JPH072932B2 - Binder resin composition - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a binder resin composition used for the purpose of protecting various plastics, cosmetics, and adhesion, and more specifically, a polyolefin resin, a polyurethane resin, a polyamide resin, an allyl resin, A paint that exhibits excellent physical properties for various synthetic resin films, sheets or molded products 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 Plastics have a lot of advantages such as high productivity, wide design freedom, light weight, rust prevention and impact resistance. It is used. In particular, polyolefin 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 characteristics. It is one of the materials with the highest expectations for elongation. However, unlike polyolefin-based synthetic resins such as polyurethane-based resins, polyamide-based resins, acrylic-based resins, polyester-based resins, etc., polyolefin-based resins are non-polar and crystalline, which makes them difficult to coat and bond. Have. Conventionally, the adhesion has been improved by activating the surface of polyolefin resin molded products by plasma treatment or gas flame treatment, but this method involves complicated steps and enormous equipment costs and time loss. In addition, there are drawbacks such as variations in the surface treatment effect due to the complexity 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 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.
Moisture resistance, gasoline resistance, etc. are inferior and do not show sufficient coating performance. Therefore, attempts have been made to use a mixture of acrylic resin and alkyd resin, etc., which have good paint properties, but since acrylic resin and alkyd resin originally have poor compatibility with chlorinated polyolefin, the gloss of the coating film decreases. , Causing a problem such as significantly impairing the appearance.

In order to improve these drawbacks, JP-A-58-719
As shown in No. 66, a coating composition obtained by copolymerizing an acrylic monomer and a chlorinated polyolefin, as seen in JP-A-59-27968, an acrylic monomer having a hydroxyl group. Copolymerized chlorinated polyolefin with the body,
A coating composition comprising a chlorinated polyolefin-modified hydroxyl group-containing acrylic copolymer and an isocyanate compound as essential components, and as shown in JP-A-62-95372, in the presence of a chlorinated polyolefin and a liquid rubber, There has been proposed an adhesive resin composition containing a hydroxyl group-containing acrylic-modified chlorinated polyolefin copolymerized with an acrylic monomer and the like and an isocyanate compound as main components.
However, in these compositions, chlorinated polyolefin, liquid rubber, and acrylic resin are essentially incompatible with each other, as described above, and therefore, even if they are copolymerized, white turbidity or two-layer separation occurs, resulting in a uniform and transparent composition. No solution is obtained. When used as a paint, a paint resin that is cloudy or has two layers separated does not provide sufficient pigment dispersion, resulting in poor gloss of the coating film and poor storage stability of the paint. Moreover, when used as an adhesive, sufficient adhesive performance cannot be obtained.

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 urethane resin mainly used for polyester and nylon film. .

The former ink composition containing a chlorinated polypropylene and a chlorinated ethylene vinyl acetate copolymer as a main binder is disclosed in, for example, JP-A-60-31670, and a chlorinated ethylene vinyl acetate copolymer is further sulfochlorinated. The ink composition is described in JP-A-55-145775. These have good ink adhesion to the untreated polypropylene film and also show good adhesion strength when laminated printed by the extrusion lamination method. However, it has poor adhesion to films of polyester, nylon, etc. 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 disclosed in JP-A-62-153366 and JP-A-62-153366.
As shown in No. 153367, it exhibits good adhesiveness to polar films such as polyester and nylon, but has no adhesiveness to untreated polypropylene, and is produced by the polypropylene extrusion lamination method. Printing is impossible.

An ink resin suitable for both printing by the extrusion-lamination method of polypropylene and laminate printing of polyester, nylon, etc. has been proposed in JP-A-64-85226. In this proposal, chlorinated polypropylene is modified with a hydroxyl group-containing vinyl monomer,
The present invention relates to a polyurethane-modified chlorinated polypropylene obtained by introducing a hydroxyl group into chlorinated polypropylene and then reacting it with a polyurethane containing a free isocyanate group. The drawback of this method is that the reaction between the chlorinated polypropylene and the hydroxyl group-containing vinyl monomer is incomplete, so that the hydroxyl group is not completely introduced into the chlorinated polypropylene and the hydroxyl group-containing vinyl monomer is formed as a homopolymer. The chlorinated polypropylene and the hydroxyl group-containing vinyl polymer are essentially incompatible with each other, resulting in cloudiness and two-layer separation. Naturally, such a polyurethane-modified chlorinated polypropylene obtained by reacting a hydroxyl group-containing chlorinated polypropylene and a free isocyanate group-containing polyurethane causes white turbidity or two-layer separation, and there is a problem that a normal binder resin cannot be obtained. is there.

[0010]

DISCLOSURE OF THE INVENTION In order to solve the above problems, the present inventors have designed a copolymer obtained by copolymerizing an acrylic monomer having a hydroxyl group with a chlorinated polyolefin and a chlorinated polydiene. The polymer shows a uniform and transparent liquid, and a coating composition in which an isocyanate compound is further added to this copolymer shows excellent adhesion to a polyolefin resin and gives a tough and glossy coating film. It was found that this was already proposed in JP-A-62-18434.

However, although this method is sufficiently effective for polyolefin resin materials used in home appliances, etc., it is resistant to the harsh conditions required for painted objects used outdoors such as automobiles and motorcycles. Gasoline resistance, flex resistance, impact resistance, etc. were somewhat insufficient. Further, when it was used as a binder resin for a laminated printing ink of a plastic film, the adhesion to a film of polypropylene, polyester, nylon or the like was good, but uneven printing occurred and it was insufficient in terms of printability.

[0012]

SUMMARY OF THE INVENTION The inventors of the present invention further examined and improved the previously proposed JP-A-62-18434, and as a result, the coating film which was a drawback of JP-A-62-18434 was found. Gasoline resistance, bending resistance, impact resistance and solution state of the binder resin shown in JP-A-64-85226 are improved, and a good binder resin for paints and laminating inks is obtained. The inventors have found that the above can be achieved, and have completed the first invention of the present invention.

That is, the first invention has a chlorine content of 5 to 50 wt.
Chlorinated polyolefin (a) chlorinated in the range of%,
Chlorinated polydiene (b) chlorinated to have a chlorine content of 5 to 50 wt%, and a monomer and / or compound containing at least one ethylenically unsaturated bond and one hydroxyl group in one molecule.
A binder resin composition obtained by reacting a resin (I) obtained by copolymerizing (c) with a polyurethane resin (II) having at least one free isocyanate group in the molecule.

As a result of further investigations by the present inventors, the resin (I), the polymer polyol (III), the organic diisocyanate (IV), and the chain extender and / or the reaction terminator, if necessary, were reacted. It was found that the binder resin composition thus obtained has a solution state improved as compared with the first invention, and a transparent and uniform solution can be obtained, and has reached the second invention of the present invention.

Chlorinated polyolefin used in the present invention
(a) is a component for imparting adhesiveness to the polyolefin resin, and it is preferable to use it in the range of 5 to 50 wt% chlorine content. 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.

As the raw material of chlorinated polyolefin, crystalline polypropylene, amorphous polypropylene, polybutene-1, polypentene-1,4-methylpentene-1, 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, polyolefin is dispersed or dissolved in a medium such as water or carbon tetrachloride, and in the presence of a catalyst or irradiation of ultraviolet rays, at 50 ° C. under pressure or normal pressure.
It is carried out by blowing chlorine gas in the temperature range of up to 120 ° C. Further, at least one kind or two kinds or more selected from air, oxygen and ozone is simultaneously blown into the chlorine blown to oxidize the chlorinated polyolefin, so that the chlorinated polyolefin (a) and the chlorinated polydiene (b) can be treated. It is an effective means for smoothly promoting the copolymerization reaction of the monomer and / or the compound (c).

Chlorinated polydiene (b) used in the present invention
Is an essential component for obtaining a uniform and transparent solution of the resin (I) during the copolymerization reaction. That is, a copolymer of an acrylic monomer and a chlorinated polyolefin, as seen in the above-mentioned JP-A-58-71966 and JP-A-59-27968, does not form a uniform and transparent solution and is separated. , While it becomes cloudy, a uniform and transparent solution can be obtained by adding the chlorinated polydiene (b) and copolymerizing as in the present invention.

The polydiene referred to in the present invention includes polybutadiene, polypentadiene, polyisoprene, etc. For example, as the above polybutadiene, an anionic polymerization method of butadiene with a metal sodium or organic sodium catalyst, a Ziegler type coordination anionic polymerization method, Liquid polybutadiene obtained by solution polymerization with a specific catalyst and a polymerization method such as a cationic polymerization method and a radical polymerization method using a Friedel-Crafts 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.

Chlorinated polydiene has a chlorine content of 5 to 50 wt.
It is preferably used in the range of%. If the chlorine content is too low, the appearance of the coating film may deteriorate and gelation may occur during the copolymerization reaction. If the chlorine content is too high, the compatibility with the chlorinated polyolefin (a) deteriorates, so that a good coating film appearance cannot be obtained and the reactivity with the monomer and / or the compound (c) also decreases.

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 irradiation of ultraviolet rays.

Monomers and / or compounds (c) having an ethylenically unsaturated bond and a hydroxyl group in one molecule used in the present invention
Is for introducing a hydroxyl group into the resin (I) according to the present invention, and examples thereof include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and 2-hydroxybutyl (meth) acrylate. A (poly) caprolactone-modified (meth) acrylate obtained by esterifying the above-mentioned hydroxyl group-containing (meth) acrylate with caprolactone (for example, Daicel Chemical Factory Co., Ltd., trade name Praxel FA, Praxel FM series) can also be used. Further, esters obtained by reacting an α, β unsaturated carboxylic acid or its anhydride with a diol, and a monomer having an ethylenically unsaturated bond and a hydroxyl group in one molecule such as 1,4-butene glycol and allyl alcohol. Any monomer or compound can be used.

The monomer and / or compound (c) may be mixed with a monomer and / or compound having at least one ethylenically unsaturated bond in one molecule. Examples of the monomer used at this time include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth)
Acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, lauryl (meth) acrylate, glycidyl (meth) acrylate, styrene, vinyl acetate, (meth) acrylonitrile, etc. Examples thereof include macromonomers having a polymerizable (meth) acryloyl group at the terminal of polystyrene or poly (meth) acrylate.

The copolymerization of the chlorinated polyolefin (a) with the chlorinated polydiene (b) and the monomer and / or compound (c) according to the present invention is carried out by solution polymerization. Aromatic solvents such as toluene and xylene are preferable as the solvent to be used, and in addition, ester solvents, ketone solvents, alcohol solvents,
It is acceptable to use an aliphatic solvent, a cycloaliphatic solvent, etc. together.

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

Copolymerization is carried out by appropriately diluting (a) and (b) with a solvent, mixing them, adding a polymerization initiator, and then heating (c).
The basic process is to gradually add and to react, but it is also possible to mix (a) with (b) and (c) in advance, add a polymerization initiator and then heat to react.

The polyurethane resin (II) used in the first invention of the present invention is basically obtained by reacting a high molecular weight polyol component and an organic diisocyanate, but if necessary, a diol component and / or a diamine component. The molecular weight may be increased by using a chain extender consisting of

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 with ethylene oxide or propylene oxide. There are glycols and the like obtained by addition. Polyester polyols include dicarboxylic acids such as adipic acid, maleic acid, succinic acid, fumaric acid, phthalic acid and sebacic acid, and ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol. ，
There are adipates obtained by polycondensing glycols such as 1,8-octamethylenediol, for example, polyethylene adipate, polybutylene adipate, polyhexamethylene adipate and the like. Further, polycaprolactone diols obtained by ring-opening polymerization of lactone can also be used.

The organic diisocyanates include aromatic, aliphatic and aliphatic diisocyanates, such as tolylene diisocyanate, xylene diisocyanate, 1,5-naphthalene diisocyanate, 1,4-tetramethylene diisocyanate and 1,6-hexadiene. There are methylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 1,4-cyclohexyl diisocyanate and the like.

As the chain extender, diol and diamine can be used. Typical examples of the diol are ethylene glycol, propylene glycol, 1,4-butanediol, 1,4-pentanediol and 1,6-hexanediol. , 2,
5-hexanediol and the like. Representative diamines include ethylenediamine, propylenediamine, hexamethylenediamine, 2,2,4-trimethylhexamethylenediamine, isophoronediamine and dicyclohexylmethane-4,4'-diamine.

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 diisocyanate compound is excessively added to the polymer polyol component, that is, NC
O / OH = range exceeding 1.0 mol, preferably 1.1 to 2.0
A polyurethane resin having at least one free isocyanate group in one molecule (I
I) can be manufactured.

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

The number average molecular weight of the polyurethane resin (II) is
Binders for paints and inks are preferred, with 1,000 to 150,000 being preferred, with 1,000 or less the gasoline resistance, moisture resistance, blocking resistance, etc. of the coating being insufficient, and with 150,000 or more the pigment dispersibility and spray workability are poor. Not suitable as a resin.

The binder resin of the first invention is obtained by reacting the above-mentioned resin (I) with polyurethane resin (II),
It can be obtained by adding a reaction terminator 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.

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

Resin (I), polymer polyol (III), organic diisocyanate (IV) used in the second invention,
The chain extender and the reaction terminator are the same as those described above.

The binder resin of the second invention is obtained by reacting the resin (I), the polymer polyol (III) and the organic diisocyanate (IV) in the range of NCO / OH = 0.1 to 2.0 mol. The molecular weight may be further increased by using a stretching agent. A reaction terminator may be used to stop the reaction of the terminal isocyanate group. As the reaction solvent, the reaction solvent used for producing the polyurethane resin (II) can be used as it is.

The binder resin of the present invention is blended with an isocyanate compound as a curing agent to obtain gasoline resistance, weather resistance, moisture resistance, hot water resistance (boil, retort resistance).
It is possible to improve coating film physical properties required for paints and inks. As the isocyanate compound used at this time,
Although the above-mentioned organic diisocyanates can be used, it is more preferable to modify these organic diisocyanates into isocyanate derivatives such as buret bodies, isocyanurate bodies, and trimethylolpropane adduct bodies.

The binder resin composition of the present invention may be used as it is, but it can be used as a paint or ink by kneading and dispersing it by adding a pigment, a solvent and other additives. Further, the composition shows a well-balanced coating property, but if necessary, alkyd resin, acrylic resin, acrylic polyol, polyester resin, polyester polyol, polyether resin, polyether polyol, polyurethane resin, chlorine It does not matter if a modified polyolefin or the like is further added and used.

[0040]

The feature of the present invention is to obtain a far more uniform and transparent binder resin solution than other similar invention products. That is, when a chlorinated polyolefin is copolymerized with a monomer or compound containing at least one ethylenically unsaturated bond and hydroxyl group, the chlorinated polyolefin itself has poor reactivity, and therefore, these copolymers and monomers at the same time. Alternatively, a homopolymer of the compound is produced. For this reason, the reaction product causes cloudy two-layer separation, but by adding a chlorinated polydiene and copolymerizing as in the present invention, a uniform and transparent solution can be obtained.

This effect of the chlorinated polydiene is that the chlorinated polydiene is a substance which is compatible with the chlorinated polyolefin and the polymer of the above-mentioned monomer or compound at an appropriate degree of chlorination. Since the reactivity with the monomer or the compound is good, it is considered that the production of these homopolymers is suppressed.
Further, when the hydroxyl group of the resin (I) is reacted with the isocyanate group of the polyurethane resin (II) as in the first invention,
Since it is considered that the amount of the homopolymer of the monomer having a hydroxyl group is small in the resin (I) for the above reasons, it is presumed that the obtained binder resin will be a uniform and transparent solution.

Further, in the second invention in which the resin (I) is simultaneously reacted with the polyol (III) and the organic diisocyanate (IV), the above-mentioned (I), (II
Since the components I) and (IV) are considered to be randomly arranged, the binder resin solution is more uniform and transparent than the binder resin of the first invention.

[0043]

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 5,000 was charged into a glass-lined reaction kettle, and 8
After adding 1 liter of carbon tetrachloride and dissolving it sufficiently at a temperature of 110 ° C and a pressure of 2 kg / cm ² , the chlorine content was 30% while irradiating with ultraviolet rays.
Chlorine gas was introduced from the bottom of the reaction vessel until it reached wt%. Next, the carbon tetrachloride was distilled off and replaced with toluene.
A toluene solution of wt% chlorinated polypropylene was obtained.

(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 15,000 was simultaneously blown with chlorine gas and air. But
A toluene solution of chlorinated polypropylene having a nonvolatile content of 30 wt% and 30 wt% was obtained.

(Prototype Example-3) Product name Nisso Polybutadiene B-3000 (Nippon Soda Co., Ltd.)
Liquid polybutadiene (500 g, number average molecular weight: 3,000) was charged into the same reaction kettle as in Prototype Example-1, and 8 liters of carbon tetrachloride was added and uniformly dissolved. The air was completely purged with nitrogen gas, the temperature was kept at 50 ° C, and the chlorine content was 30%.
Chlorine gas was introduced until it reached 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) 200 g of the chlorinated polypropylene (nonvolatile content 30 wt%) obtained in Prototype Example-1 was placed in a flask equipped with a stirrer, a thermometer, and a cooling tube for refluxing the monomer. Chlorinated polybutadiene obtained in -3 (nonvolatile content 50 wt%) 40 g, toluene
Add 40g and benzoyl peroxide 1.0g, and add 3 at 85 ℃
Stir for 0 minutes. Next, a mixture of 49 g of methyl methacrylate, 49 g of lauryl methacrylate, 2.0 g of methacrylic acid, and 20 g of 2-hydroxyethyl acrylate was added in about 3 hours, and the copolymerization reaction was further performed for several hours.
0 g was added to stop the copolymerization reaction to obtain a uniform, transparent and viscous copolymer (nonvolatile content: 40 wt%).

(Prototype Example-5) The chlorinated polypropylene (nonvolatile content 30 wt%) obtained in Prototype Example-2
%) 200 g, 80 g of chlorinated polybutadiene (nonvolatile content 50 wt%) obtained in Prototype Example-3, 200 g of toluene, 1.0 g of benzoyl peroxide, cyclohexyl methacrylate 69.
2g, 10.8g of ethyl acrylate and 20g of 2-hydroxyethyl acrylate were mixed according to the reaction method of Prototype Example-4 to obtain a uniform, transparent and viscous copolymer (nonvolatile content 40wt%). It was

(Prototype Example-6) The chlorinated polypropylene (nonvolatile content: 30 wt%) obtained in Prototype Example-1
%) 500 g, 100 g of chlorinated polybutadiene (nonvolatile content 50 wt%) obtained in Prototype Example-3, benzoyl peroxide 2
g and 20 g of 2-hydroxyethyl acrylate were used to carry out a copolymerization reaction according to the reaction method of Prototype Example-4 to obtain a uniform, transparent and viscous copolymer (nonvolatile content: 35.5 wt%).

(Prototype Example-7) The chlorinated polypropylene (nonvolatile content: 30 wt%) obtained in Prototype Example-2
%) The copolymerization reaction was carried out according to the reaction method of Prototype Example-4 in exactly the same proportion as in Prototype Example-6 except that 500 g was collected, and a uniform, transparent and viscous copolymer (nonvolatile content: 35.5 wt.
%) Was obtained.

(Prototype Example-8) Trade name Praxel L-220AL (Daicel Chemical Industry Co., Ltd.)
Made, caprolactone polymer diol, molecular weight 2,000) 4
00 g and hexamethylene diisocyanate 50.4 g were put into the same flask as in Prototype Example-4, reacted for several hours at a temperature of 80 ° C. while introducing nitrogen gas, and then toluene 300 g,
150.4 g of ethyl acetate was added to obtain a polyurethane resin having a terminal isocyanate group (nonvolatile content 50 wt%).

(Prototype Example-9) A polymer polyol (butane adipate diol, molecular weight 2,000) synthesized from adipic acid and 1,4-butanediol
0) 400 g and 84.4 g of isophorone diisocyanate were reacted in the same manner as in Prototype Example-8, and then as a chain extender.
8.6 g of 1,4-butanediol was added and the reaction was carried out for several hours. Next, 246 g of toluene and 246 g of methyl ethyl ketone were added,
A polyurethane resin having a terminal isocyanate group (nonvolatile content 50 wt%) was obtained.

Example 1 250 g of the copolymer obtained in Prototype Example-4 and 85 g of the polyurethane resin obtained in Prototype Example-8 were placed in the same flask as in Prototype Example-4, and the temperature was 85 ° C. for 5 hours. After the reaction, 22 g of toluene and 0.6 g of ethanolamine as a reaction terminator were added to stop the reaction, and a uniform, transparent and viscous reaction product (nonvolatile content 40 wt%
%) Was obtained. Next, 100g of this reaction product and 26g of titanium dioxide
Was kneaded with a sand mill for 3 hours, and then 5.2 g of isocyanate curing agent Desmodur N3390 (made by Bayer Co., hexamethylene diisocyanate system, isocyanurate body) was added, and the temperature was 13 to 15 seconds / 20 ° C in a No. 4 Ford cup. Adjust the viscosity with xylene, polypropylene plate, TX-9
33A (manufactured by Mitsubishi Petrochemical Co., Ltd.) was spray-painted. 1 at room temperature
After drying for 5 minutes, forced drying was performed at 80 ° C. for 30 minutes, and the mixture was allowed to stand in the room for 1 week, and then the coating film was tested. The results are shown in Table-1.

(Example-2) 250 g of the copolymer obtained in Prototype Example-5, 60 g of the polyurethane resin obtained in Prototype Example-8, 16 g of toluene, and 0.45 g of ethanolamine as a reaction terminator were used in the Examples. The reaction was carried out according to the method of No. 1 to obtain a homogeneous, transparent and viscous reaction product (nonvolatile content 40 wt%). Next, 100 g of this reaction product, 26 g of titanium dioxide, isocyanate curing agent desmodul Z43
70 (manufactured by Bayer, isophorone diisocyanate-based, isocyanurate body) 9.6 g, and a curing accelerator di-n-butyltin dilaurate 0.08 g in a blending ratio, and paint preparation and coating film test in the same manner as in Example-1 I went. Table of results
Shown in 1.

Example 3 250 g of the copolymer obtained in Prototype Example 4 and Praxel L-220 A
L 80 g, hexamethylene diisocyanate 7 g, and ethyl acetate 37 g were placed in the same flask as in Prototype Example-4 and reacted at a temperature of 85 ° C. for 8 hours while introducing nitrogen gas.
Toluene (46 g) and ethyl acetate (47.5 g) were added to obtain a uniform, transparent and viscous reaction product (nonvolatile content: 40 wt%). Next, 100 g of this reaction product, 26 g of titanium dioxide, 3.9 g of Desmodur N3390, an isocyanate curing agent, and 0.08 g of di-n-butyltin dilaurate as a curing accelerator were used in the same manner as in Example 1 to prepare and apply a coating composition. The membrane was tested. The results are shown in Table-1.

Example 4 250 g of the copolymer obtained in Prototype Example 5 and Praxel L-220 A
L 100 g, hexamethylene diisocyanate 9.4 g, and ethyl acetate 59.4 g were reacted according to the method of Example-3, and then toluene 70 g and ethyl acetate 34.8 g were added to give a uniform, transparent and viscous reaction. (Nonvolatile matter 40 wt%) was obtained. Next, 100 g of this reaction product, 26 g of titanium dioxide, 5.2 g of Desmodur Z4370, an isocyanate curing agent, and 0.08 g of di-n-butyltin dilaurate, a curing accelerator, were used in the same manner as in Example 1 to prepare and apply paint. The membrane was tested. The results are shown in Table-1.

Comparative Example-1 100 g of the copolymer obtained in Prototype Example-4, 26 g of titanium dioxide,
A paint preparation and a coating film test were conducted in the same manner as in Example 1 with a compounding ratio of the isocyanate curing agent Desmodur N3390 7.4 g. The results are shown in Table-1.

Comparative Example-2 100 g of the copolymer obtained in Prototype Example-5, 26 g of titanium dioxide,
Isocyanate curing agent Desmodur Z4370 12.5g,
The coating composition was adjusted and the coating film was tested in the same manner as in Example-1 with the compounding ratio of 0.08 g of the curing accelerator di-n-butyltin dilaurate. The results are shown in Table-1.

[0059]

[Table-1]

Test method-Adhesiveness 100 pieces of gougin that reach the base at 1 mm intervals are made on the coated surface, and cellophane adhesive tape is 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. The glossiness was measured by 60 ° specular reflection and the whiteness was measured by a hunter.

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

-Gasoline resistance (rubbing 100 times) Immerse absorbent cotton in Nisseki regular gasoline and coat
The state of the coating film was examined by rubbing 100 times. (Dip for 2 hours) Scratch (mark x) that reaches the base material on the coated surface,
It was immersed 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 / 2φ inch mandrel.

-Impact resistance With a DuPont type impact tester, the impact core is 1 / 2φ inch and the load is 500 g.
Was used to drop the coating film from a height of 50 cm, and the state of the coating film was examined.

(Example-5) 282 g of the copolymer obtained in Prototype Example-6, 467 g of polyurethane resin obtained in Prototype Example-9, 192 g of toluene, 191 g of methyl ethyl ketone, and 2.5 g of n-butylamine as a reaction terminator. Then, the reaction was carried out according to the method of Example-1 to obtain a uniform, transparent and viscous reaction product (nonvolatile content: 30 wt%). Next, prepare an ink using this reaction product as a binder resin,
Uncoated 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) with coating rod # 10 After coating and drying at room temperature for 24 hours, cellophane peel test and heat seal strength test were performed using cellophane adhesive tape. The results are shown in Table-2. The formulation of the ink is shown in Table-3.

Example-6: 140 g of the copolymer obtained in Prototype Example-7, 400 g of the polyurethane resin obtained in Prototype Example-9, 146 g of toluene, 146 g of methyl ethyl ketone, and 2.1 g of n-butylamine as a reaction terminator. The reaction is carried out according to the method of Example-1 at a ratio, and a uniform, transparent and viscous reaction product (nonvolatile matter 30 w
t%) was obtained. The same test as in Example-5 was conducted below.
The results are shown in Table-2.

(Example-7) 169 g of the copolymer obtained in Prototype Example-6, 100 g of a polymer polyol (butane adipate diol, molecular weight 2,000) synthesized from adipic acid and 1,4-butanediol, and isophorone diisocyanate 32.6 After adding g to a flask similar to that of Prototype Example-4 and reacting at 85 ° C. for about 10 hours while introducing nitrogen gas, 1,4-butanediol as a chain extender 4.
96 g was added and reacted for about 5 hours. After cooling toluene 177
g, methyl ethyl ketone 180 g, n-butylamine 2.15
The reaction was stopped by adding g to obtain a uniform, transparent and viscous reaction product (nonvolatile content: 30 wt%). The same test as in Example-5 was conducted below. The results are shown in Table-2.

Example-8 169 g of the copolymer obtained in Prototype Example-7, trade name Praxel L
-220AL (manufactured by Daicel Chemical Industries, Ltd., caprolactone-based polymer diol, molecular weight 2,000) 100 g and isophorone diisocyanate 32.6 g were reacted in the same manner as in Example-7, then methyl ethyl ketone 84 g, and isophorone diamine as a chain extender. 9.4 g was added and the reaction was continued for about 3 hours. After cooling toluene 129 g, methyl ethyl ketone 106 g,
2.15 g of n-butylamine, 48 g of isopropyl alcohol
Was added to stop the reaction, and a uniform, transparent and viscous reaction product (nonvolatile content: 30 wt%) was obtained. The same test as in Example-5 was conducted below. The results are shown in Table-2.

(Comparative Example-3) Trade name Supercron 803MW (chlorinated polypropylene,
Chlorine content 29.5wt%, non-volatile content 20wt%, Sanyo Kokusaku Pulp Co., Ltd. and trade name Supercron BX (chlorinated ethylene vinyl acetate copolymer, chlorine content 18wt%, non-volatile 20wt%
%, Manufactured by Sanyo Kokusaku Pulp Co., Ltd., and the same test as in Example-5 was performed. The results are shown in Table-2.

Comparative Example-4 Sanbren IB-450 (polyurethane resin, non-volatile component)
The same test as in Example-5 was conducted at 30 wt%, manufactured by Sanyo Chemical Co., Ltd. The results are shown in Table-2.

[0072]

[Table-2]

[0073]

[Table-3]

-Superclone 803MW and Superclone BX have a nonvolatile content of 20 wt% (toluene solution). Samprene IB-405 has a nonvolatile content of 30 wt% (methyl ethyl ketone / isopropanol = 2/1 solution).

Titanium dioxide (Rutile type R-820 manufactured by Ishihara Sangyo Co., Ltd.)

Carmin 6BN (Toyo Ink Mfg. Co., Ltd.)
Made, azo organic pigment.

Meat condition: Kneading with a sand mill for 2 hours.

[0078]

EFFECTS OF THE INVENTION (From the results in Table 1) Comparative Examples 1 and 2
Is a composition already proposed by the present inventors in JP-A-62-18434, and these are the compositions of the first invention (Example-1).
By modifying as described in (2) and 2), flexibility can be imparted to the coating film without impairing the excellent properties that are conventionally possessed, such as adhesion, appearance, gasoline resistance, and weather resistance. It can be seen that the flexibility and impact resistance are remarkably improved. It can be seen that in the second invention (Examples 3 and 4), in addition to the good properties of the first invention product, the uniformity and transparency of the solution are further improved.

(From the results in Table 2) The binder resin for ink of chlorinated polypropylene / chlorinated ethylene vinyl acetate copolymer shows good adhesion to PP film, but to PET and NY films. There is no practical strength. Further, the polyurethane-based binder resin for ink adheres to PET and NY films, but the adhesive strength to PP film is not sufficient. It is understood that the products of the present invention (first and second inventions) are highly versatile binder resins for inks, which have good adhesiveness to both PP films and PET and NY films.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location // C08G 18/63 NEP (56) References JP-A-59-27968 (JP, A) JP JP-A-62-18434 (JP, A) JP-A-64-85226 (JP, A) JP-A-61-215666 (JP, A) JP-A-4-4272 (JP, A) JP-A-4-132784 (JP , A) JP-A-58-91771 (JP, A)

Claims (12)

[Claims] 1. A chlorinated polyolefin (a) chlorinated to have a chlorine content of 5 to 50 wt% and a chlorine content of 5 to 50 w.
Obtained by copolymerizing a chlorinated polydiene (b) chlorinated in the range of t% with a monomer and / or compound (c) containing at least one ethylenically unsaturated bond and one hydroxyl group in one molecule. A binder resin composition obtained by reacting the obtained resin (I) with a polyurethane resin (II) containing at least one free isocyanate group in one molecule. 2. The binder resin according to claim 1, wherein 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. Composition. 3. The number average molecular weight of the polyurethane resin (II) is
The binder resin composition according to claim 1 or 2, which is 1,000 to 150,000. 4. The binder resin composition 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. 5. The binder resin composition 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. 6. A resin composition for paints and printing inks or adhesives, which comprises blending the binder resin composition according to claim 1 and 2 or 5 with an isocyanate compound as a curing agent. 7. A method for producing the binder resin composition according to claim 1, 2 or 5. 8. A chlorinated polyolefin (a) chlorinated to have a chlorine content of 5 to 50 wt% and a chlorine content of 5 to 50 w.
Obtained by copolymerizing chlorinated polydiene (b) chlorinated in the range of t% with a monomer and / or compound (c) having at least one ethylenically unsaturated bond and one hydroxyl group in one molecule A binder resin composition obtained by reacting a resin (I) with a polymer polyol (III), an organic diisocyanate (IV), and optionally a chain extender and / or a reaction terminator. 9. The binder resin according to claim 8, wherein 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. Composition. 10. The binder resin composition according to claim 8, 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. 11. A resin composition for paints and printing inks or adhesives, characterized in that the binder resin composition according to claim 8 and 9 or 10 is blended with an isocyanate compound as a curing agent. 12. A method for producing the binder resin composition according to claim 8 or 9.