JP3261695B2 - Curable binder resin composition and its use - 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 protection or cosmetics of polyolefin resins, for example, polypropylene, polyethylene, ethylene propylene copolymer, ethylene propylene diene copolymer and the like. The present invention relates to a composition which is used as a curable binder resin for a primer, a paint, a printing ink or an adhesive which has excellent adhesion and other physical properties to these sheets, films and molded articles.

[0002]

2. Description of the Related Art Plastics are widely used as materials for automobile parts, electric parts, building materials, etc. in recent years because of their high productivity, wide design freedom, and many advantages such as light weight, rust prevention and impact resistance. Used. In particular, polyolefin resins are widely used as industrial materials because of their low cost and many excellent properties such as moldability, chemical resistance, heat resistance, water resistance and good electrical properties. Elongation is one of the most promising materials. However, polyolefin resins are different from polar synthetic resins, such as polyurethane resins, polyamide resins, acrylic resins, and polyester resins, in that they are non-polar and crystalline, making them difficult to paint and bond. Having.

[0003] Conventionally, the surface of a polyolefin-based resin molded article is activated by plasma treatment or gas flame treatment to improve the adhesion. However, this method is complicated 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 automobile bumper coating have been proposed, and in particular, chlorinated polyolefins having strong adhesion to polyolefin resins. Is often used. However, chlorinated polyolefins are inferior in resistance to ultraviolet light and heat, and cannot be said to have sufficient coating film performance, and improvement thereof has been strongly desired. As a means for improving these properties, attempts have been made to use a mixture of an acrylic resin or an alkyd resin having good paint properties. However, acrylic resins and alkyd resins inherently have poor compatibility with chlorinated polyolefins, which causes problems such as a decrease in the gloss of the coating film and a significant deterioration in appearance.

In order to improve these disadvantages, Japanese Patent Application Laid-Open No. 58-719
No. 66, coating composition obtained by copolymerizing acrylic monomer and chlorinated polyolefin, JP-A-59-279
No. 68 discloses a chlorinated polyolefin-modified hydroxyl-containing acrylic copolymer obtained by copolymerizing an acrylic monomer or the like having a hydroxyl group and a chlorinated polyolefin, a coating composition containing an isocyanate compound as an essential component, 1962-9
No. 5372 discloses an adhesive resin composition containing a hydroxyl group-containing acrylic-modified chlorinated polyolefin and an isocyanate compound as main components copolymerized with an acrylic monomer having a hydroxyl group in the presence of a chlorinated polyolefin and a liquid rubber. Also, JP-A-5-9428 and JP-A-5-94910 disclose that a chlorinated polyolefin is copolymerized with a long-chain hydroxyl-containing vinyl monomer, an unsaturated carboxylic acid, an unsaturated polyester resin, etc. Compositions comprising an ultraviolet absorber and an antioxidant have been proposed. However, chlorinated polyolefins have inherently poor reactivity with the above-mentioned copolymerizable monomers and resins, so even when copolymerized with these, opacity or two-layer separation occurs, and a uniform and transparent solution cannot be obtained. It cannot be a good binder resin such as paints, primers and adhesives.

The present inventors have already proposed a method for obtaining a uniform and transparent binder resin in Japanese Patent Application No. 8-506386.
That is, a carboxylic acid-containing chlorinated polyolefin obtained by graft-polymerizing an α, β-unsaturated carboxylic acid and / or an anhydride thereof onto a polyolefin and then chlorinating the same is selected from air, oxygen, and ozone during the chlorination reaction of the polyolefin. A mixture of a chlorinated polyolefin oxidized using at least one or two or more monomers and / or a monomer containing an ethylenically unsaturated bond in one molecule and / or a hydroxyl group in one molecule. The composition is characterized in that a resin obtained by graft-copolymerization of a monomer containing is used as a main component, and an isocyanate compound or an alkyl etherified amino resin is added as a curing agent to the resin. However, although this method is also excellent as a method for obtaining a uniform and transparent binder resin, the chlorinated polyolefin becomes unstable due to oxidation treatment with oxygen or the like during the chlorination reaction, and as a result, the synthesized composition becomes It had the disadvantage of becoming unstable.

[0007]

SUMMARY OF THE INVENTION The present invention relates to a method disclosed in Japanese Patent Application No.
It solves the above-mentioned problems by improving the instability, which is a disadvantage of the composition proposed in No. 6386, and is far superior to conventional chlorinated polyolefin modified products. An object of the present invention is to provide a curable binder resin such as an agent.

[0008]

That is, the present inventors have found that the graft ratio of at least one unsaturated carboxylic acid monomer selected from carboxylic acids and / or carboxylic anhydrides is 1 to 10% by weight and chlorine In a carboxyl group-containing chlorinated polyolefin having a content of 5 to 50% by weight, a monomer containing an ethylenically unsaturated bond in one molecule and an ethylenically unsaturated bond and a hydroxyl group in one molecule represented by the following general formula (1) A curable binder resin composition characterized by comprising a resin obtained by graft copolymerization of a monomer containing a main component, and blending a polyisocyanate compound or an alkyl etherified amino resin as a curing agent with the resin, The inventors have found that the present invention has been achieved, and have accomplished the present invention.

Embedded image

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The carboxyl group-containing chlorinated polyolefin used in the present invention is obtained by melting a polyolefin and, if necessary, converting a polyolefin molten resin degraded by thermal decomposition into a batch type or a continuous type. After the unsaturated carboxylic acid monomer is graft-copolymerized in the presence of an agent, it is dispersed or dissolved in water or a solvent such as carbon tetrachloride or chloroform, and is added in the presence of a radical generator or under irradiation with ultraviolet light. 50 to 120 under pressure or normal pressure
After blowing chlorine gas in the temperature range of ℃,
The solvent can be obtained by distilling off the solvent, adding a stabilizer, and replacing the solvent with an organic solvent such as toluene or xylene. After chlorination, the chlorinated solvent is concentrated under reduced pressure,
After adding the stabilizer, the solvent can be obtained as a solid from which the solvent has been completely removed by a vented extruder or the like provided with a vent port for distilling off the solvent under reduced pressure.

As a radical generator, for example, di-tert
-Butyl peroxide, tert-butyl hydroperoxide, dicumyl peroxide, benzoyl peroxide,
tert-butyl peroxide benzoate, methyl ethyl ketone peroxide, di-tert-butyl diperphthalate
And azonitriles such as azobisisobutyronitrile.

The unsaturated carboxylic acid monomer and its anhydride used in the graft copolymerization reaction include, for example, acrylic acid, methacrylic acid, maleic acid, maleic anhydride, citraconic acid, citraconic anhydride, fumaric acid, mesaconic acid. , Itaconic acid, itaconic anhydride, aconitic acid,
Aconitic anhydride;

As the stabilizer for the chlorinated polyolefin, the stabilizer used for polyvinyl chloride, which is a chlorine-based resin, can be applied as it is. For example, calcium stearate, metal soaps such as lead stearate, lead oxide, inorganic acid salts such as tribasic lead sulfate, organic metal compounds such as dibutyltin dilaurate, dibutyltin malate, hydrotalcite compounds, epoxy compounds Kind.

However, among these, epoxy compounds are most commonly used. For example, epoxidized soybean oil or epoxidized linseed oil obtained by epoxidizing a vegetable oil having a natural unsaturated group with a peracid such as peracetic acid. Epoxidized fatty acid esters obtained by epoxidizing unsaturated fatty acid esters such as oleic acid, tall oil fatty acid and soybean oil fatty acid.
Epoxidized alicyclic compounds represented by epoxidized tetrahydrophthalate. Bisphenol A or polyhydric alcohol condensed with epichlorohydrin, for example, bisphenol A glycidyl ether, ethylene glycol glycidyl ether, propylene glycol glycidyl ether, glycerol polyglycidyl ether, sorbitol polyglycidyl ether and the like. Butyl glycidyl ether, 2-ethylhexyl glycidyl ether, decyl glycidyl ether, stearyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, sec-butyl phenyl glycidyl ether, tert
-Monoepoxy compounds represented by butylphenyl glycidyl ether, phenol polyethylene oxide glycidyl ether and the like.

The carboxyl group-containing chlorinated polyolefin used in the present invention is obtained by preparing a solution of the chlorinated polyolefin obtained by chlorinating the polyolefin by the above-mentioned method, and then adding the unsaturated carboxylic acid monomer and its anhydride in the presence of a radical generator. It can also be obtained by graft copolymerizing the product. As the radical generator, unsaturated carboxylic acid monomer and anhydride thereof used in the graft copolymerization reaction, those described above can be used as they are.

The graft ratio of the unsaturated carboxylic acid monomer and its anhydride in the carboxyl group-containing chlorinated polyolefin is preferably from 1 to 10% by weight. When the graft ratio is less than 1% by weight, graft reactivity with a monomer having an ethylenically unsaturated bond becomes insufficient, and the reaction solution becomes cloudy or separates into two layers. If the amount of the graft exceeds 10% by weight, gelation occurs during the graft reaction with a monomer having an ethylenically unsaturated bond, or the adhesion to the polyolefin deteriorates.

The chlorine content of the carboxyl group-containing chlorinated polyolefin is preferably 5 to 50% by weight. If the chlorine content is too low, the solution state will be poor, and if the chlorine content is too high, the adhesion to the polyolefin will be poor.

As a raw material of the carboxyl group-containing chlorinated polyolefin of the present invention, crystalline polypropylene, that is, isotactic polypropylene and syndiotactic polypropylene can be used, but the former is generally used. Weight average molecular weight is 10,000
~ 300,000 can be used.

Further, a propylene-α-olefin copolymer can be used as a raw material. That is, the copolymer is mainly propylene and is copolymerized with an α-olefin, and either a block copolymer or a random copolymer can be used. Examples of the α-olefin component include ethylene, 1-butene, 1-pentene, 1-hexene,
Examples thereof include 1-heptene, 1-octene, 4-methyl-1-pentene and the like. The content of the propylene component is optimally 50 to 98 mol%, and if it is less than 50 mol%, the adhesion to polypropylene is reduced. Also, 98 mol%
Exceeding the above limits the flexibility of the coating film.

Examples of the monomer containing an ethylenically unsaturated bond in one molecule used in the present invention include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, and n-butyl (meth) acrylate. , 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, lauryl (meth) acrylate, glycidyl (meth) acrylate, styrene, vinyl acetate, (meth) acrylonitrile, and the like.
Compounds such as macromonomers having a polymerizable (meth) acryloyl group at the terminal of polystyrene or poly (meth) acrylate can also be used.

The monomer having an ethylenically unsaturated bond and a hydroxyl group in one molecule represented by the following general formula (1) used in the present invention has a structure represented by the following formula and is modified with dimethyl trimethylene carbonate ( It is a compound generically referred to as (meth) acrylate.

Embedded image That is, there are four types of compounds represented by (meth) acrylic acid esters: methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and butyl (meth) acrylate. If m exceeds 4, it is not preferable because a uniform and transparent solution cannot be obtained. On the other hand, if n in the dimethyltricarbonate portion is an integer of 1 to 3 and exceeds 3, it is not preferable because a uniform transparent solution cannot be obtained.

The amount of the hydroxyl group introduced by the monomer is preferably 0.1 to 5% by weight in the binder resin obtained by graft copolymerization. If the content is less than 0.1% by weight, the reaction solution becomes cloudy or separates into two layers even if the graft copolymerization is performed, so that a uniform and transparent solution cannot be obtained. If it exceeds 5% by weight, gelation may occur during the graft copolymerization reaction, and the adhesion to polyolefin will also be poor.

The reaction method for graft-copolymerizing a carboxyl group-containing chlorinated polyolefin with a monomer containing an ethylenically unsaturated bond in one molecule and a monomer containing an ethylenically unsaturated bond and a hydroxyl group in one molecule is as follows. The basic process is to dilute the contained chlorinated polyolefin appropriately with a solvent, then heat and add a polymerization initiator, and then react while gradually adding the monomer. After the addition, the mixture may be heated and reacted.

The solvent used in the reaction is preferably an aromatic solvent such as toluene and xylene. In addition, ester solvents such as ethyl acetate and butyl acetate, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, ethanol, isopropanol and the like. Alcohol solvents such as n-butanol, aliphatic solvents, cycloaliphatic solvents and the like may be used in combination. As the polymerization initiator, the above-described radical generator can be used as it is.

The weight ratio of the carboxyl group-containing chlorinated polyolefin of the present invention to a monomer having an ethylenically unsaturated bond in one molecule and a monomer having an ethylenically unsaturated bond and a hydroxyl group in one molecule is as follows. Polyolefin / [monomer containing ethylenically unsaturated bond in one molecule] + [monomer containing ethylenically unsaturated bond and hydroxyl group in one molecule] = 90 / 10-10
/ 90 is preferred. If the amount of the carboxyl group-containing chlorinated polyolefin is too large, the weather resistance is deteriorated, and if it is too small, the adhesion to the polyolefin resin is deteriorated.

The resin obtained by the graft copolymerization of the present invention is prepared by blending an isocyanate compound or an alkyl etherified amino resin as a curing agent and curing the mixture to obtain paints and adhesives such as gasoline resistance, weather resistance, and moisture resistance. Required physical properties can be improved.

As the isocyanate compound used in the present invention, there are aromatic, aliphatic and alicyclic organic diisocyanates, such as tolylene diisocyanate, xylene diisocyanate, 1,5-naphthalene diisocyanate, and 1,4-tetramethylene diisocyanate. 1,1,6-hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, 4,4-dicyclohexylmethane diisocyanate,
4-cyclohexyl diisocyanate and the like. In addition, these organic diisocyanates may be used after being modified into isocyanate derivatives such as buret, isocyanurate, and trimethylolpropane adduct.

Further, a blocked isocyanate compound obtained by blocking the isocyanate with a blocking agent can also be used. Examples of the blocking agent include oximes such as methyl ethyl ketoxime, cyclohexanone oxime, formaldoxime and acetoaldoxime, phenols such as phenol and cresol, alcohols such as methanol, benzyl alcohol and ethylene glycol monomethyl ether, and methyl acetoacetate. Active methylenes such as dimethyl malonate, amides such as acetanilide and acetic acid amide, imides, amines, imidazoles, ureas, carbamates, imines, mercaptans, sulfites, lactams, etc. is there.

Compounds having two or more isocyanate groups per molecule, such as urethane resins having free isocyanate groups obtained by reacting the above-mentioned organic diisocyanates with high molecular polyols such as polyether polyols and polyester polyols Can be used.

A reaction catalyst can be used for the purpose of promoting the reactivity and deblocking reactivity between the resin obtained by graft copolymerization of the present invention and the isocyanate compound as a curing agent. Examples of the reaction catalyst include dibutyltin dilaurate, dibutyltin fatty acid salt, dibutyltin diacetate, and tetra-n-
Butyl-1,3-diacetoxy-distannoxane, 3-dilauryloxy-distannoxane, di-n-butyltin oxide, mono-n-butyltin oxide, stannous octylate,
Examples thereof include zinc octenoate.

The alkyl etherified amino resin used as the curing agent of the present invention is obtained by reacting an amino compound such as urea, melamine or benzoguanamine with formaldehyde to form a methylol and then etherifying with a lower alcohol such as methanol or butanol. Obtained by
For example, n-butyl etherified urea resin, isobutyl etherified urea resin, methyl etherified melamine resin, n-butyl etherified benzoguanamine resin, and the like.

Further, an acidic catalyst can be used to promote the reaction between the resin obtained by graft copolymerization and the alkyl etherified amino resin. For example, there are alcohol solutions of hydrochloric acid, salts of strong acids such as ammonium chloride, phosphates such as monobutyl phosphate, and organic sulfonic acids such as p-toluenesulfonic acid.

The amount of the curing agent to be added to the resin obtained by graft copolymerization of the present invention can be appropriately determined depending on the hydroxyl group content of the copolymerized resin. That is, in the isocyanate compound, the isocyanate group can be used in the range of 0.5 to 1.5 mol per mol of the hydroxyl group contained in the copolymer resin, and in the case of the alkyl etherified amino resin, the alkoxy group can be used in the range of 0.5 to 1.5 mol. If it is less than 0.5 mol, the effect of crosslinking is small, and if it exceeds 1.5 mol, unreacted curing agent remains, which is not preferable.

The curable binder resin composition of the present invention comprises:
The coating may be used as it is, but a pigment, a solvent, and other additives such as an ultraviolet absorber, an antioxidant, and a pigment settling inhibitor may be added, kneaded and dispersed, and used as a paint or printing ink. Further, it can be used as an adhesive for various plastics such as polypropylene resin or a primer for coating. The amount of the curable binder resin composition can be arbitrarily adjusted according to the purpose, but is preferably 10% by weight or more from the viewpoint of adhesion to various plastics and cohesive strength of the composition.

Although the curable binder resin composition alone exhibits well-balanced coating film properties, if necessary, alkyd resin, acrylic resin, polyacryl polyol, polyester resin, polyester polyol,
Polyether resins, polyether polyols, polyurethane resins, chlorinated polyolefins and the like may be further added and used.

[0035]

The feature of the present invention is that a carboxyl group-containing chlorinated polyolefin is grafted with a monomer containing an ethylenically unsaturated bond in one molecule and a monomer containing an ethylenically unsaturated bond and a hydroxyl group in one molecule. Copolymerization improves the reactivity of the chlorinated polyolefin, which is essentially inferior in reactivity, with the monomer, provides a uniform and transparent reaction solution, and is good for polyolefins that have been difficult to adhere in the past. An object of the present invention is to obtain a curable binder resin composition having excellent adhesion.

The polymer of a monomer containing an ethylenically unsaturated bond in one molecule is an essential component for forming the skeleton of the binder resin. The carboxyl group-containing chlorinated polyolefin also forms the skeleton of the binder resin, but is mainly a component for imparting adhesion to the polyolefin.

Dimethyltrimethylene carbonate-modified (meth) acrylate, a monomer containing an ethylenically unsaturated bond and a hydroxyl group in one molecule, is an important component for obtaining a uniform and transparent reaction solution. That is, the hydroxyl group in the monomer and the carboxyl group in the carboxyl group-containing chlorinated polyolefin undergo an esterification reaction, and since this is the reaction point, the graft copolymerization proceeds, so that a uniform and transparent reaction solution can be obtained. Can be On the other hand, hydroxyl group-containing monomers other than the above monomers, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth)
When the graft copolymerization reaction is carried out using acrylates or the like, the reaction solution is separated into two layers or becomes cloudy, so the specific reason is unknown, but the carboxyl group-containing chlorinated polyolefin used in the present invention and dimethyltrimethylene are used. The reaction with the carbonate-modified (meth) acrylic acid ester and the reaction with the other monomer proceeded in a well-balanced manner, whereby a uniform, transparent, and well-balanced graft copolymer could be obtained. It seems to be.

Dimethyltrimethylene carbonate-modified (meth) acrylate, which is a monomer having an ethylenically unsaturated bond and a hydroxyl group in one molecule, has a hydroxyl group which undergoes a crosslinking reaction with an isocyanate compound or an alkyletherified amino resin. It is also a component to do.

[0039]

Next, the present invention will be described in more detail by way of examples.

(Production Example 1) 6 kg of an ethylene-propylene copolymer having a melt viscosity at 180 ° C. of 2500 mPa · s and an ethylene content of 6 mol% was supplied to a stirrer and a cooling pipe for refluxing a monomer. It was placed in a fitted three-necked flask and completely dissolved in an oil bath kept constant at 180 ° C. After the atmosphere in the flask was replaced with nitrogen for about 10 minutes, 240 g of maleic anhydride was added thereto over 5 minutes while stirring, and 24 g of di-tert-butyl peroxide was added thereto.
Dissolved in 0 ml heptane and added over about 30 minutes with a metering pump. At this time, the inside of the system was maintained at 180 ° C., and the reaction was further continued for about 1 hour. Then, unreacted maleic anhydride was removed over about 30 minutes while reducing the pressure in the flask with an aspirator. Next, this product was charged into a glass-lined reaction vessel, and 100 l of chloroform was added.
After complete dissolution at 110 ° C. under a pressure of ^2.5 kg / cm ² , chlorine gas was blown in while irradiating with ultraviolet rays to perform a chlorination reaction. After completion of the reaction, chloroform as a solvent is distilled off with an evaporator, and the solvent is replaced with toluene.Second monoepoxy compound is used as a stabilizer to suppress dehydrochlorination and to suppress an increase in solution viscosity due to crosslinking during storage. Butylphenyl glycidyl ether was added at 4% by weight based on the solid content to obtain a toluene solution of a carboxyl group-containing chlorinated ethylene-propylene copolymer having a solid content of 20% by weight.
At this time, the chlorine content was 21.2% by weight (based on solids), and the graft ratio of maleic anhydride was 2.5% by weight (based on solids).

(Production Example 2) The number average molecular weight is about 150
6 kg of isotactic polypropylene, 420 g of maleic anhydride, 42 g of di-tert-butyl peroxide
Was carried out in the same manner as in Production Example 1, except that the chlorination reaction was carried out. The solvent chloroform was concentrated under reduced pressure using an evaporator, and after adding 4 wt% of sec-butylphenylglycidyl ether based on the solid content, chloroform was removed using a vented extruder equipped with a vent port for distilling off the reaction solvent under reduced pressure. Completely removed, extruded into strands, cooled with water, water-cooled pelletizer (Limited company
A solid of carboxyl group-containing chlorinated polypropylene pelletized by Katsu Seisakusho model: KM-150) was obtained. The chlorine content at this time was 24.3% by weight (based on solid content)
And the graft ratio of maleic anhydride was 4.3% by weight (based on solid content).

(Production Example-3) Melt index is 1
4 kg / min (measured according to ASTM D1238-62T) of 6 kg of isotactic polypropylene is charged into a glass-lined reaction vessel, 100 l of carbon tetrachloride is added, and 2 kg / cm ² -110 ° C. After sufficient dissolution, chlorine gas was blown from the bottom of the reactor while irradiating with ultraviolet rays to obtain a reaction solution having a chlorine content of 30% by weight. Next, after concentrating with an evaporator, te
4% by weight of rt-butylphenyl glycidyl ether was added to the solid content, and the reaction solvent carbon tetrachloride was replaced with toluene to obtain a toluene solution of chlorinated polypropylene having a solid content concentration of 30% by weight. Next, 1000 g of the chlorinated polypropylene solution was placed in a three-necked flask equipped with a stirrer, a dropping funnel, and a condenser for refluxing the monomer, the atmosphere in the flask was replaced with nitrogen, and benzoyl peroxide was added while stirring at 90 ° C. 3 g was added and the mixture was stirred for about 30 minutes. Next, 15 g of methacrylic acid was added to the dropping funnel for about 3 hours.
The mixture was charged for 0 minutes, and after further reacting for 3 hours, the concentration was adjusted to obtain a toluene solution of chlorinated polypropylene containing a carboxyl group having a solid content of 20% by weight. At this time, the chlorine content was 27.6% by weight (based on solids), and the methacrylic acid graft ratio was 4.7% by weight (based on solids).

Table 1 summarizes the carboxyl group-containing chlorinated polyolefins obtained in Production Examples 1 to 3.

[0044]

[Table 1]

Example 1 In a flask equipped with a stirrer, a thermometer and a condenser for refluxing monomers,
500 g of the carboxyl group-containing chlorinated polyolefin obtained in Production Example 1 and 250 g of toluene were charged and heated to 85 ° C. Next, 5 g of benzoyl peroxide was added,
After stirring for 0 minutes, 245 g of methyl methacrylate, 100 g of cyclohexyl methacrylate, and 1 g of methacrylic acid
0 g, dimethyl trimethylene carbonate (1 mer) modified hydroxyethyl acrylate (hereinafter referred to as HEAC)
40 g was added over about 3 hours, and a graft copolymerization reaction was further performed for about 7 hours to adjust the solid concentration to a 40% by weight toluene solution to obtain a uniform and transparent binder resin solution.
Next, an isocyanate curing agent, Sumidur N35 was added to the following composition of the primer, paint and ink.
2.5 g of hexamethylene diisocyanate, isocyanurate compound (manufactured by Sumitomo Bayer Urethane Co., Ltd.) was added, and primers, paints, and inks were adjusted by the methods described below, and then primers were formed by the methods described below. , Paints and inks were tested. Tables 2 and 3 show the results.
The results are shown in FIG.

(Example-2) Carboxyl group-containing chlorinated polyolefin solid obtained in Production Example-2 (pellet)
The 150g was dissolved in toluene 660 g, benzoyl peroxide 5g, methyl methacrylate 200 g, n-butyl methacrylate 70 g, styrene 30g, acrylic acid 10 g, dimethyl trimethylene carbonate (1 mer) modified hydroxyethyl methacrylate (hereinafter HEMA
A graft copolymerization reaction was carried out in the same manner as in Example 1 except that 35 g of the resin was collected, and the solid content concentration was adjusted to a 40% by weight toluene solution to obtain a uniform and transparent binder resin solution. Next, the primers, paints,
Based on the ink composition, 4.6 g of alkyl etherified amino resin curing agent, melan 11 (butyl etherified urea resin, manufactured by Hitachi Chemical Co., Ltd., nonvolatile content 60%), and p-toluenesulfonic acid / 36 as an acid catalyst. % Hydrochloric acid / isopropanol = 10/10/80 (weight ratio), 10 g of each solution was added, and a primer, a paint and an ink were adjusted by the method shown below, and then the primer, the paint and the ink were prepared by the method shown below. Each test was performed. Tables 2 and 3 show the results.
The results are shown in FIG.

Example 3 875 g of the carboxyl group-containing chlorinated polyolefin obtained in Production Example 3, 5 g of benzoyl peroxide, 155 g of methyl methacrylate, n-
125 g of butyl methacrylate, 5 g of methacrylic acid, H
A graft copolymerization reaction was carried out in the same manner as in Example 1 except that 35 g of EAC was collected, and the solid content concentration was reduced to 40% by weight.
The mixture was adjusted to a toluene solution to obtain a uniform and transparent binder resin solution. Next, an isocyanate curing agent, Desmodur Z4370 (manufactured by Sumitomo Bayer Urethane Co., Ltd., isophorone diisocyanate, isocyanurate) were used for the following composition of the primer, paint and ink.
After adding 4.1 g of each, and preparing primers, paints, and inks by the methods shown below, each test of the primers, paints, and inks was performed by the methods shown below. The results are shown in Tables 2, 3, and 4.

Comparative Example 1 A number average molecular weight was 5000
5 kg of isotactic polypropylene is uniformly dissolved in 80 l of carbon tetrachloride under pressure (2 kg / cm ² ),
Chlorination was performed by blowing chlorine gas while irradiating ultraviolet rays at a temperature of 00 to 110 ° C. When the chlorine content reaches about 20% by weight, the chlorine gas is converted to a chlorine / air volume ratio of about 10/9.
The gas mixture was changed to 0, and chlorination was performed slowly while performing the oxidation treatment. The degree of the oxidation treatment was determined by extracting a sample having a functional group index of 15.5 and a chlorine content of 30.2% by weight while tracking the following functional group index using an infrared spectrophotometer. It was distilled off, replaced with toluene, and oxidized chlorinated polypropylene having a solid content of 50% by weight was obtained. Functional group index = (1730 cm Absorbance / 2970Cm absorbance ^{-1 -1)} × 100 Next, a carboxyl group-containing chlorinated polypropylene 375g obtained in Production Example 1, chlorinated polypropylene 50g was oxidized, toluene 325 g, benzoyl peroxide 5
g, methyl methacrylate 255 g, methacrylic acid 10
g, cyclohexyl methacrylate 110 g, 2-hydroxyethyl acrylate (hereinafter referred to as 2HEA) 20
A graft copolymerization reaction was conducted in the same manner as in Example 1 except that g was collected, and the solid content concentration was adjusted to a 40% by weight toluene solution to obtain a uniform and transparent binder resin solution.
Next, an isocyanate curing agent, Sumidur N35 was added to the following composition of the primer, paint and ink.
2.7 g of hexamethylene diisocyanate, isocyanurate compound (manufactured by Sumitomo Bayer Urethane Co., Ltd.) was added, and primers, paints, and inks were adjusted by the method shown below, and then primers were prepared by the method shown below. , Paints and inks were tested. Tables 2 and 3 show the results.
The results are shown in FIG.

Comparative Example 2 500 g of the carboxyl group-containing chlorinated polypropylene obtained in Production Example 1 and toluene 2
A graft copolymerization reaction was carried out in the same manner as in Example 1 except that 50 g, benzoyl peroxide 5 g, methyl methacrylate 255 g, methacrylic acid 10 g, cyclohexyl methacrylate 110 g, and 2 HEA 20 g were collected. Was adjusted. The binder resin solution became cloudy and separated into two layers when allowed to stand. Next, an isocyanate curing agent, Sumidur N3500 (manufactured by Sumitomo Bayer Urethane Co., Ltd., hexamethylene diisocyanate, isocyanurate) was used for the following composition of the primer, paint and ink.
After adding 2.7 g of each, a primer, a paint, and an ink were adjusted by the method shown below, each test of the primer, the paint, and the ink was performed by the method shown below. The results are shown in Tables 2, 3, and 4.

[Primer test method] 1) Composition of primer Binder resin solution composition (40% toluene solution) 100 parts by weight Titanium dioxide 20 Carbon black 0.4 0.4 2) Preparation of primer Sand mill After kneading for about 1 hour, a curing agent was added, and the mixture was diluted and adjusted with xylene to a temperature of 12 to 13 seconds / 20 ° C. using a # 4 Ford cup. 3) Coating method Polypropylene plate (TX-933A, manufactured by Mitsubishi Chemical Corporation) ↓ Wash with neutral detergent ↓ Apply primer by air spray (film thickness 10-15μm) ↓ Dry for 15-20 minutes at room temperature ↓ Spray clear Coating (two-part curable urethane paint, film thickness 30μm) ↓ Dry for 20-30 minutes at room temperature ↓ Bake (80 ° C-30 minutes for isocyanate curing agent) (120 ° C-30 minutes for alkyl etherified amino resin curing agent ) ) ↓ After 24 hours at room temperature, conduct coating test

(Evaluation method) Adhesion One hundred squares were formed on the painted surface to reach the substrate at 1 mm intervals.
It was peeled off in the direction of 80 °, and the number of remaining streaks was examined. -Moisture resistance The coated plate was left in an atmosphere of 50 ° C and a relative humidity of 98% for 240 hours, and the state and adhesion of the coating film were examined. -Warm water resistance The coated plate was immersed in warm water of 40 ° C for 240 hours, and the state and adhesion of the coating film were examined. -Gasoline resistance A scratch (x mark) reaching the substrate was put on the coated surface, immersed in gasoline / ethanol = 9/1 (volume ratio), and the state of the coating film was examined.・ UV resistance Painted board is QUV accelerated weather resistance tester (Q-PANEL COMPANY
UV resistance was tested. The judgment of the result was based on the adhesion at each QUV exposure time, and the deterioration of the coating film was judged.

[Coating Test Method] 1) Blending Composition of Coating Binder Resin Solution Composition (40% Toluene Solution) 100 parts by weight Titanium dioxide 4.5 4.5 Carbon black 0.5 0.5 Petal 2 talc 15 〃 Silica matting agent ３ 3 〃 2) Adjustment of paint After kneading the above composition with a sand mill for about 1 hour, add a curing agent and use a # 4 Ford cup to make xylene with a viscosity of 12-13 seconds / 20 ° C. And adjusted. 3) Coating method Polypropylene plate (TX-933A, manufactured by Mitsubishi Chemical Corporation) ↓ Washed with a neutral detergent ↓ Painted with air spray (thickness: 30 μm) ↓ Dryed at room temperature for 20 to 30 minutes ↓ Bake (isocyanate curing agent) ( 80 ° C for 30 minutes in case of) (120 ° C for 30 minutes in case of alkyl etherified amino resin curing agent) ↓ After standing at room temperature for 48 hours, test coating film

(Evaluation method) Adhesion, moisture resistance and warm water resistance are the same as above. -Butter resistance A cloth impregnated with butter was adhered to the coated surface, allowed to stand at 70 ° C for 7 days, and the butter remaining on the coated surface was completely washed off, and then the adhesion of the coating film was examined. -Alkali resistance The coated plate was immersed in a 0.1N aqueous alkali solution for 120 hours, and the state of the coating film was examined.

[Ink test method] 1) Composition of ink [White ink] Binder resin solution composition (40% toluene solution) ... 100 parts by weight Titanium dioxide ... 30 〃 [Red ink] Binder resin solution composition (40% Toluene solution) 100 parts by weight Carmine 6BN 14 14 * Carmine 6BN: Azo-based organic pigment (manufactured by Toyo Ink Mfg. Co., Ltd.) 2) Preparation of ink After the above composition was kneaded with a sand mill for 3 hours, a curing agent was added. Then, the mixture was diluted with toluene and adjusted to a viscosity of 25 to 30 seconds / 20 ° C. with a # 3 Zahn cup.

(Evaluation method) Cellotape peel test The ink prepared by the above method was coated on a coating rod #
14 and untreated polypropylene film (hereinafter untreated PP)
), Corona discharge treated polypropylene film (hereinafter referred to as treated PP), and dried at room temperature for 24 hours. Then, a cellophane adhesive tape was applied to the ink-coated surface, and the coated surface was peeled off at a stretch. I checked the condition.・ Heat seal strength test Untreated PP and treated P by the same method as the cellophane peel test
P is coated with ink, dried at 50 ° C. for 5 minutes, the ink-coated surfaces are overlapped, heat-sealed at 120 ° C.-1 kg / cm ² for 2 seconds, and after 24 hours at 180 ° C. in Tensilon The peel strength was measured (tensile speed: 50
mm / min).

[0056]

[Table 2]

[0057]

[Table 3]

[0058]

[Table 4]

[0059]

The effect of the present invention is shown in Comparative Example 1 by the present inventors.
506386 is a binder resin composition proposed. Comparative Example 2 is a binder resin composition synthesized using a monomer having an unsaturated group and a hydroxyl group other than HEAC and HEMAC used in the present invention. When these are compared with the curable binder resin of the example, in the state of the binder resin solution, the example and the comparative example 1 show a uniform and transparent liquid, but the comparative example 2 becomes a cloudy two-layer separation and the graft copolymerization is carried out. It can be seen that the reactivity is inferior (Table 2).

The performance of the primer was compared with that of Example 1 in Comparative Example 1.
Is inferior in gasoline resistance and ultraviolet light resistance, and Comparative Example 2 is inferior in moisture resistance, warm water resistance, gasoline resistance and ultraviolet light resistance (Table 2). The same tendency is exhibited in the paint properties, but the butter resistance and the alkali resistance are inferior in the comparative examples to the examples (Table 3). With respect to the physical properties of the ink, the examples show good adhesion to the PP film, whereas the comparative examples are not always sufficient (Table 4). The above results show that the curable binder resin composition of the present invention is useful.

Continued on the front page (51) Int.Cl. ⁷ Identification code FI C09D 161/32 C09D 161/32 175/04 175/04 C09J 151/00 C09J 151/00 161/32 161/32 175/04 175/04 / / (C08F 255/00 (C08F 255/00 220: 26) 220: 26) (58) Field surveyed (Int. Cl. ⁷ , DB name) C09D 151/00

Claims (5)

(57) [Claims] A graft ratio of at least one unsaturated carboxylic acid monomer selected from carboxylic acids and / or carboxylic anhydrides is 1 to 10% by weight and a chlorine content is 5 to 5%.
A monomer containing an ethylenically unsaturated bond in one molecule and a monomer containing an ethylenically unsaturated bond and a hydroxyl group in one molecule represented by the following general formula (1) are added to 50% by weight of a carboxyl group-containing chlorinated polyolefin. The resin obtained by graft copolymerization , the hydroxyl content in the resin is 0.1 to
A curable binder resin composition comprising a resin of 5% by weight as a main component and an isocyanate compound or an alkyl etherified amino resin as a curing agent. Embedded image 2. A polyolefin film, comprising the curable binder resin composition according to claim 1 as an active ingredient.
Primer applicable to sheets and molded products. 3. A polyolefin-based film, comprising the curable binder resin composition according to claim 1 as an active ingredient.
Paint that can be applied to sheets and molded products. 4. A polyolefin film, comprising the curable binder resin composition according to claim 1 as an active ingredient.
Ink applicable to sheets and molded products. 5. A polyolefin film, comprising the curable binder resin composition according to claim 1 as an active ingredient.
Adhesive that can be applied to sheets and molded products.