JP2665864B2 - 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 the purpose of protecting, aesthetically and adhering various plastics, and more particularly, to a polyolefin resin, a polyurethane resin, a polyamide resin, an acrylic resin, Polyester-based resins, such as films of various synthetic resins, paints showing excellent physical properties for sheets or molded products,
The present invention relates to a binder resin composition for a printing ink or an adhesive.

[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. It has the drawback of saying. 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, JP-A-57-36128, JP-B-63-3
No. 6624 discloses a primer composition containing a chlorinated modified polyolefin as a main component.However, a primer composed of such a chlorinated product has excellent adhesion to polyolefin, but has a drawback that it is inferior in weather resistance and gasoline resistance. Its use was limited.

Japanese Patent Publication No. Sho 62-21027 proposes a surface treating 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, two-coat finishing is complicated.

As a coating composition for one-coat finishing, there are chlorinated polyolefins and cyclized rubbers which have a strong adhesive force 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. 58-719
As seen in No. 66, a coating composition obtained by copolymerizing an acrylic monomer and a chlorinated polyolefin,
As disclosed in JP-A-59-27968, an acrylic monomer having a hydroxyl group and the like and a chlorinated polyolefin are copolymerized, and a chlorinated polyolefin-modified hydroxyl-containing acrylic copolymer and an isocyanate compound as essential components. Paint composition or a hydroxyl group-containing acrylic-modified chlorinated copolymerized with an acrylic monomer having a hydroxyl group in the presence of a chlorinated polyolefin and a liquid rubber as shown in JP-A-62-95372. Adhesive resin compositions containing a polyolefin and an isocyanate compound as main components have been proposed. However, even these acrylic-modified resins have problems in weather resistance and gasoline resistance.

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.

[0010] A large number of inks for lamination used for packaging have been selectively used depending on the type of film. Today, however, the inks for lamination have been broadly classified into two types. That is, an ink composition mainly using a chlorinated polypropylene and a chlorinated ethylene-vinyl acetate copolymer mainly used for a polypropylene film, and an ink composition mainly using a urethane resin mainly used for a polyester and a nylon film as a binder. .

The former ink composition containing a chlorinated polypropylene and a chlorinated ethylene-vinyl acetate copolymer as main binders is disclosed in, for example, Japanese Patent Publication No. 60-31670, and the chlorinated ethylene-vinyl acetate copolymer is further subjected to sulfochlorination. The obtained ink composition is disclosed in JP-A-55-145775. 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-62-153367, 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.

[0013]

As described above, various coating compositions for primer and one-coat finishing, such as acryl-modified chlorinated polyolefin and acryl-modified polyolefin, have been proposed. The coating properties such as weather resistance are not sufficient. 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.

The present inventors have proposed, in Japanese Patent Application Nos. 3-293710 and 4-29898, a resin composition obtained by copolymerizing an ethylene-propylene copolymer and a radical polymerizable unsaturated monomer. However, these resin compositions were still insufficient in gasoline resistance, gloss of a coating film, and compatibility with other resins.

Further, the present inventors have proposed, in Japanese Patent Application No. 4-149841, resin compositions having improved gasoline resistance, which is the drawback described above. It was insufficient in compatibility with other resins.

The present invention relates to a binder resin composition having improved coating film glossiness and compatibility with other resins, gasoline resistance, durability, etc., which are disadvantages of the above proposal, and further to various plastic films. An object of the present invention is to provide a binder resin composition exhibiting good adhesiveness.

[0017]

That is, the present invention relates to an α-olefin polymer and / or a propylene-α-olefin copolymer containing 0.5, 0.5 and 0.5% of an α, β-unsaturated carboxylic acid and / or an anhydride thereof. After graft copolymerization of 10 to 10 wt%, chlorination, and further reaction with polyester polyol (a polyester resin obtained by condensing a polyhydric alcohol and a polybasic acid and having two or more hydroxyl groups in a molecular chain) And a binder resin composition obtained by graft copolymerizing a radically polymerizable unsaturated substance.

As the α-olefin polymer used in the present invention, for example, ethylene, propylene, 1-butene, 1-heptene, 1-octene, 1-hexene, 1-hexene
Those obtained by polymerizing α-olefins such as decene and 4-methyl-1-pentene can be exemplified.

The propylene-α-olefin copolymer is mainly propylene and an α-olefin copolymerized therewith. In particular, a random copolymer is preferable to a block copolymer. As the α-olefin component, those described above can be used.

In the present invention, the ratio between the propylene component and the α-olefin component in the copolymer is not particularly limited, but the propylene component is desirably at least 50 mol%.

Α, which is graft copolymerized to an α-olefin polymer and / or a propylene-α-olefin copolymer
Examples of β-unsaturated carboxylic acids or anhydrides thereof include (meth) acrylic acid, (anhydrous) maleic acid, (anhydrous) citraconic acid, fumaric acid, mesaconic acid, (anhydrous) itaconic acid,
(Anhydrous) aconitic acid and the like.

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

The method of graft copolymerizing an α, β-unsaturated carboxylic acid or its anhydride onto an α-olefin polymer and / or a propylene-α-olefin copolymer is carried out in the presence of a radical generator. A method in which the polymer and / or copolymer is heated and melted to a temperature equal to or higher than the melting point to cause a reaction (melting method). The polymer and / or copolymer is dissolved in an organic solvent, and then heated and stirred in the presence of a radical generator. And a known method (solution method).

In the case of the melting method, a Banbury mixer,
Since the reaction is carried out in a short time at a temperature not lower than the melting point and not higher than 300 ° C. by using a kneader or an extruder, 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. No problem. 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
-Butyl peroxyisopropyl carbonate, cumyl peroxy octoate and the like.

A chlorinated α-olefin polymer obtained by chlorinating an α-olefin polymer obtained by graft copolymerizing an α, β-unsaturated carboxylic acid or an anhydride thereof and / or a propylene-α-olefin copolymer; And / or the chlorinated propylene-α-olefin copolymer has a chlorine content of 10 to 50.
wt% can be used, preferably 15-35 wt%. If the chlorine content is low, the glossiness of the coating film and the compatibility with other resins are poor, and if the chlorine content is high, the adhesion to the polypropylene resin is poor.

The chlorinated α-olefin polymer and / or chlorinated propylene-α-olefin copolymer is obtained by adding α, β-unsaturated carboxylic acid to α-olefin polymer and / or propylene-α-olefin copolymer. After dissolving the acid or its anhydride by graft copolymerization in a chlorine-based solvent such as carbon tetrachloride, it is obtained by irradiating ultraviolet rays or by blowing gaseous chlorine in the presence of the above-mentioned organic peroxide. Can be

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.

The polyhydric alcohols include ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol,
Polypropylene glycol, neopentyl glycol,
1,2-, 1,3-, 1,4-, 2,3-butanediol, 1,5-pentanediol, 3-methyl-1,5-
One or more polyhydric alcohols such as pentanediol and 1,6-hexanediol can be used in combination.

Examples of the polybasic acids include (phthalic anhydride), (tetrahydrophthalic anhydride), hexahydrophthalic anhydride (anhydrous), methyltetrahydrophthalic anhydride (anhydrous),
(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 at least one saturated aliphatic lactone such as γ-caprolactone, δ-caprolactone, ε-caprolactone, γ-valerolactone, δ-valerolactone, β-methyl-δ-valerolactone and the like. Lactones can be used in combination.

The above polyester polyol having a hydroxyl value of 30 to 250 KOH mg / g is most suitable. 30K hydroxyl value
If it is less than OHmg / g, the curability of the paint will be poor, and if it is more than 250KOHmg / g, the water resistance will decrease.

The polyester polyol having an average molecular weight of 300 to 5,000 can be used. Average molecular weight 300
The following are inferior in durability when used as paint, and 5000
Above, a uniform solution cannot be obtained and cannot be used as a binder resin.

The added amount of the polyester polyol is chlorinated α-olefin polymer and / or chlorinated propylene-α
5 to 50% by weight based on the olefin copolymer is optimal. If it is more than 50% by weight, a gelled or 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 is a chlorinated α-olefin polymer and / or a chlorinated propylene-α-olefin copolymer obtained by graft copolymerizing an α, β-unsaturated carboxylic acid or its anhydride and further chlorinating the same. It can be introduced by esterification or transesterification with phenol, and can be carried out by heating and melting to a melting point or higher (melting method) or by dissolving it in an organic solvent such as toluene or xylene (solution method). May be any of
The solution method is preferred from the viewpoint that dehydrochlorination is suppressed and 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 above-described reaction of graft copolymerizing an α, β-unsaturated carboxylic acid or its anhydride. The reaction temperature is higher than the melting point of the polymer, and the reaction time is suitably from 10 minutes to 3 hours.

When the introduction of the polyester polyol is carried out by a solution method, the reaction temperature can be in the range of ordinary temperature to 160 ° C.,
An appropriate reaction time is 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.

The method of copolymerizing a chlorinated α-olefin polymer and / or a chlorinated propylene-α-olefin copolymer into which a polyester polyol has been introduced by the above-mentioned method and a radical polymerizable unsaturated compound involves solution polymerization. Most suitable. As the solvent to be used, the above-mentioned aromatic solvent, ester solvent, ketone solvent and the like can be used in the same manner, but it is also possible to react by adding a part of monoalcohols.

A specific method of copolymerization is to appropriately dilute the chlorinated α-olefin polymer and / or chlorinated propylene-α-olefin copolymer into which the polyester polyol has been introduced with a solvent such as toluene, and then add the resulting mixture. The basic process is to heat and react while gradually adding the radical generator and the radical polymerizable unsaturated substance. However, these may be mixed in advance, heated after the radical generator is added, and then reacted.

As the radical generator, in addition to the above-mentioned organic peroxides, azo compounds, sulfides, sulfines, diazo compounds, nitroso compounds, redox compounds and the like can be used.

Examples of the radical polymerizable unsaturated substance include 2-hydroxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate,
(Poly) caprolactone-modified (meth) acrylate obtained by esterifying hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate or 2-hydroxyethyl (meth) acrylate with caprolactones, methyl (meth) acrylate, ethyl (meth) ) Acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate,
Lauryl (meth) acrylate, styrene, vinyl acetate, (meth) acrylonitrile, glycidyl (meth) acrylate, allyl glycidyl ether, and the like.

The amount of the radically polymerizable unsaturated compound to be added depends on the amount of the chlorinated α-olefin polymer and / or chlorinated propylene.
The optimum content is 5 to 200% by weight based on the 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 more than 200 wt%, the adhesion to polyolefin will be poor.

The binder resin obtained by copolymerizing the radical polymerizable unsaturated compound having a hydroxyl group or the radical polymerizable unsaturated compound having a glycidyl group of the present invention is an isocyanate compound as a curing agent or -NH in one molecule. Group or -N
By blending a compound containing two or more H ₂ groups, it is possible to improve the coating properties required for paints and inks, such as gasoline resistance, weather resistance, moisture resistance, hot water resistance (boiling and retort properties). it can.

The content of the radical polymerizable unsaturated compound having a hydroxyl group or the radical polymerizable unsaturated compound having a glycidyl group is optimally 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 binder resin composition of the present invention may be used after being coated as it is, but it can be used as a paint or ink by 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.

[0050]

The feature of the present invention is that a binder resin solution which is much more uniform than other similar inventions, and has excellent glossiness and compatibility with other resins and improved gasoline resistance. Is to get

That is, after adding an α, β-unsaturated carboxylic acid and / or an anhydride thereof to an α-olefin polymer and / or a propylene-α-olefin copolymer and chlorinating the same, at least one Polyester polyol is partially reacted with the carboxyl group or acid anhydride group, and further is graft-copolymerized with a radical polymerizable unsaturated compound to obtain a uniform and excellent coating film gloss and excellent compatibility with other resins. A binder resin solution with improved gasoline resistance is obtained.

The α-olefin polymer and / or the propylene-α-olefin copolymer are originally poor in solubility in a solvent and poor in gasoline resistance, but the solubility is improved by chlorination. , A highly polar polyester polyol is converted to an α-olefin polymer and / or propylene
It is considered that the introduction into the α-olefin copolymer increased the polarity of the resin itself and improved the 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.

[0053]

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) A four-necked flask equipped with a stirrer, a cooling tube, a thermometer and a dropping funnel was heated at 160 ° C.
Of 300 g of isotactic polypropylene having a melt viscosity of about 4000 cps at 200 ° C., 25 g of maleic anhydride and 12 g of di-t-butyl peroxide as a radical generator were added dropwise over 2 hours. After aging for a time, a maleic anhydride graft copolymer having a graft amount of 4.4 wt% was obtained.

Next, the copolymer was charged into a glass-lined reaction vessel, 5 L of carbon tetrachloride was added, and 2 kg / cm
^The chlorine content is 24wt% while irradiating ultraviolet rays under the pressure of ^2.
Gaseous chlorine was blown from the bottom of the reaction vessel until the temperature reached.
After completion of the reaction, the solvent, carbon tetrachloride, was distilled off using an evaporator, and a 30 wt% toluene solution of a chlorinated polyolefin modified with maleic anhydride by substitution with toluene was obtained.

(Trial Production Example-2) 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%, 5 mol% of 1-butene component,
300 g of toluene was heated and dissolved in 700 g of toluene, and then 13 g of maleic anhydride and 12 g of di-t-butyl peroxide as a radical generator were added for 2 hours while stirring while maintaining the temperature of the system at 115 ° C. Then, the mixture was aged for 3 hours. After the reaction, the reaction product was cooled to room temperature, and then poured into 20 L of acetone for purification.
A 2.1% by weight maleic anhydride graft copolymer was obtained.

Next, the copolymer was charged into a glass-lined reaction vessel, and 5 L of carbon tetrachloride was added thereto.
Under the pressure of ² , while irradiating ultraviolet rays, chlorine content is 18wt%
Gaseous chlorine was blown from the bottom of the reaction vessel until the temperature reached.
After completion of the reaction, the solvent, carbon tetrachloride, was distilled off using an evaporator, and a 30 wt% toluene solution of a chlorinated polyolefin modified with maleic anhydride by substitution with toluene was obtained.

(Trial Production Example 3) A graft reaction was carried out in exactly the same manner as in Trial Production Example 2 except that 25 g of maleic anhydride was added dropwise to obtain a maleic anhydride graft copolymer having a graft amount of 4.4 wt%. This maleic anhydride graft copolymer was dissolved in toluene to prepare a 30 wt% toluene solution.

(Example 1) In a four-necked flask similar to that of Trial Production Example 1, 3 parts of 333 g of a 30 wt% toluene solution of the chlorinated maleic anhydride graft copolymer obtained in Trial Production Example 1 was added.
-Hydroxyl value 114 KOH mg / g, average molecular weight 10 obtained by condensation polymerization of -methyl-1,5-pentanediol and adipic acid.
After dissolving 20 g of 30 polyester polyol, 0.07 g of concentrated sulfuric acid was added, and an esterification reaction was performed 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 was mixed with 80 g of cyclohexyl acrylate and 20 g of 2-hydroxyethyl acrylate and 97 g of toluene was added dropwise over 3 hours. Further, a 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 chlorinated α-olefin polymer. The solid content concentration of the binder resin solution was adjusted to 40% by weight with toluene.

The compatibility between the binder resin and the other resin was tested using a 20% toluene solution. Table 1 shows the compatibility test results.

The obtained binder resin solution (solid 40)
%) After kneading 100 g and titanium dioxide 24 g in a sand mill for 3 hours, isocyanate curing agent Desmodur Z43
5.2 g of 70 (manufactured by Sumitomo Bayer Urethane Co., Ltd., isophorone diisocyanate, isocyanurate) was added,
The viscosity was adjusted with xylene at 13 to 15 seconds / 20 ° C with a No. 4 Ford cup, and a polypropylene plate, TX-933A
(Mitsubishi Yuka Co., Ltd.) was spray painted. After drying at room temperature for 15 minutes, forcible drying was performed at 80 ° C. for 30 minutes. The results are shown in Table 2.

Example 2 3-methyl-1,5-pentanediol and adipic acid were obtained by condensation polymerization of 333 g of the chlorinated maleic anhydride graft copolymer solution obtained in Prototype Example-2. After dissolving 20 g of a polyester polyol having a hydroxyl value of 214 KOH mg / g and an average molecular weight of 520, concentrated sulfuric acid was added.
07 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 in which 97 g of toluene was mixed with 80 g of cyclohexyl acrylate and 20 g of 2-hydroxyethyl acrylate and 97 g of toluene was added dropwise over 3 hours. Further, the copolymerization reaction was carried out for further 7 hours to obtain a binder resin solution obtained by graft copolymerizing a chlorinated propylene-α-olefin copolymer with a radically polymerizable unsaturated compound. The solid content concentration of the binder resin solution was adjusted to 40% by weight with toluene. A compatibility test and a paint were manufactured and a coating film test was performed in the same manner as in Example-1.

(Example 3) 3-methyl-1,5-pentanediol and adipic acid were polycondensed with 333 g of the chlorinated maleic anhydride graft copolymer solution obtained in Trial Production Example-2. After dissolving 10 g of a polyester polyol having a hydroxyl value of 214 KOH mg / g and an average molecular weight of 520, concentrated sulfuric acid was added.
07 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 radical polymerizable unsaturated substance consisting of 50 g of cyclohexyl acrylate, 30 g of methyl methacrylate and 20 g of 2-hydroxyethyl acrylate with 82 g of toluene was added for 3 hours. The resulting mixture was further dropped for 7 hours to carry out a copolymerization reaction, thereby obtaining a binder resin solution obtained by graft copolymerizing a radically polymerizable unsaturated compound with a chlorinated propylene-α-olefin copolymer.
The solid content concentration of the binder resin solution was adjusted to 40% by weight with toluene. A compatibility test and a paint were manufactured and a coating film test was performed in the same manner as in Example-1.

(Comparative Example 1) In a four-necked flask similar to that of Trial Production Example 1, 333 g of the chlorinated maleic anhydride graft copolymer solution obtained in Trial Production Example 1 was added with 0.07 g of concentrated sulfuric acid,
8.3 g of -butylperoxyisopropyl carbonate was added, and a solution obtained by mixing 67 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, and further over 7 hours. To obtain a binder resin solution in which a chlorinated α-olefin polymer was graft-copolymerized with a radically polymerizable unsaturated compound. The solid content concentration of the binder resin solution was adjusted to 40% by weight with toluene. A compatibility test and a paint were manufactured and a coating film test was performed in the same manner as in Example-1.

Comparative Example 2 3-methyl-1,5-pentanediol and adipic acid were polycondensed with 333 g of the chlorinated maleic anhydride graft copolymer solution obtained in Prototype Example-2. After dissolving 60 g of a polyester polyol having a hydroxyl value of 214 KOH mg / g and an average molecular weight of 520, concentrated sulfuric acid was added.
07 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 157 g of toluene was added dropwise over 3 hours. Further, the copolymerization reaction was carried out for further 7 hours to obtain a binder resin solution obtained by graft copolymerizing a chlorinated propylene-α-olefin copolymer with a radically polymerizable unsaturated compound. The solid content concentration of the binder resin solution was adjusted to 40% by weight with toluene. A compatibility test and a paint were manufactured and a coating film test was performed in the same manner as in Example-1.

Comparative Example 3 333 g of the maleic anhydride graft copolymer solution obtained in Prototype Example 3 was added to 3-methyl-1,
After dissolving 10 g of a polyester polyol having a hydroxyl value of 214 KOH mg / g and an average molecular weight of 520, obtained by polycondensation of 5-pentanediol and adipic acid, 0.07 g of concentrated sulfuric acid was added, and the ester was added at 110 ° C. for 2 hours. The reaction was carried out.

Next, 8.3 g of t-butyl peroxyisopropyl carbonate was added, and a solution in which 97 g of toluene was mixed with a radical polymerizable unsaturated substance consisting of 80 g of cyclohexyl acrylate and 20 g of 2-hydroxyethyl acrylate was added dropwise over 3 hours. Further, a copolymerization reaction was carried out for further 7 hours to obtain a binder resin solution in which a radical 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. A compatibility test and a paint were manufactured and a coating film test was performed in the same manner as in Example-1.

(Example-4) 100 g of the binder resin solution (solid 40%) obtained in Example-1 and 17 g of titanium dioxide were kneaded with a sand mill for 3 hours, and then appropriately diluted with toluene. −933A (Mitsubishi Yuka Corporation)
Spray Coating). After standing at room temperature for 10 minutes, a two-component urethane top coat was spray applied. 15 at room temperature
After drying for 30 minutes, the film was forcibly dried at 80 ° C. for 30 minutes, allowed to stand in a room for one week, and then subjected to a coating film test. The results are shown in Table 3.

(Example-5) Example-4 except that the binder resin solution (solid 40%) obtained in Example-2 was used.
The test was performed in the same manner as in the above.

(Example-6) Example-4 except that the binder resin solution (solid 40%) obtained in Example-3 was used.
The test was performed in the same manner as in the above.

(Comparative Example 4) Example 4 except that the binder resin solution (solid 40%) obtained in Comparative Example 1 was used.
The test was performed in the same manner as in the above.

(Comparative Example-5) Example-4 except that the binder resin solution (solid 40%) obtained in Comparative Example-2 was used.
The test was performed in the same manner as in the above.

(Comparative Example-6) Example-4 except that the binder resin solution (solid 40%) obtained in Comparative Example-3 was used.
The test was performed in the same manner as in the above.

(Example-7) 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 terephthalate were coated with a coating rod # 10. Film (hereinafter referred to as PET), nylon film (hereinafter referred to as N
Y), dried at room temperature for 24 hours, and then subjected to a cellophane tape peeling test and a heat seal strength test using a cellophane adhesive tape. Table 5 shows the results. The formulation of the ink is shown in Table 4.

(Example-8) Example-7 except that the binder resin solution (solid 40%) obtained in Example-2 was used.
The ink was prepared in the same manner as described above, and a cellophane peel test and a heat seal strength test were performed.

(Comparative Example-7) As Comparative Example-7, chlorinated polypropylene Supercron 803MW (manufactured by Sanyo Kokusaku Pulp Co., Ltd., chlorine content 29.5wt%, solid content 20wt%) and chlorinated ethylene vinyl acetate copolymer Super Clon B
The same test was conducted by preparing an ink with a mixture of X (manufactured by Sanyo Kokusaku Pulp Co., Ltd., chlorine content 18 wt%, solid content 20 wt%).

(Comparative Example-8) As Comparative Example-8, a similar test was conducted by preparing an ink using a polyurethane resin Sambrene IB-450 (manufactured by Sanyo Chemical Industries, Ltd., solid content: 30 wt%).

[0082]

[Table 1] Judgment criteria in the table ◎: good ：: slightly cloudy △: cloudy ×: two-layer separation

[0083]

[Table 2] Test results of coating film

Test Method / Adhesion 100 cross-cuts were made on the painted surface to reach the substrate at 1 mm intervals, and a cellophane adhesive tape was stuck on it and 180 °
The film was peeled off in the direction and the degree of the remaining coating film was evaluated.

Accelerated weather 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 immersion) Scratch reaching the substrate on the coated surface (×)
Was immersed in Nisseki regular gasoline for 2 hours, and the state of the coating film was examined.

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

Impact resistance A DuPont type impact tester was used.
g was dropped on a coated surface from a height of 50 cm, and the state of the coating film was examined.

[0090]

[Table 3] Judgment criteria in the table ◎: good ○: almost good △: slightly poor ×: bad

Test Method / Adhesion 100 cross-cuts were made on the painted surface to reach the substrate at 1 mm intervals, and a cellophane adhesive tape was adhered on top of it and 180 °
The film was peeled off in the direction and the degree of the remaining coating film was evaluated.

Moisture resistance The coated plate was left in an atmosphere of 50 ° C. and 98% RH for 120 hours and 240 hours, and the state of the coating film was examined.

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. (4 hours immersion) Scratch reaching the substrate on the coated surface (×)
Was immersed in Nisseki regular gasoline for 4 hours, and the state of the coating film was examined.

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

Impact resistance A DuPont type impact tester was used.
g was dropped on a coated surface from a height of 50 cm, and the state of the coating film was examined.

[0097]

[Table 4] ・ Titanium dioxide (Ishihara Sangyo Co., Ltd., rutile type R-820) ・ Carmine 6BN (Toyo Ink Mfg. Co., Ltd., azo organic pigment) ・ Ink kneading condition: Kneading with sand mill for 2 hours

[0098]

[Table 5]

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

[0100] - by heat-sealing strength test ink coating was cumene overlapped, 1 at 110 ℃ -1kg / cm ²
Heat sealing was performed under pressure bonding conditions for 2 seconds, and after 24 hours, a 180 ° peel strength test was performed using Tensilon. (Pulling speed 50
mm / min)

[0101]

【The invention's effect】

(From the results of Tables 1, 2, and 3) The binder resins of Examples -1 to 6 have excellent compatibility with other resins, and the coating compositions show good results in all of weather resistance, durability and gasoline resistance. However, the coating compositions of Comparative Examples-1 to 6 are inferior in various physical properties. In the case of Comparative Examples-1 and 4, the polyester polyol was not added, and in the case of Comparative Examples-2 and 5,
It is considered that the amount of the polyester polyol added was too large, and in Comparative Examples-3 and 6, the physical properties of the coating film were deteriorated because they were not chlorinated. From this, it can be said that the binder resin composition of the present invention is a coating resin having excellent and excellent balance in coating film properties.

(From the results in Table 5) The chlorinated polypropylene / chlorinated ethylene-vinyl acetate copolymer ink of Comparative Example-7 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-8 was PE
It adheres to T and NY films, but has insufficient adhesion strength to PP films. The inks of Examples 7 and 8 show good adhesion to PP film, PET film and NY film, indicating that the product of the present invention is a highly versatile ink binder.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification number Agency reference number FI Technical indication location C09J 175/04 JFB C09J 175/04 JFB

Claims (11)

(57) [Claims] 1. An α-olefin polymer and / or a propylene-α-olefin copolymer containing 0.5 to 10% by weight of an α, β-unsaturated carboxylic acid and / or an anhydride thereof.
A binder resin composition obtained by graft copolymerizing, chlorinating, further reacting a polyester polyol, and then graft copolymerizing a radically polymerizable unsaturated compound. 2. The binder resin composition according to claim 1, wherein the chlorine content of the chlorinated α-olefin polymer and / or the chlorinated propylene-α-olefin copolymer is 10 to 50% by weight. 3. A polyester polyol having a hydroxyl value of 30.
The binder resin composition according to claim 1, wherein the amount is from 250 to 250 KOHmg / g. 4. The polyester polyol having an average molecular weight of
The binder resin composition according to claim 1, which has a molecular weight of 300 to 5,000. 5. The method according to claim 1, wherein the amount of the polyester polyol is chlorinated α-olefin polymer and / or chlorinated propylene.
2. The binder resin composition according to claim 1, wherein the amount is 5 to 50% by weight based on the α-olefin copolymer. 6. The method according to claim 6, wherein the radically polymerizable unsaturated compound is chlorinated α-
2. The binder resin composition according to claim 1, wherein 5 to 200 wt% of the olefin polymer and / or the chlorinated propylene-α-olefin copolymer is graft-copolymerized. 3. 7. The binder resin composition according to claim 1, wherein the radically polymerizable unsaturated compound contains a hydroxyl group-containing radically polymerizable unsaturated compound at a ratio of 5 to 40% by weight. 8. 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. 9. A binder resin composition for paints, printing inks or adhesives, characterized in that an isocyanate compound is added as a curing agent to the binder resin composition according to claim 1. 10. The binder resin composition according to claim 1, wherein a curing agent is -NH group or -NH in one molecule.
_A binder resin composition for paints and printing inks or adhesives, characterized by containing a compound containing two or more groups. 11. An α-olefin polymer and / or a propylene-α-olefin copolymer containing 0.5 to 10 wt% of an α, β-unsaturated carboxylic acid and / or an anhydride thereof.
%. A method for producing a binder resin composition, which comprises graft-copolymerizing a chlorinated polyester copolymer, reacting a polyester polyol, and then graft-copolymerizing a radically polymerizable unsaturated substance in the presence of a radical generator.