JP3898636B2 - Binder resin composition, production method and use thereof - Google Patents

Description

【００５６】
【表２】

【００５７】
【表３】

【００５８】
【表４】

【００５９】
【発明の効果】
表１よりメタロセン触媒を重合触媒として製造したプロピレン系ランダム共重合体の塩素化物は、塩素含有率が低くても液状が良好である。また、表２よりメタロセン触媒を重合触媒として製造したプロピレン系ランダム共重合体の塩素化物は、従来のチーグラー・ナッタ触媒を重合触媒として製造したＩＰＰの塩素化物より耐ガソホール性が良好である。さらに、表２〜４よりメタロセン触媒を重合触媒として製造したプロピレン系ランダム共重合体の塩素化物は、ポリプロピレン素材のみならず、塩ビ、ポリカーボネート、PET、ABS、ナイロン等の素材に対しても良好な付着性を示している。従って、この塩素化プロピレン系ランダム共重合体及び／またはカルボキシル基含有塩素化ポリプロピレン系ランダム共重合体を含むバインダー樹脂組成物が、産業上有用であり、特に、塗料、接着剤、ヒートシール剤、印刷インキ、プライマー用に有効であることが分かる。[0001]
BACKGROUND OF THE INVENTION
The present invention includes polyolefin resins such as polypropylene, polyethylene, ethylene propylene copolymer, ethylene propylene diene copolymer, vinyl chloride resin, polycarbonate (PC) resin, polyethylene terephthalate (PET) resin, acrylonitrile butadiene styrene (ABS) The present invention relates to a binder resin composition used for the purpose of protecting a resin, a nylon resin or cosmetics, and a method for producing the same. More specifically, these polyolefin-based, vinyl chloride-based, polycarbonate-based, PET-based, ABS-based, nylon-based sheets, films and molded products have excellent adhesion and other physical properties, such as paints, printing inks, adhesives, or The present invention relates to a binder resin composition for a primer.
[0002]
[Prior art]
Since plastic has many advantages such as light weight, rust prevention, and wide design freedom, it has been widely used in recent years as a material for automobile parts, electrical parts, building materials and the like. 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 properties. Growth is also expected. However, unlike synthetic resins having polarity, polyolefin resins also have the disadvantage that they are difficult to bond because they are nonpolar and crystalline.
[0003]
On the other hand, as a pre-treatment for painting and bonding, it is said that the surface of the molded product is activated by plasma treatment or gas flame treatment, or a primer (primer) based on chlorinated polyolefin is applied. The method is taken.
[0004]
For example, JP-A-57-36128 and JP-B-63-36624 disclose primer compositions mainly composed of chlorinated modified polyolefins for automobile polypropylene bumper coating.
[0005]
These chlorinated primers have excellent adhesion to conventional polyolefins, but recently, there are materials that do not have sufficient adhesion due to increased rigidity and low-temperature baking, and conventional chlorinated polyolefin resins The current situation is not enough.
[0006]
In addition, chlorinated polyolefin resins show relatively good adhesion to polypropylene materials, but not enough adhesion to other materials (vinyl chloride, polycarbonate, PET, ABS, nylon). is the current situation.
[0007]
The chlorinated polyolefin resins and the like that have been proposed so far are chlorinated IPP, which is chlorinated isotactic polypropylene (hereinafter, IPP) produced using a Ziegler-Natta catalyst as a polymerization catalyst. .
[0008]
On the other hand, an adhesive using chlorinated SPP obtained by chlorinating syndiotactic polypropylene (hereinafter referred to as SPP) produced using a metallocene compound as a polymerization catalyst is disclosed (Japanese Patent No. 3045498, JP-A-7- 18016). However, this chlorinated SPP has improved solvent solubility compared to the chlorinated IPP produced by using a conventional Ziegler-Natta catalyst as a polymerization catalyst, but only exhibits excellent adhesion when the material is polypropylene. , Other materials (vinyl chloride, polycarbonate, PET, ABS, nylon) have the disadvantage of insufficient adhesion.
[0009]
[Problems to be solved by the invention]
The present invention is a binder resin that has good adhesion and gasohol resistance and excellent solvent solubility for various polyolefin-based, polyvinyl-based, polycarbonate-based, PET-based, ABS-based and nylon-based materials including polypropylene materials. An object is to provide a composition.
[0010]
[Means for Solving the Problems]
The present inventors obtained by copolymerizing propylene and another α-olefin in the presence of a metallocene catalyst, Isotactic with Mw / Mn of 2 or less A binder resin composition characterized by being a chlorinated propylene-based random copolymer having a weight-average molecular weight of 3000-250,000 obtained by chlorinating a propylene-based random copolymer to a chlorine content of 10-40% by weight, And / or obtained by copolymerizing propylene and another α-olefin in the presence of a metallocene catalyst, Isotactic with Mw / Mn of 2 or less Propylene random copolymer In Carboxyl group-containing chlorine having a weight average molecular weight of 30000 to 220,000, grafted with 0.1 to 20% by weight of α, β-unsaturated carboxylic acid or anhydride thereof and then chlorinated to a chlorine content of 10 to 40% by weight The above-mentioned problems have been solved by a binder resin composition characterized in that it is a propylene fluoride random copolymer.
[0011]
The propylene random copolymer which is a raw material of the present invention is a copolymer obtained by copolymerizing propylene as a main component with another α-olefin using a metallocene catalyst as a polymerization catalyst. Commercial products such as Wintec (manufactured by Nippon Polychem Co., Ltd.) can also be used.
[0012]
As another α-olefin which is a comonomer, at least one selected from the group consisting of ethylene or olefins having 4 or more carbon atoms can be selected. Examples of the olefin having 4 or more carbon atoms include 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene and the like. By using a metallocene catalyst, the range of comonomer that can be copolymerized can be expanded as compared with the Ziegler-Natta catalyst.
[0013]
A well-known thing can be used as a metallocene catalyst used by this invention. Specifically, a catalyst obtained by combining components (A) and (B) described below and (C) as necessary is desirable.
Component (A): a metallocene complex which is a transition metal compound of Groups 4 to 6 of the periodic table having at least one conjugated five-membered ring ligand.
Component (B): a cocatalyst (ion exchangeable layered silicate) that can activate the metallocene complex (A) by reacting the compound (B) with the metallocene complex (A).
Component (C); an organoaluminum compound.
[0014]
The propylene random copolymer of the present invention can be produced by a known method (JP 2001-206914 A). For example, the production is carried out while continuously adding alkylaluminum and metallocene catalyst while supplying propylene, ethylene and hydrogen to the reaction kettle.
[0015]
The propylene random copolymer of the present invention preferably has a melting point (hereinafter referred to as Tm) measured by a differential scanning calorimeter (hereinafter referred to as DSC) of 115 to 165 ° C. If it is higher than 165 ° C, the solvent solubility is lowered. If it is lower than 115 ° C, the adhesion to the material will be reduced. More preferably, it is a low melting point propylene-based random copolymer at 115 to 135 ° C. In addition, the measuring method of Tm by DSC in the present invention uses a DSC measuring device manufactured by Seiko Co., Ltd., takes a sample (about 5 mg), melts at 200 ° C. for 5 minutes, and then lowers the temperature to 40 ° C. at a rate of 10 ° C./min. After crystallization, the temperature was further increased to 200 ° C. at 10 ° C./min, and evaluation was made based on the melting peak temperature and melting end temperature.
[0016]
The propylene random copolymer of the present invention is one that has been thermally degraded in the presence of a radical generator at a temperature not lower than the melting point and not higher than 350 ° C. using a Banbury mixer, kneader, extruder, etc., or not thermally degraded May be used alone or in combination. The radical generator used in the reaction can be appropriately selected from known ones, and an organic peroxide compound is particularly desirable.
[0017]
Examples of the organic peroxide compounds include di-t-butyl peroxide, dicumyl peroxide, t-butyl cumyl peroxide, benzoyl peroxide, dilauryl peroxide, cumene hydroperoxide, and t-butyl hydro gen. Peroxide, 1,1-bis (t-butylperoxy) -3,5,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) -cyclohexane, cyclohexanone peroxide, t-butylperoxybenzoate , T-butylperoxyisobutyrate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisopropyl carbonate, cumylper Examples thereof include oxyoctoate.
[0018]
The chlorinated polypropylene random copolymer of the present invention can be obtained by introducing chlorine into the propylene random polymer.
[0019]
The chlorination reaction is carried out by dissolving the propylene random copolymer in a chlorine solvent such as chloroform and then irradiating it with ultraviolet light or blowing gaseous chlorine in the presence of the organic peroxide. .
[0020]
The optimum chlorine content is 10 to 40% by weight, preferably 15 to 30% by weight. Below this range, the adhesion to various materials is improved, but the solubility in organic solvents is reduced. On the other hand, if it is higher than this range, adhesion to various materials will be reduced. The chlorine content is a value measured according to JIS-K7229.
[0021]
The weight average molecular weight (hereinafter referred to as Mw) of the chlorinated propylene random copolymer used in the present invention is 3000 to 250,000. If it is less than 3000, the cohesive strength of the resin is insufficient, and if it exceeds 250,000, the handling of the ink and the adhesive decreases, which is not preferable. In the present invention, Mw is a value measured by gel permeation chromatography (hereinafter, GPC, standard substance: polystyrene resin).
[0022]
The carboxyl group-containing chlorinated polypropylene random copolymer of the present invention can be obtained by introducing α, β-unsaturated carboxylic acid and chlorine into the propylene random copolymer. It can be produced by the following two methods. That is, a method in which α, β-unsaturated carboxylic acid or its anhydride is directly graft-polymerized to a heat-degraded propylene random copolymer or a non-thermally degraded propylene random copolymer and then subjected to a chlorination reaction (First method) and a method (second method) in which an α, β-unsaturated carboxylic acid or an anhydride thereof is graft-polymerized after the chlorination reaction.
[0023]
The specific manufacturing method is illustrated below. In the first method, first, a method in which α, β-unsaturated carboxylic acid or an anhydride thereof is directly graft-copolymerized to a heat-degraded propylene random copolymer or a non-heat-degraded propylene random copolymer, A method in which the resin is heated and melted to a melting point or higher in the presence of a radical generator (melting method), and a method in which the resin is dissolved in an organic solvent and then heated and stirred in the presence of a radical generator to react. (Solution method) It can carry out by well-known methods.
[0024]
In the case of the melting method, a Banbury mixer, a kneader, an extruder or the like is used and the reaction is performed in a short time at a temperature not lower than the melting point and not higher than 350 ° C., so that there is an advantage that the operation is simple.
[0025]
On the other hand, in the solution method, it is desirable to use an aromatic solvent such as toluene or xylene as the organic solvent. However, it is also possible to use a mixture of a part of an ester solvent or a ketone solvent. . The radical generator used in the reaction can be appropriately selected from known ones, but organic peroxide compounds are particularly desirable, and the compounds described above can be used.
[0026]
However, in the case of the solution method, after graft copolymerization of α, β-unsaturated carboxylic acid or anhydride thereof, it is necessary to replace the above solvent with a chlorinated solvent such as chloroform when performing a chlorination reaction. In the first method, the melting method is preferred.
[0027]
The chlorination reaction performed after the carboxyl group modification is carried out by using a propylene random copolymer or a propylene random copolymer obtained by graft copolymerization with an α, β-unsaturated carboxylic acid or an anhydride thereof, and a chlorine-based solvent such as chloroform. Then, it is carried out by blowing gaseous chlorine in the presence of the organic peroxide while irradiating with ultraviolet rays.
[0028]
In the second method of graft polymerization of α, β-unsaturated carboxylic acid or its anhydride after chlorination reaction, first, a propylene random copolymer is dissolved in a chlorine solvent such as chloroform. After the chlorination reaction was carried out in the same manner as in the first method to produce a chlorinated propylene random copolymer, the solvent was changed to a solvent such as toluene or xylene, and then the α, β-unsaturated carboxylic acid or its anhydride was changed. The product is graft copolymerized in the presence of the organic peroxide. The reaction can be carried out at a temperature of 50 ° C. or higher and lower than the boiling point of the solvent. However, in the second method, the graft polymerization of α, β-unsaturated carboxylic acid or its anhydride is low when the reaction temperature is 50 ° C. or more and 100 ° C. or less, and when the reaction temperature is 100 ° C. or more and less than the boiling point of the solvent, chlorinated propylene. Since the random copolymer may cause dehydrochlorination, the first method is preferable to the second method.
[0029]
In the first method, the purpose of graft copolymerization of an α, β-unsaturated carboxylic acid or anhydride thereof with a propylene-based random copolymer is an overcoating when the binder resin composition of the present invention is used as a primer. It is for providing adhesiveness with. Chlorinated polyolefins are inherently low in polarity, and as such, when used as a primer (primer), adhesion to PP materials is good, but adhesion to highly polar topcoat paints (e.g. polyurethane paints, melamine paints) There is almost no sex. Therefore, it is important to increase the polarity of the chlorinated polyolefin by graft copolymerization of α, β-unsaturated carboxylic acid or its anhydride. Examples of α, β-unsaturated carboxylic acids or anhydrides that can be used include maleic acid, citraconic acid, itaconic acid, aconitic acid and their anhydrides, acrylic acid, methacrylic acid, fumaric acid, mesaconic acid, and the like. However, maleic anhydride is most suitable in consideration of the grafting property to the polyolefin resin.
[0030]
In the present invention, the amount of α, β-unsaturated carboxylic acid or its anhydride introduced by graft copolymerization is optimally 0 to 20% by weight, preferably 0 to 10% by weight. If it exceeds 10% by weight, the moisture resistance tends to decrease when used as a primer.
[0031]
The optimum chlorine content is 10 to 40% by weight, preferably 15 to 30% by weight. Below this range, the adhesion to various materials is improved, but the solubility in organic solvents is reduced. On the other hand, if it is higher than this range, adhesion to various materials will be reduced. The chlorine content is a value measured according to JIS-K7229.
[0032]
The weight average molecular weight (hereinafter referred to as Mw) of the chlorinated propylene random copolymer and carboxyl group-containing chlorinated propylene random copolymer used in the present invention is 30000 to 250,000 in the former case. If it is less than 3000, the cohesive strength of the resin is insufficient, and if it exceeds 250,000, the sprayability is lowered, which is not preferable. In the latter case, it is 30000-220000. If it is less than 30000, the cohesive strength of the resin is insufficient, and if it exceeds 220,000, the sprayability is lowered. In the present invention, Mw is a value measured by gel permeation chromatography (hereinafter, GPC, standard substance: polystyrene resin).
[0033]
Chlorinated polyolefins deteriorate with dehydrochlorination when exposed to ultraviolet light or high heat. When chlorinated polyolefin deteriorates due to dehydrochlorination, it causes deterioration of physical properties such as resin coloring and reduced adhesion to polypropylene materials, and free hydrochloric acid causes deterioration of the working environment, so it is necessary to add a stabilizer. is there. In order to acquire this effect, it is preferable to add a stabilizer 0.1 to 5weight% with respect to the resin component (solid content). An example of the stabilizer is an epoxy compound. The epoxy compound is not particularly limited, but is preferably an epoxy compound that is compatible with the chlorinated resin, having an epoxy equivalent of about 100 to 500 and having one or more epoxy groups in one molecule. For example, epoxidized soybean oil or epoxidized linseed oil obtained by epoxidizing vegetable oils with natural unsaturated groups with peracids such as peracetic acid, and unsaturated fatty acids such as oleic acid, tall oil fatty acid, soybean oil fatty acid, etc. Epoxidized fatty acid esters. Epoxidized alicyclic compounds represented by epoxidized tetrahydrophthalate. For example, bisphenol A glycidyl ether, ethylene glycol glycidyl ether, propylene glycol glycidyl ether, glycerol polyglycidyl ether, sorbitol polyglycidyl ether and the like obtained by condensing bisphenol A or polyhydric alcohol and epichlorohydrin are exemplified. Also represented by butyl glycidyl ether, 2-ethylhexyl glycidyl ether, decyl glycidyl ether, stearyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, sec-butylphenyl glycidyl ether, tert-butylphenyl glycidyl ether, phenol polyethylene oxide glycidyl ether, etc. Examples of the monoepoxy compounds are shown below. Further, metal soaps such as calcium stearate and lead stearate, organometallic compounds such as dibutyltin dilaurate and dibutylmalate, hydrotalcite compounds which are used as stabilizers for polyvinyl chloride resins can be used. These may be used in combination.
[0034]
The composition of the present invention can be used by dissolving in an organic solvent. The solution concentration may be appropriately selected depending on the use, but the coating concentration is preferably 5 to 60% by weight because the coating workability is impaired if the solution concentration is too high or too low. The solvent to be used is preferably an aromatic solvent such as toluene or xylene. In addition, an ester solvent such as ethyl acetate or butyl acetate, a ketone solvent such as methyl ethyl ketone or methyl isobutyl ketone, or an aliphatic solvent such as n-hexane or heptane. Solvent, cycloaliphatic solvents such as cyclohexane, methylcyclohexane, and ethylcyclohexane can be used. Furthermore, in order to increase the storage stability of the resin solution, alcohols such as methanol, ethanol and isopropyl alcohol, propylene glycol ethers such as propylene glycol methyl ether, propylene glycol ethyl ether and propylene glycol tertiary butyl ether are used alone or in combination. It is preferable to add 1 to 20% by weight with respect to the solvent by mixing more than one species.
[0035]
The prescription for dissolving the binder resin composition of the present invention in an organic solvent is possible by converting a chlorinated solvent such as chloroform as a reaction solvent into the above solvent using a difference in boiling points. Moreover, after adding an epoxy compound or the like as a stabilizer to the reaction solution after the reaction, the mixture is solidified by supplying to an extruder equipped with a vent provided with a suction part for solvent removal on the screw shaft part and dissolved in the solvent. May be. The solidification method is a known method such as a vented extruder equipped with an underwater cut pelletizer at the outlet of the extruder, a vented extruder, and a pelletizer that cuts strand resin. Can be implemented.
[0036]
The binder resin composition according to the present invention can be used as a paint, printing ink, adhesive, and primer applicable to polyolefin-based, vinyl chloride-based, polycarbonate-based, PET-based, ABS-based, nylon-based films, sheets, and molded products. it can. The coating may be used as it is, but a solvent, a pigment, and other additives may be added as long as the effects of the present invention are not impaired. In addition, the composition exhibits balanced coating film properties by itself, but if necessary, cyclized rubber, petroleum resin, coumarone indene resin, chlorinated polyolefin resin, acrylic resin, alkyd resin, etc. may be further added. Can be used. In particular, the binder resin composition of the present invention preferably contains 30 wt% or more.
[0037]
[Action]
One of the characteristics of the propylene random copolymer produced using a metallocene catalyst as a polymerization catalyst is that it has a lower melting point and glass transition point than the propylene random copolymer produced using a conventional Ziegler-Natta catalyst as a polymerization catalyst. There is. Therefore, it is considered that the solvent solubility is good even when the chlorine content is lowered, and the adhesion at the time of low-temperature baking is improved due to the low melting point.
[0038]
Further, as a feature of the propylene random copolymer produced using a metallocene catalyst as a polymerization catalyst, the molecular weight distribution is very narrow (Mw / Mn = about 2 or less). In addition, when graft copolymerizing an α, β-unsaturated carboxylic acid or anhydride thereof, an organic peroxide or the like is used, so that a propylene random copolymer produced using a conventional Ziegler-Natta catalyst as a polymerization catalyst is used. In the coalescence, a molecular weight decrease, that is, a low molecular weight component is always generated. However, it has been newly found that a propylene-based random copolymer produced using a metallocene catalyst as a polymerization catalyst has almost no generation.
[0039]
Although a clear reason is not known in the present invention, a propylene random copolymer produced using a metallocene catalyst as a polymerization catalyst is different from a propylene random copolymer produced using a conventional Ziegler-Natta catalyst as a polymerization catalyst, It has been found that it exhibits excellent adhesion to a wide range of materials such as PVC, polycarbonate, PET, ABS, and nylon other than polyolefin. In addition, it is considered that the gasohol resistance was improved by using a propylene random copolymer produced using a metallocene catalyst having a low low molecular weight component as a polymerization catalyst.
[0040]
【Example】
EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.
[0041]
[Example-1]
Propylene-based random copolymer (about 97% propylene-about 3% ethylene) manufactured by using a metallocene catalyst as a polymerization catalyst (manufactured by Nippon Polychem Co., Ltd. MFR = 2.0g / 10min Tm = 125 ° C) was set at a barrel temperature of 350 ° C. A propylene-based random copolymer having a melt viscosity of about 1500 mPa · s at 190 ° C. was obtained by supplying to a twin-screw extruder for thermal degradation. 500 g of this resin was charged into a glass-lined reaction kettle. Add 5L of chloroform, 2kg / cm ² Under the pressure of, gaseous chlorine was blown from the bottom of the reaction kettle while irradiating with ultraviolet rays to chlorinate. Three points were extracted in the middle, and chloroform as a solvent was distilled off with an evaporator. Then, toluene / cyclohexane = 70/30 (weight ratio) was substituted, and Epicoat 828 (manufactured by Yuka Shell Epoxy Co., Ltd.) as a stabilizer was added to the resin 2% by weight to chlorinate the resin concentration 20% by weight. A propylene random copolymer resin solution was obtained. Table 1 shows the physical properties of the resin. The obtained resin solution was allowed to stand at room temperature for 1 month, but no change was observed in the liquid state and appearance.
[0042]
[Example-2]
Glass-lined 500 g of propylene random copolymer (propylene approx. 97%-ethylene approx. 3%) (Wintech, Nippon Polychem Co., Ltd. MFR = 2.0g / 10min Tm = 125 ° C) produced using metallocene catalyst as polymerization catalyst Was put into the reaction kettle. Add 5L of chloroform, 2kg / cm ² Under the pressure of, gaseous chlorine was blown from the bottom of the reaction kettle while irradiating with ultraviolet rays to chlorinate. Three points were extracted in the middle, and chloroform as a solvent was distilled off with an evaporator. After that, it was replaced with toluene / cyclohexane = 70/30 (weight ratio), and Epiol TB (manufactured by Nippon Oil & Fats Co., Ltd.) as a stabilizer was added to 2% by weight of the resin, and a chlorinated propylene system having a resin concentration of 20% by weight. A random copolymer resin solution was obtained. Table 1 shows the physical properties of the resin. The obtained resin solution was allowed to stand at room temperature for 1 month, but no change was observed in the liquid state and appearance.
[0043]
[Example-3]
Propylene-based random copolymer (about 97% propylene-about 3% ethylene) manufactured by using a metallocene catalyst as a polymerization catalyst (manufactured by Nippon Polychem Co., Ltd. MFR = 2.0g / 10min Tm = 125 ° C) was set at a barrel temperature of 350 ° C. A propylene-based random copolymer having a melt viscosity of about 2000 mPa · s at 190 ° C. was obtained by supplying to a twin screw extruder for thermal degradation. 500 g of this resin was dissolved by heating at 190 ° C. in a four-necked flask equipped with a stirrer, a condenser, a thermometer and a dropping funnel. After performing nitrogen substitution in the flask for 10 minutes, 25 g of maleic anhydride was added over about 5 minutes with stirring, and 2 g of di-t-butyl peroxide as a radical generator was added dropwise over about 30 minutes. After continuing the reaction for another 30 minutes, unreacted maleic anhydride was removed while reducing the pressure in the flask with an aspirator. Next, this product is put into a glass-lined reaction kettle, 5 L of chloroform is added, and 2 kg / cm 2 is added. ² Under the pressure of, gaseous chlorine was blown from the bottom of the reaction kettle while irradiating with ultraviolet rays to chlorinate. 20% by weight of the chlorinated propylene random copolymer which was extracted in the middle, and after each solvent chloroform was distilled off with an evaporator, was replaced with toluene / cyclohexane = 70/30 (weight ratio) and modified with maleic anhydride % Solution was obtained. As a stabilizer, Epicoat 828 (manufactured by Yuka Shell Epoxy Co., Ltd.) was added at 4% to the resin. Table 1 shows the physical properties of the resin. The obtained resin solution was allowed to stand at room temperature for 1 month, but no change was observed in the liquid state and appearance.
[0044]
[Example-4]
Propylene random copolymer produced by using a metallocene catalyst as a polymerization catalyst in a twin screw extruder with L / D = 34 and φ = 40 mm (propylene: about 97% -ethylene: about 3%) (manufactured by Nippon Polychem Co., Ltd., MFR = 7.0) g / 10min Tm = 125 ° C.) 500 g, maleic anhydride 30 g, and dicumyl peroxide 15 g were added. The residence time is 10 minutes, the barrel temperature is 180 ° C (1st to 7th barrels), the reaction is performed, deaeration is performed in the 7th barrel, unreacted maleic anhydride is removed, and maleic anhydride-modified propylene-based random A copolymer was obtained. Put 500g of this resin into a glass-lined reaction kettle, add 5L of chloroform, and add 2kg / cm ² Under the pressure of, gaseous chlorine was blown from the bottom of the reaction kettle while irradiating with ultraviolet rays to chlorinate. Extracted in the middle of the test, each solvent chloroform was distilled off with an evaporator, substituted with toluene / cyclohexane = 70/30 (weight ratio) and modified with maleic anhydride, 20% by weight of chlorinated propylene random copolymer A solution was obtained. As a stabilizer, Epiol SB (manufactured by NOF Corporation) was added at 4% to the resin. Table 1 shows the physical properties of the resin. The obtained resin solution was allowed to stand at room temperature for 1 month, but no change was observed in the liquid state and appearance.
[0045]
[Comparative Example-1]
Isotactic polypropylene (IPP) produced using a Ziegler-Natta catalyst as a polymerization catalyst is supplied to a twin-screw extruder set at a barrel temperature of 350 ° C for thermal degradation, and the melt viscosity at 190 ° C is about 2000 mPa · s. Got IPP. Using 500 g of this resin, a chlorinated IPP resin solution having a resin concentration of 20% by weight was obtained in the same manner as in Example 1. Table 1 shows the physical properties of the resin. The obtained resin solution was allowed to stand at room temperature for 1 month, but no change was observed in the liquid state and appearance.
[0046]
[Comparative Example-2]
Using 500 g of syndiotactic polypropylene (SPP MFR = 3.7 g / 10 min), a chlorinated SPP resin solution having a resin concentration of 20% by weight was obtained in the same manner as in Example 1. The physical properties of the resin are shown in Table 1. The obtained resin solution was allowed to stand at room temperature for 1 month, but no change was observed in the liquid state and appearance.
[0047]
[Comparative Example-3]
Isotactic polypropylene (IPP) produced using a Ziegler-Natta catalyst as a polymerization catalyst is supplied to a twin-screw extruder set at a barrel temperature of 350 ° C for thermal degradation, and the melt viscosity at 190 ° C is about 2000 mPa · s. Got IPP. Using 500 g of this resin, a chlorinated IPP resin solution modified with maleic anhydride having a resin concentration of 20% by weight was obtained in the same manner as in Example 2. Table 1 shows the physical properties of the resin. The obtained resin solution was allowed to stand at room temperature for 1 month, but no change was observed in the liquid state and appearance.
[0048]
[Comparative Example-4]
Syndiotactic polypropylene (SPP MFR = 3.7g / 10min) was supplied to a twin-screw extruder set at a barrel temperature of 350 ° C to perform thermal degradation, and an SPP with a melt viscosity at 190 ° C of about 2000 mPa · s was obtained. . In the same manner as in Example 2, 500 g of this resin was used to obtain a chlorinated SPP resin solution modified with maleic anhydride having a resin concentration of 20% by weight. Table 1 shows the physical properties of the resin. The obtained resin solution was allowed to stand at room temperature for 1 month, but no change was observed in the liquid state and appearance.
[0049]
[Comparative Example-5]
In Example 1, a chlorinated propylene-based random copolymer resin solution having a resin concentration of 20% by weight was obtained without adding a stabilizer. When this resin solution was allowed to stand at room temperature for 1 month, all of the resin solutions turned reddish brown.
[0050]
[Measurement method of resin properties]
・ MFR (Melt Flow Rate)
It was measured by the melt flow rate (conditions: 230 ° C., load 2.16 kgf) of JIS-K-6758 polypropylene test method.
・ Tm
A sample (about 5 mg) was taken using a Seiko DSC measuring apparatus and melted at 200 ° C. for 5 minutes. Thereafter, the temperature was lowered to 40 ° C. at a rate of 10 ° C./min and crystallized, and then the temperature was further raised to 200 ° C. at 10 ° C./min, and the melting peak temperature and melting end temperature were evaluated.
・ Chlorine content
Measured according to JIS-K7229.
-Weight average molecular weight (Mw), number average molecular weight (Mn)
Measured by GPC (standard material: polystyrene resin). Moreover, Mw / Mn in the table indicates the molecular weight distribution.
[0051]
[Liquid test]
The obtained resin solution was allowed to stand at room temperature for 1 month, and the liquid state and appearance were visually evaluated.
Evaluation criteria
○: No change in liquid appearance after 1 month.
Δ: After 1 month, the color changed to reddish brown.
X: Gelation after one month.
[0052]
[Primer test]
100 g of the resin solutions (solid content 20%) obtained from Examples -3 and 4 and Comparative Examples 3,4 and 20 g of titanium dioxide were kneaded in a sand mill for 3 hours, and then 13 to 15 seconds / in a NO.4 Ford cup. Adjust the viscosity with xylene to 20 ° C, air spray gun for ultra-high rigidity PP plate (TX-933A, manufactured by Mitsubishi Chemical Corporation), PVC, polycarbonate (PC), PET, ABS, nylon-6 Was applied so that the film thickness was about 10 μm. Next, a two-component curable urethane coating was applied (film thickness of about 30 μm). The film was dried at 80 ° C. for 30 minutes and allowed to stand at room temperature for 24 hours for physical property evaluation. The primer test results are shown in Table 2.
・ Adhesiveness
On the coated surface, 100 grids reaching the substrate at 1 mm intervals were made, and a cellophane adhesive tape was stuck on it and peeled in the 180 ° direction, and the degree of remaining coating was judged.
-Gasohol resistance
The coated plate was immersed in regular gasoline / ethanol = 9/1 (v / v) for 120 minutes and the state of the coating film was observed.
Good: No abnormalities in the coating film
Defective; abnormal state of coating film
·water resistant
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.
Good; no peeling at all
Defective; when peeling occurs
[0053]
[Adhesion test]
・ Heat seal test
The obtained resin solution (solid content 20 wt%) was applied to untreated PP, PVC and PET with a coating rod # 14. After drying at room temperature for 24 hours, the coated surfaces are overlaid and 1 kg / cm at 80 ° C. ² Then, heat sealing was performed under pressure bonding conditions for 2 seconds. After 24 hours, 180 ° peel strength (g / cm) was measured with Tensilon (tensile speed: 50 mm / min). The adhesion test results are shown in Table 3.
[0054]
[Ink test]
100 g of the obtained resin solution (solid content 20 wt%) and 20 g of titanium dioxide were kneaded for 3 hours in a sand mill, then diluted with toluene to a viscosity of 25-30 seconds / 20 ° C. in a # 3 Zaan cup, and ink was obtained. It was adjusted. About the obtained ink, the adhesive tape peeling test and the heat seal test were done. The ink test results are shown in Table 4.
・ Adhesive tape peel test
Ink was applied to untreated PP, PVC and PET in the same manner as in the heat seal test. After drying at room temperature for 24 hours, cellophane adhesive tape was applied to the ink coated surface, and the state of the coated surface when peeled off at once was examined.
Evaluation criteria
Good: No peeling at all
Defect: state with peeling
・ Heat seal test
Same as adhesion test.
[0055]
[Table 1]

[0056]
[Table 2]

[0057]
[Table 3]

[0058]
[Table 4]

[0059]
【The invention's effect】
According to Table 1, the chlorinated product of the propylene-based random copolymer produced using the metallocene catalyst as a polymerization catalyst has a good liquid state even if the chlorine content is low. Further, from Table 2, the chlorinated product of the propylene-based random copolymer produced using a metallocene catalyst as a polymerization catalyst has better gasohol resistance than the chlorinated product of IPP produced using a conventional Ziegler-Natta catalyst as a polymerization catalyst. Furthermore, from Tables 2 to 4, the chlorinated product of the propylene-based random copolymer produced using the metallocene catalyst as a polymerization catalyst is good not only for polypropylene materials but also for materials such as vinyl chloride, polycarbonate, PET, ABS, and nylon. It shows adhesion. Therefore, a binder resin composition containing this chlorinated propylene-based random copolymer and / or carboxyl group-containing chlorinated polypropylene-based random copolymer is industrially useful, in particular, a paint, an adhesive, a heat seal agent, It turns out that it is effective for printing ink and primer.

Claims (10)

An isotactic propylene-based random copolymer having a Mw / Mn of 2 or less obtained by copolymerizing propylene and another α-olefin in the presence of a metallocene catalyst, with a chlorine content of 10 to 40% by weight A binder resin composition comprising a chlorinated, chlorinated propylene random copolymer having a weight average molecular weight of 3000 to 250,000, a stabilizer and an organic solvent. The chlorinated propylene-based random copolymer according to claim 1 is chlorinated until the chlorine content is 10 to 40% by weight after graft polymerization of 0 to 20% by weight of α, β-unsaturated carboxylic acid or its anhydride. Or chlorinated to a chlorine content of 10 to 40% by weight, and then grafted with 0 to 20% by weight of α, β-unsaturated carboxylic acid or anhydride thereof, and having a weight average molecular weight of 30000 to 220,000 A binder resin composition which is a group-containing chlorinated polypropylene random copolymer. The binder resin composition according to claim 1 or 2, wherein the propylene random copolymer has a melting point (Tm) measured by a differential scanning calorimeter (DSC) of 115 to 165 ° C. Heating a propylene random copolymer with a melting point (Tm) of 115-165 ° C by differential scanning calorimeter (DSC) obtained by copolymerizing propylene and other α-olefins in the presence of a metallocene catalyst The method for producing a binder resin composition according to claim 1 or 2, wherein the chlorinated propylene-based random copolymer is chlorinated to 10 to 40 wt% after chlorine degradation or without thermal degradation. Chlorinated propylene-based random copolymer is 0-20% by weight graft polymerization of α, β-unsaturated carboxylic acid or its anhydride, then chlorinated to 10-40% by weight or containing chlorine A carboxyl group-containing chlorinated polypropylene random copolymer obtained by grafting 0 to 20% by weight of an α, β-unsaturated carboxylic acid or its anhydride after chlorination to a rate of 10 to 40% by weight. 4. The method for producing a binder resin composition according to 4. A coating material that can be applied to polyolefin-based, vinyl chloride-based, polycarbonate-based, PET-based, ABS-based, nylon-based films, sheets, and molded articles, comprising the binder resin composition according to any one of claims 1 to 3 as an active ingredient. A printing ink that can be applied to polyolefin-based, vinyl chloride-based, polycarbonate-based, PET-based, ABS-based, nylon-based films, sheets, and molded articles, comprising the binder resin composition according to any one of claims 1 to 3 as an active ingredient. . An adhesive that can be applied to polyolefin-based, vinyl chloride-based, polycarbonate-based, PET-based, ABS-based, nylon-based films, sheets, and molded articles, comprising the binder resin composition according to any one of claims 1 to 3 as an active ingredient. . A heat seal which can be applied to polyolefin-based, vinyl chloride-based, polycarbonate-based, PET-based, ABS-based, nylon-based films, sheets and molded articles, comprising the binder resin composition according to any one of claims 1 to 3 as an active ingredient. Agent. A primer that can be applied to polyolefin-based, vinyl chloride-based, polycarbonate-based, PET-based, ABS-based, nylon-based films, sheets, and molded articles, comprising the binder resin composition according to claim 1 as an active ingredient.