JP2601748B2 - Binder resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a binder resin composition used for protecting, aesthetically and adhering various kinds of plastics, and more particularly, to a polyolefin resin, a polyurethane resin, a polyamide resin, an acrylic resin, The present invention relates to a binder resin composition for paints, printing inks, or adhesives, which exhibits excellent physical properties for films, sheets, or molded products of various synthetic resins such as polyester resins.

[0002]

2. Description of the Related Art Plastics have many advantages such as high productivity, wide design freedom, light weight, rust prevention and impact resistance. Used. In particular, polyolefin-based 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. Is one of the most promising materials.

However, unlike a synthetic resin having a polarity, such as a polyurethane resin, a polyamide resin, an acrylic resin, and a polyester resin, a polyolefin resin is nonpolar and crystalline, so that painting and bonding are difficult. There is a disadvantage that. Conventionally, the surface of a polyolefin resin molded product is activated by plasma treatment or gas flame treatment to improve the adhesion. However, this method involves a complicated process and involves a great deal of equipment cost and time loss. In addition, there are drawbacks in that 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 a polypropylene bumper coating for automobiles have been proposed. For example, Japanese Patent Publication No. Sho 62-21027 proposes a surface treatment agent obtained by modifying a propylene-α-olefin copolymer with maleic acid. However, a primer composition obtained by merely introducing maleic acid into a polyolefin has the disadvantages of poor adhesion, solvent resistance, but poor sprayability, solubility, and compatibility. In addition, it involves two-coat finishing.

[0005] Examples of coating compositions for one-coat finishing include chlorinated polyolefins and cyclized rubbers having strong adhesion to polyolefin-based resins.
Moisture resistance, gasoline resistance, etc. are poor and do not show sufficient coating film performance.

In order to improve these disadvantages, Japanese Patent Application Laid-Open No.
No. 71966, a coating composition obtained by copolymerizing an acrylic monomer and a chlorinated polyolefin, or a hydroxyl-containing acrylic compound as disclosed in JP-A-59-27968. A coating composition comprising, as essential components, a chlorinated polyolefin-modified hydroxyl group-containing acrylic copolymer obtained by copolymerizing a monomer or the like with a chlorinated polyolefin, and an isocyanate compound;
No. 2, an adhesive mainly composed of a hydroxyl group-containing acrylic-modified chlorinated polyolefin and an isocyanate compound copolymerized with an acrylic monomer having a hydroxyl group in the presence of a chlorinated polyolefin and a liquid rubber Resin compositions and the like have been proposed. However, these chlorine-containing compositions are slightly inferior in ultraviolet resistance and heat resistance, and have a problem in long-term weather resistance.

A composition containing no chlorine is disclosed in
JP-A-2-27383 discloses a method for forming a multilayer coating film comprising a resin composition obtained by copolymerizing an ethylene-propylene copolymer obtained by graft-polymerizing maleic acid with a functional group monomer and a radical polymerizable unsaturated monomer, and a crosslinking agent. Has been proposed. However, according to this method, when the copolymerization reaction is carried out at a high concentration, there is a possibility of gelling during the reaction, so that it is necessary to carry out the reaction at a very dilute concentration. For this reason, the grafting efficiency to polyolefin is very low, and a large amount of a homopolymer of a radical polymerizable unsaturated monomer is generated, so that it is difficult to obtain a uniform solution, and it is difficult to use it as a one-coat paint resin. In addition, weather resistance and gasoline resistance are required for automotive polypropylene coating, but the above-mentioned modification is used because polyolefins, which are inherently inferior to gasoline, are used as raw materials because they do not contain chlorine but have excellent weather resistance. The gasoline resistance of the product is not enough.

Japanese Unexamined Patent Publication (Kokai) No. 63-51477 discloses a copolymer of a hydrogenated styrene-butadiene-styrene block copolymer and a vinyl monomer. Gasoline resistance is not sufficient because it is a modified styrene-butadiene-styrene block copolymer with poor solvent properties, and adhesion to polypropylene is not sufficient because it is not a modified propylene-based copolymer. Not really.

On the other hand, various types of plastic films have been developed and used as food packaging materials.
Along with this, packaging forms have also been diversified, and in particular, in order to protect the contents of the package, the use of composite films by lamination has increased. A large number of inks for lamination used for packaging have been used depending on the type of film, but today, the inks for lamination have been broadly classified into two types. That is, an ink composition mainly containing a chlorinated polypropylene and a chlorinated ethylene-vinyl acetate copolymer used mainly for a polypropylene film, and an ink composition mainly containing a urethane resin mainly used for a polyester and a nylon film. .

An ink composition containing a chlorinated polypropylene and a chlorinated ethylene-vinyl acetate copolymer as a main binder is disclosed in, for example, Japanese Patent Publication No. 60-31670.
An ink composition obtained by further sulfochlorinating a chlorinated ethylene-vinyl acetate copolymer is disclosed in JP-A-55-14577.
No. 5 discloses this. These have good ink adhesion to untreated polypropylene films, but poor adhesion to films of polyester, nylon and the like.

As described in JP-A-62-153366 and JP-A-65-153367, the latter ink compositions containing a urethane-based resin as a main binder are films having polarities such as polyester and nylon. Shows good adhesion but no adhesion to untreated polypropylene film.

[0012]

As described above, various coating compositions for one-coat finishing have been proposed, such as acryl-modified chlorinated polyolefins and acryl-modified polyolefins. However, coating properties such as gasoline resistance and weather resistance have been proposed. Is not enough. On the other hand, conventional printing inks have a problem in that the substrate film is limited, or the adhesion is insufficient even if the substrate film has general versatility.

Therefore, the present inventors have disclosed in Japanese Patent Application No. 03-293.
No. 710 and Japanese Patent Application No. 04-29898 propose resin compositions in which an ethylene-propylene copolymer and a radical polymerizable unsaturated monomer are copolymerized. However, these resin compositions are still in view of gasoline resistance. It was not enough.

The present invention has been studied variously in order to improve the gasoline resistance which was a drawback of the above proposal,
An object of the present invention is to provide a binder resin composition excellent in properties such as gloss and durability of a coating film, and a binder resin composition exhibiting good adhesion to various plastic films.

[0015]

That is, in the present invention, an α, β-unsaturated carboxylic acid and / or an anhydride thereof are graft copolymerized with a propylene-α-olefin copolymer in an amount of 0.5 to 10% by weight. Then, a polyester polyol (obtained by polycondensation of a polyhydric alcohol and a polybasic acid, and having 2
Polyester resin having at least two hydroxyl groups)
-A binder resin composition obtained by partially reacting with an unsaturated carboxylic acid and / or an anhydride thereof and further graft copolymerizing a radically polymerizable unsaturated compound.

The propylene-α-olefin copolymer used in the present invention comprises mainly propylene and
It is obtained by copolymerizing an olefin, and a random copolymer is more preferable than a block copolymer. Examples of the α-olefin component include ethylene, 1-butene, 1-heptene, 1-octene, 1-hexene, 1-decene,
-Methyl-1-pentene and the like.

In the present invention, the ratio of the propylene component to the α-olefin component in the copolymer is not particularly limited, but it is desirable that the propylene component be at least 50 mol%. Examples of the α, β-unsaturated carboxylic acid or its anhydride graft-copolymerized with a propylene-α-olefin copolymer include (meth) acrylic acid, (anhydride) maleic acid, (anhydrous) citraconic acid, and fumaric acid. , Mesaconic acid, itaconic acid (anhydride), aconitic acid (anhydride) and the like.

In the present invention, the amount of the α, β-unsaturated carboxylic acid or its anhydride introduced by graft copolymerization is optimally 0.5 to 10% by weight. 0.5% by weight
If the amount is less, the obtained composition is separated into two layers, and a good paint or ink cannot be obtained. If it is 10% by weight or more, it gels during the reaction and cannot be used as a binder resin.

In the propylene-α-olefin copolymer,
A method of graft copolymerizing an α, β-unsaturated carboxylic acid or an anhydride thereof is a method in which a propylene-α-olefin copolymer is heated and melted to a melting point or higher in the presence of a radical generator (melting method). , A method of dissolving a propylene-α-olefin copolymer in an organic solvent, and then heating and stirring in the presence of a radical generator to cause a reaction (solution method);
It can be performed by a known method. In the case of the melting method, the reaction is performed in a short time at a temperature of not less than the melting point and not more than 300 ° C. by using a Banbury mixer, a kneader, an extruder, or the like, so that there is an advantage that the operation is simple. On the other hand, in the solution method, it is desirable to use an aromatic solvent such as toluene or xylene as an organic solvent, but it is also possible to use a mixture of an ester solvent, a ketone solvent, etc. . The radical generator used in the reaction can be appropriately selected from known ones, and an organic peroxide compound is particularly desirable.

Examples of the above-mentioned organic peroxide compounds include di-t-butyl peroxide, dicumyl peroxide, t-butyl cumyl peroxide, benzoyl peroxide, dilauryl peroxide, cumene hydroperoxide and t-butyl peroxide. -Butyl hydroperoxide,
1,1-bis (t-butylperoxy) -3,5,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) -cyclohexane, cyclohexanone peroxide, t-butylperoxybenzoate, t- Butylperoxyisobutyrate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisopropyl carbonate,
Cumyl peroxy octoate and the like.

The polyester polyol used in the present invention can be obtained by subjecting the following polyhydric alcohol and polybasic acid to condensation polymerization by a known method, and by ring-opening polymerization of an aliphatic lactone.

Examples of polyhydric alcohols include ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol,
Polypropylene glycol, neopentyl glycol,
One kind of 1,2-, 1,3-, 1,4-, 2,3-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, etc. The above polyhydric alcohols can be used in combination.

The polybasic acids include (phthalic anhydride), (tetrahydrophthalic anhydride), hexahydrophthalic anhydride, (methyltetrahydrophthalic anhydride),
(Anhydrous) trimetic acid, (anhydrous) pyromellitic acid, isophthalic acid, terephthalic acid, (anhydrous) maleic acid, fumaric acid, itaconic acid, adipic acid, azelaic acid, sebacic acid, (anhydrous) succinic acid, lactic acid, (anhydrous ) One or more polybasic acids such as dodecenylsuccinic acid can be used in combination.

Examples of the aliphatic lactone include one or more saturated aliphatic lactones such as γ-caprolactone, δ-caprolactone, ε-caprolactone, γ-valerolactone, δ-valerolactone, β-methyl-δ-valerolactone. Lactones can be used in combination.

Most preferably, the above-mentioned polyester polyol has a hydroxyl value of 30 to 250 KOHmg / g. If the hydroxyl value is less than 30 KOHmg / g, the curability of the coating composition becomes poor, and if it is more than 250 KOHmg / g, the water resistance is reduced.

The polyester polyol having an average molecular weight of 300 to 5000 can be used. Those having an average molecular weight of 300 or less are inferior in durability when used as a paint,
If it is more than 5000, a uniform solution cannot be obtained and cannot be used as a binder resin.

The addition amount of the polyester polyol is 5 to 50% by weight based on the propylene-α-olefin copolymer.
Is optimal. If the content is more than 50% by weight, gelation or a uniform solution cannot be obtained during the reaction, and the water resistance is lowered, so that it cannot be used as a binder resin. If the amount is less than 5% by weight, the effect of the addition is small, and good inks and paints cannot be obtained.

The polyester polyol can be introduced by esterification or transesterification with a propylene-α-olefin copolymer grafted with an α, β-unsaturated carboxylic acid or an anhydride thereof. Either a method of heating and melting and reacting (melting method) or a method of dissolving and reacting in an organic solvent such as toluene or xylene (solution method) may be used, but the solution method is preferred from the viewpoint that the reaction can be performed uniformly. .

When the polyester polyol is introduced by a melting method, it can be carried out by the same method and apparatus as in the case of the above-described reaction of graft copolymerizing an α, β-unsaturated carboxylic acid or its anhydride. The reaction is carried out at a temperature higher than the melting point of the polymer, and the reaction time is suitably from 10 minutes to 3 hours.

When the polyester polyol is introduced by a solution method, the reaction temperature can be in the range of ordinary temperature to 160 ° C., and the reaction time is suitably 1 to 5 hours. As the solvent, an aromatic solvent, an ester solvent, a ketone solvent or the like can be used in the same manner as described above.

In the case of introducing the polyester polyol by any method, a catalyst such as an inorganic acid, an organic acid, or a tertiary amine may be used, but the reaction can of course be performed without using a catalyst.

Solution polymerization is most suitable for the method of copolymerizing a propylene-α-olefin copolymer into which a polyester polyol has been introduced by the above method with a radically polymerizable unsaturated compound. The solvent used is the aforementioned aromatic solvent,
Ester-based solvents, ketone-based solvents and the like can be used in the same manner, but the reaction can also be carried out by adding a part of monoalcohols.

A specific method of copolymerization is as follows. A propylene-α-olefin copolymer into which a polyester polyol has been introduced is appropriately diluted with a solvent such as toluene, and then heated to form a radical generator and a radical polymerizable unsaturated polymer. The basic process is to react while gradually adding substances, but these may be mixed in advance, heated after adding a radical generator, and then reacted. As the radical generator, azo compounds, sulfides, sulfines, diazo compounds, nitroso compounds, redox compounds and the like can be used in addition to the above-mentioned organic peroxides.

Examples of the radical polymerizable unsaturated compound include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate and 2-hydroxyethyl (meth) acrylate. (Poly) caprolactone-modified (meth) acrylate esterified with caprolactones, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, cyclohexyl (meth) acrylate, 2- Examples include ethylhexyl (meth) acrylate, lauryl (meth) acrylate, styrene, vinyl acetate, (meth) acrylonitrile, glycidyl (meth) acrylate, and allyl glycidyl ether.

The optimal amount of the radical polymerizable unsaturated compound is 5 to 200% by weight based on the propylene-α-olefin copolymer. If the content is less than 5% by weight, the solubility in a solvent and the dispersibility of a pigment are inferior, and sufficient performance cannot be obtained in the case of an ink or paint. If it is at least 200% by weight, the adhesion to polyolefin will be poor.

The binder resin of the present invention is used as a curing agent in an isocyanate compound or in a molecule of -NH group or -NH.
_By compounding two or more compounds containing _two groups,
The coating film properties required for paints and inks, such as gasoline resistance, weather resistance, moisture resistance, hot water resistance (boiling and retort properties), can be improved.

The content of the radical polymerizable unsaturated compound having a hydroxyl group or the radical polymerizable unsaturated compound having a glycidyl group is most preferably 5 to 40% by weight. If the amount is less than this, poor curing occurs when the film is formed, and if it is more than this, the adhesion to the substrate is reduced.

As the isocyanate compound, organic diisocyanates such as tolylene diisocyanate, 1,6-hexamethylene diisocyanate and isophorone diisocyanate can be used. These organic diisocyanates can be used as buret, isocyanurate and trimethylolpropane. It is preferable to use a modified isocyanate derivative such as an adduct.

Compounds containing two or more --NH or --NH ₂ groups in one molecule include aliphatic amines such as ethylenediamine, diethylenetriamine, triethylenetetramine and pentaethylenehexamine, isophoronediamine, 1,3 -Alicyclic polyamines such as diaminocyclohexane, aromatic amines such as m-xylenediamine, polyamide resins obtained by reacting with polymerized fatty acids and the like can be used.

The vanider resin composition of the present invention may be used as it is after being coated, but it can be used as a paint or ink after adding and kneading a pigment, a solvent and other additives. The composition alone shows well-balanced coating film properties, but if necessary, alkyd resin, acrylic resin, polyacryl polyol, polyester resin, polyester polyol, polyether resin, polyether polyol, polyurethane resin, A chlorinated polyolefin or the like may be further added and used.

[0041]

The feature of the present invention is to obtain a binder resin solution which is far more uniform and excellent in gasoline resistance than other similar inventions. That is, propylene-
After adding an α, β-unsaturated carboxylic acid and / or an anhydride thereof to the α-olefin copolymer, at least one polyester polyol is partially reacted with the carboxyl group or the acid anhydride group, Furthermore, a binder resin solution which is uniform and excellent in gasoline resistance can be obtained by graft copolymerizing a radical polymerizable unsaturated substance.

The propylene-α-olefin copolymer originally has no resistance to gasoline and the gasoline resistance is somewhat improved by copolymerizing an acrylic monomer, but is not sufficient. However, it is considered that the introduction of a highly polar polyester polyol into the propylene-α-olefin copolymer increases the polarity of the resin itself and improves gasoline resistance. Further, it is considered that the solubility was improved in the polar solvent and the dispersibility of the pigment were improved due to the imparted polarity, and a binder resin solution exhibiting good coating film properties was obtained.

[0043]

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

(Trial Production Example-1) In a four-necked flask equipped with a stirrer, a condenser, a thermometer and a dropping funnel, a propylene-α-olefin copolymer (propylene component 75
(Mol%, ethylene component 20 mol%, 1-butene component 5 mol%, weight average molecular weight 75,000) 300 g of toluene was dissolved in 700 g of toluene by heating, and then maleic anhydride was added while stirring while maintaining the system temperature at 115 ° C. 13 g and 12 g of di-t-butyl peroxide as a radical generator were each added to 2 g.
The mixture was dropped over a period of time, and then aged for 3 hours. After cooling to room temperature after the reaction, the reaction product was poured into 20 L of acetone and purified to obtain a maleic anhydride graft copolymer having a graft amount of 2.1% by weight.

(Trial Production Example 2) A reaction was carried out in exactly the same manner as in Trial Production Example 1 except that 25 g of maleic anhydride was added dropwise to obtain a maleic anhydride graft copolymer having a graft amount of 4.4% by weight. .

Example 1 In a four-necked flask similar to that of Trial Production Example 1, 100 g of the maleic anhydride graft copolymer obtained in Trial Production Example 1 and 3-methyl-1,5-pentanediol were added. Hydroxyl value 114 obtained by condensation polymerization of adipic acid
After dissolving 20 g of a polyester polyol having a KOH mg / g and an average molecular weight of 1030 in 233 g of toluene, 0.07 g of concentrated sulfuric acid was added and an esterification reaction was carried out at 110 ° C. for 2 hours.

Next, 8.3 g of t-butyl peroxyisopropyl carbonate was added, and a solution in which 97 g of toluene and a radically polymerizable unsaturated substance consisting of 80 g of cyclohexyl acrylate and 20 g of 2-hydroxyethyl acrylate were mixed was added dropwise over 3 hours. The copolymerization reaction was further performed for 7 hours to obtain a binder resin solution in which a radically polymerizable unsaturated compound was graft-copolymerized with a propylene-α-olefin copolymer. The solid content concentration of the binder resin solution was adjusted to 40% by weight with toluene.

The obtained binder resin solution (solid 40)
%) And 24 g of titanium dioxide are kneaded with a sand mill for 3 hours, and then 5.2 g of an isocyanate curing agent Desmodur Z4370 (manufactured by Sumitomo Bayer Urethane Co., Ltd., isophorone diisocyanate, isocyanurate).
, And 13 to 15 seconds / 20 with a No. 4 Ford cup.
The viscosity was adjusted with xylene so that the temperature became ℃, and spray-painted on a polypropylene plate, TX-933A (manufactured by Mitsubishi Yuka Co., Ltd.). After drying at room temperature for 15 minutes, forcibly drying at 80 ° C. for 30 minutes, and leaving it to stand in a room for one week, the coating film was tested by the following test method. The results are shown in Table 1.

Example 2 100 g of the maleic anhydride graft copolymer obtained in Experimental Example 2 and a hydroxy value of 214 KOH mg obtained by condensation polymerization of 3-methyl-1,5-pentanediol and adipic acid. After dissolving 20 g of a polyester polyol having an average molecular weight of 520 / g in 233 g of toluene, 0.07 g of concentrated sulfuric acid was added to carry out an esterification reaction at 110 ° C. for 2 hours.

Next, 8.3 g of t-butyl peroxyisopropyl carbonate was added, and a solution obtained by mixing 97 g of toluene with a radically polymerizable unsaturated substance consisting of 80 g of cyclohexyl acrylate and 20 g of 2-hydroxyethyl acrylate was added dropwise over 3 hours. The copolymerization reaction was further performed for 7 hours to obtain a binder resin solution obtained by graft copolymerizing a radically polymerizable unsaturated compound with a propylene-α-olefin copolymer. The solid content concentration of the binder resin solution was adjusted to 40% by weight with toluene. A coating material was manufactured and a coating film test was performed in the same manner as in Example 1, and the results are shown in Table 1.

Example 3 100 g of maleic anhydride graft copolymer obtained in Experimental Example 2 and a hydroxy value of 214 KOHmg obtained by condensation polymerization of 3-methyl-1,5-pentanediol and adipic acid. After dissolving 10 g of a polyester polyol having an average molecular weight of 520 / g in 233 g of toluene, 0.07 g of concentrated sulfuric acid was added and esterification was carried out at 110 ° C. for 2 hours.

Next, 8.3 g of t-butyl peroxyisopropyl carbonate was added, and a solution obtained by mixing a radically polymerizable unsaturated substance composed of 50 g of cyclohexyl acrylate, 30 g of methyl methacrylate and 20 g of 2-hydroxyethyl acrylate with 92 g of toluene was added. The mixture was dropped over a period of time, and the copolymerization reaction was further performed for 7 hours to obtain a binder resin solution in which a radically polymerizable unsaturated compound was graft-copolymerized with a propylene-α-olefin copolymer. The solid content concentration of the binder resin solution is 40
It was adjusted to wt%. A coating material was manufactured and a coating film test was performed in the same manner as in Example 1, and the results are shown in Table 1.

(Comparative Example 1) In a four-necked flask similar to that of Trial Production Example 1, 100 g of the maleic anhydride graft copolymer obtained in Trial Production Example 1 was dissolved in 233 g of toluene. 0.07 g and 8.3 g of t-butylperoxyisopropyl carbonate were added, and 80 g of cyclohexyl acrylate and 2-hydroxyethyl acrylate 2 were added.
0 g of radically polymerizable unsaturated substance and 67 g of Toern
Was added dropwise over 3 hours, and a copolymerization reaction was further performed for 7 hours to obtain a binder resin solution obtained by graft copolymerizing a radically polymerizable unsaturated compound with a propylene-α-olefin copolymer. . The solid content concentration of the binder resin solution was adjusted to 40% by weight with toluene. Example-1
In the same manner as described above, a paint was produced and a coating film test was performed. The results are shown in Table 1.

Comparative Example 2 Maleic anhydride graft copolymer 10 obtained in Experimental Example 2
0g and a hydroxy value of 214 KOHm obtained by condensation polymerization of 3-methyl-1,5-pentanediol and adipic acid.
g / g, polyester polyol 6 having an average molecular weight of 520
0 g was dissolved in 233 g of toluene.
7 g was added and esterification was performed at 110 ° C. for 2 hours.

Next, 8.3 g of t-butylperoxyisopropyl carbonate was added, and a solution obtained by mixing a radically polymerizable unsaturated substance consisting of 80 g of cyclohexyl acrylate and 20 g of 2-hydroxyethyl acrylate with 97 g of toluene was added dropwise over 3 hours. The copolymerization reaction was further performed for 7 hours to obtain a binder resin solution obtained by graft copolymerizing a radically polymerizable unsaturated compound with a propylene-α-olefin copolymer. The solid content concentration of the binder resin solution was adjusted to 40% by weight with toluene. A coating material was manufactured and a coating film test was performed in the same manner as in Example 1, and the results are shown in Table 1.

[0056]

[Table 1] Judgment criteria in the table ◎ Good ○ Almost good △ Somewhat bad × Bad

Test Method / Adhesion A grid of 100 pieces was formed on the painted surface to reach the substrate at 1 mm intervals, and a cellophane adhesive tape was adhered to the grid to form a grid.
The film was peeled off in the ° direction, and the determination was made based on the extent to which the coating film remained.

Accelerated weathering resistance A carbon arc type sunshine weather meter was used. The whiteness was measured with a Hunter, and the glossiness was measured with a 60 ° specular gloss meter.

Warm water resistance The coated plate was immersed in warm water of 40 ° C. for 120 hours and 240 hours, and the state of the coating film was examined.

Gasoline resistance (rubbing 100 times) Nisseki regular gasoline was impregnated with absorbent cotton, the coated surface was rubbed 100 times, and the state of the coating film was examined. (2 hours of immersion) A scratch (x) reaching the substrate was put on the coated surface, immersed in Nisseki regular gasoline for 2 hours, and the state of the coated film was examined.

Bending resistance The test piece was bent 180 ° with a 1 / 2-inch inch mandrel, and the state of the coating film was examined.

Impact resistance A DuPont type impact tester was used.
Using 00g, drop from the height of 50cm on the painted surface,
The state of the coating film was examined.

Example 4 An ink was prepared with the binder resin solution (solid 40%) obtained in Example 1, and an untreated polypropylene film (hereinafter referred to as untreated PP) and polyethylene phthalate were coated with a coating rod # 10. After coating on a film (hereinafter referred to as PET) and a nylon film (hereinafter referred to as NY), respectively, and drying at room temperature for 24 hours, a cellophane peel test and a heat seal strength test were performed using a cellophane adhesive tape by the following test method. went. The results are shown in Table 3. Table 2 shows the ink formulation.
It was shown to.

(Example-5) An ink was prepared with the binder resin solution (solid 40%) obtained in Example-2, and uncoated PP, PET, and NY were coated with a coating rod # 10, and room temperature was maintained for 24 hours. , And a cellophane peel test and a heat seal strength test were performed using a cellophane adhesive tape. The results are shown in Table 3. The formulation of the ink is shown in Table 2.

(Comparative Example 3) Chlorinated polypropylene Supercron 803 MW (manufactured by Sanyo Kokusaku Pulp Co., Ltd., chlorine content 29.5 wt%, solid content 20 wt%) and chlorinated ethylene vinyl acetate copolymer Supercron BX (Sanyo) Kokusaku Pulp Co., Ltd., chlorine content 18wt%, solid content 20wt
%) Of the mixture was used to prepare an ink, and a similar test was performed. The results are shown in Table 3.

Comparative Example 4 Polyurethane Resin Sambren IB-450 (manufactured by Sanyo Chemical Industries, Ltd., solid content 30)
wt%) and the same test was performed. The results are shown in Table 3.

[0067]

[Table 2] ・ Titanium dioxide (Ishihara Sangyo Co., Ltd., rutile type R-82)
0) ・ Carmine 6BN (Azo-based organic pigment manufactured by Toyo Ink Mfg. Co., Ltd.) ・ Ink kneading condition: Kneading with sand mill for 2 hours

[0068]

[Table 3]

Cellophane tape peeling test A cellophane adhesive tape was stuck on the ink-coated surface, and the peeling state of the coated surface when peeled off at a stretch was determined.

Heat Seal Strength Test The ink-coated surfaces were overlaid, heat sealed at 110 ° C.-1 kg / cm ² for 1 second, and after 24 hours, a 180 ° peel strength test was performed with Tensilon. (Pulling speed 50mm / min)

[0071]

(From the results in Table 1)
The coating compositions of Comparative Examples 1 and 2 show good results in all of weather resistance, durability and gasoline resistance, but the coating compositions of Comparative Examples-1 and 2 are inferior in various physical properties. In the case of Comparative Example-1, since no polyester polyol was added,
In the case of 2, it is considered that the added amount of the polyester polyol is too large, thereby deteriorating the physical properties of the coating film. From this, it can be said that the binder resin composition of the present invention is a coating resin having excellent coating film properties and a good balance.

(From the results in Table 3) The ink of the chlorinated polypropylene / chlorinated ethylene vinyl acetate copolymer system of Comparative Example-3 shows good adhesion to the PP film.
PET and NY films have no adhesion and are far from practical strength. The polyurethane-based ink of Comparative Example-4 was PE
It adheres to T and NY films, but has insufficient adhesion strength to PP films. The inks of Examples 3 and 4 are PP
It shows good adhesiveness to both films and PET and NY films, indicating that the product of the present invention is a highly versatile ink binder.

Claims (14)

(57) [Claims] 1. A graft polymerization of a propylene-α-olefin copolymer with 0.5 to 10% by weight of an α, β-unsaturated carboxylic acid and / or an anhydride thereof. A binder resin composition obtained by reacting a polyol and further graft copolymerizing a radically polymerizable unsaturated compound. 2. The polyester polyol having a hydroxyl value of 3
The binder resin composition according to claim 1, wherein the amount is from 0 to 250 KOHmg / g. 3. The binder resin composition according to claim 1, wherein the polyester polyol has an average molecular weight of 300 to 5,000. 4. The amount of the polyester polyol to be added is 5 to 50% by weight based on the propylene-α-olefin copolymer.
The binder resin composition according to claim 1, which is 5. The binder resin composition according to claim 1, wherein the radical polymerizable unsaturated material is graft-copolymerized with the propylene-α-olefin copolymer by 5 to 200% by weight. 6. The binder resin composition according to claim 1, wherein the radically polymerizable unsaturated substance contains a hydroxyl group-containing radically polymerizable unsaturated substance at a ratio of 5 to 40% by weight. 7. The binder resin composition according to claim 1, wherein the radically polymerizable unsaturated compound contains a glycidyl group-containing radically polymerizable unsaturated compound at a ratio of 5 to 40% by weight. 8. A binder resin composition for coatings, characterized by blending an isocyanate compound as a curing agent with the binder resin composition according to claim 1. Description: 9. A binder resin composition for printing ink, wherein an isocyanate compound is blended as a curing agent into the binder resin composition according to claim 1. Description: 10. A binder resin composition for an adhesive, wherein an isocyanate compound is blended as a curing agent with the binder resin composition according to any one of claims 1 to 6. 11. A compound containing two or more —NH groups or —NH ₂ groups in one molecule as a curing agent is added to the binder resin composition according to any one of claims 1 to 5 and 7. A binder resin composition for a paint, characterized by comprising: 12. A compound containing two or more —NH groups or —NH ₂ groups in one molecule as a curing agent in the binder resin composition according to any one of claims 1 to 5 and 7. A binder resin composition for a printing ink, comprising: 13. A compound containing two or more —NH groups or —NH ₂ groups in one molecule as a curing agent is added to the binder resin composition according to any one of claims 1 to 5 and 7. A binder resin composition for an adhesive. 14. A method for producing the binder resin composition according to claim 1.