JP2001064396A - Coating resin composition for polyolefinic resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a coating resin composition excellent in compatibility with a polyol resin and adhesion to a polyolefin base material by subjecting a carboxyl group-containing chlorinated polyolefin, obtained by graft modification by an α,β-unsaturated caboxylic acid and/or an anhydride thereof, to an esterification reaction with a polyol resin. SOLUTION: An esterification reaction product is obtained by reacting a carboxyl group-containing chlorinated polyolefin having a graft ratio of 1-10 wt.%, obtained by reacting an α,β-unsaturated carboxylic acid such as maleic acid and/or an anhydride thereof with a chlorinated polyolefin, with a polyol resin in a weight ratio of 99/1 to 50/50. With this sterification reaction product are admixed a polyol resin such as an alkyd resin, a solvent, a pigment, and the like, to give a coating composition. The chlorinated polyolefin is a polypropylene, a propylene/α-olefin copolymer, or the like, each having a chlorine content of 10-50 wt.%. As the polyol resin, there can be exemplified an acrylic polyol, a polyesterpolyol, or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coating resin composition used for the purpose of protecting or cosmetically protecting a polyolefin resin, for example, polypropylene, polyethylene, ethylene propylene copolymer, and the like. The present invention relates to a composition which is used as a binder resin for a primer, a paint, an ink or an adhesive which has excellent adhesiveness to a molded article and other excellent physical properties.

[0002]

2. Description of the Related Art Plastics are widely used as materials for automobile parts, electric parts, building materials, etc. in recent years because of their high productivity, wide design freedom, and many advantages such as light weight, rust prevention and impact resistance. Used. In particular, polyolefin resins are widely used as industrial materials because of their low cost and many excellent properties such as moldability, chemical resistance, heat resistance, water resistance and good electrical properties. Elongation is one of the most promising materials. However, polyolefin resins are different from polar synthetic resins, such as polyurethane resins, polyamide resins, acrylic resins, and polyester resins, in that they are non-polar and crystalline, making them difficult to paint and bond. Having.

[0003] Conventionally, the surface of a polyolefin-based resin molded article is activated by plasma treatment or gas flame treatment to improve the adhesion. However, this method is complicated and requires a large amount of equipment and time. It has drawbacks such as a large loss, and the surface treatment effect varies due to the complexity of the shape of the molded product and the effects of pigments and additives in the resin.

As a method of coating without such a pretreatment, various primer compositions such as those found in automobile bumper coating have been proposed, and in particular, chlorinated polyolefins having strong adhesion to polyolefin resins. Is often used. However, chlorinated polyolefins are inferior in resistance to ultraviolet light and heat, and cannot be said to have sufficient coating film performance, and improvement of these has been strongly desired. As a means for improving these properties, attempts have been made to use a mixture of an acrylic resin or an alkyd resin having good paint properties. However, acrylic resins and alkyd resins inherently have poor compatibility with chlorinated polyolefins, and thus cause problems such as poor dispersion of pigments and a reduction in gloss of the coating film, and significantly impairing the appearance.

For example, JP-A-54-127436 discloses 2,2
A resin composition for coating obtained by mixing an alkyd resin containing 2,4-trimethylpentane-1,3-diol as a polyol component and a chlorinated polyolefin, and JP-A-61-2
No. 8561, acrylic-modified chlorinated polypropylene, and a graft polymer of polyester and alkyd resin,
There has been proposed a resin composition for coatings containing a graft polymer of polyester and polyisocyanate as a main component.
However, chlorinated polyolefins are inherently poorly compatible with the various polyol resins described above, so that even when mixed with these, opacity or two-layer separation occurs, and a uniform and transparent solution cannot be obtained. It cannot be a binder resin such as a primer or an adhesive.

JP-A-7-10940 proposes a binder resin composition obtained by reacting a polyester polyol and a radically polymerizable unsaturated compound with a carboxyl group-containing chlorinated polyolefin. Since gelation and a decrease in compatibility may occur due to a cross-linking reaction accompanying the grafting of the unsaturated substance, this also cannot be a good binder resin for paints, primers, adhesives and the like.

[0007]

SUMMARY OF THE INVENTION The present invention provides a coating resin composition for a polyolefin-based resin having excellent compatibility with an acrylic resin or an alkyd resin and having sufficient adhesion to a polyolefin substrate. With the goal.

[0008]

Means for Solving the Problems The present inventors have conducted various experiments in order to solve the above-mentioned problems, and as a result, they have been selected from α, β-unsaturated carboxylic acids and / or acid anhydrides thereof. The chlorinated polyolefin obtained by graft-modification using one or more compounds is subjected to an esterification reaction with a polyol resin, and the coating resin composition for a polyolefin resin obtained is compatible with various polyol resins. ,
The inventors have found that the dispersibility of the pigment and the adhesion to the polyolefin substrate are excellent, and have reached the present invention.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The carboxyl group-containing chlorinated polyolefin used in the present invention is obtained by melting a polyolefin and, if necessary, converting a polyolefin molten resin degraded by thermal decomposition into a batch type or a continuous type. After the unsaturated carboxylic acid monomer is graft-copolymerized in the presence of an agent, it is dispersed or dissolved in water or a solvent such as carbon tetrachloride or chloroform, and is added in the presence of a radical generator or under irradiation with ultraviolet light. After blowing chlorine gas at a temperature range of 50 to 120 ° C under pressure or normal pressure, the chlorination reaction is performed, and then the solvent is distilled off to obtain a solution product in which a stabilizer is added and replaced with an organic solvent such as toluene or xylene. Can be. After chlorination, the chlorinated solvent is concentrated under reduced pressure, a stabilizer is added, and then the solvent is completely removed by a vented extruder or the like equipped with a vent port for distilling off the solvent under reduced pressure. You can also get.

As a radical generator, for example, di-tert
-Butyl peroxide, tert-butyl hydroperoxide, dicumyl peroxide, benzoyl peroxide,
tert-butyl peroxide benzoate, methyl ethyl ketone peroxide, di-tert-butyl diperphthalate
And azonitriles such as azobisisobutyronitrile. Examples of the unsaturated carboxylic acid monomer and its anhydride used in the graft copolymerization reaction include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, citraconic acid, citraconic anhydride, fumaric acid, mesaconic acid, and itaconic acid. , Itaconic anhydride, aconitic acid, aconitic anhydride and the like.

As the stabilizer for the chlorinated polyolefin, the stabilizer used for polyvinyl chloride, which is a chlorine-based resin, can be applied as it is. For example, calcium stearate, metal soaps such as lead stearate, lead oxide, inorganic acid salts such as tribasic lead sulfate, organic metal compounds such as dibutyltin dilaurate, dibutyltin malate, hydrotalcite compounds, epoxy compounds Kind. However, among these, epoxy compounds are most commonly used. For example, epoxidized soybean oil or epoxidized linseed oil obtained by epoxidizing a vegetable oil having a natural unsaturated group with a peracid such as peracetic acid. Epoxidized fatty acid esters obtained by epoxidizing unsaturated fatty acid esters such as oleic acid, tall oil fatty acid and soybean oil fatty acid. Epoxidized alicyclic compounds represented by epoxidized tetrahydrophthalate. Bisphenol A or polyhydric alcohol and epichlorohydrin condensed, for example, bisphenol A glycidyl ether,
Ethylene glycol glycidyl ether, propylene glycol glycidyl ether, glycerol polyglycidyl ether, sorbitol polyglycidyl ether and the like. Also, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, decyl glycidyl ether, stearyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, sec-butyl phenyl glycidyl ether, tert-butyl phenyl glycidyl ether, phenol polyethylene oxide glycidyl ether, etc. Monoepoxy compounds.

The carboxyl group-containing chlorinated polyolefin used in the present invention is obtained by preparing a solution of the chlorinated polyolefin obtained by chlorinating the polyolefin by the above-mentioned method, and then adding the unsaturated carboxylic acid monomer and its anhydride in the presence of a radical generator. It can also be obtained by graft copolymerizing the product. As the radical generator, unsaturated carboxylic acid monomer and anhydride thereof used in the graft copolymerization reaction, those described above can be used as they are.

The starting polyolefin for the carboxyl group-containing chlorinated polyolefin used in the present invention is preferably a crystalline polypropylene, a propylene-α-olefin copolymer or a propylene-butene-ethylene copolymer which is a terpolymer. . What is crystalline polypropylene?
It refers to isotactic polypropylene and syndiotactic polypropylene, and the former is generally used. Those having a weight average molecular weight of 10,000 to 300,000 can be used.

On the other hand, the propylene-α-olefin copolymer is obtained by copolymerizing α-olefin with propylene as a main component, and can be used as either a block copolymer or a random copolymer. Examples of the α-olefin component include ethylene, 1-butene, 1-pentene, and 1-pentene.
Hexene, 1-heptene, 1-octene, 4-methyl-1-pentene and the like can be exemplified. The content of the propylene component is optimally 50 to 98 mol%, and if it is less than 50 mol%, the adhesion to polypropylene is reduced. On the other hand, if it exceeds 98 mol%, the flexibility of the coating film becomes poor.

The polyol resin used in the present invention is a polyhydric alcohol having two or more hydroxyl groups in a molecule, and is an acrylic polyol, a polyester polyol, a polyether polyol, an epoxy polyol, a cellulose acetate butyrate, a nitrified cotton, an alkyd resin. Or a modified product thereof.

Acrylic polyl is an acrylic resin obtained by copolymerizing a monomer having a hydroxyl group such as a hydroxyl ester of (meth) acrylic acid and a (meth) acrylic acid ester monomer. The polyester polyol is a polyester resin obtained by subjecting a dibasic acid and an excess polyhydric alcohol to an esterification reaction.

The polyether polyol is a resin containing, as a main component, polypropylene glycol obtained by addition-polymerizing propylene oxide or ethylene oxide to a polyhydric alcohol. The epoxy polyol is a solid epoxy resin having a hydroxyl group or an amine-modified resin of bisphenol A type epoxy resin. Further, cellulose acetate butyrate is a cellulose derivative obtained by further butyrylating a partially acetylated product of cellulose. Nitrified cotton is a cellulose derivative obtained by treating a cellulose raw material such as paper or cotton with a mixed solution of sulfuric acid and nitric acid.

An alkyd resin is a type of polyester resin obtained by a polycondensation reaction between a polyhydric alcohol and a polybasic acid. Glycerin as a polyhydric alcohol component,
Examples of polybasic acid components such as pentaerythritol and ethylene glycol include phthalic anhydride, maleic anhydride, and rosin / maleic anhydride adduct.

The chlorine content of the carboxyl group-containing chlorinated polyolefin is preferably from 10 to 50% by weight. Chlorine content 5
If it exceeds 0% by weight, the adhesion to the polyolefin will be poor, and if the chlorine content is less than 10% by weight, the solution state will be poor.

The graft ratio of the unsaturated carboxylic acid monomer and its anhydride in the carboxyl group-containing chlorinated polyolefin is preferably 1 to 10% by weight. If the graft ratio exceeds 10% by weight, gelation occurs during an esterification reaction with a polyol resin having a hydroxyl group or the like, and adhesion to a polyolefin becomes poor. When the graft ratio is less than 1% by weight, adhesion to the overcoat is deteriorated, and the amount of the generated ester is limited, so that the contribution to the compatibility and the dispersibility of the pigment is reduced.

The carboxyl group-containing chlorinated polyolefin is esterified with a polyol resin by appropriately diluting the carboxyl group-containing chlorinated polyolefin with a solvent, premixing the polyol resin, adding a catalyst, and then heating. It is basically to react. The solvent used in the reaction is preferably an aromatic solvent such as toluene and xylene, and an ester solvent such as ethyl acetate and butyl acetate; a ketone solvent such as methyl ethyl ketone and methyl isobutyl ketone; ethanol, isopropanol;
Alcohol solvents such as n-butanol, aliphatic solvents, cycloaliphatic solvents and the like may be used in combination.

Examples of the catalyst used in the esterification reaction include acidic catalysts such as sulfuric acid, p-toluenesulfonic acid, naphthalenesulfonic acid, methanesulfonic acid, and sulfate.
Organic tin compounds such as butyltin malate, other antimony trioxide, alumina and the like.

In the present invention, the weight ratio of the carboxyl group-containing chlorinated polyolefin to the polyol resin is from 99/1 to 50.
It is preferably in the range of / 50. If the ratio of the carboxyl group-containing chlorinated polyolefin exceeds 99 parts by weight, the chlorinated polyolefin component increases when used as a resin for one-coat paints, which causes problems such as poor weather resistance and yellowing and gloss reduction. On the other hand, if the ratio of the carboxyl group-containing chlorinated polyolefin is less than 50 parts by weight, the chlorinated polyolefin component as an adhering component is insufficient, and the adhesion to the polyolefin substrate is poor.

The coating resin composition exhibits well-balanced coating film properties by itself, and further includes various polyol resins such as acrylic polyol, polyester polyol, polyether polyol, epoxy polyol, cellulose acetate butyrate, and nitrated cotton. , 90/10 to 90/90, other resins such as alkyd resin or its modified product
By mixing at a weight ratio of, more coating film properties can be expected. When the ratio of the coating resin composition exceeds 90 parts by weight, the chlorinated polyolefin component increases when used as a resin for one-coat paint, and therefore, problems such as poor weather resistance and yellowing or gloss reduction occur. On the other hand, when the ratio of the coating resin composition is less than 10 parts by weight, the chlorinated polyolefin component as an adhering component is insufficient, and the adhesion to the polyolefin substrate is poor.

The present invention also relates to a polyolefin resin comprising a mixture of a carboxyl group-containing chlorinated polyolefin and a polyol resin and / or a mixture of the esterification product and a polyol resin, especially an alkyd resin or a modified product thereof. The present invention relates to a coating resin composition for use.

The coating resin composition for a polyolefin resin of the present invention may be used after being coated as it is, but it may contain a pigment, a solvent, and other additives such as an ultraviolet absorber, an antioxidant, and a pigment settling inhibitor. It can be kneaded and dispersed and used as a paint or printing ink. Furthermore,
It can also be used as an adhesive for various plastics such as polypropylene resin or a primer for coating.

[0027]

The feature of the present invention is that the chlorinated polyolefin containing a carboxyl group is subjected to an esterification reaction with a polyol resin having a hydroxyl group, whereby the compatibility between the chlorinated polyolefin and various polyol resins and the dispersibility of the pigment are improved. An object of the present invention is to provide a coating resin composition for a polyolefin-based resin which improves the adhesion and shows good adhesion even to a polyolefin which has conventionally been difficult to adhere.

That is, the reaction product obtained by esterifying the carboxyl group in the carboxyl group-containing chlorinated polyolefin and the hydroxyl group in the polyol resin acts as a compatibilizer, thereby improving the compatibility between the chlorinated polyolefin and various polyol resins. It is thought that it is made. Furthermore, the dispersibility with the pigment is also improved, and the separation and gelation of the pigment in the paint can be prevented. In addition, it is considered that the adhesiveness is improved by being uniformly mixed with an additive such as an alkyd resin having good paint physical properties.

[0029]

Next, the present invention will be described in more detail by way of examples. (Production Example 1) Ethylene-propylene copolymer 6k having a melt viscosity at 180 ° C. of 2500 mPa · s and an ethylene content of 6 mol%
g was placed in a three-necked flask equipped with a stirrer and a condenser for refluxing the monomer, and was completely melted in an oil bath kept constant at 180 ° C. After the atmosphere in the flask was replaced with nitrogen, 240 g of maleic anhydride was introduced over about 5 minutes while stirring, and then 24 g of di-tert-butyl peroxide was added to the flask.
After dissolving in 0 ml of heptane, the solution was introduced from a dropping funnel over about 30 minutes. At this time, the inside of the system was maintained at 180 ° C., and the reaction was further continued for about 1 hour. Then, unreacted maleic anhydride was removed over about 30 minutes while reducing the pressure inside the flask with an aspirator.

Next, this product was charged into a glass-lined reaction vessel, 100 liters of chloroform was added, and then completely dissolved at 100 ° C. under a pressure of 2.5 kg / cm ² .
Further, azobisisobutyronitrile was added in an amount of 0.1
After the addition by weight, chlorine gas was blown in from the bottom of the reaction vessel while maintaining the temperature at 90 ° C. to perform a chlorination reaction. After the completion of the reaction, chloroform as the solvent was distilled off using an evaporator.
Toluene / cyclohexane = 65/35 (w / w) was replaced with a mixed solvent, and Epiol TB (epichlorohydrin derivative, manufactured by Nippon Oil & Fats Co., Ltd.) was added as a stabilizer at 4% to the solid content to adjust the concentration, A mixed solution of a carboxyl group-containing chlorinated ethylene-propylene copolymer having a solid content of 20% by weight in toluene and cyclohexane was obtained. At this time, the chlorine content was 18.0% by weight (based on solid content), and the graft ratio of maleic anhydride was 2.5% by weight (based on solid content).

(Production Example 2) The same melting reaction as in Production Example 1 was carried out except that 6 kg of isotactic polypropylene having a number average molecular weight of about 15,000, 420 g of maleic anhydride and 42 g of di-tert-butyl peroxide were used. Next, a chlorination reaction was performed in the same manner. The solvent chloroform was concentrated under reduced pressure by an evaporator, and a hydrotalcite compound was added as a stabilizer at 4% by weight based on the solid content.Then, a vented extruder equipped with a vent port for distilling off the reaction solvent under reduced pressure was used. Chloroform was completely removed, extruded into strands, cooled with water, and a solid of carboxyl group-containing chlorinated polypropylene pelletized with a water-cooled pelletizer (Model: KM-150, Katsu Seisakusho Co., Ltd.) was obtained. At this time, the chlorine content was 35.0% by weight (based on solids), and the graft ratio of maleic anhydride was 4.3% by weight (based on solids).

(Production Example 3) 6 kg of a propylene-butene-ethylene copolymer having a weight-average molecular weight of 120,000, a propylene component of 75 mol% and an ethylene component of 8 mol% was charged into a glass-lined reactor, and 100 liters were added. After completely dissolving under the condition of ² kg / cm ² -110 ° C,
Chlorine gas was blown from the bottom of the reaction vessel while irradiating ultraviolet rays to obtain a reaction solution having a chlorine content of 12% by weight. Next, after concentration by an evaporator, 4% by weight of Epiol TB as a stabilizer was added to the solid content, and then carbon tetrachloride as a reaction solvent was replaced with toluene, and chlorinated propylene having a solid content concentration of 30% by weight was used. -A toluene solution of a butene-ethylene copolymer was obtained. Next, 1,000 g of this chlorinated propylene-butene-ethylene copolymer toluene solution was placed in a three-necked flask equipped with a stirrer, a dropping funnel, and a condenser for refluxing the monomer, and the atmosphere in the flask was replaced with nitrogen. While stirring at 90 ° C., 3 g of benzoyl peroxide was added, and the mixture was further stirred for about 30 minutes. Next, 15 g of methacrylic acid was added from the dropping funnel over about 30 minutes, and after further reacting for 3 hours, the concentration was adjusted. I got At this time, the chlorine content was 11.3% by weight (based on solids), and the graft ratio of methacrylic acid was 4.7% by weight (based on solids).
Met.

The carboxyl group-containing chlorinated polyolefins obtained in Production Examples 1 to 3 are summarized in Table 1.

[Table 1]

(Production Example 4) 500 g of the carboxyl group-containing chlorinated polyolefin obtained in Production Example 1 and phthalkid V901
(Vinyl-modified alkyd resin, manufactured by Hitachi Chemical Co., Ltd., solid content: 50% by weight) 10.5 g was mixed in a three-necked flask equipped with a stirrer and a condenser, and di-n-octyltin dilaurate was added to the resin. After adding 0.1% by weight based on the solid content, the temperature was increased to 85%.
The reaction was carried out for 5 hours while maintaining the temperature at 0 ° C, and the concentration was adjusted with toluene to produce a coating resin composition (1) for a polyolefin-based resin having a solid content of 20% by weight.

(Production Example 5) 500 g of the carboxyl group-containing chlorinated polyolefin obtained in Production Example-1 and cellulose acetate butyrate (acetyl group content: 14% by weight, butyryl group content: 37% by weight, solid content: 100) (% By weight) in a three-necked flask equipped with a stirrer and a condenser, and added with 0.1% by weight of p-toluenesulfonic acid relative to the resin solid content.
The reaction was carried out for 5 hours while maintaining the temperature at 85 ° C., and the concentration was adjusted with toluene to produce a coating resin composition (2) for a polyolefin resin having a solid content of 20% by weight.

(Production Example 6) 100 g of the carboxyl group-containing chlorinated polyolefin obtained in Production Example-2 and LR-193 (acryl polyol, manufactured by Mitsubishi Rayon Co., Ltd., solid content: 60% by weight) 29.4
g, 400 g of toluene were mixed in a three-necked flask equipped with a stirrer and a condenser, and after adding di-n-butyltin dilaurate to the resin solids by 0.5% by weight, the temperature was maintained at 85 ° C. The reaction was carried out for 5 hours, and the concentration was adjusted with toluene to produce a coating resin composition (3) for a polyolefin resin having a solid content of 20% by weight.

(Production Example 7) 100 g of the carboxyl group-containing chlorinated polyolefin obtained in Production Example-2 and desmophen 690 (polyester polyol, manufactured by Sumitomo Bayer Urethane Co., Ltd.,
Solid content: 100% by weight) 33.3 g, 400 g of toluene were mixed in a three-necked flask equipped with a stirrer and a condenser, and after adding 0.5% by weight of antimony trioxide to the resin solid content, the temperature was increased to 85%. The reaction was carried out for 5 hours while maintaining the temperature at 0 ° C, and the concentration was adjusted with toluene to produce a coating resin composition (4) for a polyolefin resin having a solid content of 20% by weight.

(Production Example 8) 500 g of the carboxyl group-containing chlorinated polyolefin obtained in Production Example-3 and 1900 U of desmophen
(Polyether polyol, Sumitomo Bayer Urethane Co., Ltd.
81.8 g) was mixed in a three-necked flask equipped with a stirrer and a condenser, and 0.1% by weight of alumina was added to the resin solids.The temperature was maintained at 85 ° C. While
The reaction was carried out for 5 hours, and the concentration was adjusted with toluene to produce a coating resin composition (5) for a polyolefin resin having a solid content of 20% by weight.

(Production Example 9) 500 g of the carboxyl group-containing chlorinated polyolefin obtained in Production Example-3 and Kuraray polyol P-
1010 (Polyester polyol, manufactured by Kuraray Co., Ltd., solid content:
(100% by weight) was mixed in a three-necked flask equipped with a stirrer and a condenser, and 0.1% by weight of concentrated sulfuric acid was added to the resin solids. An esterification reaction was performed.

Next, 8.4 g of t-butyl peroxyisopropyl carbonate was added, and cyclohexyl acrylate 80 was added.
g and 2-hydroxyethyl acrylate 20 g of a radical polymerizable unsaturated substance were added dropwise over 3 hours, and then 6
The copolymerization reaction was performed over a period of time, and the concentration was adjusted with toluene to produce a coating resin composition (6) for a polyolefin resin having a solid content of 20% by weight.

(Examples 1 to 5) Each of the polyol resins used for the esterification reaction was added to the coating resin compositions (1) to (5) for the polyolefin resin obtained in Production Examples 4 to 8 at a solid content ratio. Mixing was performed so that the ratios were 3/1, 1/1, and 1/3, and the compatibility of the solution with a dry film was observed. The solution was adjusted to a concentration of 20% by weight, and the solution state (compatibility) after standing for 3 days was observed. The dried film is coated on a glass plate with a coating rod # 20 and dried at room temperature.
(Compatibility) was observed. Table 2 shows the results.

(Comparative Examples 1 to 5) The polyol resins shown in Examples 1 to 5 were added to the carboxyl group-containing chlorinated polyolefin obtained in Production Examples 1 to 3 at a solid content ratio of 3/1, 1/1, The mixture was mixed so as to have a ratio of 1/3, and the compatibility between the solution and the dried film was observed in the same manner as in Examples 1 to 5. The result is displayed
3 is shown.

[0043]

[Table 2]

[0044]

[Table 3]

(Examples 6 and 7 and Comparative Examples 6 and 7) Primers were prepared with the compositions shown in Table 4 and performance tests of the primers were performed. Table 5 shows the results.

[0046]

[Table 4]1) Preparation of the primer After kneading the primer composition for 1 hour with a sand mill,
For a viscosity of 12-13 seconds / 20 ° C with Ford Cup # 4
It was prepared by diluting with xylene. 2) Coating method Primer was washed with isopropyl alcohol
Film thickness of 10 to 15 on olefin base material (ultra-high rigidity polypropylene)
Paint using air spray to a thickness of 15 μm
After drying at room temperature for two minutes, apply a two-part curable urethane coating
Spray paint to a thickness of about 30μm, 20-30 minutes
After drying at room temperature, perform forced drying at 80 ° C for 30 minutes.
After being allowed to stand in the room for 3 days, it was subjected to a coating film test. 3) Evaluation method of coating filmAdhesiveness  Make 100 grids that reach the base at 2 mm intervals on the painted surface,
Adhere the cellophane adhesive tape on top of it and turn it 180 °
, And the number of remaining grids was checked.・Moisture resistance  Leave the painted plate in an atmosphere of 50 ° C and 98% relative humidity for 240 hours,
The state and adhesion of the coating film were examined.・Warm water resistance  Immerse the coated board in 40 ° C warm water for 240 hours,
The adhesion was examined.・Gasoline resistance  Dip a painted plate with both ends cut in regular gasoline
Time to peel off about 2 mm from the edge of the cut painted surface
Was determined.

[0047]

[Table 5]

(Examples 8 and 9 and Comparative Examples 8 and 9) Basecoat paints having the compositions shown in Table 6 were prepared, and performance tests of the basecoat paints were performed. Table 7 shows the results.

[0049]

[Table 6] 1) Preparation of base coat paint The above base coat paint composition was shaken for 1 hour with a shaker, and then diluted with xylene to a viscosity of 12 to 13 seconds / 20 ° C. using a Ford cup # 4. 2) Coating method The base coat paint is coated on a polyolefin substrate (ultra-high rigidity polypropylene) washed with isopropyl alcohol.
Paint using air spray to 30-35μm, 5
After drying at room temperature for ~ 10 minutes, a clear coat paint (two-part curable urethane) is spray-coated so that the film thickness is about 10 μm, dried at room temperature for 20-30 minutes, and then at 80 ° C for 30 minutes Was subjected to forced drying, left in a room for 3 days, and then subjected to a coating film test. 3) Evaluation method of coating film ・ Adhesion, moisture resistance, hot water resistance and gasoline resistance are the same as above.

[0050]

[Table 7] (Examples 10 and 11 and Comparative Examples 10 and 11) One-coat paints were prepared with the compositions shown in Table 8, and performance tests of the one-coat paint were performed. Table 9 shows the results.

[0051]

[Table 8]1) Preparation of one-coat paint The above-mentioned one-coat paint composition was kneaded with a sand mill for 1 hour.
After that, it becomes viscosity of 12-13 seconds / 20 ° C with Ford cup # 4
And diluted with xylene as described above. 2) Coating method One coat paint was washed with isopropyl alcohol
Approximate film thickness on polyolefin substrate (ultra-high rigidity polypropylene)
Apply using air spray to a thickness of 30μm,
After drying at room temperature for 0 minutes, forcibly dry at 80 ° C for 30 minutes.
The test was performed for 3 days after being left in a room for 3 days. 3) Evaluation method of coating filmAdhesion, moisture resistance, warm water resistance  Same as above.・Gloss  It was measured by a 60 ° specular reflection glossmeter.・Butter resistance  Attach a cloth soaked with butter on the painted surface,
After standing for a day, completely remove the butter remaining on the painted surface
After that, the adhesion of the coating film was examined.・Alkali resistance  Immerse the coated plate in 0.1N alkaline aqueous solution for 120 hours,
The state of the membrane was examined.・Pigment dispersibility  After letting the one-coat paint stand for 3 days, observe the paint condition
did.

[0052]

[Table 9]

Examples 12 to 17 Inks having the compositions shown in Table 10 were prepared, and a performance test of the ink was performed. The result is displayed
12

(Comparative Examples 12 to 17) Inks having the compositions shown in Table 11 were prepared, and performance tests of the inks were performed. The result is displayed
13

[0055]

[Table 10]

[0056]

[Table 11]1) Preparation of ink After the above ink composition was kneaded for 3 hours with a sand mill,
To a viscosity of 25-30 seconds / 20 ° C
Prepared by diluting with water. 2) Evaluation methodCellophane adhesive tape peel test  Apply the ink prepared by the above method to coating rod # 1
4 Untreated polypropylene film (hereinafter referred to as untreated PP)
), Corona discharge treated polypropylene film (hereinafter treated
(Referred to as PP) and dried at room temperature for 24 hours
After that, paste the cellophane adhesive tape on the ink coated surface,
The peeled state of the coated surface when peeled off at a stretch was examined.・Heat seal strength test  Untreated PP in a similar manner for cellophane adhesive tape peel test
And treated PP were coated with ink and dried at room temperature for 24 hours
After that, the ink coated surface is overlaid, 120 ℃ -1kg / cm^TwoFor 2 seconds
Heat sealing under the crimping condition of
Was measured at 180 ° C (tensile speed: 50 mm / mi
n).・Storage stability test  After measuring the initial viscosity of the ink using a B-type viscometer, 40
After letting it stand at ℃ for 1 week, measure the viscosity again and
The viscosity change of the ink was examined.

[0057]

[Table 12]

[0058]

[Table 13]

[0059]

The compatibility with the various polyol resins of the comparative examples is considerably inferior to the examples. As for the primer performance, Comparative Example 6 is inferior in gasoline resistance as compared with the Examples, and Comparative Example 7 is inferior in adhesion, moisture resistance, hot water resistance and gasoline resistance. In the properties of the base coat paint, Comparative Example 8 is inferior in moisture resistance, hot water resistance and gasoline resistance as compared with the examples, and Comparative Example 9 is inferior in adhesion, moisture resistance, hot water resistance and gasoline resistance. . The properties of the one-coat paint also show the same tendency as in the case of the base coat paint, but are inferior in gloss, butter resistance, alkali resistance and pigment dispersibility in the comparative examples to the examples. With respect to the physical properties of the ink, the examples show good adhesion to the PP film, while the comparative examples are not always sufficient. From the above results, it is understood that the coating resin composition for a polyolefin resin of the present invention is useful.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J031 AA03 AA12 AA20 AA47 AA49 AA53 AB01 AB02 AB06 AC03 AD01 AF12 4J038 BA061 BA062 CB171 CB172 CG141 CG142 CH121 CH122 CP081 CP082 DB001 DB002 DB391 DB392 DD101 DD102 DD121 DF122 GA01 NA12 PB05 PB07 PB09 PC08

Claims (9)

[Claims] 1. A carboxyl group-containing chlorinated polyolefin obtained by graft modification using one or more compounds selected from α, β-unsaturated carboxylic acids and / or acid anhydrides thereof. A coating resin composition for a polyolefin resin obtained by an esterification reaction with a polyol resin. 2. The polyol resin is an acrylic polyol,
Polyester polyol, polyether polyol, epoxy polyol, cellulose acetate butyrate,
Claims are nitrified cotton, alkyd resin or a modified product thereof.
2. The coating resin composition for a polyolefin resin according to 1 above. 3. The coating resin composition for a polyolefin resin according to claim 1, wherein the chlorinated polyolefin containing a carboxyl group has a chlorine content of 10 to 50% by weight. 4. A graft ratio of one or more compounds selected from α, β-unsaturated carboxylic acids and / or acid anhydrides of a carboxyl group-containing chlorinated polyolefin is from 1 to 10% by weight. The coating resin composition for a polyolefin resin according to any one of claims 1 to 3. 5. The coating resin composition for a polyolefin resin according to claim 1, wherein the weight ratio of the carboxyl group-containing chlorinated polyolefin to the polyol resin is in the range of 99/1 to 50/50. . 6. A coating resin for a polyolefin resin obtained by mixing the coating resin composition for a polyolefin resin according to any one of claims 1 to 5 and a polyol resin in a weight ratio of 90/10 to 10/90. Composition. 7. The polyol resin is an acrylic polyol,
Polyester polyol, polyether polyol, epoxy polyol, cellulose acetate butyrate,
The polyolefin resin coating composition according to claim 6, which is a nitrified cotton, an alkyd resin or a modified product thereof. 8. A coating resin composition for a polyolefin resin comprising an esterification reaction product of a carboxyl group-containing chlorinated polyolefin and a polyol resin and / or a mixture of the esterification reaction product and a polyol resin. 9. The coating composition for a polyolefin resin according to claim 8, wherein the polyol resin mixed with the esterification reaction product is an alkyd resin or a modified product thereof.