the present invention, a urethane prepolymer compound (iii) obtained by further reacting the isocyanurate ring-containing polymer (ui-1-1) with a polyhydroxy compound is used.
-1-2) or a urethane prepolymer compound (iii-1-3) obtained by reacting a polyhydroxy compound and a polyisocyanate.

Urethane prepolymer compound (ii) used in the present invention
i-1-2) or (iii-1-3) is a polyhydroxy compound such as a polyether polyol, a polyester polyol, or a mixture thereof, and an excess of the above-mentioned isocyanurate ring-containing polymer (iii-1-1). ) or the mixture of the above-mentioned diisocyanate compound and isocyanurate ring-containing polymer (iii-1-1) are reacted in the same manner as in the production method of a normal NCO-containing urethane prepolymer. Alternatively, the urethane prepolymer compound containing only the diisocyanate compound and the isocyanurate ring-containing polymer described above can be separately produced and mixed together.

Preferred examples of the polyether polyols include -formula % (where R is a polyhydric alcohol residue; (OR,) is a polyether polyol consisting of an oxyalkylene group having an alkylene group having 2 to 4 carbon atoms. Oxyalkylene chain; n is a number indicating the degree of polymerization of the oxyalkylene group and has a molecular weight of 100 to 4,500
p is preferably a number corresponding to 2 to 4).

Preferred examples of the polyhydric alcohol corresponding to R in the above formula include aliphatic dihydric alcohols (e.g. ethylene glycol, propylene glycol, 1,4-butylene glycol, neopentane glycol), trihydric alcohols (e.g. : Glycerin, trioxyisobutane, 1,2
．． 3-butanetriol, 1,2,3-pentanetriol, 2-methyl-1,2,3-propanetriol, 2-methyl-2,3,4-butanetriol, 2-ethyl-L2,3-butanetriol , 2,3.4-pentanetriol, 2.3.4-hexanetriol, 4
-Propyl-3,4,5-hebutanetriol, 2.4
-dimethyl-2,3,4-pentanetriol, pentamethylglycerin, pentaglycerin, L2,4-butanetriol, L2,4-pentanetriol, trimethylolpropane, etc.), tetrahydric alcohol (e.g. erythritol, pentaerythritol) , 1,2,3.4-pentanetetrol, 2,3,4.5-hexanetetrol, 1,2,3°5-pentanetetrol, 1,3,4.
5-hexanetetrol, etc.), trihydric alcohols (e.g., adonitol, arabitol, xylitol, etc.), hexahydric alcohols (e.g., sorbitol, mannitol, iditol, etc.), and the like.

Also, preferred as the polyhydric alcohol are dihydric to tetrahydric alcohols, with propylene glycol, glycerin and the like being particularly preferred.

In addition, the polyether polyol represented by the above-mentioned formula is
It can be produced by adding an alkylene oxide having 2 to 4 carbon atoms to such a polyhydric alcohol by a conventional method so as to have a desired molecular weight.

In addition, as alkylene oxide having 2 to 4 carbon atoms,
Examples include ethylene oxide, propylene oxide, and butylene oxide, and it is particularly preferable to use propylene oxide.

Examples of the polyester polyols include conventionally known polyesters produced from polycarboxylic acids and polyhydric alcohols, and polyesters obtained from lactams.

Examples of such polycarboxylic acids include henzhentricarboxylic acid, adipic acid, succinic acid, superric acid, sebacic acid, oxalic acid, methyladipic acid, glutaric acid, pimelic acid, azelaic acid, phthalic acid, terephthalic acid, isophthalic acid, and thiophthalic acid. Any suitable carboxylic acid such as dipropionic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid or the like can be used.

In addition, examples of polyhydric alcohols include ethylene glycol, propylene glycol, 1,4-butanediol,
1,3-butanediol, 1,5-bentanediol,
1,6-hexanediol, bis(hydroxymethylchlorohexane), diethylene glycol, 2,2-dimethylpropylene glycol, L3,6-hexanediol, trimethylolpropane, pentaerythritol,
Any suitable polyhydric alcohol such as sorbitol, glycerin or the like can be used.

In addition, polytetramethylene glycol, polycaprolactone glycol, etc. can also be used as the polyhydroxyl compound.

Urethane prepolymer compound (ii) used in the present invention
i-1-2) or (iii-1-3) is a polyhydroxy polyether polyol, a polyester polyol, a mixture thereof, or a mixture of these and an OH group-containing glyceride such as castor oil. It can be obtained by reacting a compound with the above-mentioned isocyanurate ring-containing polymer, or a mixture of the above-mentioned diisocyanate compound and isocyanurate ring-containing polymer. Alternatively, the urethane prepolymer containing only the diisocyanate compound and the isocyanurate ring-containing polymer described above can be produced separately and mixed together.

Urethane prepolymer compound (iii-1-2) or (
When obtaining iii-1-3), the molar ratio of the above-mentioned isocyanurate ring-containing polymer or the above-mentioned mixture of the diisocyanate compound and isocyanurate ring-containing polymer and the polyhydroxy compound is usually set to (isocyanurate ring-containing polymer compound or mixture of diisocyanate compound and isocyanurate ring-containing polymer)/polyhydroxy compound=1.
The ratio is 5 to 3.5/1, preferably 2.0 to 3.0/1.

Further, the NC0% of the prepolymer is usually 1 to 20%, preferably 2 to 15%.

Further, the preferred blending ratio of the isocyanurate ring-containing polymer and the diisocyanate compound or the urethane prepolymer compound of the diisocyanate compound is as follows: isocyanurate ring-containing polymer/diisocyanate compound or urethane prepolymer compound of the diisocyanate compound = 10 to 1
0010 to 90 (weight ratio).

Urethane prepolymer compound (iii-1-2) or (
ui-1-3) can be obtained by a conventional method.

When carrying out the urethane prepolymer production reaction, the reaction temperature is usually 40 to 110°C, preferably 50 to 100°C. When carrying out the urethane prepolymer production reaction, known urethane polymerization catalysts such as dibutyltin dilaurate, stannous octoate, stannous octoate, lead octylate, lead naphthenate, zinc octylate, etc. are used to accelerate the reaction. It is also possible to use organometallic compounds and tertiary amine compounds such as triethylenediamine and triethylamine.

In addition, blocking agents used in the blocked German cyanate compound (Mountain-1) include active methylene compounds, such as diester malonate (diethyl malonate, etc.), acetylacetone, acetoacetate (ethyl acetoacetate, etc.); oxime compounds, Examples include acetoxime, methyl ethyl ketoxime (MEK oxime), methyl isobutyl ketoxime (MIBK oxime), and the like. Among these, suitable blocking agents vary depending on the type of isocyanurate ring-containing polymer and the baking temperature when plastisol is applied, but generally those having a dissociation temperature for regenerating isocyanate groups are in the range of 100 to 160°C. . Particularly preferred blocking agents are oxime compounds (particularly ketooximes). Ketoximes are particularly advantageous because they easily react with isocyanates and the dissociation temperature of the block is relatively low compared to other ketoximes.

The blocking reaction for obtaining the blocked isocyanate compound (ill-1) contained in the tackifier of the present invention is carried out by a known reaction method. The amount of blocking agent added is usually 1 equivalent or more or more than 2 equivalents based on the free isocyanate group.
It is less than equivalent, preferably 1.05 to 1.5 equivalent.

Usually, the above-mentioned isocyanurate ring-containing polymer (iii-
1-1), urethane prepolymer compound (iii-1-
In the blocking reactions 2) and (iii-1-3), a blocking agent is added in the final reaction.

Also, urethane prepolymer compound (iii-1-2)
Alternatively, when (iii-1-3) is subjected to a blocking reaction, a blocking agent can be added at any stage and reacted to obtain a blocked urethane prepolymer.

The blocking agent can be added at the end of a predetermined polymerization, or at the beginning of the polymerization, or partially added at the beginning of the polymerization and the rest at the end of the polymerization. Preferably, it is added at the end of polymerization.

In this case, the isocyanate % (for example, measured by the method described in "Polyurethane", published by Maki Shoten, 1960, p. 21) may be used as a standard for the completion of the predetermined polymerization. The reaction temperature when adding a blocking agent is usually 50 to 150°C, preferably 60 to 150°C.
It is 20°C. The reaction time is about 1 to 7 hours. During the reaction, it is also possible to accelerate the reaction by adding the above-mentioned known catalyst for urethane polymerization. Further, any amount of the plasticizer of the present invention may be added.

Further, the blocked isocyanate compound (iii-1) is a blocked isocyanate compound of the above-mentioned isocyanurate ring-containing polymer, an isocyanurate ring-containing polymer, or a blocked urethane preform of a mixture of a diisocyanate compound and an isocyanurate ring-containing polymer. One or a mixture of two or more polymeric compounds may be used.

It is also possible to use a mixture of the above-mentioned blocked urethane prepolymer compound containing only a diisocyanate compound and the above-mentioned blocked urethane prepolymer compound containing an isocyanurate ring-containing polymer, which are produced separately.

Preferred polyamide amines used in the carboxyl group-containing butadiene-acrylonitrile copolymer-modified polyamide amine (iii-2) of the present invention are those obtained from a polyamine and a fatty acid, a dibasic acid, or a derivative thereof. .

Also included in the polyamide amines of the present invention are imidacillin ring-containing amidoamine compounds obtained by reacting polyamines capable of forming imidacillin rings under reaction conditions that form imidacillin rings.

Here, the polyamines used in the production of polyamide amines include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexazine, hexaethylenehebutamine, heptaethyleneoctamine, nonaethylenedecamine, di-1,2 -propane triamine, and other diamines such as aminoethylethanolamine and aminoethylpropanolamine can also be used within the scope of the present invention. In addition to the above, ethylenediamine, N-aminoethylpiperazine, etc. can be used.

Further, aromatic polyamines (phenylene diamine, tolylene diamine, xylylene diamine, etc.) and alicyclic polyamines (cyclohexylene diamine, isophorone diamine, etc.) can also be used. Furthermore, mixtures of two or more of these can also be used.

On the other hand, fatty acids or their derivatives include butyric acid, valeric acid,
Saturated fatty acids with carbon atoms of 4 or more, such as caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, hehenic acid, and their esters, tuccinic acid, lindelic acid, lauroleic acid, Zolic acid, fisetoleic acid, myristoleic acid, seamarinic acid, petroselic acid, oleic acid, elaidic acid, linoleic acid, linoleaidic acid, eleostearic acid, liluic acid, parinaric acid, arachidonic acid and their esters, acrylic acid, Methacrylic acid, maleic acid and their esters, tall oil fatty acids and their esters obtained from valve manufacturing waste liquid, drying oils, semi-drying oils, or dimer acids obtained by polymerization of these free fatty acids,
Examples include polymerized fatty acids such as trimer acids and esters thereof. Here, the above-mentioned drying oil or semi-drying oil includes:
Examples include soybean oil, linseed oil, tung oil, eno oil, cottonseed oil, sunflower oil, safflower oil, and dehydrated castor oil, which contain highly unsaturated fatty acids such as linoleic acid and lylunic acid.

Furthermore, polymers of acrylic acid and luic acid, adipic acid,
Saturated dibasic acids such as sebacic acid and azelaic acid, esters thereof, unsaturated linear dibasic acids, unsaturated branched dibasic acids,
These esters can also be used, with trade names such as D
AICID-550 (manufactured by Harima Kasei Kogyo ■, product name), 0
3K-DAUL-16 (manufactured by Okamura Oil Co., Ltd., product name), 0
5K-DAUB-20 (same) or the like can also be used.

When these polyamines and fatty acids, dibasic acids, or derivatives thereof are mixed in a known molar ratio using a known method to form an imidacillin ring, the molar ratio is 170 to 320 molar ratios under normal pressure.
°C1 Preferably 250 to 290 °C, and if the formation of imidacillin ring is not particularly intended, at normal pressure, 120 to 290 °C
The reaction may be carried out at 200°C, preferably 140 to 180°C, and any reaction can also be carried out at a lower reaction temperature by being under reduced pressure.

Furthermore, as fatty acids, dibasic acids and/or their derivatives, it is preferable to use polymerized fatty acids or dibasic acids alone, or a mixture of these with saturated fatty acids or unsaturated fatty acids. By appropriately adjusting the reaction time, a compound containing a desired amide bond can be obtained.

Furthermore, the carboxyl group-containing butadiene-acrylonitrile copolymer-modified polyamide amine (iii-2) of the present invention
A preferred carboxyl group-containing butadiene-acrylonitrile copolymer used in
) Hiker CTBNs (BF Goodr
ich), Nilapol DN-601 (manufactured by Nippon Zeon), which has a C0OH group at the end or within the molecule, Nilapol 1
072 (manufactured by Nippon Zeon) and the like, and a butadiene-acrylonitrile copolymer conjugated with maleic acids can also be used.

The average molecular weight of the carboxyl group-containing butadiene-acrylonitrile copolymer used in the present invention is 2.000 to 2.
0.000 is preferable, more preferably 3,000-8
,000, and the carboxyl group equivalent is preferably 1,0
00 to 7,000, more preferably 1,200 to 3,0
It is 00. The carboxyl group-containing butadiene-acrylonitrile copolymer with a molecular weight higher than the above range is solid and compatible with epoxidized fatty acid esters for modification, amines, plasticizers, and prollado isocyanate compounds.
It is not preferred because the solubility becomes low.

The weight ratio of the polyamide amines and the carboxyl group-containing butadiene-acrylonitrile copolymer of the carboxyl group-containing butadiene-acrylonitrile copolymer modified polyamide amine (iii-2) of the present invention is Polymer-5 to 97/95 to 3 (weight ratio) is preferred,
More preferably polyamide amines/carboxyl group-containing butadiene-acrylonitrile copolymer-20 to 95
/80 to 5 (weight ratio). If the content of the carboxyl group-containing butadiene-acrylonitrile copolymer is less than the above range, sufficient improvement in adhesion and water resistance will not be observed, and if the content is more than the above range, the viscosity will be too high and workability will be impaired. is bad and undesirable.

The method for producing a carboxyl group-containing butadiene-acrylonitrile copolymer-modified polyamide amine (iii-2) of the present invention includes the production of a carboxyl group-containing butadiene-acrylonitrile copolymer during the production of a polyamide amine from the aforementioned fatty acid, dibasic acid, or a derivative thereof and a polyamine. A method of simultaneously reacting copolymers, a method of reacting an adduct of a carboxyl group-containing butadiene-acrylonitrile copolymer and an epoxidized fatty acid ester with a polyamide amine as exemplified in JP-A-62-273224, and a method of reacting a polyamide amine with a carboxyl group-containing butadiene-acrylonitrile copolymer and an epoxidized fatty acid ester. The butadiene-acrylonitrile copolymer containing butadiene-acrylonitrile copolymer was reacted in advance with the polyamines used in the production of the above-mentioned polyamide amines (trade name: Hiker ATBNs (Go
(manufactured by odrich), etc., and a method of mixing with the above-mentioned polyamide amine.

In the adhesion promoter (iii) of the present invention, the blending ratio of the blocked isocyanate compound (iii-1) and the carboxyl group-containing butadiene-acrylonitrile copolymer-modified polyamide amine (iii-2) is such that the blocked isocyanate compound (stone- 1)/Carboxyl group-containing butadiene-acrylonitrile copolymer-modified polyamide amine (Mountain-2) -5 to 95/95 to 5 (weight ratio) is preferred.

The composition of the present invention includes the above (i), (ii), and (iii).
) In addition to the components, various additives such as fillers or stabilizers can also be included. Examples of fillers include inorganic fillers (calcium carbonate, talc, diatomaceous earth, kaolin, etc.) and organic fillers (cellulose powder, powdered rubber, recycled rubber, etc.). Stabilizers include metal soaps (calcium stearate, aluminum stearate, etc.), inorganic acid salts (dibasic phosphites, dibasic sulfates, etc.), and organic metal compounds (dibutyltin dilaurate, dibutyltin dilaurate, dibutyltin dilaurate, etc.). malate, etc.). Further, coloring agents such as pigments can also be optionally added.

Although the ratio of each component in the vinyl chloride plastisol composition of the present invention is not particularly limited, the following combination may be used, for example.

Normal range Preferred range (i) 10-50% by weight 20-40% by weight
(ii) 10-50% by weight 20-40% by weight (iii) 0.1-30% by weight 0.5-1
5% by weight Filler 0-70% by weight 10-60% by weight Stabilizer 0-3% by weight 0.1-2% by weight The vinyl chloride plastisol composition of the present invention can be produced by kneading in a conventional manner. .

In the composition of the present invention, if the adhesion promoter (mountain) is less than 0.1% by weight, no effect will be obtained, and if it exceeds 30% by weight, the plastisol will become hard after curing, which is not preferred.

The composition of the present invention can be applied to various metal surfaces and various undercoated surfaces of metals, but is also useful on cationic electrodeposition coated surfaces. As cationic electrodeposition coating, ordinary electrodeposition coating,
For example, there is a method in which an adduct of an epoxy resin and a primary or secondary amine is made water-soluble by neutralizing it with an acid, and the adduct is coated together with a blocked isocyanate on the metal surface of the cathode by applying a direct current.

The amount of the vinyl chloride plastisol composition of the present invention applied to the painted surface is usually 1000 to 5000 g/unit, and the film thickness is 0.3 to 2II11. After application, 110~
Cured by heating at 200°C12O for 40 minutes. The application method may be any conventional method, for example, a method in which the material is supplied from a pressure pump and then discharged and applied using a flow gun, airless spray, or the like.

〔Effect of the invention〕

As described above, the vinyl chloride plastisol composition of the present invention containing the above components (i), (ii), and (ji) has the following properties compared to conventional vinyl chloride plastisol/epoxy resin systems or vinyl chloride plastisol/acrylic resin systems: It has improved adhesion to metal surfaces, and also has improved adhesion and discoloration during high temperature heat treatment compared to vinyl chloride plastisol/epoxy resin/block German cyanurate system. Furthermore, compared to a system in which blocked isocyanate is used, storage stability and discoloration resistance during high-temperature heat treatment were significantly improved.

Therefore, as detailed above, the vinyl chloride plastisol composition of the present invention can be baked on various metal surfaces and various undercoated surfaces of metal (cationic electrodeposition painted surfaces, etc.) at a temperature of 110 to 200°C for 30 minutes or less. It adheres strongly under certain conditions, does not foam, and has excellent adhesion after immersion in hot water and heat treatment.
Furthermore, there is no coloring or fading even after high-temperature heat treatment, and the vinyl chloride plastisol composition has excellent storage stability, making it useful as a body sealer or undercoat paint for automobile bodies.

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

Production of Blocked Isocyanate Equivalent III-1 Production Example 1 100 parts by weight of L6-hexamethylene diisocyanate (HDI) was placed in a 500-capacity glass flow flask with a sliding lid equipped with a thermometer, stirrer, and nitrogen-sealed tube. 0.1 part by weight of potassium caprate was added as a nurate catalyst, the air in the flask was replaced with nitrogen, and the reaction was carried out at 40"C for 6 hours with stirring to obtain a pale yellow transparent liquid. This reaction solution was stopped. After adding 0.07 parts by weight of phosphoric acid as a reagent and stirring at 40°C for 1 hour, free HDI was removed using a molecular distillation device.The resulting liquid was a pale yellow transparent liquid and was NG.
O content 21.0%, free) IDI 0.7%, viscosity 25
00cps/25°C, IR spectrum 1680cm-
A strong absorption characteristic of the isocyanurate ring was observed in '.

Furthermore, 50 parts by weight of dioctyl phthalate (DOP) was mixed with 100 parts by weight of this IDI isocyanurate, and 50 parts by weight of methyl ethyl ketoxime (MEK oxime) (MEK oxime/NCO゛ equivalent ratio = 1.15) was gradually added as a blocking agent. In addition, the reaction was carried out at 60 DEG C. for 12 hours, and it was confirmed that the NCO absorption in the IR spectrum of 2260cn+-' had completely disappeared, yielding a blocked isocyanate compound (2) having a blocked isocyanate equivalent of 400.

Production Example 2 100 parts by weight of isophorone diisocyanate (IPDI) and 0.1 parts by weight of potassium caprate were charged, and Production Example 1 was prepared.
0.07 parts by weight of phosphoric acid was added as a terminator, and free IPDI was removed using a molecular distillation apparatus.
Isocyanurate of IPDI was obtained.

Furthermore, 100 parts by weight of isocyanurate of this IPDI
OP 50 parts by weight, MEK, txime 5o parts by weight (ME
K oxime/NGO equivalent ratio = 1.2) was added and reacted in the same manner as in Production Example 1, resulting in blocked isocyanate equivalent = 4.
50 blocked isocyanate compounds (2) were obtained.

Production Example 3 In a four-way flask equipped with a stirrer, a thermometer, and a nitrogen gas inlet tube, 500 parts by weight of Adecanyx F1212-5" 0.1 part by weight of dibutyltin dilaurate DOP
Prepare 121.4 parts by weight, 60
Reacted for 16 hours at C, then gradually added 190 parts by weight of MEK oxime, and reacted at 80 C for 13 hours to obtain a blocked isocyanate compound in which the NCO groups were completely blocked.
I got it.

Production Example 4 In a four-flow flask equipped with a stirrer, thermometer and nitrogen gas inlet tube, 500 parts by weight of Coronate HX D
OP 200 parts by weight Adeka New Ace F1212-5" 50 parts by weight dibutyltin dilaurate 0.1 parts by weight MEK oxime 220 parts by weight were charged and reacted in the same manner as in Production Example 3 to obtain Pro-Nucdoisocyanate compound (2).

Book: Production Example 5 of HDI-based isocyanurate compound manufactured by Nippon Polyurethane Industry ■ CR Hardener 〇-270''' 700
2300 parts by weight of Hiker ATBN 1300×16'' were mixed to obtain a butadiene-acrylonitrile copolymer-modified polyamide amine (A).

*1: Polymerized fatty acid polyamide amine manufactured by NCR ■, amine value -300 ■KoH/g *2: Goodr
Production example 6 of carboxyl group-containing butadiene-acrylonitrile copolymer-modified amidoamine manufactured by Ich Co., Ltd. In a four-flow flask equipped with a stirrer, a thermometer, and a nitrogen gas inlet tube, 500 parts by weight of dimer acid 500 parts by weight of tall oil fatty acid 503 parts by weight of triethylenetetramine Part hiker CTBN BO
Add 150 parts by weight of OX8” and 200 parts by weight.
``C Reacted with dehydration for 25 hours to achieve amine value of 320K
A butadiene-acrylonitrile copolymer-modified polyamide amine (B) of OH/g was obtained.

*: Production example 7 of carboxyl group-containing butadiene-acrylonitrile copolymer manufactured by Goodrich In a four-flow flask equipped with a stirrer, thermometer and nitrogen gas inlet tube, DN-601'' 300 parts by weight of epoxidized butyl ester of linseed oil fatty acid was added. Add 50 parts by weight of triethanolamine and 0.5 parts by weight, and heat at 150°C.
Addition reaction was carried out for 5 hours at 180°C, 21,750 parts by weight of polyamide amine ACR hardener H-280'' was added, and butanol was removed at 180°C for 3 hours, and then amidation reaction was carried out to obtain an amine value of 280 KOH/ A butadiene-acrylonitrile copolymer-modified polyamide amine (C) of g was obtained.

* Carboxyl group-containing butadiene-acrylonitrile copolymer manufactured by Nippon Zeon Aji *2: Polyamide amine manufactured by NCR ■ Amine value 3
20■KOH/g Examples 1 to 13 Polyvinyl chloride powder (a) (Zeon 121 manufactured by Nippon Zeon)
) 60 parts, polyvinyl chloride powder (b) (Nippon Zeon Zeon 103ZX) 20 parts, dioctyl phthalate (D
OP) 100 parts, calcium carbonate (a) (Shiroishi Calcium Shiroenka CC) 80 parts, calcium carbonate (b) (
Shiraishi Calcium Whiten SB) 20 parts, titanium oxide (Titan Kogyo KR-380) 3 parts, anti-aging agent 1
．． A vinyl chloride plastisol composition was prepared by adding the adhesion promoter (iii) as shown in Table 1 to 5 parts and 0.5 parts of the fluidity regulator, kneading, and vacuum defoaming. This composition was evaluated for adhesion and burning after gelation on a cationic electronic signboard.

The results are shown in the table below.

Comparative Examples 1 to 13 In the same vinyl chloride plastisol compositions as in Examples 1 to 13, instead of the adhesion promoter (iii), blocked isocyanate compounds (1) to (3) alone or butadiene were used as shown in Table 2. Acrylonitrile copolymer-modified polyamide amine (A) to (C) alone, or blocked isocyanate compound (■) not containing an isocyanurate ring-containing polymer and butadiene-acrylonitrile copolymer-modified polyamide amine (A), isocyanurate of TDI A blocked isocyanate compound of p-oxybenzoic azide 2-ethylhexyl ester of the compound alone, or this blocked isocyanate compound and butadiene-acrylonitrile copolymer-modified polyamide amine (B), ACR hardener H-270 alone, or blocked Isocyanate compound ■ and ACR hardener H-2
70 was tested.

The test results are shown in Table 2.

(Note) Book 1.40"c hot water x Adhesion after 7 days; 102
Adhesion after 3 days at °C and 140
°C x 20 minutes 4, adhesive strength evaluation method; nail peeling 5, burning evaluation method (140 °C x 20 minutes) 6, 40
'C Storage stability (after 3 days) (thickening...X Examples 1-1
3, as in Comparative Examples 1 to 13, the adhesion promoter (ji)
If any one of (iii-1) blocked isocyanate compound and (iii-2) butadiene-acrylonitrile copolymer-modified polyamide amine is missing, it will be inferior in terms of adhesion and burning. Further, when the isocyanurate ring-containing polymer is not included as in Comparative Example 9, the adhesiveness is poor. Furthermore, when a blocked isocyanate compound of the TDI isocyanurate compound is used as in Comparative Example 10.11, storage stability is poor. or,
When polyamide amine is used as in Comparative Example 12.13, it is inferior in terms of burn resistance, hot water adhesiveness, and storage stability at 40°C, and the vinyl chloride plastisol composition of the present invention has poor adhesive strength and burn resistance. Significant improvements in discoloration and storage stability at 40°C were observed.

Example 14 A vinyl chloride plastisol composition according to the present invention having the composition shown in Table 3 was tested for use as a body sealer and undercoat for automobile bodies. The results are shown in Table-3.

The method for producing vinyl chloride plastisol was as in Example 1.

Comparative Example 14 A similar test was conducted using the same formulation of vinyl chloride plastisol as in Example 14 except that ACR hardener H-270 was added instead of the adhesion promoter (mountain). The results are shown in Table-3.

Table 3 (Note) $1; Ba-Zn stabilizer manufactured by Adeka Argus *2; 0.5 m of vinyl chloride plastisol on two electrodeposited plates
Measurements were made after applying the coating to a thickness of m and baking it at 130°C for 20 minutes.

It has been found that the vinyl chloride plastisol composition of the present invention has excellent adhesion to cationic electronic signs.

Applicant's agent Kaoru Furutani (3 other people)

Claims (1)

[Claims] 1. (i) vinyl chloride polymer and/or copolymer, (i
i) as a plasticizer and (iii) as an adhesion promoter, an isocyanurate ring-containing polymer (iii-1-1) obtained by polymerizing an aliphatic and/or alicyclic diisocyanate is blocked with a blocking agent. The obtained blocked isocyanate compound (
iii-1) and carboxyl group-containing butadiene-acrylonitrile copolymer-modified polyamide amine (iii-1)
2) A vinyl chloride plastisol composition comprising: 2, (i) vinyl chloride polymer and/or copolymer, (i
i) a plasticizer and (iii) an isocyanurate ring-containing polymer obtained by polymerizing an aliphatic and/or alicyclic diisocyanate as an adhesion promoter (iii-1-1), and the isocyanurate ring-containing polymer A blocked isocyanate compound (iii-1) obtained by blocking a urethane prepolymer compound (iii-1-2) obtained by reacting compound (iii-1-1) with a polyhydroxy compound with a blocking agent.
) and a carboxyl group-containing butadiene-acrylonitrile copolymer-modified polyamide amine (iii-2). 3, (i) vinyl chloride polymer and/or copolymer, (i
i) A plasticizer and (iii) an isocyanurate ring-containing polymer obtained by polymerizing an aliphatic and/or alicyclic diisocyanate as an adhesion promoter (iii-1-1), the isocyanurate ring-containing polymer Urethane prepolymer compound obtained by reacting (iii-1-1) with a polyhydroxy compound (
iii-1-2), and a blocked isocyanate compound (i) obtained by blocking a urethane prepolymer compound (iii-1-3) obtained by reacting a polyhydroxy compound and a polyisocyanate with a blocking agent.
ii-1) and carboxyl group-containing butadiene-acrylonitrile copolymer-modified polyamide amine (iii-2)
) A vinyl chloride plastisol composition comprising: