WO2013121871A1 - Composition de polymère contenant du propylène chloré modifiable par oxydation et son procédé de fabrication - Google Patents

Composition de polymère contenant du propylène chloré modifiable par oxydation et son procédé de fabrication Download PDF

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WO2013121871A1
WO2013121871A1 PCT/JP2013/051814 JP2013051814W WO2013121871A1 WO 2013121871 A1 WO2013121871 A1 WO 2013121871A1 JP 2013051814 W JP2013051814 W JP 2013051814W WO 2013121871 A1 WO2013121871 A1 WO 2013121871A1
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oxidation
propylene
modified
chlorinated
polypropylene
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PCT/JP2013/051814
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Japanese (ja)
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賢一郎 磯本
忠宣 船坂
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東洋紡株式会社
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Priority to KR1020147015728A priority Critical patent/KR20140125347A/ko
Priority to CN201380004636.7A priority patent/CN104024282A/zh
Publication of WO2013121871A1 publication Critical patent/WO2013121871A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/06—Oxidation

Definitions

  • the present invention relates to an oxidatively modified chlorinated propylene-containing polymer composition from which polar component impurities and low molecular weight components are removed, and a method for producing the same.
  • Typical chlorinated propylene-containing polymers are chlorinated polypropylene and chlorinated propylene- ⁇ -olefin copolymers. These are adhesive components (binder components) for polypropylene substrates, such as paints, inks and adhesives. Widely used in applications such as agents.
  • the oxidatively modified chlorinated polypropylene is mainly used as an adhesion-imparting agent for an OPP film of an ink binder blended in polyurethane, which can be used for various materials, and is a useful compound.
  • oxidation-modified chlorination method for a propylene-containing polymer for example, polypropylene
  • a chlorinated solvent for example, chloroform
  • the method of dissolving the oxidatively modified propylene-containing polymer obtained by oxidizing polypropylene in advance in only the chlorinated solvent listed in 2) above, chlorinating, and then replacing the solvent with another solvent as it is is a radical generator during chlorination. Since it is necessary to use (for example, ultraviolet rays, organic peroxides, azo compounds, etc.), the associated apparatus, temperature management, and pressure management are indispensable. Specifically, a dedicated device is required for ultraviolet irradiation. In addition, when using an organic peroxide or an azo compound, temperature control in consideration of the half-life temperature is necessary, and it is necessary to add continuously or intermittently until chlorine gas is thermally decomposed. .
  • JP-A-48-8856 (particularly the above 1)) JP-A-1-301703 (particularly 2)
  • the present invention has a step of chlorinating an oxidatively-modified propylene-containing polymer with a mixed solvent of chloroform and water, so that it is less colored and has compatibility with polyurethane resins from which polar component impurities and low molecular weight components have been removed.
  • the present inventors have found that the above object can be achieved when the following oxidation-modified chlorinated propylene-containing polymer composition is adopted, and the present invention is completed. It came.
  • the present invention relates to the following oxidation-modified chlorinated propylene-containing polymer composition and a method for producing the same. 1. It is obtained by dispersing at least one oxidation-modified propylene-containing polymer of oxidation-modified polypropylene and an oxidation-modified propylene- ⁇ -olefin copolymer in a mixture containing chloroform and water and chlorinating at a temperature of 130 ° C. or less. Oxidation-modified chlorinated propylene-containing polymer composition. 2. Item 2.
  • composition according to Item 1 wherein the oxidation-modified polypropylene and the oxidation-modified propylene- ⁇ -olefin copolymer are isotactic polymers. 3.
  • Item 3. The composition according to Item 1 or 2, wherein the oxidation-modified polypropylene and the oxidation-modified propylene- ⁇ -olefin copolymer are synthesized using a metallocene catalyst. 4).
  • Item 4. The composition according to any one of Items 1 to 3, wherein the oxidation-modified degree of the oxidation-modified polypropylene and the oxidation-modified propylene- ⁇ -olefin copolymer is an acid value of 5 mgKOH / g or more. 5.
  • Item 6 The composition according to any one of Items 1 to 5, wherein a water-insoluble epoxy group-containing compound is added to the resulting chlorination reaction solution after chlorination of the oxidation-modified propylene-containing polymer. 7).
  • a binder for printing ink comprising the composition according to any one of items 1 to 6 as a main component. 8).
  • Oxidation-modified chlorination in which at least one oxidation-modified propylene-containing polymer of oxidation-modified polypropylene and an oxidation-modified propylene- ⁇ -olefin copolymer is dispersed in a mixture containing chloroform and water and chlorinated at a temperature of 130 ° C. or lower.
  • a method for producing a propylene-containing polymer composition in which at least one oxidation-modified propylene-containing polymer of oxidation-modified polypropylene and an oxidation-modified propylene- ⁇ -olefin copolymer is dispersed in a mixture containing chloroform and water and chlorinated at a temperature of 130 ° C. or lower.
  • the present invention removes impurities of a chlorinated polar component and low molecular weight components into an aqueous phase and an emulsified phase by using a mixed solvent of chloroform and water when chlorinating an oxidation-modified propylene-containing polymer.
  • a low-colored and high-quality oxidatively modified chlorinated propylene-containing copolymer can be obtained.
  • the oxidatively modified chlorinated propylene-containing copolymer obtained in the present invention is excellent in compatibility with a polyurethane resin, excellent in adhesion to various materials (particularly OPP) of an ink binder blended in polyurethane, and The target product can be produced efficiently.
  • At least one oxidation-modified propylene-containing polymer of oxidation-modified polypropylene and an oxidation-modified propylene- ⁇ -olefin copolymer is dispersed in a mixture containing chloroform and water to obtain a dispersion, and then sealed. It is preferable that the oxidation-modified propylene-containing polymer is chlorinated by introducing chlorine gas into the dispersion while heating the dispersion at a temperature of 130 ° C. or lower.
  • the oxidatively modified chlorinated propylene-containing polymer is dissolved in the chloroform-containing phase, and the by-produced hydrogen chloride is dissolved in water to become a hydrochloric acid-containing phase.
  • the reaction solution is allowed to stand to separate and remove the hydrochloric acid-containing phase.
  • an emulsified phase containing impurities of polar components and low molecular weight oxidatively modified chlorinated propylene may be generated at the interface between the chloroform-containing phase and the hydrochloric acid-containing phase, it is preferably removed together with the hydrochloric acid-containing phase.
  • a water-insoluble epoxy group-containing compound to the reaction solution after chlorination because the chloroform-containing phase and the hydrochloric acid-containing phase can be separated in a short time.
  • An oxidatively modified chlorinated propylene-containing polymer composition obtained by removing a hydrochloric acid-containing phase and an emulsified phase to obtain a chloroform-containing phase and then distilling off the chloroform from the chloroform-containing phase, and a method for producing the same .
  • composition of the present invention having the above characteristics is obtained by fractionating only the chloroform-containing phase excluding the hydrochloric acid-containing phase and the emulsified phase, so that the low-color and high-quality oxidative modification does not contain polar impurities or low-molecular weight components.
  • a chlorinated propylene-containing polymer composition can be obtained.
  • the propylene-containing polymer at least one of polypropylene and a propylene- ⁇ -olefin copolymer is used.
  • the propylene- ⁇ -olefin copolymer is a copolymer in which ⁇ -olefin is copolymerized mainly with propylene.
  • ⁇ -olefin for example, one kind or several kinds of ethylene, 1-butene, 1-heptene, 1-octene and the like can be used. Of these ⁇ -olefins, ethylene and 1-butene are preferred.
  • the ratio of the propylene component to the ⁇ -olefin component of the propylene- ⁇ -olefin copolymer is not limited, but the propylene component is preferably 60 mol% or more, and more preferably 90 mol% or more.
  • Both the polypropylene and the propylene- ⁇ -olefin copolymer are preferably isotactic polymers.
  • Isotactic polymers exhibit a relatively high degree of crystallinity, and crystallinity can be controlled by chlorination.
  • the propylene-containing polymer is provided with solubility in various organic solvents, it can be crystallized by increasing the chlorine content.
  • the solubility in an organic solvent is lowered, but high crystallinity can be maintained by setting the chlorine content low.
  • the chlorine content is not limited to this range, but is preferably 25 to 45% by weight, more preferably 30 to 40% by weight in the present invention.
  • the solubility in an ester solvent or a ketone solvent used as a solvent for printing ink is poor. If the chlorine content exceeds 45% by weight, a polypropylene substrate such as an OPP film is used. Adhesiveness to is poor. Polypropylene and propylene- ⁇ -olefin copolymers synthesized using a metallocene catalyst are preferable because they have uniform crystallinity and excellent solubility in solvents.
  • At least one oxidation-modified propylene-containing polymer of oxidation-modified polypropylene and an oxidation-modified propylene- ⁇ -olefin copolymer is used as a raw material for performing the chlorination reaction.
  • the oxidative modification is carried out by a known method by hot melting or dissolving in a solvent in at least one propylene-containing polymer of polypropylene and propylene- ⁇ -olefin copolymer, and performing thermal degradation while introducing oxygen.
  • An oxygen-containing group is introduced into the ⁇ -olefin molecule.
  • the oxygen-containing groups such as carbonyl group, carboxyl group, and hydroxyl group are mixed in the propylene or ⁇ -olefin molecule.
  • compatibility with the polyurethane for ink becomes good.
  • peroxides such as benzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, tert-butyl hydroperoxide, azobisisobutyronitrile, azobis It can be modified more quickly than the use of azo compounds such as isopropionitrile.
  • the oxidation-modified polypropylene and the oxidation-modified propylene- ⁇ -olefin copolymer may be used as the oxidation-modified polypropylene and the oxidation-modified propylene- ⁇ -olefin copolymer.
  • the degree of oxidative modification is not limited to such a range, but in the present invention, the acid value according to ASTM D-1386 is used as an index, and the value is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more.
  • the above-mentioned oxidation-modified propylene-containing polymer is dispersed in a mixture containing chloroform and water to obtain a dispersion.
  • the main purpose of use of water is to absorb hydrogen chloride produced as a by-product during chlorination, to simplify the production process of the target product, and to polar impurities and low molecular weight oxidative modification after chlorination.
  • Most of the chlorinated propylene is dissolved and removed, and the amount of water used may be set according to the amount of by-produced hydrogen chloride.
  • the hydrochloric acid concentration in the hydrochloric acid-containing phase after the reaction is 10 Set to ⁇ 30% by weight.
  • the weight ratio of the oxidatively modified propylene-containing polymer, chloroform and water in the dispersion is not limited, but is preferably 1: 8 to 20: 0.8 to 2, and 1: 9 to 15: 0.9 to 1.8 is more preferable.
  • the oxidatively modified propylene-containing polymer is chlorinated by introducing chlorine gas into the dispersion while heating the dispersion at a temperature of 130 ° C. or lower in a sealed state.
  • the dispersion is heated at a temperature of 130 ° C. or lower under hermetic conditions.
  • the temperature is not limited as long as it is within the above-mentioned range, but the maximum reached temperature during chlorination is preferably 110 to 130 ° C, more preferably 115 to 125 ° C, in order to ensure the solubility of the oxidation-modified propylene-containing polymer. .
  • the dispersion contains water
  • oxygen is stably and efficiently oxidized by introducing chlorine to continuously generate oxygen radicals (O.) in the reaction system by the following reaction.
  • the modified propylene-containing polymer can be chlorinated. Specifically, hypochlorous acid is first produced by the reaction of water or hydroxide ions with chlorine, and then oxygen radicals are produced by the decomposition of hypochlorous acid.
  • the amount of chlorine gas introduced is not limited, but the chlorine content of the chlorinated oxidatively modified propylene-containing polymer is preferably 25 to 45% by weight.
  • the chlorine content is not limited to this range, but is preferably 25 to 45% by weight, more preferably 30 to 40% by weight in the present invention.
  • Hydrogen chloride is by-produced by the introduction of chlorine gas, but since most of the hydrogen chloride is dissolved in water, excessive pressure control or the like is not necessary in the production method of the present invention.
  • chlorination is performed in a sealed state, it is preferable in that a large chlorine utilization rate can be secured as compared with chlorination using only a conventional chlorinated solvent.
  • the weight average molecular weight of the chlorinated oxidation-modified propylene-containing polymer obtained in the present invention is not limited, but is preferably 3000 to 100,000. If it is less than 3000, the cohesive force becomes weak and the adhesion to the polypropylene substrate may be poor. On the other hand, when it exceeds 100,000, the compatibility with polyurethane and the dissolved state in a solvent may be deteriorated.
  • a more preferred weight average molecular weight is 10,000 to 50,000.
  • the obtained chlorination reaction solution is allowed to stand, and then the chloroform-containing phase is collected.
  • the aqueous phase (hydrochloric acid-containing phase) and the emulsified phase near the interface contain impurities of chlorinated polar components and low molecular weight oxidatively modified chlorinated polypropylene.
  • the content of chlorinated polar component impurities or low molecular weight oxidation-modified chlorinated polypropylene increases, coloring tends to occur, resulting in poor adhesion and blocking resistance necessary for ink applications. Therefore, by removing only the chloroform-containing phase, excluding the hydrochloric acid-containing phase and the emulsified phase at the interface, it is possible to efficiently obtain an object with little coloration.
  • the chloroform-containing phase and the hydrochloric acid-containing phase can be phase-separated in a short time.
  • the water-insoluble epoxy group-containing compound preferably has an action of aggregating fine water particles in the reaction solution (action as an emulsion breaker).
  • phenyl glycidyl ether examples include monoepoxy compounds such as -butylphenyl glycidyl ether, 4-chlorophenyl glycidyl ether, 4-methoxyphenyl glycidyl ether, 2-biphenyl glycidyl ether, 1-naphthyl glycidyl ether, 2-ethylhexyl glycidyl ether, and allyl glycidyl ether.
  • monoepoxy compounds such as -butylphenyl glycidyl ether, 4-chlorophenyl glycidyl ether, 4-methoxyphenyl glycidyl ether, 2-biphenyl glycidyl ether, 1-naphthyl glycidyl ether, 2-ethylhexyl glycidyl ether, and allyl glycidyl ether
  • bisphenol A type epoxy compounds obtained by polycondensation reaction of bisphenol A and epichlorohydrin in various proportions bisphenol F type epoxy compounds obtained by polycondensation reaction of bisphenol F and epichlorohydrin in various proportions, unsaturated Examples thereof include epoxidized soybean oil and epoxidized linseed oil obtained by reacting a vegetable oil having a group with a peracid such as peracetic acid.
  • polyfunctional epoxy compounds such as hydrogenated bisphenol A diglycidyl ether, diglycidyl o-phthalate, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether and the like are also exemplified.
  • the addition amount of the water-insoluble epoxy group-containing compound is not limited, but is preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the chlorinated oxidation-modified propylene-containing polymer in the reaction solution, and 0.3 More preferred is ⁇ 2 parts by weight.
  • the standing time after the addition of the epoxy group-containing compound is not limited as long as the phase separation can be sufficiently performed. In the present invention, it is preferably 2 hours or less, and more preferably 1 hour or less. As described above, when a water-insoluble epoxy group-containing compound is added, phase separation can be performed in a significantly short time, so that the target product can be produced efficiently.
  • a chlorinated oxidation-modified propylene-containing polymer is included in the chloroform-containing phase, and a known fractionation method can be used as the fractionation method.
  • Chlorinated oxidatively modified propylene-containing polymer is obtained by distilling off chloroform from the chloroform-containing phase.
  • the temperature and pressure conditions for distilling off the chloroform from the chloroform-containing phase are not limited, but it is preferable in terms of efficiency to gradually reduce the pressure from the state above the boiling point (61 ° C.) of chloroform. 70 ° C. is preferable, and 25 to 65 ° C. is more preferable.
  • the pressure condition is preferably ⁇ 0.09 to 0.08 MPa, more preferably ⁇ 0.08 to 0.05 MPa.
  • the target composition can be obtained by the following following process 1 or process 2.
  • Step 1 is a step of feeding a high-concentration chloroform solution of a chlorinated oxidation-modified propylene-containing polymer to an extruder and granulating and removing the chlorinated oxidation-modified propylene-containing polymer while distilling off the remaining chloroform. It is.
  • the temperature condition and pressure condition at the time of extrusion are not limited, but feeding from a high temperature and low vacuum state gradually to a low temperature and high vacuum state is preferable in terms of the efficiency of the production method, and the extruder temperature is preferably 50 to 150 ° C. More preferred is ⁇ 140 ° C.
  • the extruder pressure condition is preferably ⁇ 0.099 to ⁇ 0.080 MPa, more preferably ⁇ 0.099 to ⁇ 0.090 MPa.
  • the obtained solid material of the oxidatively modified chlorinated propylene-containing polymer can be used after being dissolved in a desired solvent.
  • Step 2 is a step of adding a desired solvent to a high-concentration chloroform solution of a chlorinated oxidation-modified propylene-containing polymer and dissolving it, and distilling off the chloroform and the solvent in the same manner as the above-mentioned chloroform distillation conditions. The same operation is repeated until the residual amount of chloroform substantially disappears, and then dissolved in a desired solvent to obtain an oxidatively modified chlorinated propylene-containing copolymer solution.
  • aromatic hydrocarbons such as toluene and xylene having good solubility are convenient, but non-tolueneization tends to be required in ink applications.
  • -Ester solvents such as propyl and isopropyl acetate
  • ketone solvents such as acetone and methyl ethyl ketone
  • alicyclic hydrocarbons such as cyclohexane and methylcyclohexane can be used.
  • ethyl acetate, n-propyl acetate, methyl ethyl ketone, and methylcyclohexane are preferable.
  • the oxidatively modified chlorinated propylene-containing polymer obtained as described above is less colored, and the impurities of polar components and the content of low molecular weight components are also low. Therefore, it can be used as a composition having excellent compatibility with polyurethane resins and excellent adhesion to various materials (especially OPP) of ink binders blended in polyurethane.
  • Example 1 In a 5 L glass-lined reaction can, 400 g of GMT-2520 (manufactured by Gong Myoung Technologies Co., melt viscosity 90 mPa ⁇ s at 180 ° C., acid value 20 KOH mg / g, melting point 157 ° C.), which is an oxidized modified isotactic polypropylene, 3900 g of chloroform and 630 g of deionized water were added and sealed, and the inside of the reaction vessel was heated while stirring and dispersing the liquid in the reaction vessel. When the temperature inside the can reached 110 ° C., chlorine was introduced at a rate of 180 g / hour, and the temperature inside the can was maintained at 100 to 120 ° C.
  • GMT-2520 manufactured by Gong Myoung Technologies Co., melt viscosity 90 mPa ⁇ s at 180 ° C., acid value 20 KOH mg / g, melting point 157 ° C.
  • the introduction of chlorine was stopped at the stage where 485 g of chlorine was introduced 2 hours and 40 minutes after the start of chlorine introduction, and the stirring of the liquid was continued for 10 minutes.
  • the temperature inside the can was kept at 80 to 100 ° C. and allowed to stand for 3 hours, it separated into an upper hydrochloric acid-containing phase and a lower chloroform solution, and an emulsified phase was slightly observed between the upper and lower phases. .
  • the upper and emulsified phases contained chlorinated polar component impurities.
  • ethyl acetate After adding ethyl acetate and dissolving, repeating the same process of distilling off the mixed solution of chloroform and ethyl acetate twice, ethyl acetate was added and dissolved so that the solid content was 29% by weight.
  • 16 g of p-tert-butylphenyl glycidyl ether was added to obtain an ethyl acetate solution having a solid content of 30% by weight of oxidatively modified chlorinated polypropylene.
  • the obtained oxidatively modified chlorinated polypropylene had a chlorine content of 34.5% by weight, an acid value of 15 KOHmg / g, a weight average molecular weight of 16000, and a Gardner color number of the solution of 2.
  • Example 2 is the same as Example 1 except that the amount of deionized water charged is 820 g, 635 g of chlorine is introduced over 3 hours and 40 minutes, and the amount of stabilizer p-tert-butylphenylglycidyl ether is 18 g. The same operation was performed.
  • the obtained oxidatively modified chlorinated polypropylene had a chlorine content of 44.8% by weight, an acid value of 14 KOHmg / g, a weight average molecular weight of 17000, and a Gardner color number of the solution of 2.
  • Example 3 is the same as Example 1 except that the amount of deionized water charged is 450 g, 350 g of chlorine is introduced over 2 hours, and the amount of stabilizer p-tert-butylphenylglycidyl ether is 15 g. The operation was performed. The obtained oxidatively modified chlorinated polypropylene had a chlorine content of 25.4% by weight, an acid value of 16 KOHmg / g, a weight average molecular weight of 15,000, and a Gardner color number of 2.
  • the obtained oxide-modified propylene ethylene copolymer had a melt viscosity of 220 mPa ⁇ s at 180 ° C., an acid value of 7 KOH mg / g, and a melting point of 134 ° C.
  • Example 4 In Example 1, the same operation as in Example 1 was performed except that the oxidation-modified propylene ethylene copolymer synthesized in Prototype Example 1 was used.
  • the obtained oxidatively modified chlorinated polypropylene had a chlorine content of 34.7% by weight, an acid value of 5 KOH mg / g, a weight average molecular weight of 21,000, and a Gardner color number of the solution of 2.
  • Example 5 In Example 2, the same operation as in Example 2 was performed except that the oxidation-modified propylene ethylene copolymer synthesized in Prototype Example 1 was used.
  • the obtained oxidatively modified chlorinated polypropylene had a chlorine content of 44.9% by weight, an acid value of 5 KOH mg / g, a weight average molecular weight of 22000, and a Gardner color number of the solution of 2.
  • Example 6 In Example 1, after the introduction of chlorine, the liquid was continuously stirred for 10 minutes, and then 2.4 g of p-tert-butylphenylglycidyl ether, which is a water-insoluble epoxy group-containing compound, was added. After the stirring was stopped, the temperature inside the can was kept at 80 to 100 ° C. and left to stand for 1 hour. As a result, the upper hydrochloric acid-containing phase and the lower chloroform-containing phase were clearly separated. The other operations were the same as in Example 1.
  • the obtained oxidatively modified chlorinated polypropylene had a chlorine content of 34.5% by weight, an acid value of 15 KOHmg / g, a weight average molecular weight of 16000, and a Gardner color number of the solution of 2.
  • Comparative Example 1 400 g of GMT-2520 used in Examples 1 to 3 and 4600 g of chloroform were sealed in a 5 L glass-lined reaction can, and the inside of the reaction can was heated while stirring the liquid in the reaction can. When the temperature inside the can reached 110 ° C., chlorine was introduced at a rate of 180 g / hour, and the temperature inside the can was maintained at 100 to 120 ° C. While controlling the pressure in the reaction can, every time the pressure exceeded 0.6 MPa, the pressure in the reaction can was released and lowered to 0.5 MPa. The released gas was absorbed in 1 L of 19% by weight sodium hydroxide aqueous solution.
  • the introduction of chlorine was stopped at the stage where 515 g of chlorine was introduced after 2 hours and 50 minutes had elapsed from the start of the introduction of chlorine, and the stirring of the liquid was continued for 10 minutes.
  • the reaction solution was transferred to a 4 L glass-lined reaction can, and 3600 g of chloroform was distilled off under conditions of a can internal temperature of 35 to 75 ° C. and a can internal pressure of ⁇ 0.08 to 0.08 MPa. Subsequently, 800 g of ethyl acetate was added and dissolved at a can internal temperature of 55 to 75 ° C.
  • the mixed solution of chloroform and ethyl acetate was distilled off under the conditions of a can internal temperature of 35 to 75 ° C and a can internal pressure of -0.08 to 0.08 MPa. did.
  • ethyl acetate and dissolving After adding ethyl acetate and dissolving, repeating the same process of distilling off the mixed solution of chloroform and ethyl acetate twice, ethyl acetate was added and dissolved so that the solid content was 29% by weight.
  • 16 g of p-tert-butylphenyl glycidyl ether was added to obtain an ethyl acetate solution having a solid content of 30% by weight of oxidatively modified chlorinated polypropylene.
  • the obtained oxidatively modified chlorinated polypropylene had a chlorine content of 34.6% by weight, an acid value of 15 KOHmg / g, a weight average molecular weight of 15000, and
  • Comparative Example 2 In Comparative Example 1, the same operation as in Comparative Example 1 was performed except that the oxidation-modified propylene ethylene copolymer synthesized in Prototype Example 1 was used.
  • the obtained oxidatively modified chlorinated polypropylene had a chlorine content of 34.8% by weight, an acid value of 5 KOHmg / g, a weight average molecular weight of 20,000, and a Gardner color number of 6.
  • Comparative Example 3 In Comparative Example 1, the same operation as Comparative Example 1 was performed except that the propylene ethylene copolymer not subjected to oxidation modification used in Prototype Example 1 was used.
  • the obtained oxidatively modified chlorinated polypropylene had a chlorine content of 34.7% by weight, a weight average molecular weight of 45000, and a Gardner color number of the solution of 6.
  • Example 4 In Example 1, the same operation as in Example 1 was carried out except that the propylene ethylene copolymer not subjected to oxidative modification used in Prototype Example 1 was used.
  • the obtained oxidatively modified chlorinated polypropylene had a chlorine content of 34.7% by weight, a weight average molecular weight of 45000, and a Gardner color number of 2.
  • Compatibility Test Examples 1 to 5 and Comparative Examples 1 to 3 were prepared by using the oxidatively modified chlorinated propylene-containing polymer with a polyurethane resin for printing ink (Samprene IB-501 and Samprene IB-911, both with a solid content of 30% by weight, Sanyo Kasei Kogyo Co., Ltd.) was mixed at a solid content weight ratio of 5/95, applied to a glass plate with a bar coater No. 8, and dried at 25 ° C. for 24 hours.
  • the evaluation criteria are ⁇ clear, ⁇ slightly cloudy, and X cloudiness.
  • the results are shown in Table 1.
  • Adhesion test A mixed solution of an oxidation-modified chlorinated propylene-containing polymer and a polyurethane resin for printing ink (solid content 30 wt% solution) used in the compatibility test was mixed in the following composition to prepare an ink.
  • white pigment Ishihara Sangyo Co., Ltd. rutile titanium oxide type PF-742 was used.
  • Resin solution of Examples or Comparative Examples 35 parts by weight
  • White pigment 30 parts by weight n-propyl acetate 15 parts by weight Ethyl acetate 10 parts by weight Isopropyl alcohol 10 parts by weight
  • the resulting white ink was coated with an OPP film (biaxially stretched polypropylene, corona-treated surface, Toyobo Pyrene Film-OT P2161), PET film (biaxially stretched polyester film, corona-treated surface, Toyobo Ester Film T6140) with a # 8 bar coater. And ONY film (biaxially stretched nylon film, corona-treated surface, Toyobo Harden Film N1102). Cellophane tape (Nichiban cello tape) was applied to the coated surface, and the state of the coated surface was observed when the cellophane tape was rapidly removed. The evaluation criteria were as follows: ⁇ no peeling, ⁇ slight peeling, and most X peeling. The results are shown in Table 1.
  • the number of colors was measured according to JIS K 5600-2-1.
  • a low color and high quality oxidatively modified chlorinated propylene-containing copolymer can be obtained.
  • the oxidatively modified chlorinated propylene-containing copolymer obtained in the present invention is excellent in compatibility with a polyurethane resin, excellent in adhesion to various materials (particularly OPP) of an ink binder blended in polyurethane, and The target product can be produced efficiently.

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Abstract

L'invention concerne un procédé de fabrication avec lequel, du fait d'avoir une étape pour chlorer un polymère contenant du propylène modifiable par oxydation à l'aide d'un solvant mixte de chloroforme et d'eau, il est possible de produire plus efficacement que dans le passé une composition de polymère contenant du propylène chloré modifiable par oxydation qui manifeste peu de décoloration, ne contient pas d'impuretés de composants polarisants ou de composants de faible masse moléculaire, a une excellente compatibilité avec des résines polyuréthane et manifeste une excellente adhésion de liants d'encre contenant du polyuréthane quand elle est utilisée pour diverses matières (en particulier OPP). Au moins un polymère contenant un propylène modifiable par oxydation choisi parmi un polypropylène modifiable par oxydation et un copolymère propylène-α-oléfine modifiable par oxydation est dispersé dans un mélange contenant du chloroforme et de l'eau et chloré à une température de 130°C ou moins pour obtenir une composition de polymère contenant un propylène chloré modifiable par oxydation.
PCT/JP2013/051814 2012-02-17 2013-01-29 Composition de polymère contenant du propylène chloré modifiable par oxydation et son procédé de fabrication WO2013121871A1 (fr)

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KR1020147015728A KR20140125347A (ko) 2012-02-17 2013-01-29 산화 변성 염소화 프로필렌 함유 중합체 조성물 및 그의 제조 방법
CN201380004636.7A CN104024282A (zh) 2012-02-17 2013-01-29 含氧化改性氯化丙烯的聚合物的组合物及其制造方法

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