JPH06239958A - Binder resin composition - Google Patents

Abstract

PURPOSE:To obtain a binder resin composition useful for a coating material, a printing ink or an adhesive exhibiting excellent properties respectively for sheet, film or a molding of various kinds of synthetic resins. CONSTITUTION:This binder resin composition is synthesized by copolymerizing (a) a chlorinated polyolefin chlorinated within a range of 5 to 50wt.% chlorine content, (b) a chlorinated polydiene chlorinated within a range of 5 to 50wt.% chlorine content and (c) a monomer and/or a compound containing an ethylenic unsaturated bond and one or more hydroxyl groups in one molecule, reacting (d) the resultant hydroxyl group-containing chlorinated resin with an organic diisocyanate, reacting the obtained resin (I) with a polyurethane resin (II) containing one or more free isocyanate groups in one molecule in the presence of a chain-lengthening agent and terminating the reaction using a terminator as necessary. A production method therefor is also provided.

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 types of plastics, cosmetics and adhesion, and more specifically, a polyolefin resin, a polyurethane resin, a polyamide resin, an acrylic resin, A paint that exhibits excellent physical properties for films, sheets or molded products of various synthetic resins such as polyester resins,
The present invention relates to a binder resin composition for printing ink or adhesive.

[0002]

2. Description of the Related Art Plastic has a lot of advantages such as high productivity, wide design freedom, light weight, rust prevention, and impact resistance. In recent years, it has been widely used as a material for automobile parts, electric parts, building materials, etc. It is used. In particular, polyolefin-based resins are widely used as industrial materials because they are inexpensive and have many excellent properties such as moldability, chemical resistance, heat resistance, water resistance, and good electrical properties. It is one of the most anticipated materials for elongation.

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. It has the drawback.

Therefore, conventionally, the adhesion is improved by activating the surface of the polyolefin resin molded article by plasma treatment or gas flame treatment, but this method involves complicated steps and requires a large amount of equipment and time. However, there are drawbacks such as variations in the surface treatment effect due to the complicated loss 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 found in the coating of polypropylene bumpers for automobiles have been proposed, but this involves a very complicated two-coat finish.

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

[0007] In order to improve these drawbacks, JP-A-58-719
As seen in JP 66, a coating composition obtained by copolymerizing an acrylic monomer and a chlorinated polyolefin,
As can be seen in JP-A-59-27068, a chlorinated polyolefin-modified hydroxyl group-containing acrylic copolymer obtained by copolymerizing a chlorinated polyolefin with an acrylic monomer having a hydroxyl group, and an isocyanate compound as an essential condition. And a hydroxyl group-containing acrylate-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. Adhesive resin compositions containing polyolefins and isocyanate compounds as main components have been proposed. However, these compositions are hard to be said to be a well-balanced coating film because the coating film is hard and the impact resistance and flex resistance are poor.

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 the contents of the packaging, 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 exhibit good adhesion when laminated printed by the extrusion lamination method. However, it is poor in adhesiveness to films such as polyester and nylon, 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 polarities such as polyester and nylon as disclosed in JP-A-62-153366 and JP-A-62-153367. However, it has no adhesion to the untreated polypropylene film, and printing by the polypropylene extrusion lamination method is impossible.

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

[0012]

Prior to the present invention, the inventors of the present invention copolymerized a mixture of a chlorinated polyolefin and a chlorinated polydiene with a monomer containing an ethylenically unsaturated bond and a hydroxyl group in one molecule. The "binder resin composition" prepared by reacting the hydroxyl group-containing chlorinated resin, the polymer polyol, and the organic diisocyanate has already been proposed in JP-A-4-168174. However, this method has a drawback that a chlorinated polyolefin cannot be arbitrarily contained in the binder resin composition.

Further, the present inventors have made a "binder resin composition obtained by reacting a resin obtained by reacting a hydroxyl group-containing chlorinated polyolefin with an organic diisocyanate and a polyurethane resin having a free isocyanate group with a chain extender. Has already been proposed in Japanese Patent Application No. 4-87937. According to this method, it is possible to optionally include a chlorinated polyolefin in the binder resin, but a uniform and highly transparent reaction liquid could not be obtained. Therefore, when a paint or an ink is made using the binder resin, there is a problem in storage stability because the pigment precipitates during storage and causes two-layer separation.

The present invention solves this problem, and an object thereof is to provide a binder resin such as a paint, a primer, a printing ink or an adhesive, which is far superior to conventional chlorinated polyolefin modified products. . It is also an object to provide a production method for obtaining a uniform and transparent modified product of chlorinated polyolefin when modifying the chlorinated polyolefin.

[0015]

Means for Solving the Problems That is, the inventors of the present invention have found that the chlorinated polyolefin (a) chlorinated to have a chlorine content of 5 to 50 wt% and a chlorine content of 5 to 50 wt%. A chlorinated polydiene (b) chlorinated into a monomer and a monomer and / or compound (c) containing at least one ethylenically unsaturated bond in one molecule, and / or a hydroxyl group-containing chlorinated resin (c) The resin (I) obtained by reacting d) with an organic diisocyanate in a molar ratio of isocyanate group / hydroxyl group of 0.2 to 2.0 and a polyurethane resin containing at least one free isocyanate group in one molecule (II It was found that a binder resin composition obtained by reacting a) with a chain extender and, if necessary, stopping the reaction with a reaction terminator solves the above-mentioned problems, and has accomplished the present invention.

The chlorinated polyolefin (a) used in the present invention is a component for imparting adhesiveness to the polyolefin resin, and the chlorine content is preferably used in the range of 5 to 50 wt%. If the chlorine content is too low, the solution state at low temperatures and the appearance of the coating film will deteriorate. If the chlorine content is too high, the adhesion to the polyolefin resin will decrease.

Raw materials for 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 chlorination of polyolefin can be easily carried out by an ordinary reaction method. For example, a polyolefin is dispersed or dissolved in a medium such as water or carbon tetrachloride, and chlorine gas is blown in the temperature range of 50 to 120 ° C under pressure or normal pressure in the presence of a catalyst or irradiation of ultraviolet rays. Be seen. Further, at least one kind or two or more kinds selected from air, oxygen, and ozone are simultaneously blown into the blown chlorine to oxidize the chlorinated polyolefin.
Chlorinated polyolefin (a) and chlorinated polydiene (b)
And an effective means for smoothly proceeding the copolymerization reaction of the monomer and / or the compound (c).

The chlorinated polydiene (b) used in the present invention is an essential component for obtaining a uniform and transparent solution of the resin (d) during the copolymerization reaction, and the chlorine content is 5 It is preferably used in the range of 50 wt%. If the chlorine content is too low, the appearance of the coating film may be poor, and gelation may occur during the copolymerization reaction. On the other hand, if the chlorine content is too high, the compatibility with the chlorinated polyolefin (a) may be poor, which is good. A good coating film appearance cannot be obtained, and the reactivity with the monomer and / or compound (c) is also reduced. The raw material of chlorinated polydiene includes polybutadiene, polypentadiene, polyisoprene and the like.For example, as the above polybutadiene, an anionic polymerization method using metal sodium or an organic sodium catalyst, ptadien, Ziegler-type coordination anionic polymerization method, Friedel craft Liquid polybutadiene obtained by solution polymerization by a specific catalyst and a polymerization method such as a cationic polymerization method and a radical polymerization method using a catalyst, and also includes those having a hydroxyl group, a carboxyl group, and an acid anhydride group.
As other polydiene, there are liquid rubbers having unsaturated groups such as liquid polychloroprene, liquid polypentadiene, and liquid polyisoprene. The chlorination reaction of polydiene can be carried out in the same manner as in the above-mentioned polyolefin, but it can be carried out at room temperature without catalyst and without ultraviolet light.

The monomer and / or compound (c) used in the present invention which has an ethylenically unsaturated bond and a hydroxyl group in one molecule has a hydroxyl group introduced into the chlorinated polyolefin (a) and the chlorinated polydiene (b). To obtain the hydroxyl group-containing chlorinated resin (d), and examples thereof include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth) acrylate. (Poly) caprolactone-modified (meth) acrylate obtained by esterifying the contained (meth) acrylate with caprolactone (for example, Daicel Chemical Industries, Ltd., trade name Praxel FA, Praxel F
A series) can also be used.

Further, in the monomer and / or compound (c),
A monomer and / or compound containing at least one ethylenically unsaturated bond in one molecule may be mixed and used. Examples of the monomer used at this time include (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, and the compounds include polystyrene and poly (meth) acrylate. There is a macromonomer having a polymerizable (meth) acryloyl group at the terminal.

The weight ratio of (a) and (b) is 95/5 to 50/50.
And the weight ratio of (c) is 3 to 75 with respect to 100 of (a) and (b), and the hydroxyl group-containing chlorinated resin (d) is obtained. When (b) is less than 5% in the mixing ratio of (a) and (b), the reaction solution of (d) becomes cloudy, 2
Phase separation occurs, and a binder resin composition having good transparency cannot be obtained. If (b) exceeds 50%, gelation occurs during the copolymerization reaction.

Graft copolymerization of the chlorinated polyolefin (a) and chlorinated polydiene (b) with the monomer and / or compound (c) according to the present invention is carried out by solution polymerization. The solvent to be used is preferably an aromatic solvent such as toluene or xylene, and may be used in combination with an ester solvent, a ketone solvent, an alcohol solvent, an aliphatic solvent, a cycloaliphatic solvent or the like. As the polymerization initiator,
There are peroxides such as benzoyl peroxide and di-tert-butyl peroxide, and azonitriles such as azobisisobutyronitrile.

The graft copolymerization is carried out by appropriately diluting (a) and (b) with a solvent, mixing them, adding a polymerization initiator and then heating, and gradually reacting with (c). Is the basic process, but (a) and (b) and (c)
May be mixed in advance, a polymerization initiator may be added, and then heated to react. The resin (I) obtained by reacting the hydroxyl group-containing chlorinated resin (d) used in the present invention with an organic diisocyanate requires that the terminal functional group is an isocyanate group, but the isocyanate group / hydroxyl group molar ratio is 0.2. ~ 2.
Within the range of 0, it is possible to appropriately select the reaction conditions.

The organic diisocyanates that can be used include aromatic, aliphatic and alicyclic diisocyanates, such as 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 is basically obtained by reacting a polymer polyol and an organic diisocyanate, but it is necessary. A high molecular weight may be obtained by using a chain extender composed of a diol component and / or a diamine component.

The polymer polyols include polyether polyols and polyester polyols, and the polyether polyols include, for example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polycarbonate diols, bisphenol A and ethylene oxide or propylene oxide. There are glycols and the like obtained by addition. Polyester polyols are obtained by polycondensing dicarboxylic acids such as adipic acid, maleic acid, succinic acid, fumaric acid, phthalic acid and sebacic acid with glycols such as ethylene glycol, neopentyl glycol and 1,8-octamethylenediol. There are adipates that can be used, such as polyethylene adipate, polybutylene adipate, and polyhexamethylene diadipate. Further, polycaprolactone diols obtained by ring-opening polymerization of lactone can also be used.
As the organic diisocyanate, those mentioned above can be used as they are.

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

The amount of the chain extender added to the free isocyanate of the resin (I) and the polyurethane resin (II) is such that the amino group or hydroxyl group / free isocyanate group (molar ratio) = 0.2.
It is in the range of ~ 2.0. The amount of the chain extender added can be determined, for example, as follows. When the product reacted with an organic diisocyanate was measured by IR, it was 2250 on the IR chart.
A peak of free isocyanate appears at cm ^-1 . This peak decreases when a chain extender or a reaction terminator is added to the reaction solution and reacted. Therefore, when the reaction is carried out only with the chain extender, the free isocyanate of the reaction liquid obtained by mixing the resin (I) and the polyurethane resin (II) is measured by IR, and the chain extender is added until the peak disappears.

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 excessively added to the above-mentioned polymer polyol component, that is, an isocyanate group / hydroxyl group is in a range exceeding 1.0 mol, preferably 1.1
The polyurethane resin (II) having at least one free isocyanate group in one molecule can be obtained by reacting in the range of up to 2.0 mol and further using a chain extender if it is necessary to increase the molecular weight.

As reaction solvents for obtaining the resin (I) and the polyurethane resin (II), aromatic solvents such as toluene and xylene, ester solvents such as ethyl acetate, propyl acetate and butyl acetate, methyl ethyl ketone and methyl isobutyl are used. Ketone-based solvents such as ketones and alcohol-based solvents such as ethanol, isopropanol and n-butanol may be used alone or in combination.

The number average molecular weight of the polyurethane resin (II) is preferably 1,000 to 150,000. If the number is 1,000 or less, the coating film will have insufficient gasoline resistance, moisture resistance, blocking resistance, etc. It is not suitable as a binder resin for paints and inks because of poor sprayability and spray paintability.

The binder resin of the present invention is obtained by reacting the above resin (I) with the polyurethane resin (II) in the presence of a chain extender. . Further, if necessary, a reaction terminator may be added to stop the reaction. Examples of the reaction terminator include monoalcohols such as methanol, ethanol and isopropanol, and monoamines such as monoethylamine, n-propylamine and n-butylamine. Further, amino alcohols such as ethanolamine, propanolamine and butanolamine can also be used.

When the reaction is carried out by using the chain extender and the reaction terminator in combination, the chain extender is the resin (I) and the polyurethane resin (I
The peak of free isocyanate in the reaction mixture containing I)
As 100, it is desirable to add the peak reduction in the range of 50 to 80%. The reaction terminator is added until the residual free isocyanate peak after the chain extension reaction disappears.

The weight mixing ratio when synthesizing the binder resin is as follows: resin (I) / polyurethane resin (II) = 5/95 to 95
/ 5 is a preferable range for carrying out the present invention.

The binder resin of the present invention is blended with an isocyanate compound as a curing agent to obtain coating film properties required for paints and inks such as gasoline resistance, weather resistance, moisture resistance, hot water resistance (boil, retort). Can be improved. As the isocyanate compound used at this time, the organic diisocyanates described above can be used,
These organic diisocyanates, burette body,
It is more preferable to modify it into an isocyanate derivative such as an isocyanurate body or a trimethylolpropane adduct body before use.

The binder resin of the present invention may be used by coating as it is, but it can be used as a paint or an ink by adding a pigment, a solvent and other additives, kneading and dispersing. Further, the binder resin shows a balanced coating property by itself, but if necessary, an alkyd resin, an acrylic resin, a polyacrylic polyol, a polyester resin, a polyester polyol, a polyether resin, a polyether polyol, a polyurethane resin. ,
There is no problem if chlorinated polyolefin or the like is further added and used.

[0038]

The feature of the present invention is that a much more uniform and transparent binder resin solution can be obtained as compared with other similar invention products, and the chlorinated resin component is contained in the binder resin composition. It can be optionally contained. That is, when a chlorinated polyolefin and a monomer or compound containing at least one ethylenically unsaturated bond and at least one hydroxyl group are copolymerized, the reactivity of the chlorinated polyolefin itself is poor, and therefore, a single amount of these copolymers and A homopolymer of the body or compound is formed. For this reason, the reaction product becomes cloudy and separates into two layers, but by adding a chlorinated polydiene and copolymerizing as in the present invention, a uniform and transparent solution can be obtained.

The effect of the chlorinated polydiene is that the chlorinated polydiene is a substance which is compatible with the chlorinated polyolefin, the above-mentioned monomer or the polymer of the compound at an appropriate degree of chlorination, and the above-mentioned monomer. Alternatively, it is considered that it is derived from the fact that the formation of these homopolymers is suppressed because the reactivity with the compound is good. Therefore, in the case of the resin (I) obtained by reacting the hydroxyl group-containing chlorinated resin (d) with an organic diisocyanate, it is considered that there are few homopolymers of a monomer having a hydroxyl group in the resin (I) for the above reason. Of the chlorinated resin containing hydroxyl groups and the polyurethane resin, the isocyanate group is surely introduced into each of the components by a separate system to extend the chain, thereby integrating the originally poorly compatible binder resin. The composition is a much more uniform and transparent solution than other similar inventions, and the invention of Japanese Patent Application No. 4-87937 has already been proposed by the present inventors.
The storage stability of paints and inks is better than that of No.

Further, the chlorinated resin having an isocyanate group and the polyurethane resin having an isocyanate group at the end of the molecule are linked by a chain extender to obtain a high molecular weight, so that the component ratio of the chlorinated resin and the polyurethane resin is arbitrarily set. Can be set. This means that the present invention is a further advance of the one disclosed in JP-A-4-168174.

[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) 500 g of isotactic polypropylene having a number average molecular weight of 50,000 was charged into a glass-lined reaction kettle, 8 liters of carbon tetrachloride was added, and the temperature was 110 ° C. and the pressure was 2 kg / cm ² . After fully dissolved,
While irradiating with ultraviolet rays, chlorine gas was introduced from the bottom of the reaction vessel until the chlorine content became 30 wt%. Next, carbon tetrachloride was distilled off and the residue was replaced with toluene to obtain a toluene solution of chlorinated polypropylene having a nonvolatile content of 50 wt%.

(Prototype Example-2) Chlorination was carried out in the same manner as in Prototype Example-1 except that 500 g of isotactic polypropylene having a number average molecular weight of 35,000 was simultaneously blown with chlorine gas and air. Nonvolatile content at 30 wt%
A toluene solution of 50 wt% chlorinated polypropylene was obtained.

(Prototype Example-3) 500 g of trade name Nisso Polybutadiene B-3000 (manufactured by Nippon Soda Co., Ltd., liquid polybutadiene, number average molecular weight of 3,000) was charged into a reaction kettle similar to that of Prototype Example-1 and 8 liters were charged. Of carbon tetrachloride was added and uniformly dissolved. The air was completely purged with nitrogen gas, the temperature was kept at 50 ° C., and chlorine gas was introduced until the chlorine content became 30 wt%. Thereafter, in the same manner as in Prototype Example-1, a toluene solution of chlorinated polybutadiene having a nonvolatile content of 50 wt% was obtained.

(Prototype Example-4) In a flask equipped with a stirrer, a thermometer, and a cooling tube for refluxing a monomer, the chlorinated polypropylene obtained in Prototype Example-1 (nonvolatile content: 50 wt.
%) 240 g, chlorinated polybutadiene obtained in Trial Production Example-3 (nonvolatile content 50 wt%) 80 g, benzoyl peroxide 0.8
g, and stirred at 85 ° C. for 30 minutes. Next, a mixture of 24.0 g of 2-hydroxyethyl acrylate and 24.0 g of toluene was added over about 1 hour, and a graft copolymerization reaction was further performed for about 3 hours to give a hydroxyl group-containing chlorinated resin (nonvolatile content 50 wt%).
Got

(Prototype Example-5) 240 g of chlorinated polypropylene (nonvolatile content 50 wt%) obtained in Prototype Example-2, 80 g of chlorinated polybutadiene (nonvolatile content 50 wt%) obtained in Prototype Example-3, 0.8 g of benzoyl peroxide And stirred for 30 minutes at 85 ° C., then 24.0 g of 2-hydroxyethyl acrylate,
A mixture of 24.0 g of toluene was subjected to a graft copolymerization reaction in the same manner as in Prototype Example-4, and a hydroxyl group-containing chlorinated resin (nonvolatile content 50
wt%) was obtained.

(Prototype Example-6) 320 g of the chlorinated polypropylene (nonvolatile content: 50 wt%) obtained in Prototype Example-2 and 0.8 g of benzoyl peroxide were added, and the mixture was stirred at 85 ° C for 30 minutes. Next, 24.0 g of 2-hydroxyethyl acrylate and toluene
Graft copolymerization reaction of 24.0 g of the mixture was carried out in the same manner as in Prototype Example-4, and hydroxyl group-containing chlorinated polypropylene (nonvolatile component
50 wt%) was obtained.

(Prototype Example-7) In a flask similar to that of Prototype Example-4, 240 g of chlorinated polypropylene (nonvolatile content 50 wt%) obtained in Prototype Example-2 and chlorinated polybutadiene (nonvolatile) obtained in Prototype Example-3 (50 minutes by weight), toluene (240 g) and benzoyl peroxide (2.0 g) were added, and the mixture was stirred at 85 ° C for 30 minutes. Next, a mixture of 98 g of methyl methacrylate, 98 g of lauryl methacrylate, 4 g of methacrylic acid, and 40 g of 2-hydroxyethyl acrylate was added in 3 hours, and after a graft copolymerization reaction for several hours, 200 g of toluene was added to stop the reaction. A hydroxyl group-containing chlorinated resin (nonvolatile content 40 wt%) was obtained.

(Prototype Example-8) 150 g of chlorinated polypropylene (nonvolatile content 50 wt%) obtained in Prototype Example-2, 50 g of chlorinated polybutadiene (nonvolatile content 50 wt%) obtained in Prototype Example-3, 200 g of toluene, benzoylper Oxide 1.0g, cyclohexyl methacrylate 69.2g, ethyl acrylate 1
Graft copolymerization reaction was carried out at a compounding ratio of 0.8 g and 20 g of 2-hydroxyethyl acrylate according to the reaction method of Prototype Example-6 to obtain a hydroxyl group-containing chlorinated resin (nonvolatile content 40%).

(Prototype Example-9) 200 g of chlorinated polypropylene (nonvolatile content 50 wt%) obtained in Prototype Example-2 and toluene 200
g, benzoyl peroxide 1.0 g, cyclohexyl methacrylate 69.2 g, ethyl acrylate 10.8 g, 2-
Graft copolymerization reaction was carried out according to the reaction method of Prototype Example-8 at a compounding ratio of 20 g of hydroxyethyl acrylate to obtain a hydroxyl group-containing chlorinated polypropylene (nonvolatile content 40 wt%).

(Prototype Example-10) Trade name Praxel L-22
400 g of 0AL (manufactured by Daicel Chemical Industries, Ltd., caprolactone-based polymer diol, molecular weight 2,000) and 67.2 g of hexamethylene diisocyanate were put in the same flask as in Prototype Example-4, and the temperature was 85 ° C. while introducing nitrogen gas. After reacting for several hours, 300 g of toluene and 167.2 g of ethyl acetate were added to obtain a polyurethane resin having a terminal isocyanate group (nonvolatile content 50 wt%).

(Prototype Example-11) 400 g of a polymer polyol (butane adipate diol, molecular weight 2,000) synthesized from adipic acid and 1,4-butanediol and 88.8 g of isophorone diisocyanate were reacted in the same manner as in Prototype Example-9. And 1,4-butanediol as a chain extender.
8.6 g was added and reacted for several hours. Then toluene 248.7
g, 248.7 g of methyl ethyl ketone, and a polyurethane resin with an isocyanate group at the end (nonvolatile content 50 wt
%) Was obtained.

(Example-1) 200 g of hydroxyl group-containing chlorinated resin obtained in Prototype Example-4, 25.0% of isophorone diisocyanate
g was put in the same flask as in Prototype Example-4, and 4
After reacting for a period of time, 351.5 g of toluene and 467 g of the polyurethane resin obtained in Prototype Example-11 were added and cooled to 50 ° C., and chain extension reaction was carried out while gradually adding 20.5 g of isophoronediamine. After cooling, 337.8 g of methyl ethyl ketone and 113.7 g of isopropanol were added, and the binder resin (nonvolatile
25 wt%) was obtained.

Next, the solution of the binder resin and the transparency of the coating film were observed. The transparency of the coating film was evaluated by coating the binder resin on a glass plate with an applicator so that the film thickness after drying at room temperature would be 30 microns, and drying the coating film for 24 hours. In addition, white ink was prepared with the binder resin, and a storage stability test and an adhesive strength test were performed. The storage stability test is for observing the pigment settling property during storage at 40 ° C, and the adhesion strength test is for coating rod # 4 with untreated polypropylene film (hereinafter referred to as untreated PP), corona discharge treated polypropylene film (hereinafter treated with PP). Called),
A polyethylene terephthalate film (hereinafter referred to as PET) and a nylon film (hereinafter referred to as NY) were applied, dried for 24 hours, and then subjected to a cellophane tape peeling test using a cellophane adhesive tape and a heat seal strength test. . The results are shown in Table 1. The formulation of the ink is shown in Table 2.

(Example-2) 200 g of hydroxyl group-containing chlorinated resin obtained in Prototype Example-5 and 25.0 of isophorone diisocyanate
g, the polyurethane resin 467 g obtained in Prototype Example-11, 20.5 g of isophoronediamine, 351.5 g of toluene, 337.8 g of methyl ethyl ketone, and 113.7 g of isopropanol were reacted according to the method of Example-1 to give a uniform and transparent mixture. A binder resin (nonvolatile content 25 wt%) was obtained. The same test as in Example-1 was performed below. The results are shown in Table 1.

(Example-3) 200 g of hydroxyl group-containing chlorinated resin obtained in Prototype Example-5 and 25.0 of isophorone diisocyanate
g, 300 g of the polyurethane resin obtained in Prototype Example-11, 7.7 g of isophoronediamine, 259.0 g of toluene, 272.2 g of methyl ethyl ketone, and 86.8 g of isopropanol. After the reaction was carried out according to the method of Example-1, 6.6 g N-Butylamine was added to stop the reaction to obtain a uniform and transparent binder resin (nonvolatile content: 25 wt%). Hereinafter, the same test as in Example-1 was performed. The results are shown in Table 1.

(Comparative Example-1) Trade name Super Klon 80
3MW (chlorinated polypropylene, chlorine content 29.5%, non-volatile content 20wt%, Sanyo Kokusaku Pulp Co., Ltd.) and trade name Supercron BX (chlorinated ethylene vinyl acetate copolymer,
The same test as in Example-1 was conducted using a mixture of chlorine content of 18 wt%, nonvolatile content of 20 wt% and Sanyo Kokusaku Pulp Co., Ltd. The results are shown in Table 1.

(Comparative Example-2) Trade name Sanbren IB-4
The same test as in Example-1 was conducted with 50 (polyurethane resin, non-volatile content 30 wt%, manufactured by Sanyo Kasei Co., Ltd.).

Comparative Example-3 200 g of hydroxyl group-containing chlorinated polypropylene obtained in Prototype Example-6, 25.0 g of isophorone diisocyanate, and polyurethane resin obtained in Prototype Example-11 467
g, isophorone diamine 20.5 g, toluene 351.5 g,
Methyl ethyl ketone 337.8g, isopropanol 113.7
Reaction was carried out according to the method of Example 1 at a compounding ratio of g to obtain a binder resin (nonvolatile content 25 wt%). Examples below-
The same test as 1 was performed. The results are shown in Table 1.

[0060]

[Table 1]

Binder resin transparency test: The solution was placed in a transparent glass bottle, and the coating film was applied on a transparent glass plate with an applicator so that the film thickness after drying at room temperature would be 30 microns, The transparency of each of the samples dried for 24 hours was observed and judged. ◎: Very good ○: Good △: Slightly opaque
×: Cloudy

Cellophane tape peeling test The cellophane adhesive tape was attached to the ink coated surface and peeled off at once, and the peeled state was judged. ◎: Very good ○: Good △: Somewhat bad
×: defective

Heat seal strength test: Overlap the ink coated surfaces and make 1 at 1 ° C and 1 kg / cm ² .
Heat sealing was performed under pressure bonding conditions for 2 seconds, and after 24 hours, a 180 ° peel strength test (pulling speed 50 mm / min) was performed using Tensilon and measurement was performed.

Storage stability test The ink was placed in a transparent glass bottle and stored at 40 ° C., and the sedimentation separation of the pigment of the ink after one month was observed and judged. ◎: Very good ○: Good △: Somewhat bad
×: defective

[0065]

[Table 2]

・ Super Clone 803MW 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.) Made, rutile type R-8
20) ・ Carmine 6BN (Azo organic pigment, manufactured by Toyo Ink Mfg. Co., Ltd.) ・ Molding conditions: Kneading in a sand mill for 2 hours

(Example-4) 250 g of hydroxyl group-containing chlorinated resin obtained in Prototype Example-7, hexamethylene diisocyanate
14.4 g, 40 g of the polyurethane resin obtained in Prototype Example-10, 10.7 g of isophorone diamine as a chain extender, and 36.8 of toluene.
g, and 10.9 g of isopropanol at a blending ratio of Example-1.
The reaction was carried out according to the above method to obtain a uniform and transparent binder resin (nonvolatile content 40%).

Next, 100 g of this binder resin and 26 g of titanium dioxide were kneaded in a sand mill for 3 hours, and then 3.2 g of isocyanate curing agent Desmodur N3390 (manufactured by Bayer, hexamethylene diisocyanate system, isocyanurate body) was added, and No. 4 was added. The viscosity was adjusted with xylene to a temperature of 13 to 15 seconds / 20 ° C. with a Ford cup, and spray coating was performed on a polypropylene plate, TX-933A (manufactured by Mitsubishi Petrochemical Co., Ltd.). After being dried at room temperature for 15 minutes, forcedly dried at 80 ° C. for 30 minutes and allowed to stand in the room for 1 week, the coating film was tested. The results are shown in Table 3.

(Example-5) 250 g of hydroxyl group-containing chlorinated resin obtained in Prototype Example-8, hexamethylene diisocyanate
10.8 g, 60 g of the polyurethane resin obtained in Prototype Example-10, 8.8 g of isophorone diamine as a chain extender, toluene 33.2
g, isopropanol 11.2 g in the blending ratio of Example-1
The reaction was carried out according to the above method to obtain a uniform and transparent binder resin (nonvolatile content 40%).

Next, 100 g of this binder resin, 26 g of titanium dioxide, and isocyanate curing agent desmodul Z43.
70 (manufactured by Bayer, isophorone diisocyanate type,
Isocyanurate body) With a blending ratio of 5.2 g, Example-4
A paint preparation and a coating film test were conducted in the same manner as in (1). The results are shown in Table 3.

(Comparative Example 4) A coating composition was prepared in the same manner as in Example 4 with the compounding ratios of 100 g of the hydroxyl group-containing chlorinated resin obtained in Prototype Example-8, 26 g of titanium dioxide and 7.4 g of isocyanate curing agent Desmodur N3390. And the coating film was tested. The results are shown in Table 3.

Comparative Example 5 100 g of the hydroxyl group-containing chlorinated resin obtained in Prototype Example-8, 26 g of titanium dioxide, 12.5 g of Desmodur Z4370, an isocyanate curing agent, and 0.08 g of di-n-butyltin dilaurate curing accelerator. The paint preparation and the coating film test were performed in the same manner as in Example-4. The results are shown in Table 3.

Comparative Example-6 250 g of hydroxyl group-containing chlorinated polypropylene obtained in Prototype Example-9, 10.8 g of hexamethylene diisocyanate, polyurethane resin obtained in Prototype Example-10
The reaction was carried out according to the method of Example 1 at a mixing ratio of 60 g, isophoronediamine 8.8 g as a chain extender, toluene 33.2 g, and isopropanol 11.2 g to obtain a binder resin (nonvolatile content 40%).

Next, 100 g of this binder resin, 26 g of titanium dioxide, and an isocyanate curing agent desmodul Z43.
70 (manufactured by Bayer, isophorone diisocyanate type,
Isocyanurate body) With a blending ratio of 5.2 g, Example-4
A paint preparation and a coating film test were conducted in the same manner as in (1). The results are shown in Table 3.

[0075]

[Table 3]

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. ◎: Very good ○: Good △: Slightly bad ×: Bad

Accelerated weather resistance A carbon arc type sunshine weather ometer was used. The glossiness was measured by 60 ° specular reflection, and the whiteness was measured by a hunter.

・ Gasoline resistance "rubbing 100 times": Soak cotton in absorbent cotton,
The coated surface was rubbed 100 times to judge the state of the coating film. ⊚: Very good O: Good Δ: Slightly bad ×: Poor “Dip 2 hours”: Scratches (marked X) reaching the base material were put on the coated surface, and immersed in gasoline for 2 hours to judge the state of the coating film. ◎: Very good ○: Good △: Slightly bad ×: Bad

Bending resistance The state of the coating film was judged by bending 180 ° with a 1/2 φ inch mandrel. ◎: Very good ○: Good △: Slightly bad ×: Bad
XX: Extremely poor

-Impact resistance A DuPont type impact tester has a hammer core of 1 / 2φ inch and a load of 500 g.
Was used to drop on the coated surface from a height of 50 cm to determine the state of the coating film. ◎: Very good ○: Good △: Slightly bad ×: Bad
XX: Extremely poor

Storage stability test The paint was put in a transparent glass bottle and stored at 40 ° C, and the sedimentation and separation of the pigment of the paint after one month was observed and judged. ◎: Very good ○: Good △: Slightly bad ×: Bad

[0082]

【The invention's effect】

The ink binder resin of the chlorinated polypropylene / chlorinated ethyne vinyl acetate copolymer system of Comparative Example-1 (from the results in Table 1) exhibits good adhesion to the PP film, but adheres to the PET and NY films. There is no property and it is far from practical strength. The polyurethane-based binder resin of Comparative Example-2 adheres to PET and NY films, but PP
Adhesive strength to the film is not sufficient. Japanese Patent Application 4-87
Comparative Example-3, which is a urethane-modified chlorinated polypropylene-based binder resin proposed in No. 937, has good adhesion to both PP film and PET / NY film, but has poor ink storage stability. On the other hand, the product of the present invention is not only excellent in adhesiveness to these films but also excellent in storage stability of ink, and it is understood that it is a binder resin for ink having high versatility.

Comparative Examples 4 and 5 (from the results in Table 3)
It is a composition obtained by graft-copolymerizing a chlorinated polypropylene or chlorinated polybutadiene with an acrylic monomer having a hydroxyl group and other acrylic monomers, but is inferior in flex resistance and impact resistance. Comparative Example 6 was proposed in Japanese Patent Application No. 4-87937, in which a composition obtained by graft-copolymerizing an acrylic monomer having a hydroxyl group and another acrylic monomer on chlorinated polypropylene is further urethane-modified. By
Improves flex resistance and impact resistance, but poor storage stability of paint. On the other hand, the product of the present invention imparts flexibility to the coating film without impairing the excellent properties conventionally possessed, such as adhesion, gasoline resistance, and weather resistance, and is remarkably excellent in flex resistance and impact resistance. It can be seen that this is improved and the storage stability of the paint is also excellent.

Claims (12)

[Claims] 1. A chlorinated polyolefin (a) chlorinated to have a chlorine content of 5 to 50 wt%, and a chlorinated polydiene (b) chlorinated to have a chlorine content of 5 to 50 wt%. Monomer and / or compound (c) containing at least one ethylenically unsaturated bond and one hydroxyl group in one molecule
A hydroxyl group-containing chlorinated resin (d) copolymerized with a resin (I) obtained by reacting an organic diisocyanate, and a polyurethane resin (II) containing at least one free isocyanate group in one molecule, A binder resin composition obtained by reacting with a stretching agent. 2. The weight ratio of (a) and (b) is 95/5 to 50 /.
It is in the range of 50, and the weight ratio of (c) is 100 in (a) and (b).
The binder resin composition according to claim 1, which is obtained by copolymerizing in the range of 3 to 75 to obtain the hydroxyl group-containing chlorinated resin (d). 3. The amount of the chain extender added to the free isocyanate of the resin (I) and the polyurethane resin (II) is amino group or hydroxyl group / free isocyanate group (molar ratio) =
The binder resin composition according to claim 1 or 2, which has a range of 0.2 to 2.0. 4. The binder resin composition according to any one of claims 1 to 3, wherein the resin (I) is obtained by reacting at an isocyanate group / hydroxyl group molar ratio of 0.2 to 2.0. 5. The vanider resin composition according to claim 1, which is obtained by reacting the resin (I) with the resin (II) with a chain extender and stopping the reaction with a reaction terminator. . 6. The monomer and / or compound (c) is a mixture with a monomer and / or compound containing at least one ethylenically unsaturated bond in one molecule.
The binder resin composition according to any one of 1 to 6 above. 7. The banter resin composition according to claim 1, wherein the polyurethane resin (II) has a number average molecular weight of 1,000 to 150,000. 8. The binder resin according to claim 1, which is obtained by reacting the resin (I) and the polyurethane resin (II) in a weight ratio of 5/95 to 95/5. Composition. 9. The banter according to claim 1, which is obtained by subjecting the chlorinated polyolefin (a) to oxidation treatment with air and / or oxygen and / or ozone during the chlorination reaction of the polyolefin. Resin composition. 10. A coating composition, a printing ink, or a resin composition for an adhesive, comprising an isocyanate compound as a curing agent in the binder resin composition according to any one of claims 1 to 9. 11. A method for producing the binder resin composition according to any one of claims 1 to 10. 12. A paint, a printing ink or an adhesive, which uses the binder resin composition according to any one of claims 1 to 10.