JP3328442B2 - Primer composition and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a primer composition and a method for producing the same, and more particularly to a primer composition having excellent adhesion to a material such as polypropylene and the like, free from stringing and sagging, excellent in workability, and a paint component and a primer component. The present invention relates to a primer composition and a method for producing the same, which are suitable as such.

[0002]

2. Description of the Related Art A surface of a molded product of a polyolefin such as polypropylene is coated to increase its added value. However, polyolefins generally have poor polarity, poor adhesion of paints, and are difficult to paint.
Further, the adhesion of the obtained coating film is poor. Therefore, conventionally, the surface of a molded article has been treated with a primer in advance to improve the adhesion of paint and the adhesion of a coating film. By the way, it has been known that modified polyolefins are useful as components of paints and primers. For example, the present inventors use a propylene / ethylene copolymer modified by graft copolymerization of maleic anhydride as a primer to obtain a primer coating exhibiting good adhesion to both a material to be coated and a coating material. And proposed earlier (Japanese Patent Publication No. 59-42).
No. 693, Japanese Patent Publication No. Sho 62-21027). Similarly, modified chlorinated polypropylene has been proposed (Japanese Patent Publication No. 03-62170, Japanese Patent Application Laid-Open No. 02-911).
No. 67, Japanese Unexamined Patent Application Publication No. 03-52983, Japanese Unexamined Patent Application Publication No.
3-229772, etc.). It has been found that the above-mentioned modified product has good coating performance as a coating component or a primer component.

[0003]

However, in order for the paint component or the primer to be put to practical use, the coating film obtained has good coating performance,
Excellent paint workability is required. In this respect, the conventional primer or the above-mentioned modified product sometimes fails to exhibit good coating workability due to stringing at the time of coating or sagging of the coated surface. For example, a paint component or primer composed of a modified product having a high molecular weight may cause stringing at the time of coating. On the other hand, a coating component or a primer composed of a modified product having a low molecular weight has a reduced solution viscosity and sags on a coated surface. In addition, when the solid content concentration is increased by lowering the molecular weight, the solution viscosity increases and sagging can be prevented, but there is a problem that stringing occurs.

[0004] Therefore, a first object of the present invention is to provide a coating film obtained by coating a material with good coating performance,
An object of the present invention is to provide a primer composition which has an appropriate solution viscosity, is excellent in coating workability since stringing and sagging do not occur during coating work, and is suitable as a paint component, a primer and the like.

A second object of the present invention is to provide a primer composition having the above-mentioned excellent properties by applying various properties such as adhesion in response to coating conditions such as high-pressure spraying or other coating methods. It is an object of the present invention to provide a method that can be manufactured without reducing.

[0006]

In order to achieve the first object, the present invention provides (A) at least one kind selected from unsaturated carboxylic acids and their anhydrides, which are graft copolymerized with polyolefin. Chlorination containing 0.1 to 10% by weight of a graft copolymerized unit consisting of the following, wherein at least a part of the carboxyl group of the grafted copolymerized unit is bonded to an epoxy compound and the chlorine content is 5 to 35% by weight: An object of the present invention is to provide a primer composition comprising a modified polyolefin resin and (B) an organic solvent.

In order to attain the second object, the present invention provides a method for producing the primer composition, wherein a polyolefin is graft-copolymerized with at least one selected from unsaturated carboxylic acids and anhydrides thereof. And a method for producing a primer composition comprising a step of reacting a chlorinated modified polyolefin obtained by chlorination with an epoxy compound in the presence of an organic solvent and a catalyst.

Hereinafter, the primer composition of the present invention (hereinafter, referred to as the primer composition)
The “composition of the present invention” and a method for producing the same (hereinafter, referred to as “the method of the present invention”) will be described in detail.

The composition of the present invention has a graft copolymer unit composed of at least one selected from unsaturated carboxylic acids and anhydrides thereof, and at least a part of the carboxyl groups of the graft copolymer unit is an epoxy compound. And chlorinated modified polyolefin resin (A). The polyolefin, which is the main component of the chlorinated modified polyolefin resin (A),
It is a homopolymer or a copolymer of one or more α-olefins. As the α-olefin, for example,
Ethylene, 1-butene, 1-pentene, 4-methyl-1
-Pentene, 3-methyl-1-pentene, 1-hexene, 2-methyl-1-pentene, 1-heptene and the like. In particular, when the composition of the present invention is used as a paint or primer for coating a material to be coated made of polypropylene, 60 to 100 mol% of propylene and 40 to 40% of α-olefin other than propylene are used.
A copolymer consisting of 0 mol% is preferred. Examples of the α-olefin other than propylene include ethylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 3-
Examples thereof include methyl-1-pentene and 1-hexene, and ethylene and 1-butene are particularly preferable.

The graft monomer constituting the graft copolymerized unit of the chlorinated modified polyolefin resin (A) is at least one selected from unsaturated carboxylic acids and anhydrides thereof. Examples of the unsaturated carboxylic acid and its anhydride as the graft monomer include maleic acid,
Unsaturated dicarboxylic acids such as itaconic acid, citraconic acid, allylsuccinic acid, glutaconic acid, nadic acid, methylnadic acid, tetrahydrophthalic acid and methylhexahydrophthalic acid, and anhydrides thereof. One of these graft monomers may be used alone or a combination of two or more thereof may be simultaneously graft-copolymerized with the polyolefin. Among these unsaturated carboxylic acids and anhydrides thereof, acid anhydrides are preferable, and maleic anhydride and nadic anhydride are particularly preferable.

[0011] The content of the graft monomer in the chlorinated modified polyolefin (A) is set at 0.1 from the viewpoint that a primer composition capable of forming a coating film having excellent paint adhesion and water resistance can be obtained. It is 1 to 10% by weight, preferably 0.2 to 7% by weight, more preferably 0.3 to 5% by weight.

Further, a chlorinated modified polyolefin (A)
Is a compound in which a part of the carboxyl group of the graft copolymerized unit is bonded to an epoxy compound. This epoxy compound is used in an amount of 0.1 to 3 relative to a part of the carboxyl group of the graft copolymerized unit, usually the carboxy group.
Those which are combined in a double equivalent ratio are preferred. As the epoxy compound, those having an epoxy equivalent in the range of 50 to 2500, preferably 100 to 1000 (weight per equivalent of epoxy) are used. The molecular weight is
Usually 150 to 5000, preferably 200 to 3000
belongs to. Specific examples of the epoxy compound include sorbitol polyglycidyl ether, sorbitan polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, triglycidyl-tris (2-hydroxyethyl) isocyanurate, and glycerol. Polyglycidyl ether, trimethylolpropane polyglycidyl ether, resorcinol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, ethylene, polyethylene glycol diglycidyl ether, propylene, polypropylene glycol diglycidyl ether, poly Tetramethylene glycol diglycidyl ether, allyl glycol Jill ether, 2
-Ethylhexyl glycidyl ether, phenyl glycidyl ether, phenol (ethylene oxide) glycidyl ether, pt-butylphenyl glycidyl ether, lauryl alcohol (ethylene oxide) glycidyl ether, diglycidyl adipic ester,
O-phthalic acid glycidyl ester, hydroquinone diglycidyl ether, bisphenol A diglycidyl ether, bisphenol S diglycidyl ether, terephthalic acid diglycidyl ester, glycidyl phthalimide, dibromophenyl glycidyl ether, dibromoneopentyl glycol diglycidyl ether, and the like. it can. These may be used alone or in combination of two or more kinds in the chlorinated modified polyolefin (A). Among them, bisphenol A diglycidyl ether, t-butylphenyl glycidyl ether and 2-ethylhexyl glycidyl ether are particularly preferred.

Further, the chlorinated modified polyolefin resin (A) has good compatibility with the organic solvent (B), so that no insoluble matter remains, and the chlorinated modified polyolefin resin (A) is applied to a material to be coated, and has excellent coating appearance, and In terms of obtaining a primer composition that forms a coating film having high cohesion, the chlorine content is 5 to 35% by weight.
And 15 to 30% by weight.

Further, the composition of the present invention comprises an organic solvent (B)
Is included. Examples of the organic solvent (B) include aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as hexane, heptane, octane, and decane; and alicyclic hydrocarbons such as cyclohexane, cyclohexene, and methylcyclohexane. Hydrogen, ethanol, aliphatic alcohols such as isopropyl alcohol, acetone,
Examples thereof include ketone solvents such as methyl isobutyl ketone and methyl ethyl ketone, and halogenated hydrocarbons such as trichloroethylene, dichloroethylene and chlorobenzene. These may be used alone or in a mixture of two or more. Among these, aromatic hydrocarbons are preferred,
In particular, an alkyl group-substituted aromatic hydrocarbon is preferable.

The content of the chlorinated modified polyolefin resin (A) and the organic solvent in the composition of the present invention is not particularly limited, but is usually 5 to 50 parts by weight of the organic solvent based on the chlorinated modified polyolefin resin (A). (B) 95-5
The proportion is 0 parts by weight, and preferably the proportion is 93 to 55 parts by weight of the organic solvent (B) based on 7 to 45 parts by weight of the chlorinated modified polyolefin resin (A).

Further, the composition of the present invention may contain, if necessary, various stabilizers such as antioxidants, weather stabilizers and heat resistance inhibitors, coloring agents such as inorganic pigments and organic pigments, and conductive materials such as carbon black and ferrite. A component such as an imparting agent may be contained.

Examples of the pigment used include cadmium pigments such as titanium oxide, zinc white, lead white, lead red, cuprous oxide, red iron oxide, iron black, cadmium yellow, etc., molybdenum red, silver vermilion, and the like. Examples include graphite, zinc chromate, chromium oxide, navy blue, carbon black, precipitated barium sulfate, barite powder, ordinary light calcium carbonate, ultrafine calcium carbonate, alumina white, and white carbon. These may be used alone or in combination of two or more.

The production of the composition of the present invention comprises the steps of: (a) graft-copolymerizing a polyolefin with at least one selected from unsaturated carboxylic acids and anhydrides thereof and chlorinating the polyolefin with an organic compound; A method comprising a step of reacting with an epoxy compound in the presence of a solvent and a catalyst, or (b) a modified polyolefin obtained by graft copolymerizing a graft monomer with a polyolefin in the presence of an organic solvent and a catalyst. After the reaction, the method can be carried out according to a method including a step of chlorination. In these methods, when an epoxy compound with low reactivity or a catalyst with low activity is used, the chlorination is completed because there is no generation of hydrochloric acid or the like during the reaction and the production equipment is not damaged. Is preferred.

In the method (a), the chlorinated modified polyolefin is produced by graft copolymerizing (a) -1 polyolefin with at least one selected from unsaturated carboxylic acids and anhydrides thereof. Chlorination Step (a) -2 After chlorinating the polyolefin, it may be carried out according to any of the steps of graft copolymerizing at least one selected from unsaturated carboxylic acids and anhydrides thereof. In particular, the chlorination is preferably performed according to the step (a) -1 performed after the graft copolymerization.

(A) [(a) -1 and (a) -2
Or the method of (b), wherein the polyolefin or a chlorinated polyolefin obtained by chlorinating the polyolefin is graft-copolymerized with at least one graft monomer selected from unsaturated carboxylic acids and anhydrides thereof. There is no particular limitation, and various known methods can be used. For example, a method of dissolving a polyolefin or a chlorinated polyolefin in an organic solvent, adding the graft monomer and the radical polymerization initiator, and heating and stirring to graft copolymerize: melting the polyolefin or the chlorinated polyolefin by heating. Then, the graft monomer and the radical polymerization initiator are added to the obtained melt, and the mixture is stirred to carry out graft copolymerization: or a method in which each component is supplied to an extruder to carry out graft copolymerization: polyolefin or chlorination. After the polyolefin powder is impregnated with a solution in which the graft monomer and the radical polymerization initiator are dissolved in an organic solvent, the copolymer is heated to a temperature at which the powder does not dissolve, and graft copolymerization is performed.

The radical polymerization initiator used in the graft copolymerization is not particularly limited as long as it promotes the graft copolymerization reaction between the polyolefin and the graft monomer. For example, an organic peroxide, an organic perester, and an azo compound are mentioned, and an organic peroxide and an organic perester are particularly preferable.

Specific examples of the organic peroxide or organic perester include benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, and di-peroxide.
tert-butyl peroxide, 2,5-dimethyl-
2,5-di (peroxybenzoate) hexyne-3,
1,4-bis (tert-butylperoxyisopropyl) benzene, lauroyl peroxide, tert-butylperacetate, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3,2.5
-Dimethyl-2,5-di (tert-butyl peroxide) hexane, tert-butylbenzoate, ter
t-butyl perphenyl acetate, tert-butyl perisobutyrate, tert-butyl per-sec-
Octoate, tert-butyl perpivalate, cumyl perpivalate, tert-butyl perdiethyl acetate and the like can be mentioned. Further, specific examples of the azo compound include azobis-isobutylnitrile, dimethylazoisobutylnitrile and the like. Among these,
Dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3,2,5-dimethyl-
2,5-di (tert-butylperoxy) hexane,
Dialkyl peroxides such as 1,4-bis (tert-butylperoxyisopropyl) benzene are preferred.

In the graft copolymerization, the ratio of the radical polymerization initiator / graft monomer used is usually 1/100 to 3/5, preferably 1/20 to 1/2, in molar ratio.
Range.

In the present invention, (a) [(a) -1, (a)-
2] In the method of (b), the step of chlorinating the polyolefin or chlorinating the modified polyolefin obtained by graft-copolymerizing a graft monomer with the polyolefin is carried out by using the polyolefin or the modified polyolefin obtained as described above. The reaction can be performed in a state where the polyolefin is dissolved in a suitable solvent or in a state where the polyolefin is dispersed.

Examples of the solvent used for the chlorination include aliphatic hydrocarbons such as hexane, heptane, octane, decane, dodecane and tetradodecane, and lipids such as methylcyclopentane, cyclohexane, methylcyclohexane, cyclooctane and cyclododecane. Acyclic hydrocarbons, benzene, toluene, xylene, ethylbenzene, cumene, ethyltoluene, aromatic hydrocarbons such as trimethylbenzene, diisopropylbenzene, chlorobenzene, bromobenzene, o-dichlorobenzene, carbon tetrachloride, carbon tetrabromide, chloroform , Bromoform, trichloroethane, trichloroethylene, tetrachloroethane, halogenated hydrocarbons such as tetrachloroethylene, and water are preferred.

The chlorination reaction can be carried out by introducing chlorine gas into a solvent in which a polyolefin or a modified polyolefin is dissolved or dispersed until a predetermined chlorine content is reached. In carrying out this chlorination reaction, it is possible to irradiate ultraviolet light or visible light or to use a radical generator for the purpose of efficiently proceeding the reaction. The temperature of the chlorination reaction is usually 50 to 120 ° C., and the reaction time is generally in the range of about 0.5 to 5 hours.

The intrinsic viscosity [η] of the modified polyolefin after chlorination is preferably from 0.15 to 0.85 dl / g, particularly preferably from 0.20 to 0.75 dl / g.

Further, according to the present invention, (a) [(a) -1,
In the method (a) -2] or (b), a step of reacting the chlorinated modified polyolefin or the modified polyolefin with an epoxy compound to bond the carboxyl group of the graft copolymerized unit with the epoxy group of the epoxy compound. Can be performed in the presence of an organic solvent and a catalyst.

Examples of the catalyst used include amines such as pyridine, isoquinoline, quinoline, N, N-dimethylcyclohexylamine, triethylamine and benzyldimethylamine and salts thereof, stannous chloride (hydrated),
Tin (hydration), tin acetate, 2-ethyl hexane tin, tin octylate, tin compounds such as dimethyl diethyl tin and the like can be mentioned. In particular, it is preferable to use a tin-based catalyst because the reaction can be performed without discoloration of the solution.

The proportion of the catalyst used is usually 1/20 to 1/2 by weight relative to the epoxy compound to be reacted.

The organic solvent used is usually preferably carried out in the above-mentioned solvent. Reaction temperature is 50 to 150
C. is preferred.

The reaction mixture containing the chlorinated modified polyolefin resin (A) thus obtained and the organic solvent (B) used in each reaction may be used as it is as the composition of the present invention or as necessary. The composition of the present invention can be used by adjusting the concentration of the organic solvent (B) or the chlorinated modified polyolefin resin (A). Organic solvent (B) or chlorinated modified polyolefin resin (A)
Can be adjusted according to a method of adding or removing the organic solvent (B) or a method of adding or removing the chlorinated modified polyolefin resin (A). In addition, it goes without saying that the solvent used in the reaction may be appropriately replaced with another organic solvent (B).

The composition of the present invention is effective for improving the adhesion of a coating material by being applied to the surface of a molded article made of an olefin-based polymer or copolymer, or another polymer.

The composition of the present invention includes, for example, polyolefins such as high-pressure polyethylene, medium-low-pressure polyethylene, polypropylene, poly-4-methyl-pentene and polystyrene, ethylene-propylene copolymer, ethylene-butene copolymer, It can be suitably used for molded articles made of an olefin copolymer such as a propylene / butene copolymer.

Further, the composition of the present invention can be used, in addition to the above-mentioned polyolefins and olefin-based copolymers, to molded articles composed of polypropylene and synthetic rubber, polyamide resins, unsaturated polyester resins, polybutylene terephthalate resins, polycarbonate resins and the like. Molded products such as automobile bumpers, and also surface treatments of steel plates and electrodeposited steel plates. In addition, undercoating is applied to the surface coated with a paint, primer, adhesive, etc. mainly composed of polyurethane resin, fatty acid-modified polyester resin, oil-free polyester resin, melamine resin, epoxy resin, etc. Can be used to form a coating film having excellent sharpness, low-temperature impact resistance and the like.

In particular, the composition of the present invention can be used for molded articles made of polyolefin such as polypropylene, molded articles such as automobile bumpers made of polypropylene and synthetic rubber, SMC molded articles using unsaturated polyester resin, epoxy resin, etc. Resin R-RIM molded product, glass fiber reinforced polyamide resin molded product, polyurethane resin molded product,
It is suitable for undercoating a cationic electrodeposition coated steel sheet or the like to improve the adhesion of paint to the surface of these molded articles.

The molded article to which the composition of the present invention is applied is prepared by mixing the above-mentioned various polymers or resins with any of the known molding methods such as injection molding, compression molding, hollow molding, extrusion molding and rotational molding. It may be formed by a method.

The composition of the present invention is particularly applicable to a molded article to which the composition is applied, even when the composition contains an inorganic filler such as talc, zinc white, glass fiber, titanium white, magnesium sulfate or the like, a pigment or the like. Form a primer coating with good film adhesion.

The molded article may also contain various stabilizers, ultraviolet absorbers, hydrochloric acid absorbers and the like in addition to the above. Examples of preferably used stabilizers include, for example, 2,
6-di-t-butyl-4-methylphenol, tetrakis [methylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate)] methane, metaoctadecyl-3
-(4'-hydroxy-3,5-di-t-butylphenyl) propionate, 2,2'-methylenebis (4-methyl-6-t-butylphenol), 4,4'-butylidenebis (3-methyl-6 -T-butylphenol),
4,4'-thiobis (3-methyl-6-t-butylphenol), 2,2-thiobis (4-methyl-6-t-butylphenol), 1,3,5-trimethyl-2,4
Phenolic stabilizers such as 6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene and 1,3,5-tris (2-methyl-4-hydroxy-5-t-butylphenol) butane , Dilauryl thiodipropionate, distearyl thiodipropionate and the like, and phosphorus-based stabilizers such as tridecyl phosphite and trinonyl phenyli phosphite.

Examples of preferably used ultraviolet absorbers include 2-hydroxy-4-octoxybenzophenone, 2-ethylhexyl-2-cyano-3,3-diphenyl acrylate, and paraoctylphenyl salicylate. it can. As the hydrochloric acid absorbent, for example, calcium stearate is preferably used.

As a method for applying the composition of the present invention to the surface of a molded article, spray coating is suitable. For example, the composition is sprayed on the surface of the molded article by a spray gun. The coating on the molded article may be performed at room temperature. After the coating, the coating is dried by an appropriate method such as natural drying or forced heating drying to form a coating film.

As described above, after the composition of the present invention is applied to the surface of a molded article and dried, a paint is applied to the surface of the molded article by a method such as electrostatic coating, spray coating, or brush coating. can do. After applying the paint,
It may be performed by a method of overcoating. The paint used is not particularly limited, but the primer composition of the present invention is
When using solvent-type thermoplastic acrylic resin paint, solvent-type thermosetting acrylic resin paint, acrylic-modified alkyd resin paint, epoxy resin paint, polyurethane resin paint, melamine resin paint, etc. This is preferable because a primer film having high adhesiveness can be formed. After applying the paint, the coating film is cured according to an ordinary method of heating with a nichrome wire, infrared ray, high frequency or the like, and a molded article having a desired coating film on the surface can be obtained. The method for curing the coating film can be appropriately selected depending on the material and shape of the molded product, the properties of the paint used, and the like.

The composition of the present invention can be applied to a wide range of uses other than the above-mentioned use as a primer of molded articles by utilizing its features. It is needless to say that the present invention can be applied to such uses.

[0044]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. In the following Examples and Comparative Examples, the physical properties of the coating film were tested as follows.

Cross-cut test A test piece having a cross-cut was prepared in accordance with the cross-cut test described in JIS K 5400, and a cellotape (Nichiban Co., Ltd. product) was stuck on the cross-cut. The cellophane tape was quickly pulled in the 90 ° direction to be peeled off, and the evaluation was made based on the number of grids that were not peeled out of 100 grids.

Peeling strength A coating film was prepared on a substrate, and a cut was made to a width of 1 cm using a cutter blade until the blade reached the substrate, and the end of the coating film was peeled off. Was pulled in the 180 ° direction at a speed of 50 mm / min to determine the peel strength.

The test piece was immersed in water at 40 ° C. for 240 hours, and then subjected to a grid test and a peel test.

Solution viscosity According to JIS K5400, Ford Cup No.
4 was used to measure the number of seconds dropped at 25 ° C.

Stringiness Using a coating gun (Iwata Weider-W-88-13HG5), spraying the gun with an atomizing pressure of 5 kg / cm ² and a single nozzle opening, the sample solution was placed in a coating bus at a temperature of 30 ° C. Is sprayed, and it is observed whether or not spider-like stringing occurs. If there is at least one stringing, it is determined that stringing is present.

Sagging property A dry polypropylene film with a dry film thickness of 5 μm
The sample solution is sprayed so as to reach m, and it is visually observed whether or not the sample solution sags before it dries.

(Example 1) <Maleic anhydride graft copolymerization of polypropylene> [η] containing 4.3 mol% of ethylene: 3 kg of 0.8 dl / g polypropylene, 30 g of maleic anhydride and 2,
After 3-g of 5-dimethyl-2,5-di (t-butylperoxy) hexyne-3 was previously mixed with a Hensiel mixer, the mixture was supplied to a twin-screw extruder (PCM-45, manufactured by Ikegai Iron Works, Ltd.). The mixture was melt-kneaded at a temperature of 230 ° C. and a rotation speed of 260 rpm to cause a reaction, and the obtained maleic anhydride-modified polypropisan was granulated into pellets. When the grafted amount of maleic anhydride in the obtained maleic anhydride graft-modified polypropylene was measured, it was 0.6% by weight.

<Chlorination of Maleic Anhydride Graft-Modified Polypropylene> The maleic anhydride graft-modified polypropylene obtained above was completely dissolved in a chlorobenzene solvent at 110 ° C., and the temperature was maintained and light was completely blocked. Then, chlorination was performed by introducing chlorine gas. The reaction time was about 2 hours. A large excess of methanol was added to the obtained reaction mixture to precipitate a reaction product, which was separated by filtration, washed repeatedly with methanol, and dried under reduced pressure to obtain a chlorinated modified polypropylene. The chlorine content of this chlorinated modified polypropylene is 22% by weight, and [η] is 0.44 d.
1 / g.

This chlorinated modified polypropylene was dissolved in toluene to prepare a 23% by weight toluene solution. Ford Cup No. According to No. 4, the solution viscosity of this solution was measured to be 30 seconds.

<Reaction with epoxy compound> 400 g of the above toluene solution, 4.76 g of bisphenol A diglycidyl ether and 0.4 g of tin 2-ethylhexanoate were added to
The mixture was heated and mixed at 80 ° C. for 8 hours to obtain a primer composition. The content of the maleic anhydride graft copolymerized unit of the chlorinated modified polypropylene in the obtained primer composition was 0.5% by weight, and the chlorine content was 22% by weight. The solution viscosity of this primer composition is 2
It was 53 seconds at 3%. The hue was 2 in Gardner No.

Further, 100 g of the obtained primer composition
In addition, 180 g of xylene and 20 g of methyl ethyl ketone
Was added to prepare a spray liquid. The obtained spray liquid is spray-coated on a polypropylene (Mitsui Petrochemical Industries, Ltd., X84S) square plate whose surface has been wiped with isopropyl alcohol, and then top-coated paint (white) (Planit, Dainippon Paint Co., Ltd.) # 800) was applied to a dry film thickness of 40 μm to form a coating film. After leaving at room temperature for 10 minutes, it was placed in a 100 ° C. air oven and baked for 30 minutes. Painting workability at this time (stringing, sagging),
In addition, a grid test at the initial stage of the coating film and after the water resistance test, and a peel strength were evaluated or measured, and the results are shown in Table 1.

Example 2 400 g of the chlorinated modified polypropylene obtained in Example 1, 5.20 g of t-butylphenylglycidyl ether and 0.4 g of 2-ethylhexanetin were heated and mixed at 80 ° C. for 8 hours. A primer composition was manufactured. The content of the maleic anhydride graft copolymerized unit of the chlorinated modified polypropylene in the obtained primer composition was 2.3% by weight, and the chlorine content was 22% by weight. The solution viscosity of this primer composition was 40 seconds at a solid content concentration of 23%, and the Gardner No. was 2.

A coating test of the obtained primer composition was carried out in the same manner as in Example 1, and coating workability (stringing and sagging properties), a cross-cut test at the initial stage of the coating film and after a water resistance test, and Table 1 shows the measurement results of the peel strength.

Example 3 The procedure of Example 1 was repeated except that the amounts of maleic anhydride and 5-dimethyl-2,5-di (t-butylperoxy) hexyne-3 were changed to 120 g and 12 g, respectively. A modified polypropylene was obtained. The graft amount of the resulting modified polypropylene was 2.9.
% By weight. When the obtained modified polypropylene was chlorinated in the same manner as in Example 1, [η] of the obtained chlorinated modified polypropylene was 0.32 dl / g.

When the above chlorinated modified polypropylene was dissolved in toluene to prepare a toluene solution having a concentration of 23% by weight, the solution viscosity of the obtained toluene solution was 15 seconds.

Next, the above toluene solution was reacted with an epoxy compound in the same manner as in Example 1 to obtain a primer composition. The solution viscosity of the obtained primer composition was 35.
Seconds. The hue was 2 in Gardner No.

A coating test of the obtained primer composition was carried out in the same manner as in Example 1, and coating workability (stringing and sagging properties), a cross-cut test at the initial stage of the coating film and after a water resistance test, and Table 1 shows the measurement results of the peel strength.

(Example 4) A catalyst used for reacting t-butylphenylglycidyl ether with chlorinated modified polypropylene was an amine-based catalyst (U-CAT-SA- manufactured by San Apro Co.) 102)
A primer composition was obtained in the same manner as in Example 2, except that the primer composition was changed to The solution viscosity of the obtained primer composition solution was 23 seconds. The hue was 5 in Gardner No.

A coating test of the obtained primer composition was carried out in the same manner as in Example 1, and the coating workability (stringing and sagging), the cross-cut test of the coating film at the initial stage and after the water resistance test, and Table 1 shows the measurement results of the peel strength.

Comparative Example 1 Instead of the polypropylene used in Example 1, an ethylene content of 3.6 mol% was used.
[Η] A maleic anhydride graft-modified propylene / ethylene copolymer was obtained in the same manner as in Example 1 except that 1.5 dl / g of a propylene / ethylene copolymer was used. The resulting maleic anhydride graft-modified propylene
The graft amount of the ethylene copolymer was 0.55% by weight. This maleic anhydride graft-modified propylene / ethylene copolymer was chlorinated in the same manner as in Example 1. The obtained chlorinated modified propylene / ethylene copolymer had a maleic anhydride graft copolymerized unit content of 0.4% by weight, a chlorine content of 22% by weight, and [η] of 1.1 d.
1 / g and the solution viscosity was 120 seconds.

Example 1 was carried out using the obtained toluene solution.
A coating test was performed in the same manner as described above. Table 1 shows the results.

(Comparative Example 2) A coating test similar to that of Example 1 was conducted using the chlorinated modified polypropylene obtained in Example 1 as a sample without reacting with the epoxy compound.
Table 1 shows the results.

[0067]

[0068]

According to the primer composition of the present invention, a coating film obtained by coating a material has good coating film performance, has an appropriate solution viscosity, and does not cause stringing or sagging during coating work. Therefore, the coating workability is excellent. Therefore, the primer composition of the present invention is suitable as a paint component or a primer.

Further, according to the method of the present invention, the primer composition having the above-mentioned excellent properties can be reduced in various properties such as adhesion in accordance with coating conditions such as high-pressure spraying or other coating methods. It can be manufactured without making it work.

──────────────────────────────────────────────────続 き Continuing on the front page (51) Int.Cl. ⁷ Identification symbol FI C09D 151/06 C09D 151/06 (72) Inventor Takuta Tachida 1-2-1, Waki, Waki-machi, Kuga-gun, Yamaguchi Prefecture Mitsui Oil JP-A-2-91167 (JP, A) JP-A-5-222320 (JP, A) JP-A-60-99138 (JP, A) JP-A-3-229772 ( JP, A) JP-A-4-89832 (JP, A) JP-A-1-256556 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 255/02 C08F 8/00 -8/50

Claims (7)

(57) [Claims] (1) a graft copolymer unit comprising at least one kind selected from unsaturated carboxylic acids and anhydrides thereof, which is graft copolymerized with (A) a polyolefin;
A chlorinated modified polyolefin resin containing 10% by weight, at least a part of the carboxyl group of the graft copolymerized unit is bonded to an epoxy compound, and has a chlorine content of 5 to 35% by weight; A primer composition comprising: 2. The primer composition according to claim 1, comprising (A) 5 to 50 parts by weight of the chlorinated modified polyolefin resin and (B) 95 to 50 parts by weight of a periodic solvent. 3. The method according to claim 1, wherein the polyolefin is propylene 60 to 60.
The primer composition according to claim 1, comprising 100 mol% and 40 to 0 mol% of another α-olefin. 4. A chlorinated modified polyolefin obtained by graft-copolymerizing a polyolefin with at least one selected from unsaturated carboxylic acids and anhydrides thereof and chlorinating the resulting mixture with an epoxy compound in the presence of an organic solvent and a catalyst. And producing the primer composition. 5. A chlorinated modified polyolefin obtained by graft copolymerizing a polyolefin with at least one selected from unsaturated carboxylic acids and anhydrides thereof and then chlorinating the resulting mixture with an epoxy compound in the presence of an organic solvent and a catalyst. The method for producing a primer composition according to claim 4, comprising a step of reacting the primer composition. 6. An epoxy compound obtained by chlorinating a polyolefin and graft-copolymerizing at least one selected from unsaturated carboxylic acids and anhydrides thereof in the presence of an organic solvent and a catalyst. The method for producing a primer composition according to claim 4, comprising a step of reacting the primer composition. 7. The catalyst according to claim 4, wherein said catalyst is a tin-based catalyst.
The method for producing a primer composition according to any one of the above.