JP3965697B2 - Chlorinated polyolefin binder resin composition with good solvent resistance - Google Patents

Description

  The present invention relates to a binder resin composition used for the purpose of protection or cosmetics of polyolefin-based resins such as polypropylene, polyethylene, ethylene-propylene copolymer, ethylene-propylene-diene copolymer, etc. The present invention relates to a chlorinated polyolefin composition used as a binder resin for primers and paints, which is excellent in solvent resistance, adhesion and other physical properties and excellent in stability to films and molded products.

  Plastics are highly productive, have a wide range of design freedom, and have many advantages such as light weight, rust prevention, impact resistance, etc. In recent years, they have been widely used as materials for automobile parts, electrical parts, building materials, food packaging films, etc. It has been 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 properties. Is one of the most promising materials. However, unlike the synthetic resins with polarity, such as polyurethane resins, polyamide resins, acrylic resins, polyester resins, etc., polyolefin resins have the disadvantage that they are nonpolar and crystalline, making them difficult to paint and bond. Have.

  For the coating and adhesion of such difficult-to-adhere polyolefin resins, low chlorinated polyolefins having a strong adhesion to polyolefin resins have been conventionally used as binder resins. In addition, low chlorinated polypropylene or low chlorinated propylene-α-olefin copolymer containing carboxylic acid and / or carboxylic acid anhydride has been proposed as a primer for coating a polyolefin-based molded article or a binder resin for coating. (For example, see Patent Document 1, Patent Document 2, Patent Document 3, Patent Document 4, and Patent Document 5).

  In recent years, primers for polyolefin-based molded products are required not only for adhesion but also for solvent resistance, particularly gasohol resistance. However, the above chlorinated acid-modified polyolefin does not have sufficient gasohol resistance. Improvement is desired.

  In order to improve the gasohol resistance, it can be improved by adding a monoepoxy compound and / or resin to the chlorinated acid-modified polyolefin (see, for example, Patent Document 6), or a α grafted with the chlorinated acid-modified polyolefin. It has been proposed to improve a part of the β-unsaturated carboxylic acid anhydride by ring-opening with water (see, for example, Patent Document 7). However, all of these require the removal of unreacted acid monomers and the like with a solvent before chlorination, which has the disadvantage that the production process increases and the production cost increases.

JP-A-57-36128 Japanese Patent Publication No. 63-50381 JP 59-166534 A Japanese Examined Patent Publication No. 63-36624 Japanese Patent Laid-Open No. 10-168123 Japanese Patent Laid-Open No. 9-235433 JP 2001-114843 A

  The present invention solves the above problems and is excellent in adhesion and solvent resistance to polyolefin, particularly in gasohol resistance, good in solvent solubility, good storage stability, and chlorinated polyolefin used for coatings. An object is to provide a binder resin composition.

  The present inventors have (a) chlorinated a polyolefin obtained by graft polymerization of 0.1 to 10% by weight with an α, β-unsaturated carboxylic acid and / or a derivative thereof in a chlorine content of 10 to 20% by weight. (B) A polyolefin obtained by graft polymerization of 0 to 10% by weight with α, β-unsaturated carboxylic acid and / or a derivative thereof, based on 100 parts by weight of the chlorinated acid-modified polyolefin, has a chlorine content of 20 to 45% by weight. By mixing 5 to 50 parts by weight of chlorinated polyolefin or chlorinated acid-modified polyolefin chlorinated in the range, solvent solubility and storage stability while maintaining adhesion to polyolefin and solvent resistance, especially gasohol resistance Has been found to be favorable, leading to the present invention.

  In general, the higher the molecular weight and the lower the chlorine content, the better the solvent resistance. On the other hand, the solvent solubility is poor and gelation occurs as soon as it is made into a solution. A feature of the present invention is that chlorinated polyolefin or chlorinated acid-modified polyolefin having a relatively high chlorine content and a low molecular weight is good in solvent resistance, but has a high molecular weight and low chlorine content. By mixing with the chlorinated acid-modified polyolefin, the solubility was improved while maintaining the solvent resistance.

  Solvent resistance is good because low molecular weight, high chlorine content chlorinated polyolefins or chlorinated acid-modified polyolefins that are easily soluble in the solvent when applied to coatings are high solubility, low chlorine content chlorinated polymers. Intricately entangled with acid-modified polyolefins at the molecular level, resulting in high molecular weight, low chlorine content chlorination to prevent elution of low molecular weight, high chlorine content chlorinated polyolefin or chlorinated acid modified polyolefin by solvent It is considered that the solvent resistance of the acid-modified polyolefin is maintained. On the other hand, the solubility was improved because chlorinated polyolefins with low molecular weight, high chlorine content, or chlorinated acid modified polyolefins that are easily soluble in solvents, polymers that are difficult to dissolve in solvents, and chlorinated with low chlorine content. It is thought that it assists the solvation formation of acid-modified polyolefin.

  Examples of the polyolefin that is a raw material of the present invention include crystalline polypropylene and propylene-α-olefin copolymer. Crystalline polypropylene is isotactic polypropylene, and those having a weight average molecular weight of 10,000 to 300,000 can be used. The propylene-α-olefin copolymer is a copolymer of propylene as a main component and an α-olefin copolymerized therewith, 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, 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 lowered, and if it exceeds 98 mol%, the flexibility of the coating film is deteriorated. The polyolefin may be a polyolefin polymerized by using a conventional Ziegler-Natta catalyst as a polymerization catalyst, or may be a polyolefin polymerized using a metallocene compound developed in recent years as a polymerization catalyst for polyolefins. Further, any of the above polyolefins that have been pretreated by thermal degradation can be used, and crystalline polypropylene, propylene-α-olefin copolymer, or those thermally degraded, each alone or in combination. You may mix and use above.

  The chlorinated polyolefin or acid-modified chlorinated polyolefin of the present invention refers to the former by introducing chlorine into the polyolefin resin, and the latter to the polyolefin resin by α, β-unsaturated carboxylic acid and / or a derivative thereof, and Although it can be obtained by introducing chlorine, it can be produced by the following method.

  In an acid-modified chlorinated polyolefin, first, α, β-unsaturated carboxylic acid and / or a derivative thereof are graft-copolymerized onto a polyolefin resin. The method is to heat and melt the polyolefin to a melting point or higher in the presence of a radical generator. And the like (melting method) and the method of dissolving the polyolefin in an organic solvent and then reacting by heating and stirring in the presence of a radical generator (solution method). In the case of the melting method, a Banbury mixer, a kneader, an extruder or the like is used and heated and melted at a temperature of not lower than the melting point and not higher than 300 ° C., so that there is an advantage that the operation is simple and the reaction can be performed in a short time. On the other hand, in the solution method, it is preferable to use an aromatic solvent such as toluene or xylene as a reaction solvent. The reaction temperature is 100 to 180 ° C., and there is a feature that a uniform graft polymer can be obtained with few side reactions.

  Examples of the organic peroxide compound used in the graft reaction of α, β-unsaturated carboxylic acid anhydride include di-t-butyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, and benzoyl peroxide. Oxide, dilauryl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, 1,1-bis (t-butylperoxy) -3,5,5-trimethylcyclohexane, 1,1-bis (t-butyl) Peroxy) -cyclohexane, cyclohexanone peroxide, t-butylperoxybenzoate, t-butylperoxyisobutyrate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxy-2 -Ethylhexanoate, t-butylperoxyisopropyl Examples include carbonate and cumyl peroxyoctoate.

  Examples of the α, β-unsaturated carboxylic acid and / or derivative thereof which are graft copolymerized with the polyolefin resin include maleic acid, maleic anhydride, fumaric acid, citraconic acid, citraconic anhydride, mesaconic acid, itaconic acid, anhydrous Itaconic acid, aconitic acid, aconitic anhydride, hymic anhydride and the like can be exemplified, but maleic anhydride is most suitable in consideration of grafting property to polyolefin resin. The amount of α, β-unsaturated carboxylic acid and / or derivative thereof introduced by graft copolymerization is a main component. (A) The chlorinated acid-modified polyolefin in claim 1 is 0.1 to 10% by weight. Optimum, preferably 1-8% by weight. If the amount is less than 0.1 part by weight, sufficient adhesion between the obtained primer composition and the top coat cannot be obtained, and if it exceeds 10% by weight, gelation occurs during chlorination. On the other hand, the amount of (b) chlorinated polyolefin or chlorinated acid-modified polyolefin used in combination is optimally 0 to 10% by weight, preferably 0 to 5% by weight. If it exceeds 10% by weight, gelation occurs during chlorination.

  The chlorination reaction performed after the acid modification or without performing the acid modification on the polyolefin resin described above is performed under ultraviolet irradiation after dissolving the acid-modified polyolefin resin or the polyolefin resin in a chlorine-based solvent such as chloroform. Alternatively, it is carried out by blowing chlorine gas in the temperature range of 50 to 140 ° C. under normal pressure or under pressure in the presence or absence of a catalyst. The chlorine content to be introduced by the chlorination reaction is the main component, and (a) the chlorinated acid-modified polyolefin in claim 1 is optimally 10 to 20% by weight, preferably 13 to 18% by weight. When it is less than 10% by weight, the solvent solubility cannot be improved even when used in combination with (b) as a chlorinated polyolefin-based binder resin composition, and when it exceeds 20% by weight, the solvent resistance of (a) chlorinated acid-modified polyolefin is not improved. Properties, particularly gasohol resistance, are reduced.

  On the other hand, the introduction amount of (b) chlorinated polyolefin or chlorinated acid-modified polyolefin used in combination is optimally 20 to 45% by weight, preferably 30 to 45% by weight. If it is less than 20% by weight, the solvent solubility cannot be improved when used in combination with (a) as a chlorinated polyolefin binder resin composition. If it exceeds 45% by weight, (a) Solvent resistance, especially gasohol resistance, cannot be maintained when used together. Catalysts used for the chlorination reaction include 2,2-azobis (2-methylbutyronitrile), 2,2-azobisisobutyronitrile, 2,2-azobis in addition to the above organic peroxide compounds. Azonitriles such as (2,4-dimethylvaleronitrile) and 2,2-azobis (4-methoxy-2,4-dimethylvaleronitrile) can be used.

  The method for producing the chlorinated polyolefin-based binder resin solution composition of the present invention comprises (a) a chlorinated acid-modified polyolefin and (b) a chlorinated polyolefin or a chlorinated acid-modified polyolefin according to claim 1, After completion, the chlorinated solvent such as chloroform is distilled off under reduced pressure, and after substitution with aromatic hydrocarbon and / or alicyclic hydrocarbon and / or aliphatic hydrocarbon and / or polar solvent, solid content This can be achieved by mixing 5 to 50 parts by weight of (b) with respect to 100 parts by weight of (a), but after completion of the chlorination reaction, it is dissolved in a chlorinated solvent such as chloroform. This can also be achieved by mixing (b) at a solid content ratio of 5 to 50 parts by weight with respect to 100 parts by weight and then substituting the solvent. In addition, after solidifying the chlorinated acid-modified polyolefin or the chlorinated polyolefin by mixing (a) chlorinated acid-modified polyolefin and (b) chlorinated polyolefin or chlorinated acid-modified polyolefin, respectively, by the method shown below, It may be dissolved in a solvent.

  The solidification method of the chlorinated polyolefin composition of the present invention comprises (a) a chlorinated acid-modified polyolefin and (b) a chlorinated polyolefin or a chlorinated acid-modified polyolefin, respectively This can be achieved by distilling off the reaction solvent under reduced pressure and drying the concentrated reaction solution with a drum dryer. Also, instead of using a drum dryer, the reaction solvent is completely removed with a vented extruder equipped with a vent port for distilling off the reaction solvent under reduced pressure, and the solid material of the chlorinated polyolefin composition is extruded into a strand, and an underwater cutter. It can also be achieved by pelletizing with a water-cooled pelletizer or the like. Alternatively, instead of solidifying each independently, after the chlorination reaction is completed, in a state dissolved in a chlorine-based solvent such as chloroform, (a) 5 to 50 parts by weight of solid (b) with respect to 100 parts by weight It can also be achieved by mixing at a fractional ratio and then solidifying by the above method.

  In any case, the solid content ratio is optimally 5 to 50 parts by weight, preferably 15 to 35 parts by weight of (b) with respect to (a) 100 parts by weight. If it is less than 5 parts by weight, the solvent solubility of the obtained chlorinated polyolefin-based binder resin and the stability at low temperature are extremely poor, and if it exceeds 50 parts by weight, the solvent resistance of the obtained chlorinated polyolefin-based binder resin, In particular, gasohol resistance cannot be maintained.

  Further, the weight average molecular weight of polystyrene resin as a standard measured by gel permeation chromatography (GPC) of (a) chlorinated acid-modified polyolefin resin in claim 1 obtained is 80,000 to 150,000. Preferably there is. If it is less than 80,000, the solvent resistance when used in combination with (b) as a chlorinated polyolefin binder resin, in particular, gasohol resistance cannot be maintained, and if it exceeds 150,000, (b) Even when used in combination, solvent solubility and stability at low temperatures deteriorate.

  Moreover, it is preferable that the weight average molecular weight measured by GPC of (b) chlorinated acid modification | denaturation polyolefin or chlorinated polyolefin used together is 5,000-30,000. If it is less than 5,000, the solvent resistance at the time of using (a) together as a chlorinated polyolefin binder resin, in particular, gasohol resistance cannot be maintained, and if it exceeds 30,000, (a) is obtained as a chlorinated polyolefin binder resin. Solvent solubility when used in combination and stability at low temperatures deteriorate.

  As a method for adjusting the weight average molecular weight, it can be adjusted by using a Banbury mixer, a kneader, an extruder, or the like, and by reducing heat in the presence or absence of a radical generator at a temperature of the melting point or higher and 350 ° C. or lower. The radical generator used for the reaction can be appropriately selected from known ones, but the organic peroxides described above are particularly desirable. Alternatively, it can be adjusted by utilizing a chemical change such as β-cleavage that occurs during acid modification.

  Solvents used above include toluene, xylene as aromatic hydrocarbons, cyclohexane, methylcyclohexane, ethylcyclohexane as alicyclic hydrocarbons, n-hexane, heptane as aliphatic hydrocarbons, acetone, methylethylketone as polar solvents. Examples thereof include ketone solvents such as methyl isobutyl ketone, ester solvents such as ethyl acetate and butyl acetate, and alcohol solvents such as methanol, ethanol and isopropyl alcohol, and these can be used alone or in admixture of two or more. Further, the solid content concentration when dissolved in the solvent may be appropriately selected depending on the use, but if the solid content concentration is too high or too low, the coating workability is impaired, so the resin concentration is 5 to 35% by weight. Is preferred.

  Chlorinated polyolefins deteriorate with dehydrochlorination when exposed to ultraviolet light or high heat. When chlorinated polyolefins deteriorate due to dehydrochlorination, the coloring of the resin and physical properties such as reduced adhesion to the polyrefine base material begin, and the free hydrochloric acid causes deterioration of the working environment. It is essential. As the stabilizer, an epoxy compound or oxetane compound having an oxirane ring or an oxetane ring in the molecule, and these resins can be used. Examples of the epoxy compound include epoxidized soybean oil and epoxidized linseed oil obtained by epoxidizing a vegetable oil having a natural unsaturated group with a peracid, and unsaturated fatty acids such as oleic acid, tall oil fatty acid, soybean oil fatty acid, and the like. Epoxy fatty acid esters, epoxidized alicyclic compounds represented by epoxidized tetrahydrophthalate, condensed bisphenol A and polyhydric alcohols and epichlorohydrin, for example, bisphenol A glycidyl ether, ethylene glycol glycidyl ether, propylene glycol glycidyl ether And glycerol polyglycidyl ether and sorbitol polyglycidyl ether. 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. And monoepoxy compounds. An oxetane compound is a compound having one or more oxetane rings in one molecule. Examples of the compound having one oxetane ring include 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, and 3-ethyl-3- (phenoxymethyl) oxetane. Examples of the compound having two or more oxetane rings include 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, di [1-ethyl (3- Oxetanyl)] methyl ether, 1,4-bis [(1-ethyl-3-oxetanyl) methoxy] benzene, 1,3-bis [(1-ethyl-3-oxetanyl) methoxy] benzene, 4,4′-bis [(3-Ethyl-3-oxetanyl) methoxy] biphenyl, phenol novolac oxetane and the like can be exemplified.

  The chlorinated polyolefin-based binder resin composition of the present invention can be used as it is as a primer, paint, ink, adhesive, heat sealant, pigment, solvent, other additives, After kneading and dispersing, it can also be used as a primer, paint or ink. In addition, the binder resin alone has a well-balanced coating film property. If necessary, an alkyd resin, an acrylic resin, a polyacrylic polyol, a polyester resin, a polyester polyol, a polyurethane resin, a chlorinated polyolefin and the like can be further added. It can be used.

  The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.

  [Production Example 1] 5 parts by weight of maleic anhydride and 2 parts by weight of diculummiperoxide were mixed with 100 parts by weight of an ethylene-propylene copolymer having an ethylene content of about 3 mol% produced using a metallocene catalyst as a polymerization catalyst. And it supplied to the twin-screw extruder of L / D = 60 and (phi) = 40mm using the fixed quantity feeder. The residence time was 15 minutes, the barrel temperature was 200 ° C. (3rd to 7th barrels), and the unreacted maleic anhydride was removed by decompression at the 9th barrel, so that maleic anhydride-modified ethylene-propylene was removed. A copolymer was obtained.

  Next, 3 kg of this product was put into a glass-lined reaction kettle, 40 L (liter, hereinafter the same) chloroform was added and dissolved sufficiently at a temperature of 110 ° C. under a pressure of 0.3 MPa. 5 g of bisisobutyronitrile was added, and chlorine gas was blown in while controlling the pressure in the kettle at 0.3 MPa to obtain a reaction solution having a chlorine content of 15% by weight. Next, chloroform as a reaction solvent was distilled off with an evaporator and replaced with toluene. Epiol SB (manufactured by Nippon Oil & Fats Co., Ltd.) as a stabilizer was added to 4% of resin to obtain a chlorinated acid-modified ethylene-propylene copolymer having a solid content concentration of 20% by weight (toluene solution). The obtained chlorinated acid-modified ethylene-propylene copolymer was analyzed by gel permeation chromatography (GPC; manufactured by HLC8120GPC Tosoh Corp.). As a result, the weight average molecular weight (Mw) was 110,000.

  [Production Example 2] Chlorinated in the same manner as in Production Example 1 except that 3 kg of crystalline polypropylene having a weight average molecular weight of 20,000, 40 L of chloroform, and 5 g of azobisisobutyronitrile were collected, and the chlorine content was 30 A chlorinated polypropylene (solid content concentration: 20% by weight; toluene solution) having a weight% and Mw of 15,000 was obtained.

  [Production Example 3] Maleic anhydride is 4 parts by weight per 100 parts by weight of an ethylene-propylene copolymer having a melt index of 14 g / min (measured according to ASTM D1238-621T) and an ethylene content of 5 mol%. Then, 2 parts by weight of diwalm peroxide was mixed and fed to a twin screw extruder with L / D = 34 and φ = 40 mm using a quantitative feeder. The residence time was 10 minutes, the barrel temperature was 180 ° C. (1st barrel to 6th barrel), and the unreacted maleic anhydride was removed by reducing the pressure in the 7th barrel. A copolymer was obtained.

  Next, chlorination was performed in the same manner as in Production Example-1, except that 3 kg of this product, 40 L of chloroform, and 5 g of azobisisobutyronitrile were collected. Chlorinated acid having a chlorine content of 19% by weight and Mw of 130,000 A modified ethylene-propylene copolymer (solid content concentration 20% by weight; toluene solution) was obtained.

  [Production Example-4] 3 kg of the maleic anhydride-modified ethylene-propylene copolymer obtained in Production Example-3 and 15 L of methyl ethyl ketone (MEK) were placed in a three-necked flask equipped with a stirrer and a cooling tube for refluxing the solvent. The mixture was stirred in a water bath kept constant at 80 ° C. for 3 hours to remove low molecular weight components. After stirring, MEK was filtered and dried at 70 ° C. for 20 hours to obtain a maleic anhydride-modified ethylene-propylene copolymer from which low molecular weight components had been removed.

  Next, chlorination was performed in the same manner as in Production Example-1, except that 3 kg of this product, 40 L of chloroform, and 5 g of azobisisobutyronitrile were collected. Chlorinated acid having a chlorine content of 19% by weight and Mw of 135,000 A modified ethylene-propylene copolymer (solid content concentration 20% by weight; toluene solution) was obtained.

  [Production Example-5] A three-necked flask equipped with 5 kg of ethylene-propylene copolymer having a weight average molecular weight of 30,000 and an ethylene content of 3 mol%, equipped with a stirrer, a dropping funnel and a cooling tube for refluxing the monomer. And was completely melted in an oil bath kept constant at 180 ° C. After replacing the nitrogen in the flask for about 10 minutes, 180 g of maleic anhydride was added over about 5 minutes while stirring, and then 15 g of di-tert-butyl peroxide was dissolved in 50 mL of heptane and added from a dropping funnel. It was added over about 30 minutes. At this time, the inside of the system was kept at 180 ° C., and the reaction was further continued for 1 hour, and then unreacted maleic anhydride was removed over about 1 hour while reducing the pressure in the flask with an aspirator.

  Next, except that 3 kg of this product, 40 L of chloroform, and 5 g of azobisisobutyronitrile were collected, chlorination was carried out in the same manner as in Production Example 1, and chlorination with a chlorine content of 40% by weight and Mw of 20,000. An acid-modified ethylene-propylene copolymer (solid concentration 20% by weight; toluene solution) was obtained.

  [Production Example-6] 3 kg of propylene terpolymer having a weight average molecular weight of 100,000, ethylene content of 3 mol% and 1-butene content of 1 mol%, maleic anhydride 200 g, di-tert- Except for collecting 20 g of butyl peroxide, maleic anhydride modification was carried out in the same manner as in Production Example 4 to obtain a maleic anhydride modified propylene terpolymer.

  Next, except that 3 kg of this product, 40 L of chloroform, and 5 g of azobisisobutyronitrile were collected, chlorination was performed in the same manner as in Production Example-1, and the chlorination was 13% by weight in chlorine content and 85,000 Mw. An acid-modified propylene-based terpolymer (solid content concentration 20% by weight; toluene solution) was obtained.

  [Production Example-7] Production Example-1 except that 3 kg of ethylene-propylene copolymer having a weight average molecular weight of 35,000 and an ethylene content of 4 mol%, chloroform 40 L, and 5 g of azobisisobutyronitrile were collected. Was chlorinated in the same manner as above to obtain a chlorinated polypropylene (solid content concentration 20% by weight; toluene solution) having a chlorine content of 21% by weight and Mw of 30,000.

  [Production Example-8] Production Example except that 3 kg of crystalline polypropylene having a melt index of 18 g / min (measured according to ASTM D1238-621T), 180 g of maleic anhydride, and 20 g of di-tert-butyl peroxide are collected. Maleic anhydride modification was carried out in the same manner as in -4 to obtain maleic anhydride modified polypropylene.

  Next, except that 3 kg of this product, 40 L of chloroform, and 5 g of azobisisobutyronitrile were collected, chlorination was carried out in the same manner as in Production Example-1, and the chlorination was 21% by weight of chlorine and Mw was 60,000. An acid-modified polypropylene (solid content concentration 20% by weight; toluene solution) was obtained.

  [Production Example-9] Low molecular weight components were removed in the same manner as in Production Example-4, except that 3 kg of maleic anhydride-modified polypropylene obtained in Production Example-8 and MEK15L were collected.

  Next, except that 3 kg of this product, 30 L of chloroform, and 5 g of azobisisobutyronitrile were collected, chlorination was performed in the same manner as in Production Example-1, and chlorination with a chlorine content of 21% by weight and Mw of 63,000. An acid-modified polypropylene (solid content concentration 20% by weight; toluene solution) was obtained.

  The contents of the chlorinated acid-modified polyolefin and the chlorinated polyolefin obtained in Production Examples-1 to 9 are summarized in Table 1.

［実施例−１〜３］ 製造例−１で得た固形分２０重量％の塩素化酸変性エチレン−プロピレン共重合物トルエン溶液１００重量部に対し、製造例−２で得た固形分２０重量％の塩素化ポリプロピレントルエン溶液を１０重量部混合（実施例−１；固形分比；１００対１０）することにより、塩素化ポリオレフィン系樹脂組成物のトルエン溶液を得た（固形分２０重量％）。同様に製造例−５で得た塩素化酸変性エチレン−プロピレン共重合体、及び製造例−７で得た塩素化エチレン−プロピレン共重合体を、それぞれ４０重量部（実施例−２；固形分比；１００対４０）及び２５重量部（実施例−３；固形分比；１００対２５）混合することにより、塩素化ポリオレフィン系樹脂組成物の２０重量％トルエン溶液をそれぞれ得た。

[Examples 1-3] The solid content of 20 wt% obtained in Production Example-2 with respect to 100 parts by weight of the chlorinated acid-modified ethylene-propylene copolymer toluene solution having a solid content of 20 wt% obtained in Production Example-1. % Of chlorinated polypropylene toluene solution was mixed with 10 parts by weight (Example-1; solid content ratio: 100 to 10) to obtain a toluene solution of a chlorinated polyolefin resin composition (solid content 20% by weight) . Similarly, 40 parts by weight of each of the chlorinated acid-modified ethylene-propylene copolymer obtained in Production Example-5 and the chlorinated ethylene-propylene copolymer obtained in Production Example-7 (Example-2; solid content) Ratio: 100 to 40) and 25 parts by weight (Example-3; solid content ratio: 100 to 25) were mixed to obtain a 20 wt% toluene solution of the chlorinated polyolefin resin composition, respectively.

  [Examples 4 to 6] The solid content of 20% by weight obtained in Production Example-2 with respect to 100 parts by weight of the chlorinated acid-modified ethylene-propylene copolymer toluene solution having a solid content of 20% by weight obtained in Production Example-3. A toluene solution of a chlorinated polyolefin resin composition was obtained (solid content 20 wt%) by mixing 10 parts by weight of a 10% chlorinated polypropylene toluene solution (Example-4; solid content ratio; 100 to 10). . Similarly, 40 parts by weight of each of the chlorinated acid-modified ethylene-propylene copolymer obtained in Production Example-5 and the chlorinated ethylene-propylene copolymer obtained in Production Example-7 (Example-5; solid content ratio) 100 to 40) and 25 parts by weight (Example-6; solid content ratio; 100 to 25) were mixed to obtain a 20 wt% toluene solution of the chlorinated polyolefin resin composition, respectively.

  [Examples 7 to 9] Solid content 20 obtained in Production Example-2 with respect to 100 parts by weight of the chlorinated acid-modified propylene terpolymer toluene solution having a solid content of 20% by weight obtained in Production Example-6. A toluene solution of a chlorinated polyolefin resin composition was obtained (solid content 20% by weight) by mixing 10 parts by weight of a 10% by weight chlorinated polypropylene toluene solution (Example-7; solid content ratio: 100 to 10). ). Similarly, 40 parts by weight of each of the chlorinated acid-modified ethylene-propylene copolymer obtained in Production Example-5 and the chlorinated ethylene-propylene copolymer obtained in Production Example-7 (Example-8; solid content) Ratio: 100 to 40) and 25 parts by weight (Example-9; solid content ratio: 100 to 25) were mixed to obtain a 20 wt% toluene solution of the chlorinated polyolefin resin composition, respectively.

  Table 2 shows the contents of the chlorinated polyolefin resin compositions obtained in Examples-1 to 9.

［比較例−１〜６］ 製造例−３、４、６、７、８及び９を単独で用いた場合を、それぞれ比較例−１、２、３、４、５及び６とした。

[Comparative Examples-1 to 6] The cases where Production Examples-3, 4, 6, 7, 8, and 9 were used alone were referred to as Comparative Examples-1, 2, 3, 4, 5, and 6, respectively.

  [Comparative Examples-7 to 8] 20 wt% solid content obtained in Production Example-5 with respect to 100 parts by weight of the chlorinated acid-modified ethylene-propylene copolymer toluene solution having a solid content of 20 wt% obtained in Production Example-1. % Of chlorinated acid-modified ethylene-propylene copolymer toluene solution was mixed by 80 parts by weight (Comparative Example-7; solid content ratio: 100: 80) to obtain a toluene solution of a chlorinated polyolefin resin composition. (Solid content 20% by weight). Similarly, by mixing 60 parts by weight of the chlorinated ethylene-propylene copolymer obtained in Production Example-7 (Comparative Example-8; solid content ratio; 100: 60), 20 of the chlorinated polyolefin resin composition was obtained. A weight% toluene solution was obtained.

  [Comparative Examples-9 to 10] The solid content of 20 weight% obtained in Production Example-5 with respect to 100 parts by weight of the chlorinated acid-modified ethylene-propylene copolymer toluene solution having a solid content of 20 weight% obtained in Production Example-3. A toluene solution of a chlorinated polyolefin resin composition was obtained by mixing 80 parts by weight of a chlorinated acid-modified ethylene-propylene copolymer toluene solution (Comparative Example-9; solid content ratio: 100: 80). (Solid content 20% by weight). Similarly, by mixing 60 parts by weight of the chlorinated ethylene-propylene copolymer obtained in Production Example-7 (Comparative Example-10; solid content ratio: 100 to 60), 20 of the chlorinated polyolefin resin composition was obtained. A weight% toluene solution was obtained.

  [Comparative Examples 11-12] The solid content 20 obtained in Production Example-5 with respect to 100 parts by weight of the chlorinated acid-modified propylene terpolymer toluene solution having a solid content of 20% by weight obtained in Production Example-6. A toluene solution of a chlorinated polyolefin resin composition was obtained by mixing 80 parts by weight of a chlorinated acid-modified ethylene-propylene copolymer toluene solution by weight (Comparative Example-11; solid content ratio: 100 to 80). (20 wt% solid content). Similarly, by mixing 60 parts by weight of the chlorinated ethylene-propylene copolymer obtained in Production Example-7 (Comparative Example-12; solid content ratio; 100 to 60), 20 of the chlorinated polyolefin resin composition was obtained. A weight% toluene solution was obtained.

  The contents of the chlorinated polyolefin resin compositions obtained in Comparative Examples 1 to 12 are shown in Table 3.

〈プライマー試験〉
実施例１〜９及び比較例１〜１２より得られた樹脂溶液（固形分２０重量％）１００ｇと二酸化チタン２０ｇをサンドミルで３時間混練した後、Ｎｏ．４フォードカップで１３〜１５秒／２０℃になるようにキシレンで粘度調製を行い、超高剛性ポリプロピレン（ＰＰ）板（ＴＸ−９３３Ａ、三菱化学（株）製）にエアー式スプレーガンによって膜厚が約１０μｍになるように塗装した。次に、２液硬化型ウレタン塗料を塗装した（膜厚約３０μｍ）。８０℃で３０分間乾燥し、室温にて４８時間放置し物性試験を行った。プライマー試験結果を表４に示す。

<Primer test>
After kneading 100 g of the resin solutions (solid content 20 wt%) obtained from Examples 1 to 9 and Comparative Examples 1 to 12 with 20 g of titanium dioxide in a sand mill, Viscosity was adjusted with xylene so that it would be 13 to 15 seconds / 20 ° C. in a 4 Ford cup, and the film thickness was applied to an ultra-high rigidity polypropylene (PP) plate (TX-933A, manufactured by Mitsubishi Chemical Corporation) with an air spray gun. Was coated to be 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 48 hours to conduct a physical property test. The primer test results are shown in Table 4.

〔試験方法〕
・付着性：
塗面上に１ｍｍ間隔で素地に達する１００個の碁盤目を作り、その上にセロハン粘着テープを密着させて１８０度方向に引き剥がし、塗膜の残存する碁盤目の数を数えた。
・耐ガソホール性：
塗装板をレギュラーガソリン／エタノール＝９／１（ｖ／ｖ）に１２０分間浸漬し、塗膜の状態を観察した。
・耐水性：
４０℃の温水に塗装板を２４０時間浸漬し、塗膜の状態と付着性を調べた。

〔Test method〕
・ Adhesiveness:
On the coated surface, 100 grids reaching the substrate at 1 mm intervals were made, and a cellophane adhesive tape was closely adhered to the coated surface and peeled in the direction of 180 degrees, and the number of grids remaining on the coating film was counted.
-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.
·water resistant:
The coated plate was immersed in warm water at 40 ° C. for 240 hours, and the state and adhesion of the coating film were examined.

Good: no peeling at all, poor: peeling occurred (low temperature stability test)
When the resin solutions (solid content 20% by weight) obtained in Examples 1 to 9 and Comparative Examples 1 to 12 were stored in an atmosphere of 20 ° C., −5 ° C., and −10 ° C., the solution state of each solution (low temperature Table 5 shows the stability.

〈塗料試験〉
実施例１〜９、比較例１〜１２で得られた溶液樹脂（固形分２０重量％）を、バインダー樹脂として以下の配合で塗料へ調整した。

<Paint test>
The solution resins (solid content 20% by weight) obtained in Examples 1 to 9 and Comparative Examples 1 to 12 were prepared as binder resins in the following formulation.

Binder resin (20% toluene solution): 100 parts by weight Alkyd resin (Phthalkid V904 Hitachi Chemical): 15 〃
TiO2: 5 〃
Carbon black: 1 〃
Petal: 2 〃
Talc: 15 〃
Silica matting agent: 5 〃
After the composition was kneaded in a sand mill for about 1 hour, It was prepared by diluting with toluene so that the viscosity was 12 to 13 seconds / 20 ° C. in a 4 Ford cup. Each paint was spray-applied to an ultra-high rigidity PP plate so that the dry film thickness was about 30 μm, dried at room temperature for 30 minutes, and then baked at 80 ° C. for 30 minutes. The test piece was left at room temperature for 48 hours, and the same test as the primer test was performed. The results are shown in Table 6.

Claims (4)

(A) A polyolefin obtained by graft polymerization of 0.1 to 10% by weight with an α, β-unsaturated carboxylic acid and / or a derivative thereof is chlorinated in a chlorine content of 10 to 20% by weight , and the weight average molecular weight is 100 parts by weight of chlorinated acid-modified polyolefin of 80,000 to 150,000 , (b) polyolefin containing 0-10% by weight graft polymerization with α, β-unsaturated carboxylic acid and / or derivative thereof, containing chlorine Good solvent resistance by mixing 5 to 50 parts by weight of chlorinated polyolefin or chlorinated acid-modified polyolefin having a weight average molecular weight of 5,000 to 30,000 chlorinated at a rate of 20 to 45% by weight Chlorinated polyolefin binder resin composition. As an active ingredient a chlorinated polyolefin binder resin composition according to claim 1, a primer for polyolefin films, sheets or moldings. As an active ingredient a chlorinated polyolefin binder resin composition according to claim 1, polyolefin films, sheets or coatings for moldings. (A) A polyolefin produced by graft polymerization of 0.1 to 10% by weight of an α, β-unsaturated carboxylic acid and / or a derivative thereof using a metallocene catalyst as a polymerization catalyst, and having a chlorine content of 10 to 20% by weight. (B) α, β-unsaturated carboxylic acid and / or derivative thereof is 0 to 10 weights per 100 weight parts of chlorinated acid-modified polyolefin chlorinated with % Graft polymerized polyolefin produced using a metallocene catalyst as a polymerization catalyst, chlorinated in a chlorine content of 20 to 45% by weight, chlorinated polyolefin or chlorinated with a weight average molecular weight of 5,000 to 30,000 A chlorinated polyolefin binder resin composition having good solvent resistance, comprising 5 to 50 parts by weight of an acid-modified polyolefin.