JPH05105841A - Binder resin composition - Google Patents

Abstract

PURPOSE:To prepare the title compsn. which is excellent in storage stability and gives a coating film excellent in resistance to gasoline and durability by grafting a radical polymerizable unsatd. compd. onto a modified propylene-alpha- olefin copolymer having reactive unsatd. groups in the presence of a monoalcohol. CONSTITUTION:A propylene-alpha-olefin copolymer is grafted with 1.0-10wt.% alpha,beta- unsaid. carboylic acid and/or its anhydride [e.g. (meth)acrylic acid or maleic acid (anhydride)]. Part of groups derived from the acid and/or its anhydride in the resulting product are reacted with 0.5-10wt.% reactive unsatd. compd. having at least one hydroxyl, glycidyl, amino, or amide group [e.g. 2- hydroxyethyl (meth)acrylate]. Onto the reaction product is grafted a radical- polymerizable unsatd. compd. [e.g. methyl (meth)acrylate] in the presence of a monoalcohol to give a graft copolymer, which is used as the main component for preparing the title compsn.

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 various plastics, cosmetics and adhesion, and more specifically, a polyolefin resin, a polyurethane resin, a polyamide resin, an acrylic resin, TECHNICAL FIELD The present invention relates to a binder resin composition for paints, printing inks, or adhesives, which has excellent properties for polyester resins, various synthetic resin films, sheets, or molded products.

[0002]

2. Description of the Related Art In recent years, plastics have many advantages such as high productivity, wide design freedom, light weight, rust prevention, and impact resistance. Therefore, in recent years, plastics have been used as materials for automobile parts, electric parts, building materials, etc. Many are used. In particular, polyolefin resins are widely used as industrial materials because they have many excellent properties such as low cost, moldability, chemical resistance, heat resistance, water resistance, and good electrical properties. Growth is one of the most anticipated materials.

However, unlike a synthetic resin having a polarity, such as a polyurethane resin, a polyamide resin, an acrylic resin, a polyester resin, a polyolefin resin is non-polar and crystalline, so that it is difficult to coat or bond it. There is a drawback to say.

Therefore, conventionally, the surface of the polyolefin resin molded product is subjected to plasma treatment or gas flame treatment to be activated to improve the adhesion, but this method involves complicated steps and requires a large amount of equipment and time. However, there is a drawback that the surface treatment effect varies due to the complicated loss of the shape of the molded product and the influence of pigments and additives in the resin.

As a method of coating without such a pretreatment, various primer compositions such as those used for coating polypropylene bumpers of automobiles have been proposed. For example, Japanese Patent Publication No. 62-21027 proposes a surface treating agent obtained by modifying a propylene-α-olefin copolymer with maleic acid. However, a primer composition obtained by only introducing maleic acid into a polyolefin has the drawbacks of poor sprayability, solubility and compatibility, although it has adhesion and solvent resistance. In addition, it is complicated with a two-coat finish.

As a coating composition for one-coat finishing, there are chlorinated polyolefin, chlorinated rubber and the like which have a strong adhesive force to a polyolefin resin, but the weather resistance,
Moisture resistance, gasoline resistance, etc. are inferior and do not show sufficient coating film performance. Therefore, attempts have been made to mix and use acrylic resins and alkyd resins having good paint properties, but originally acrylic resins and alkyd resins have poor compatibility with chlorinated polyolefins, which reduces the gloss of the coating film, This causes problems such as a marked loss of appearance.

[0007] In order to improve these drawbacks, JP-A-58-719
As seen in Japanese Patent Publication No. 96, a coating composition obtained by copolymerizing an acrylic monomer and a chlorinated polyolefin,
As seen in JP-A-59-27968, copolymerized with a chlorinated polyolefin and an acrylic monomer having a hydroxyl group, chlorinated polyolefin modified hydroxyl group-containing acrylic copolymer and an isocyanate compound as essential components And 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 seen in JP-A-62-95372. An adhesive resin composition containing a polyolefin and an isocyanate compound as main components has been proposed. However, the composition containing these chlorine is
It is slightly inferior in UV resistance and heat resistance and has a problem in long-term weather resistance.

On the other hand, as a chlorine-free composition, JP-A-62-27308 discloses an ethylene-propylene copolymer graft-polymerized with maleic acid, a functional group monomer and a radical-polymerizable unsaturated monomer. A method for forming a multilayer coating film comprising a copolymerized resin composition and a crosslinking agent has been proposed. However, also in this method, when the copolymerization reaction is carried out at a high concentration, gelation may occur during the reaction, and therefore it is necessary to carry out the reaction at a very dilute concentration. For this reason, the graft copolymerization efficiency to polyolefin is very low, a homopolymer of a radically polymerizable unsaturated monomer is produced, and two layers are separated unless a step such as refining occurs, and it cannot be used as it is.

On the other hand, various kinds of plastic films have been developed and used as food packaging materials.
Along with this, packaging forms have been diversified, and in particular, in order to protect packaging contents, the use of laminated composite films is increasing. As the laminating ink used for these packaging, a large number of inks are properly used depending on the type of film, but today, the laminating ink is roughly classified into two types. That is, an ink composition mainly composed of chlorinated polypropylene and chlorinated ethylene vinyl acetate copolymer mainly used for polypropylene film, and an ink composition mainly composed of polyester resin and urethane resin mainly used for nylon film. ..

The former ink composition containing a chlorinated polypropylene and a chlorinated ethylene vinyl acetate copolymer as a main binder is disclosed, for example, in JP-B-60-31670, and a chlorinated ethylene vinyl acetate copolymer is further sulfochlorinated. The ink composition prepared is disclosed in JP-A-55-145775. These have good ink adhesion to the untreated polypropylene film, and also show good adhesion when laminated printed by the extrusion lamination method. However, it has poor adhesion to films of polyester, nylon and the like, and is not suitable as a printing ink for lamination to these films.

The latter ink composition containing a urethane resin as a main binder is a film having polarity such as polyester and nylon as disclosed in JP-A-62-153366 and JP-A-62-153367. However, it does not adhere to untreated polypropylene film at all, and printing by the polypropylene extrusion lamination method is impossible.

[0012]

SUMMARY OF THE INVENTION In order to solve the above problems, the present inventor has added 0.1 to 20 α, β-unsaturated carboxylic acid or its anhydride to a propylene-α-olefin copolymer. % By Graft Copolymerization, followed by bonding a reactive unsaturated compound having at least one hydroxyl group, glycidyl group or amino group, and then graft copolymerizing a radical polymerizable unsaturated compound, and containing a resin. A coating composition for a polyolefin resin, characterized by
It was already proposed in Japanese Patent Application No. 2-23373.

However, the reaction solution varnish obtained by this method thickens with time and has a problem in storage stability. Further, there is a drawback that the coating film is inferior in gasoline resistance and durability because it is not crosslinked by the curing agent.

[0014]

[Means for Solving the Problems] Therefore, the present inventors further examined and improved the above-mentioned Japanese Patent Application No. 2-23373, and as a result, the storage stability, the gasoline resistance and durability of the coating film were improved. The inventors have found that the properties such as the above can be improved and have completed the present invention.

That is, in the present invention, 1.0 to 10% by weight of an α, β-unsaturated carboxylic acid and / or an anhydride thereof is graft-copolymerized with a propylene-α-olefin copolymer, and then at least one hydroxyl group, 0.5 to 10% by weight of a reactive unsaturated compound having a glycidyl group, an amino group or an amide group is partially reacted with an α, β-unsaturated carboxylic acid and / or its anhydride, and the radical is further present in the presence of a monoalcohol. A binder resin composition obtained by graft-copolymerizing a polymerizable unsaturated substance.

As described above, the present invention further limits the range of the α, β-unsaturated carboxylic acid and / or its anhydride and reactive unsaturated compound shown in the above-mentioned Japanese Patent Application No. 2-23373. Moreover, the addition of monoalcohol improves the properties such as storage stability and gasoline resistance and durability of the coating film.

[0017]

The propylene-α-olefin copolymer used in the present invention comprises propylene as a main component and an α-olefin copolymerized therein, 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, 4-methyl-1-pentene and the like.

In the present invention, the ratio of the propylene component and the α-olefin component in the copolymer is not particularly limited, but the propylene component is preferably 50 mol% or more. Further, as the α, β-unsaturated carboxylic acid or its acid anhydride graft-copolymerized with the propylene-α-olefin copolymer, (meth) acrylic acid, (anhydrous) maleic acid, (anhydrous) citraconic acid, fumaric acid Acid, mesaconic acid, (anhydrous) itaconic acid, (anhydrous) aconitic acid, etc. are mentioned.

In the present invention, the amount of the α, β-unsaturated carboxylic acid or its acid anhydride introduced by graft copolymerization is optimally 1.0 to 10% by weight. If the amount is less than 1.0% by weight, the resulting composition will separate into two layers and a good paint or ink cannot be obtained. If it exceeds 10% by weight, it gels during the reaction and cannot be used as a binder resin.

In the propylene-α-olefin copolymer,
The method for graft-copolymerizing an α, β-unsaturated carboxylic acid or an acid anhydride thereof is a method in which a propylene-α-olefin copolymer is heated and melted at a melting point or higher in the presence of a radical generator to react (melting method. ), A method in which a propylene-α-olefin copolymer is dissolved in an organic solvent and then heated and stirred in the presence of a radical generator to cause a reaction (solution method)
Etc. can be performed by a known method.

In the case of the melting method, a Banbury mixer, a kneader, an extruder or the like is used and the reaction is carried out at a temperature above the melting point and below 300 ° C. in a short time, 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 the organic solvent, but it is also possible to partially mix and use an ester solvent, a ketone solvent or the like. .. The radical generator used in the reaction can be appropriately selected from known ones, but organic peroxide compounds are particularly desirable.

Examples of the organic peroxide compounds include benzoyl peroxide, di-tert-butyl peroxide, dicumyl peroxide, lauroyl peroxide, tert-peroxybenzoate, cumene hydroperoxide and the like. Be done.

Propylene-grafted with α, β-unsaturated carboxylic acid or its acid anhydride in the present invention
The carboxyl group or acid anhydride group possessed by the α-olefin copolymer forms an ester, amide or imide with a reactive unsaturated compound having at least one hydroxyl group, chrysidyl group, amino group or amide group. It is possible to chemically bond. That is, the reactive unsaturated substance can be introduced into the propylene-α-olefin copolymer by such a reaction method.

The reactive unsaturated compound having at least one hydroxyl group, glycidyl group, amino group or amide group used in the present invention may be, for example, 2-hydroxyethyl (meth) having a hydroxyl group. ) Acrylate, 2-hydroxypropyl (meth) acrylate, 2
There are (poly) caprolactone-modified (meth) acrylates obtained by esterifying 2-hydroxybutyl (meth) acrylate and 2-hydroxyethyl (meth) acrylate with caprolactones. Examples of those having a glycidyl group include glycidyl (meth) acrylate and allyl glycidyl ether. Allylamine and the like have an amino group. Examples of those having an amide group include acrylamide, N-methylol acrylamide, and N-butoxymethyl acrylamide.

The method for introducing the reactive unsaturated compound is α, β
-A method in which a propylene-α-olefin copolymer grafted with an unsaturated carboxylic acid or an acid anhydride thereof is melted by heating at a melting point or higher to react (melting method), or dissolved in an organic solvent such as toluene or xylene. Either reaction (solution method) may be used, but the solution method is preferable from the viewpoint that the reaction can be carried out uniformly.

When the reactive unsaturated substance is introduced by the melting method, it may be carried out by the same method and apparatus as in the case of the reaction of graft-copolymerizing the α, β-unsaturated carboxylic acid or its acid anhydride. Although possible, it is necessary to introduce the reactive unsaturated compound after the radical generator has completely disappeared because the double bond is attacked if the radical remains. The reaction temperature is not lower than the melting point of the polymer and not higher than the boiling point of the reactive unsaturated substance, and the reaction time is suitably 10 minutes to 3 hours.

When the reactive unsaturated substance is introduced by the solution method, the reaction temperature can be in the range of normal temperature to 160 ° C., and the reaction time is appropriately 1 to 20 hours. As the solvent, aromatic solvents, ester solvents, ketone solvents and the like can be used in the same manner as described above.

In any case of introducing the reactive unsaturated compound, it is desirable to use a catalyst such as an inorganic acid, an organic acid or a tertiary amine. Of course, the reaction can be carried out without using a catalyst.

The amount of the reactive unsaturated substance added is propylene-α.
0.5 to 10% by weight is optimal with respect to the olefin copolymer. If the amount added exceeds 10% by weight, it will gel during the reaction and cannot be used as a binder resin. If the amount added is less than 0.5% by weight, the resulting composition will separate into two layers and a good ink or paint will be obtained. Absent.

Solution polymerization is most suitable for the method of copolymerizing the reactive unsaturated group introduced into the trunk polymer by the above-mentioned method with the radically polymerizable unsaturated compound which can be polymerized with the reactive unsaturated group. The solvent used is the aromatic solvent described above, an ester solvent,
Although a ketone solvent or the like can be used in the same manner, a uniform binder resin composition of the present invention having good storage stability can be obtained by adding a part of monoalcohols and reacting.

Examples of monoalcohols include methanol, ethanol, propanol and butanol. The addition amount of monoalcohol is appropriately 2 to 20% by weight in the reaction solvent. After the completion of the copolymerization reaction, the residual monoalcohol may be removed by distillation and used or may be left as it is without any problem in the practice of the present invention, and may be appropriately selected according to the purpose of use.

A specific copolymerization method is as follows: a propylene-α-olefin copolymer into which a reactive unsaturated group is introduced,
The basic process is to appropriately dilute with a solvent containing a monoalcohol, add a radical generator, and then heat the mixture to gradually add the radically polymerizable unsaturated compound to the reaction. After the agent is added, it may be heated and 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 organic peroxides. Examples of the radically polymerizable unsaturated compound include 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 and the like, and at least one hydroxyl group or glycidyl group described above. There are radically polymerizable unsaturated compounds and the like.

The amount of radical-polymerizable unsaturated compound added is 5 to 500 with respect to the propylene-α-olefin copolymer.
Weight percent is optimal. If the amount added is less than 5% by weight, the solubility in the solvent, the pigment dispersibility, etc. will be poor and sufficient performance will not be obtained in the case of an ink or paint. If it exceeds 500% by weight, the adhesion to polyolefin will be poor.

The binder resin of the present invention is an isocyanate compound or a --NH group in one molecule as a curing agent.
By blending a compound containing two or more _two groups,
It is possible to improve coating film properties required for paints and inks, such as gasoline resistance, weather resistance, moisture resistance, hot water resistance (boil, retort).

As the above-mentioned 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 a buret body, an isocyanurate body,
It is preferably used after being modified into an isocyanate derivative such as a trimethylolpropane adduct.

Examples of the compound containing two or more --NH groups or --NH ₂ groups in one molecule include ethylenediamine, diethylenetriamine, triethylenetetramine,
Polyamides obtained by reacting with aliphatic amines such as pentaethylenehexamine, isophoronediamine, alicyclic polyamines such as 1,3-diaminocyclohexane, aromatic amines such as m-xylenediamino, and polymerized fatty acids. Resin etc. can be used.

The binder resin composition of the present invention may be used by coating as it is, but it can be used as a paint or ink by kneading it by adding a pigment, a solvent and other additives. Further, the composition shows well-balanced coating film physical properties by itself, but if necessary, alkyd resin, acrylic resin, polyacrylic polyol, polyester resin, polyester polyol, polyether resin, polyether polyol, polyurethane resin Further, chlorinated polyolefin or the like may be further added and used.

A feature of the present invention is to obtain a binder resin solution that is far more uniform and has excellent storage stability as compared with other similar inventions. That is, propylene-α-
After adding α, β-unsaturated carboxylic acid and / or its anhydride to the olefin copolymer, at least one hydroxyl group, glycidyl group, amino group or amide group is added to the carboxyl group or acid anhydride group. Reactive unsaturated groups are introduced by esterifying, amidating, or imidizing the respective reactive unsaturated compounds to chemically bond them, and the reactive unsaturated groups are used as reaction points to form radically polymerizable unsaturated groups. By subjecting the product to graft copolymerization in the presence of a monoalcohol, a binder resin solution having a uniform and excellent storage stability can be obtained.

The reason why the binder resin solution is uniform and excellent in storage stability is that the propylene-α-olefin copolymer is originally nonpolar, but if the above method is used, polar acrylic or styrene is used as propylene. It is possible that the graft copolymerization can be reliably carried out on the -α-olefin copolymer, and as a result, polarity is imparted and the solubility in the solvent and the pigment dispersibility are improved. When radical-polymerizable unsaturated compounds are graft-copolymerized in the presence of monoalcohol, the free carboxyl group or acid anhydride group contained in the trunk polymer is masked by monoalcohol and the side reaction is stopped. Stability seems to be improved.

[0041]

EXAMPLES The present invention will now be described in more detail by way of examples, which should not be construed as limiting the invention thereto.

(Prototype Example-1) In a four-necked flask equipped with a stirrer, a cooling tube, 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 25,000) 300 g was dissolved by heating in 700 g of toluene, and the system temperature was maintained at 140 ° C. with stirring to give 30 g of maleic anhydride and di-te as a radical generator.
12 g of rt-butyl peroxide was added dropwise over 2 hours, followed by aging for 3 hours. After the reaction, the reaction product was cooled to room temperature and then poured into 20 liters of acetone for purification to obtain a maleic anhydride graft copolymer having a graft amount of 6.5% by weight.

(Prototype Example-2) The reaction was carried out in the same manner as in Prototype Example-1 except that 15 g of maleic anhydride was added dropwise to obtain a maleic anhydride graft copolymer having a graft amount of 3.4% by weight.

(Example-1) In a four-necked flask similar to Prototype Example-1, 100 g of the maleic anhydride graft copolymer obtained in Prototype Example-1 was dissolved in 200 g of toluene, and then concentrated sulfuric acid 0.07 was added. g, 2-hydroxyethyl methacrylate 2.5
g was added and the esterification reaction was carried out at 100 ° C. for 2 hours. Next, the system temperature was cooled to 85 ° C., 20 g of isopropyl alcohol was added, and then radical-polymerizable unsaturated compound consisting of 45 g of methyl methacrylate and 5 g of isobutyl methacrylate and 1.5 g of benzoyl peroxide were dissolved in 10 g of toluene. Solution was added dropwise over 3 hours,
The copolymerization reaction was continued for 8 hours to obtain propylene-α.
A binder resin solution was obtained by graft-copolymerizing a radically polymerizable unsaturated substance with an olefin copolymer. The solid content concentration of the binder resin solution was adjusted to 40 wt% with toluene, placed in a completely sealed container, and stored in an atmosphere of 40 ° C, and the change in viscosity with time was observed. The results are shown in Table 1.

(Example-2) The esterification reaction was carried out in the same manner as in Example-1 except that 100 g of the maleic anhydride graft copolymer obtained in Prototype Example-2 and 2.2 g of 2-hydroxyethyl acrylate were collected. It was Next, 10 g of isopropyl alcohol and 50 of cyclohexyl methacrylate
g was sampled, and the copolymerization reaction was performed in exactly the same manner as in Example 1 except that 1.5 g of benzoyl peroxide was dissolved in 20 g of toluene, and the change with time of the viscosity of the binder resin solution obtained was observed. The results are shown in Table 1.

Example 3 An esterification reaction was carried out in the same manner as in Example 1 except that 100 g of the maleic anhydride graft copolymer obtained in Prototype Example-2 was collected. Next, 15 g of isopropyl alcohol, 70 g of toluene, 60 g of cyclohexyl methacrylate, and n-butyl methacrylate.
19 g and 21 g of 2-hydroxyethyl acrylate were collected, and a copolymerization reaction was carried out in the same manner as in Example 1 except that 2 g of benzoyl peroxide was dissolved in 20 g of toluene to obtain a binder resin solution. After the isopropyl alcohol remaining in the binder resin solution was distilled off and replaced with toluene, the solid content concentration was adjusted to 40 wt% and the Example-
As with 1, the change in viscosity with time was observed. The results are shown in Table 1.

Example 4 An esterification reaction exactly the same as in Example 1 was carried out, and then isopropyl alcohol was used.
15 g of toluene, 70 g of methyl methacrylate, 60 g of methyl methacrylate, 12 g of isobutyl methacrylate, 28 g of glycidyl methacrylate were collected and obtained by the same copolymerization reaction as in Example 1 except that 2 g of benzoyl peroxide was added to 20 g of toluene. The change in viscosity of the binder resin with time was observed. The results are shown in Table 1.

Comparative Examples-1 to 4 Copolymerization reactions were carried out under exactly the same conditions as in Examples-1 to 4 except that the isopropyl alcohol added during the copolymerization reaction of Examples-1 to 4 was replaced with toluene. Binder resin solutions of Comparative Examples-1 to 4 corresponding to Examples-1 to 4 were obtained. The solid content concentration was adjusted to 40 wt% and the change in viscosity with time was observed in the same manner as in Example-1. The results are shown in Table 1.

[0049]

[Table 1] ● B-type viscometer was used for viscosity measurement. The measurement temperature is 25 ℃. ● The unit in the table is centipoise (cp).

Example 5 100 g of the binder resin solution (solid 40%) obtained in Example 3 and 26 g of titanium dioxide were kneaded in a sand mill for 3 hours, and then an isocyanate curing agent Desmodur Z4370 (Sumitomo Bayer Urethane Co., Ltd. ), Isophorone diisocyanate system, isocyanurate body) 12.9 g was added, and a No. 4 Ford cup was used for 13
Viscosity is adjusted with xylene to -15 seconds / 20 ° C, polypropylene plate, TX-933A (manufactured by Mitsubishi Petrochemical Co., Ltd.)
Spray painted on. After drying at room temperature for 15 minutes, at 80 ℃
The coating film was tested after forced drying for 30 minutes and allowed to stand in the room for 1 week. The results are shown in Table 2.

Example 6 100 g of the binder resin solution (solid 40%) obtained in Example 4 and 26 g of titanium dioxide were kneaded in a sand mill for 3 hours, and then the amine-based curing agent Epomate B-002 (oiled shell) was used. 4 g of Epoxy Co., Ltd., heterocyclic amine epoxy curing agent) was added, and Example-
Paint preparation and coating film tests were conducted in the same manner as in No. 5. The results are shown in Table 2.

(Comparative Example 5) Chlorinated polypropylene Super Clone 832L (manufactured by Sanyo Kokusaku Pulp Co., Ltd., chlorine content 27 wt%, solid content 30 wt%) 35 g and polyacrylic polyol Desmofen A-160 (Sumitomo Bayer Urethane Co., Ltd. ), Solid content 60%, hydroxyl group content 2.7% vs soli
d) 35g, titanium dioxide 26g, death module Z437
A paint preparation and a coating film test were conducted in the same manner as in Example-5 with a compounding ratio of 12.2 g. The results are shown in Table 2.

[0053]

[Table 2]

Test method ● Adhesion 100 grids that reach the substrate at 1 mm intervals were made on the coated surface, and cellophane adhesive tape was adhered on it to make 180 °
It was peeled off in the direction and judged by the extent to which the coating film remained.

Accelerated weather resistance A carbon arc type sunshine weather meter was used. Whiteness was measured by Hunter and gloss was measured by a 60 ° specular gloss meter.

● Resistance to hot water Immerse the coated plate in hot water at 40 ° C for 120 hours and 240 hours,
The state of the coating film was examined.

● Gasoline resistance (rubbing 100 times) The absorbent cotton was impregnated with Nisseki Regular Gasoline, and the coated surface was rubbed 100 times to examine the state of the coating film. (Dip for 2 hours) A scratch (x) reaching the base material was put on the coated surface, and soaked in Nisseki Regular Gasoline for 2 hours, and the state of the coating film was examined.

Bending Resistance The state of the coating film was examined by bending 180 ° with a 1/2 φ inch mandrel.

● Impact resistance DuPont type impact tester, impact core 1 / 2φ inch, load 500
g was dropped from a height of 50 cm on the coated surface to examine the state of the coating film.

(Example-7) An ink was prepared with the binder resin solution (solid 40%) obtained in Example-1, and uncoated polypropylene film (hereinafter referred to as treated PP) and polyethylene terephthalate film were coated with coating rod # 10. (Hereinafter referred to as PET), nylon film (hereinafter referred to as N
(Referred to as Y) and dried at room temperature for 24 hours, and then subjected to cellophane tape peel test and heat seal strength test using cellophane adhesive tape. These results are shown in Table 4.
It was shown to. The formulation of the ink is shown in Table 3.

Example-8 An ink was prepared using the binder resin solution (solid 40%) obtained in Example-2, and the same test as in Example-7 was conducted. The results are shown in Table 4.

(Comparative Example 6) Chlorinated polypropylene Supercron 803MW (manufactured by Sanyo Kokusaku Pulp Co., Ltd., chlorine content 29.5% by weight, solid content 20% by weight) and chlorinated ethylene vinyl acetate copolymer Supercron BX (Sanyo). The ink was prepared with a mixture of Kokusaku Pulp Co., Ltd., chlorine content 18% by weight, solid content 20% by weight, and the same test as in Example-7 was conducted. The results are shown in Table 4.

Comparative Example 7 Polyurethane Resin Sambrene IB-450 (manufactured by Sanyo Chemical Co., Ltd., solid content)
The ink was adjusted with 30 wt%) and the same test as in Example-7 was performed. The results are shown in Table 4.

[0064]

[Table 3] * Titanium dioxide (Ishihara Sangyo Co., Ltd., rutile type R-82
0) * Carmine 6BN (Azo organic pigment manufactured by Toyo Ink Mfg. Co., Ltd.) * Ink kneading conditions: Kneading in a sand mill for 2 hours

[0065]

[Table 4]

Cellophane Peeling Test The cellophane adhesive tape was attached on the ink coated surface and peeled off at once, and the peeled state of the coated surface was evaluated.

● Heat-seal strength test: Overlap the ink-coated surfaces and make 1 at 110 ° C-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 5
0mm / min)

[0068]

【The invention's effect】

As can be seen from the results of Table 1 (from the results of Table 1)
The binder resin solutions 1 to 4 showed almost no thickening even when stored at 40 ° C. for 1 month, but Comparative Examples -1 to 4
The binder resin solution (1) has increased in viscosity or gelated over time. This shows that the binder resin of the present invention has excellent storage stability.

(From the results of Table 2) The coating compositions of Examples 5 and 6 showed good results in weather resistance, hot water resistance, gasoline resistance and low temperature physical properties, but the coating composition of Comparative Example 5 The composition has poor physical properties. In the case of Comparative Example-5, since it is a binder resin in which a commercially available polyacrylic polyol and chlorinated polypropylene are simply mixed, the poor compatibility of the both and the poor UV resistance of the chlorinated polypropylene reduce the physical properties of the coating film. It seems that there is. From this, it can be said that the binder resin of the present invention is a uniform and well-balanced coating resin.

(From the results in Table 4) The ink of Comparative Example 6 of the chlorinated polypropylene / chlorinated ethylene vinyl acetate copolymer system showed 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-7 is PET,
Although it adheres to NY film, it does not have sufficient adhesion strength to PP film. The inks of Examples-7 and 8 showed good adhesiveness to both PP film, PET and NY film, and it is understood that the products of the present invention are highly versatile ink binders.

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[Procedure amendment]

[Submission date] January 24, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] Claim 5

[Correction method] Change

[Correction content]

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] 0002

[Correction method] Change

[Correction content]

[0002] Plastics have been widely used as materials for automobile parts, electric parts, building materials, etc. in recent years because they have many advantages such as high productivity, wide design freedom, light weight, rust prevention and impact resistance. ing. In particular, polyolefin resins are widely used as industrial materials because they have many excellent properties such as low cost, moldability, chemical resistance, heat resistance, water resistance, and good electrical properties. Growth is one of the most anticipated materials.

[Procedure 3]

[Document name to be amended] Statement

[Name of item to be corrected] 0023

[Correction method] Change

[Correction content]

Propylene-grafted with α, β-unsaturated carboxylic acid or its acid anhydride in the present invention
The carboxyl group or acid anhydride group possessed by the α-olefin copolymer forms an ester, amide or imide with a reactive unsaturated compound having at least one hydroxyl group, glycidyl group, amino group or amide group. It is possible to chemically bond. That is, the reactive unsaturated substance can be introduced into the propylene-α-olefin copolymer by such a reaction method.

[Procedure amendment 4]

[Document name to be amended] Statement

[Item name to be corrected] 0040

[Correction method] Change

[Correction content]

The reason why the binder resin solution is uniform and excellent in storage stability is that the propylene-α-olefin copolymer is originally nonpolar, but if the above method is used, polar acrylic or styrene is used as propylene. Graft copolymerization can be reliably carried out on the -α-olefin copolymer, and as a result, polarity is imparted, and solubility in a solvent and pigment dispersibility are improved. When radical-polymerizable unsaturated compounds are graft-copolymerized in the presence of monoalcohol, the free carboxyl group or acid anhydride group contained in the trunk polymer is masked by monoalcohol and the side reaction is stopped. Stability seems to be improved.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0060

[Correction method] Change

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(Example-7) An ink was prepared with the binder resin solution (solid 40%) obtained in Example-1, and uncoated polypropylene film (hereinafter referred to as untreated PP) and polyethylene terephthalate film were coated with coating rod # 10. (Hereinafter referred to as PET) and a nylon film (hereinafter referred to as NY) were applied, dried at room temperature for 24 hours, and then subjected to cellophane tape peeling test and heat seal strength test using a cellophane adhesive tape. The results are shown in Table 4. The formulation of the ink is shown in Table 3.

[Procedure correction 6]

[Document name to be amended] Statement

[Correction target item name] 0063

[Correction method] Change

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(Comparative Example-7) Polyurethane resin An ink was prepared with Sambrene IB-450 (manufactured by Sanyo Chemical Co., Ltd., solid content: 30 wt%), and the same test as in Example-7 was conducted. The results are shown in Table 4.

Claims (6)

[Claims] 1. A propylene-α-olefin copolymer is graft-copolymerized with an α, β-unsaturated carboxylic acid and / or its acid anhydride in an amount of 1.0 to 10% by weight, and at least one hydroxyl group or glycidyl group is then added. , 0.5 to 10% by weight of a reactive unsaturated compound having an amino group or an amide group is partially reacted with the above α, β-unsaturated carboxylic acid and / or its acid anhydride, and further in the presence of a monoalcohol. A binder resin composition containing a substance obtained by graft-copolymerizing a polymerizable unsaturated substance as a main component. 2. The radically polymerizable unsaturated compound is contained in an amount of 5 to 500% by weight based on the propylene-α-olefin copolymer.
The binder resin composition according to claim 1, which is graft-copolymerized. 3. The binder resin composition according to claim 1 or 2, wherein an isocyanate compound or a compound containing two or more —NH groups or —NH ₂ groups in one molecule is blended as a curing agent. , Binder resin compositions for paints and printing inks or adhesives. 4. The binder resin according to claim 1, wherein the reactive unsaturated substance is any one of 2-hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, allylamine and acrylamide. Composition. 5. The radically polymerizable unsaturated compound is methyl (meth) acrylate, n-butyl (meth) acrylate,
The binder resin composition according to any one of claims 1 to 4, which is any one of isobutyl (meth) acrylate, 2-hydroxyethyl acrylate, and microhexyl (meth) acrylate. 6. The method for producing the binder resin composition according to claim 1 or 2.