JP2839218B2 - Method for producing 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 method for producing a binder resin composition used for the purpose of protecting, cosmetically and adhering various plastics, and more particularly, to a polyolefin resin, a polyurethane resin, a polyamide resin, and the like.
The present invention relates to a method for producing 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 acrylic resins and polyester resins.

[0002]

2. Description of the Related Art Plastics have a high productivity and a high degree of freedom in design, and can be measured,
Since it has many advantages such as rust prevention and impact resistance, it has recently been widely used as a material for automobile parts, electric parts, building materials and the like. In particular, polyolefin resins are inexpensive and have many excellent properties such as moldability, chemical resistance, heat resistance, water resistance and good electrical properties, so they are widely used as industrial materials and their demand will grow in the future. Is one of the most promising materials.

However, polyolefin resins are different from polar synthetic resins such as polyurethane resins, polyamide resins, acrylic resins, polyester resins, etc., and are difficult to paint and mount because they are non-polar and crystalline. It has the drawback of saying.

Therefore, conventionally, the surface of a polyolefin resin molded article is activated by plasma treatment or gas flame treatment to improve the adhesion. However, this method has a complicated process and requires a large amount of equipment and time. It has drawbacks such as a large loss, and the surface treatment effect varies due to the complexity of the shape of the molded product and the effects of pigments and additives in the resin. As a method of coating without such a pretreatment, various primer compositions such as those found in automotive polypropylene bumper coating have been proposed, but these are very complicated with a two-coat finish.

[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. For this reason, attempts have been made to use a mixture of acrylic resin and alkyd resin having good paint properties.
However, acrylic resin and alkyd resin originally have poor compatibility with chlorinated polyolefin, so the gloss of the coating film decreases,
Problems such as remarkably impairing the appearance are caused.

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, and an acrylic monomer having a hydroxyl group as disclosed in JP-A-59-27968. Paint composition containing a chlorinated polyolefin-modified hydroxyl-containing acrylic copolymer obtained by copolymerizing a chlorinated polyolefin with a chlorinated polyolefin and an isocyanate compound as an essential component, and a chlorinated copolymer as disclosed in JP-A-62-95372. An adhesive resin composition containing a hydroxyl group-containing acryl-modified chlorinated polyolefin copolymerized with an acrylic monomer having a hydroxyl group in the presence of a polyolefin and a liquid rubber and an isocyanate compound as main components has been proposed. However, these compositions are also hard to say that the coating film is hard and the impact resistance and the bending resistance are inferior and the coating film is well-balanced.

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, the use of composite films by lamination has been increasing in order to keep the contents of the package secret. A large number of inks for laminating are used depending on the type of film.
They are being broadly divided into types. That is, an ink composition mainly containing chlorinated polypropylene and a chlorinated ethylene-vinyl acetate copolymer mainly used for a polypropylene film, and an ink composition mainly containing polyester and urethane resin mainly used for a nylon film. .

The former ink composition containing chlorinated polypropylene and chlorinated ethylene-vinyl acetate copolymer as main binders 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-55-145775.
No. in the official gazette. These have good ink adhesion to an untreated polypropylene film, and exhibit good adhesion even when printed by extrusion lamination. However, they have poor adhesion to films of polyester, nylon, etc., and are not suitable as printing inks for lamination.

As described in JP-A-62-153366 and JP-A-62-153667, the latter ink composition containing a urethane-based resin as a main binder is used to form a polar film such as polyester and nylon. Although it shows good adhesiveness, it has no adhesion to an untreated polypropylene film, and printing by a polypropylene extrusion lamination method is impossible.

JP-A-64-85226 proposes an ink resin suitable for both printing by the extrusion lamination method of polypropylene and laminating printing of polyester, nylon film and the like. This proposal relates to a polyurethane-modified chlorinated polypropylene obtained by modifying a chlorinated polypropylene with a hydroxyl group-containing vinyl monomer or the like, introducing a hydroxyl group into the chlorinated polypropylene, and then reacting with a free isocyanate group-containing polyurethane. However, this method has a disadvantage that the extrusion lamination strength of polypropylene is not sufficient because the content of chlorinated polypropylene in the composition is limited.

[0011]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a method for producing a binder resin composition for a paint, which is capable of one-coat coating on various plastic molded articles and has a well-balanced coating film performance. I do. Still another object of the present invention is to provide a method for producing a binder resin for a laminating ink and an adhesive for various plastic films.

The present inventors have developed a chlorinated polyolefin (a) obtained by oxidizing the polyolefin with at least one or more selected from air, oxygen and ozone during the chlorination reaction of the polyolefin and one molecule of the chlorinated polyolefin. The hydroxyl group-containing chlorinated polyolefin obtained by graft copolymerizing a monomer and / or compound (b) containing at least one ethylenically unsaturated bond and a hydroxyl group has a molar ratio of isocyanate group / hydroxyl group of 0.
Resin (I) having a terminal isocyanate functional group obtained by reacting an organic diisocyanate in the range of 2 to 2.0
And a polyurethane resin (II) containing at least one free isocyanate group in one molecule, reacted with a chain extender and, if necessary, terminated with a reaction terminator to obtain a binder resin composition, The present inventors have found that the above object has been achieved, and have accomplished the present invention.

The chlorinated polyolefin (a) used in the present invention is a component for imparting adhesion to the polyolefin resin, and at least one or two or more selected from air, oxygen and ozone during chlorine blowing. More than one species are simultaneously blown to oxidize the chlorinated polyolefin, and the one obtained is used.

By the oxidation treatment, a functional group is introduced into the chlorinated polyolefin. Therefore, the monomer and / or the compound (b) containing at least one ethylenically unsaturated bond and one hydroxyl group in one molecule are used. The graft copolymerization reaction easily occurs easily, the copolymerization reaction product (homopolymer) of the monomers decreases, and the liquid becomes better as compared with a chlorinated polyolefin that is not oxidized.

The raw materials of the chlorinated polyolefin include crystalline polypropylene, amorphous polypropylene, polybutene-1, polypentene-1, 4-methylpentene-1,
There are low density or high density polyethylene, ethylene-propylene copolymer, ethylene-propylene-diene copolymer and the like.

The chlorine content is preferably used in the range of 5 to 50% by weight. If the chlorine content is less than 5 wt%, the solution state at low temperatures and the appearance of the coating film deteriorate, and the chlorine content is 5 wt%.
If it exceeds 0 wt%, the adhesion to the polyolefin-based resin decreases.

The chlorination of polyolefin can be easily carried out by a usual reaction method. For example, a polyolefin is dispersed or dissolved in a medium such as water or carbon tetrachloride, and under pressure or normal pressure in the presence of a catalyst or under irradiation of ultraviolet light.
This is performed by blowing chlorine gas in a temperature range of 0 to 120 ° C.

The monomer and / or compound (b) having an ethylenically unsaturated bond and a hydroxyl group in one molecule used in the present invention is obtained by introducing a hydroxyl group into a chlorinated polyolefin and converting the hydroxyl group-containing chlorinated polyolefin (c). To obtain 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate,
-Hydroxybutyl (meth) acrylate and the like, and the (hydroxy) -containing (meth) acrylate is esterified with caprolactone (poly) caprolactone-modified (meth).
Acrylates (for example, Daicel Chemical Industries, Ltd., trade name Placcel FA, Placcel FM series, etc.) can also be used. Esters obtained by reacting α, β unsaturated carboxylic acids or their anhydrides with diols;
Any monomer or compound having an ethylenically unsaturated bond and a hydroxyl group in one molecule, such as 1,4-butene glycol and allyl alcohol, can be used.

The monomer and / or compound (b) may have 1
A mixture of monomers and / or compounds containing at least one ethylenically unsaturated bond in the molecule may be used. As the monomer used at this time, for example, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate,
There are 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, lauryl (meth) acrylate, glycidyl (meth) acrylate, styrene, vinyl acetate, (meth) acrylonitrile, and the like. Examples of the compound include polystyrene and poly (meth) acrylate. There is a macromonomer having a polymerizable (meth) acryloyl group at a terminal.

The graft copolymer of the chlorinated polyolefin (a) and the monomer and / or the compound (b) according to the present invention is produced by solution polymerization. The solvent to be used is preferably an aromatic solvent such as toluene and xylene. In addition, an ester solvent, a ketone solvent, an alcohol solvent, an aliphatic solvent, a cycloaliphatic solvent and the like may be used in combination.

Examples of the polymerization initiator include peroxides such as benzoyl peroxide and di-tert-butyl peroxide and azonitriles such as azobisisobutyronitrile.

The basic method of graft copolymerization is that the above (a) is diluted appropriately with a solvent, mixed, heated after adding a polymerization initiator, and reacted while gradually adding (b). Where (a) and (b) are pre-mixed,
After the addition of the polymerization initiator, the reaction may be performed by heating.

In the resin (I) obtained by reacting the hydroxyl group-containing chlorinated polyolefin (c) and the organic diisocyanate used in the present invention, the terminal functional group must be an isocyanate group. If the ratio is in the range of 0.2 to 2.0, it is possible by appropriately selecting the reaction conditions.

The organic diisocyanates that can be used include:
There are aromatic and aliphatic and alicyclic diisocyanates, for example, tolylene diisocyanate, xylene diisocyanate, 1,5-naphthalene diisocyanate,
There are 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1,4-cyclohexyl diisocyanate and the like.

The polyurethane resin (II) containing at least one free isocyanate group in one molecule used in the present invention can be obtained basically by reacting a high molecular polyol with an organic diisocyanate. Accordingly, the molecular weight may be increased by using a chain extender comprising a diol component and / or a diamine component.

Examples of the high molecular polyol include polyether polyols and polyester polyols. Examples of the polyether polyols include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polycarbonate diols, bisphenol A and ethylene oxide or propylene oxide. And glycols obtained by adding On the other hand, as polyester polyols, adipic acid, maleic acid, succinic acid,
Dicarboxylic acids such as fumaric acid, phthalic acid and sebacic acid and ethylene glycol, neopentyl glycol, 1,8-
There are adipates obtained by polycondensation of glycols such as octamethylenediol, such as polyethylene adipate, polybutylene adipate, and polyhexamethylene adipate. Polycaprolactone diols obtained by ring-opening polymerization of lactone can also be used.
The above-mentioned organic diisocyanate can be used as it is.

Examples of the chain extender include diol components such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,4-pentanediol, 1,6-hexanediol, and 2,5-hexanediol.
As the diamine component, ethylenediamine, propylenediamine, hexamethylenediamine, 2,2,4-trimethylhexamethylenediamine, isophoronediamine,
4,4'-dicyclohexylmethanediamine and the like.

As a reaction method for obtaining the polyurethane resin (II), a conventionally known method for producing a polyurethane resin may be used. For example, an organic isocyanate is added in excess to the above-mentioned high molecular polyol component, that is, the isocyanate group / hydroxyl group is allowed to react in a range exceeding 1.0 mol, preferably in a range of 1.1 to 2.0 mol, and a high molecular weight If necessary, a chain extender can be used to obtain a polyurethane resin (II) having at least one free isocyanate group in one molecule.

Resin (I) and polyurethane resin (II)
As a reaction solvent for obtaining an aromatic solvent such as toluene and xylene, an ester solvent such as ethyl acetate, propyl acetate and butyl acetate, a ketone solvent such as methyl ethyl ketone and methyl isobutyl ketone, ethanol, isopropanol, n- Alcohol solvents such as butanol can be used alone or in combination.

The number average molecular weight of the polyurethane resin (II) is preferably from 1,000 to 150,000,
If it is less than 000, the gasoline resistance, moisture resistance, blocking resistance and the like of the coating film become insufficient, and if it exceeds 150,000, the pigment dispersibility and the spray coating property are inferior and are not suitable as binder resins for paints and inks.

The binder resin of the present invention can be obtained by reacting the above-mentioned resin (I) with the polyurethane resin (II) in the presence of a chain extender. Can also be obtained by stopping. As a reaction terminator, methanol, ethanol,
There are monoalcohols such as isopropanol and monoamines such as monoethylamine, n-propylamine and n-butylamine. Also, amino alcohols such as ethanolamine, propanolamine and butanolamine can be used. The weight mixing ratio when synthesizing the binder resin is such that the resin (I) and the polyurethane resin (II) = 5/95.
~ 95/5 is a preferred range for practicing the present invention.

The binder resin of the present invention contains gasoline resistance, weather resistance, moisture resistance and hot water resistance (boiling and retorting properties) by blending an isocyanate compound as a curing agent.
Etc. and the physical properties of the coating film required for paints and inks can be improved. As the isocyanate compound used at this time, the above-mentioned organic diisocyanates can be used, but it is more preferable to use these organic diisocyanates by modifying them into isocyanate derivatives such as buret, isocyanurate, and trimethylolpropane adducts. .

The binder resin of the present invention may be used as it is by coating, but it can be used as a paint or ink after kneading and dispersing by adding a pigment, a solvent and other additives. In addition, the binder resin alone exhibits 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.

[0034]

The feature of the present invention is that a chlorinated polyolefin component can be arbitrarily contained in the binder resin composition, and a uniform and transparent solution is obtained. In other words, the chlorinated polyolefin having an isocyanate group and the polyurethane resin having an isocyanate group at the terminal of the molecule are linked to each other by a chain extender to increase the amount of the component, so that the component ratio between the chlorinated polyolefin and the polyurethane resin is arbitrarily set. it can. In addition, by introducing isocyanate groups into each component of the chlorinated polyolefin and the polyurethane resin in a separate system and extending the chain, both of which are originally incompatible with each other are integrated, so that the binder resin is uniform and transparent. It seems to be a solution.

[0035]

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 Preparation of Chlorinated Polyolefin (a)) 500 g of isotactic polypropylene having a number average molecular weight of 35,000 was charged into a glass-lined reactor, and 8 liters of carbon tetrachloride was added. Temperature 110 ° C,
After sufficiently dissolving at a pressure of 2 kg / cm ² , chlorine gas and air were introduced from the bottom of the reactor while irradiating ultraviolet rays until the chlorine content reached 30 wt%. Next, carbon tetrachloride was distilled off and replaced with toluene to obtain a toluene solution of chlorinated polypropylene having a nonvolatile content of 50% by weight.

(Trial Example 2 Preparation of Hydroxyl-Containing Chlorinated Polyolefin (a)) In a flask equipped with a stirrer, a thermometer and a condenser for refluxing the monomer, the chlorinated polypropylene obtained in Trial Example-1 ( 1,000 g of nonvolatile content (50 wt%) and 2.5 g of benzoyl peroxide were added and stirred at 85 ° C. for 30 minutes. Next, 2-hydroxyethyl acrylate 1
A mixture of 7.5 g and 17.5 g of toluene was added over about 1 hour, and a graft copolymerization reaction was further performed for about 3 hours to obtain a hydroxyl group-containing chlorinated polypropylene (nonvolatile content: 50 wt%).
I got

(Trial Production Example-3 Preparation of Hydroxyl-Containing Chlorinated Polyolefin (a)) In a flask similar to that of Trial Production Example-2, 200 g of the chlorinated polypropylene obtained in Trial Production Example-1 (non-volatile content: 50 wt%),
200 g of toluene and 1.0 g of benzoyl peroxide were added, and the mixture was stirred at 85 ° C. for 30 minutes. Next, 69.2 g of cyclohexyl methacrylate, ethyl acrylate 1
A mixture of 0.8 g and 20 g of 2-hydroxyethyl acrylate was added in about 3 hours, and after a graft copolymerization reaction was further performed for several hours, 100 g of toluene was added to stop the reaction. Min 4
0 wt%).

(Trial Example-4 Preparation of Resin (II)) 400 g of Placcel L-220AL (caprolactone-based polymer diol, molecular weight 2,000, manufactured by Daicel Chemical Industries, Ltd.) and 67.2 g of hexamethylene diisocyanate were used. The mixture was charged into a flask similar to that of Prototype Example-2 and reacted at 85 ° C. for several hours while introducing nitrogen gas. Then, 300 g of toluene and 167.2 g of ethyl acetate were added, and a polyurethane resin having an isocyanate group at a terminal (non-volatile) 50 wt%).

(Trial Production Example-5 Preparation of Resin (II)) 400 g of a polymer polyol (butane adipate diol, molecular weight 2,000) synthesized from adipic acid and 1,4-butanediol, isophorone diisocyanate 8
After reacting 8.8 g in the same manner as in Prototype Example-4, 8.6 g of 1,4-butanediol was further added as a chain extender and reacted for several hours. Next, 248.7 g of toluene and 248.7 g of methyl ethyl ketone were charged, and a polyurethane resin having an isocyanate group at a terminal (non-volatile content: 50 wt.
%).

Example 1 Hydroxyl-containing chlorinated polypropylene 20 obtained in Experimental Example 2
0 g and 6.5 g of isophorone diisocyanate-
After putting in the same flask as in Example 2 and reacting at 85 ° C. for 4 hours, 158 g of toluene and 300 g of the polyurethane resin obtained in Prototype Example-5 were added, the mixture was cooled to 50 ° C., and 14.1 g of isophoronediamine was gradually added. The chain elongation reaction was performed while performing the reaction. After cooling, 163 g of methyl ethyl ketone, 64.0 g of isopropanol, and 1.5 g of n-butylamine were added to stop the reaction, and a uniform and transparent binder resin (nonvolatile content 30 wt%) was obtained.

Next, an ink is prepared with the binder resin,
Coating rod # 4 converts untreated polypropylene film (hereinafter referred to as untreated PP), corona discharge treated polypropylene film (hereinafter referred to as treated PP), polyethylene terephthalate film (hereinafter referred to as PET), nylon film (hereinafter referred to as NY) Apply each, 24
After drying at room temperature for a period of time, a cellophane tape peeling test and a heat seal strength test were performed using a cellophane adhesive tape.
Table 1 shows the results. The formulation of the ink is shown in Table 2.

(Comparative Example 1) Supercron 803 MW (chlorinated polypropylene, chlorine content: 29.5 wt%, nonvolatile content: 20 wt%,
Sanyo Kokusaku Pulp Co., Ltd.) and trade name Supercron BX
(Chlorinated ethylene vinyl acetate copolymer, chlorine content 18
wt%, nonvolatile content 20wt%, Sanyo Kokusaku Pulp Co., Ltd.
The same test as in Example 1 was performed with the mixture of Example 1). Table 1 shows the results.

(Comparative Example 2) The same test as in Example 1 was performed using Sambren IB-450 (trade name, polyurethane resin, nonvolatile content: 30% by weight, manufactured by Sanyo Chemical Industry Co., Ltd.). Table 1 shows the results.

[0045]

[Table 1] -Cellophane tape peeling test A cellophane adhesive tape was stuck to the ink-coated surface, and the peeling state was determined when the cellophane tape was peeled off at a stretch.・ Heat seal strength test 110 ℃ -1kg / cm
Heat-sealing was carried out under pressure bonding conditions of ² seconds for 1 second, and after 24 hours, a 180 ° peel strength test was performed with Tensilon. (Pulling speed 50mm / min)

[0046]

[Table 2] -Super Clone 803 MW and Super Clone BX have a nonvolatile content of 20 wt% (toluene solution) Sambrene IB-450 has a nonvolatile content of 30 wt% (methyl ethyl ketone / isopropanol = 2/1 solution)-Titanium dioxide (Ishihara Sangyo Co., Ltd., rutile type R) -8
20) ・ Carmine 6BN (Toyo Ink Mfg. Co., Ltd., azo organic pigment) ・ Meat condition: Kneading with sand mill for 2 hours

(Example-2) Hydroxyl-containing chlorinated polypropylene 25 obtained in prototype example-3
0 g, hexamethylene diisocyanate 10.8 g, 60 g of the polyurethane resin obtained in Prototype Example-4, 8.8 g of isophoronediamine, 33.2 g of toluene, and 11.2 g of isopropanol were reacted according to the method of Example-1. Perform a uniform and transparent binder resin (nonvolatile content 40
wt%).

Next, 100 g of the binder resin and 26 g of titanium dioxide were kneaded with a sand mill for 3 hours, and then 5.2 g of Desmodur Z4370 (manufactured by Bayer, isophorone diisocyanate, isocyanurate) was added. 13 in 4 Ford Cup
The viscosity was adjusted with xylene so that the temperature became １５15 seconds / 20 ° C., followed by spray coating on a polypropylene plate, TX-933A (manufactured by Mitsubishi Yuka Co., Ltd.). After drying at room temperature for 15 minutes, forced drying was performed at 80 ° C. for 30 minutes, and allowed to stand in a room for one week, after which the coating film was tested. Table 3 shows the results.

Comparative Example 3 Except that 500 g of isotactic polypropylene having a number average molecular weight of 50,000 was not simultaneously blown with air,
Chlorination was carried out in exactly the same manner as in Prototype Example-1 to obtain a toluene solution of chlorinated polypropylene having a chlorine content of 30 wt% and a nonvolatile content of 50 wt%. 160 g of this chlorinated polypropylene (non-volatile content 50 wt%), toluene 12
0 g, benzoyl peroxide 1.0 g, methyl methacrylate 49 g, lauryl methacrylate 49 g, methacrylic acid 2 g, 2-hydroxyethyl acrylate 2
A graft copolymerization reaction was carried out at a blending ratio of 0 g according to the reaction method of Prototype Example-3 to obtain a hydroxyl-containing chlorinated polyolefin. This hydroxyl-containing chlorinated polyolefin 100
g, 26 g of titanium dioxide, 7.4 g of Desmodur N3390, an isocyanate curing agent, in Example-2.
Preparation of paint and test of coating film were performed in the same manner as described above. Table 3 shows the results.

Comparative Example 4 Hydroxyl-Containing Chlorinated Polyolefin 10 Obtained in Prototype Example 3
0 g, titanium dioxide 26 g, isocyanate curing agent Desmodur Z4370 12.5 g, curing accelerator di-n
A paint preparation and a coating film test were carried out in the same manner as in Example 2 at a blending ratio of 0.08 g of -butyltin dilaurate. Table 3 shows the results.

[0051]

[Table 3]

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 the grid to obtain 18
The film was peeled off in the direction of 0 °, and the degree of the remaining coating film was determined.

○ Accelerated weather resistance A carbon arc type sunshine weather ometer was used. Gloss was measured at 60 ° specular reflection, and whiteness was measured with a hunter.

○ 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) 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 mark) reaching the substrate was put on the coated surface, immersed in gasoline for 2 hours, and the state of the coating film was examined.

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

衝 撃 Impact resistance Impact resistance Using a Dupont impact tester, using a hammer φ inch and a load of 500 g, the coating film was dropped from a height of 50 cm on a coated surface, and the state of the coating film was examined.

[0058]

(From the results in Table 1) The chlorinated polypropylene / chlorinated ethylene-vinyl acetate copolymer-based ink binder resin of Comparative Example 1 shows good adhesion to the PP film. NY film has no adhesion and is far from practical strength. The polyurethane-based binder resin of Comparative Example 2 was PET, NY.
It adheres to the film, but has insufficient adhesive strength to the PP film. The product of this invention is PE
It can be seen that this is a highly versatile ink binder resin having good adhesion to T and NY films.

(From the results in Table 3) Comparative Examples -3 and 4 are compositions obtained by graft copolymerization of an acrylic monomer having a hydroxyl group on chlorinated polypropylene and another acrylic monomer. Is further urethanized by a method as in the present invention, thereby imparting flexibility to the coating film without impairing the superior properties possessed conventionally, such as adhesion, appearance, gasoline resistance, weather resistance and the like. It can be seen that bending resistance and impact resistance were remarkably improved.

Further, by using a chlorinated polyolefin oxidized to introduce a functional group into the chlorinated polyolefin, a monomer containing at least one ethylenically unsaturated bond and one hydroxyl group in one molecule is used. The graft copolymerization reaction with the polymer and / or the compound (b) easily occurs, the copolymerization reaction product (homopolymer) between the monomers decreases, and the liquid is compared with the chlorinated polyolefin which is not oxidized. Becomes better. Further, by performing the oxidation treatment, the gloss of the coating film is increased, and the performance that the heat seal strength is better than that of the chlorinated polyolefin which is not subjected to the oxidation treatment is obtained.

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁶ Identification symbol FI C09J 175/04 C09J 175/04 (56) References JP-A-4-168174 (JP, A) JP-A-62-18434 (JP) JP-A-2-70786 (JP, A) JP-A-62-250087 (JP, A) JP-A-4-209673 (JP, A) JP-A-1-292020 (JP, A) 59-140269 (JP, A) JP-A-4-132783 (JP, A) JP-A-6-41488 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C08G 18/00 -18/87 C09D 175/00-175/16 C09J 175/00-175/16 C08F 8/20 C09D 11/10

Claims (7)

(57) [Claims] 1. During the chlorination reaction of polyolefin, air,
A chlorinated polyolefin (a) oxidized by at least one or two or more selected from oxygen and ozone;
At least one ethylenically unsaturated bond and hydroxyl group in the molecule
A hydroxyl group-containing chlorinated polyolefin (c) obtained by graft-copolymerizing a monomer and / or compound (b) containing the same and a resin (I) having an isocyanate functional group at a terminal obtained by reacting an organic diisocyanate; A method for producing a binder resin composition, comprising reacting a polyurethane resin (II) containing at least one free isocyanate group in a molecule with a chain extender. 2. The method for producing a binder resin composition according to claim 1, wherein the oxidized chlorinated polyolefin (a) is chlorinated to a chlorine content of 5 to 50 wt%. 3. The production of the binder resin composition according to claim 1, wherein the resin (I) is obtained by reacting in a molar ratio of isocyanate group / hydroxyl group of 0.2 to 2.0. Method. 4. A resin (I) and a polyurethane resin (II)
The method for producing a binder resin composition according to any one of claims 1 to 3, wherein the reaction is terminated with a chain extender and the reaction is terminated with a reaction terminator. 5. A monomer having at least one ethylenically unsaturated bond and / or a compound containing at least one ethylenically unsaturated bond and / or a hydroxyl group in one molecule of the compound (b). The method for producing a binder resin composition according to any one of claims 1 to 4, which is a mixture with a body and / or a compound. 6. The method for producing a binder resin composition according to claim 1, wherein the number average molecular weight of the polyurethane resin (II) is 1,000 to 150,000. 7. Resin (I) and polyurethane resin (II)
The method for producing a binder resin composition according to any one of claims 1 to 6, wherein the reaction is performed in a weight ratio of 5/95 to 95/5.