WO2013121871A1 - Polymer composition containing oxidation-modifiable chlorinated propylene and method for producing same - Google Patents

Polymer composition containing oxidation-modifiable chlorinated propylene and method for producing same Download PDF

Info

Publication number
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
Authority
WO
WIPO (PCT)
Prior art keywords
oxidation
propylene
modified
chlorinated
polypropylene
Prior art date
Application number
PCT/JP2013/051814
Other languages
French (fr)
Japanese (ja)
Inventor
賢一郎 磯本
忠宣 船坂
Original Assignee
東洋紡株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 東洋紡株式会社 filed Critical 東洋紡株式会社
Priority to KR1020147015728A priority Critical patent/KR20140125347A/en
Priority to CN201380004636.7A priority patent/CN104024282A/en
Publication of WO2013121871A1 publication Critical patent/WO2013121871A1/en

Links

Classifications

    • 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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

Provided is a production method with which, by virtue of having a step for chlorinating an oxidation-modifiable propylene-containing polymer using a mixed solvent of chloroform and water, it is possible to produce more efficiently than in the past a polymer composition containing oxidation-modifiable chlorinated propylene that shows little discoloration, contains no polarizing component impurities or low-molecular-weight components, has excellent compatibility with polyurethane resins, and shows excellent adhesion of ink binders containing polyurethane when used for a variety of materials (particularly OPP). At least one polymer containing oxidation-modifiable propylene selected from oxidation-modifiable polypropylene and oxidation-modifiable propylene-α-olefin copolymer is dispersed in a mixture containing chloroform and water and chlorinated at a temperature of 130ºC or lower to obtain a polymer composition containing oxidation-modifiable chlorinated propylene.

Description

酸化変性塩素化プロピレン含有重合体組成物およびその製造方法Oxidation-modified chlorinated propylene-containing polymer composition and method for producing the same
　本発明は、極性成分の不純物や低分子量成分を除去した酸化変性塩素化プロピレン含有重合体組成物、およびその製造方法に関する。塩素化されたプロピレン含有重合体としては、塩素化ポリプロピレン及び塩素化プロピレン－α－オレフィン共重合体が代表的であり、これらはポリプロピレン基材に対する接着成分（バインダー成分）として、塗料、インキ、接着剤等の用途で幅広く利用されている。その中でも酸化変性塩素化ポリプロピレンは、各種素材に使用可能な、ポリウレタンに配合したインキ用バインダーのＯＰＰフィルムへの接着付与剤として主に利用されており、有用な化合物である。 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-α-olefin copolymers. These are adhesive components (binder components) for polypropylene substrates, such as paints, inks and adhesives. Widely used in applications such as agents. Among them, 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.
　従来、プロピレン含有重合体（例えば、ポリプロピレン）の酸化変性塩素化方法としては、１）ポリプロピレンの塩素化反応中あるいは塩素化反応後に空気、酸素、オゾン等を吹き込むことにより酸化処理する方法、２）塩素系溶剤（例えば、クロロホルム）のみに、予めポリプロピレンを酸化処理した酸化変性ポリプロピレンを溶解し、塩素化した後、そのまま他の溶剤に溶剤置換する方法が知られている（例えば、特許文献１）。 Conventionally, as an oxidation-modified chlorination method for a propylene-containing polymer (for example, polypropylene), 1) a method in which air, oxygen, ozone or the like is blown in during or after the chlorination reaction of polypropylene, 2) A method is known in which oxidatively modified polypropylene obtained by oxidizing polypropylene in advance is dissolved only in a chlorinated solvent (for example, chloroform), chlorinated, and then replaced with another solvent as it is (for example, Patent Document 1). .
　しかしながら、上記従来技術の酸化変性塩素化方法には、次のような問題がある。 However, the above-mentioned conventional oxidation-modified chlorination method has the following problems.
　上記１）の酸化変性塩素化方法は、空気、酸素、オゾン等を吹き込むことで、塩素と反応時に副生する塩化水素、および空気、酸素、オゾン等は反応容器中に同時に滞留する状態となり、塩素化反応を阻害し、塩素利用率が低下する影響がある。また、反応中は、反応容器に圧力がかからない状態、または圧力コントロールの管理を行うことにより、反応時に副生する塩化水素ガスや未反応塩素と同時に、空気、酸素、オゾン等のガスも系外へ放出する必要があることから、酸化変性度の管理を困難なものとしている。つまり、塩素化、酸化ともコントロールが困難である。 In the oxidation-modified chlorination method of 1) above, by blowing air, oxygen, ozone, etc., hydrogen chloride produced as a by-product during the reaction with chlorine, and air, oxygen, ozone, etc., will stay in the reaction vessel at the same time. The chlorination reaction is hindered and the chlorine utilization rate is affected. In addition, during the reaction, pressure in the reaction vessel is not applied, or pressure control is managed, so that hydrogen chloride gas and unreacted chlorine produced as a by-product during the reaction, as well as gases such as air, oxygen, ozone, etc. Therefore, it is difficult to control the degree of oxidative modification. That is, it is difficult to control both chlorination and oxidation.
　上記２）に挙げた塩素系溶剤のみに、予めポリプロピレンを酸化処理した酸化変性プロピレン含有重合体を溶解し、塩素化した後、そのまま他の溶剤に溶剤置換する方法は、塩素化時にラジカル発生剤（例えば、紫外線、有機過酸化物、アゾ系化合物等）を用いる必要があるため、これに伴う装置、温度管理、圧力管理が不可欠となる。具体的には、紫外線照射には専用装置が必要となる。また、有機過酸化物やアゾ系化合物を用いる場合には半減期温度を考慮した温度管理が必要であり、塩素ガスが熱分解するまで連続的に、または間欠的に添加することが必要である。更に、反応時に副生する塩化水素ガスを系外へ放出する必要がある点で圧力管理が必要である上、塩素利用率が低くならざるを得ない問題もある。また、酸化変性プロピレン含有重合体には酸化減成された低分子量成分を多く含むことから、塩素化反応により、塩素化された極性成分の不純物や低分子量の酸化変性塩素化ポリプロピレンを多く含む状態となり、着色が起こりやすく、インキ用途に必要な接着性や耐ブロッキング性等が不良になる（例えば、特許文献２）。 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. . Furthermore, pressure management is necessary because hydrogen chloride gas produced as a by-product during the reaction needs to be released out of the system, and there is a problem that the chlorine utilization rate must be lowered. In addition, since the oxidation-modified propylene-containing polymer contains a large amount of low-molecular-weight components that have undergone oxidation degradation, the polymer contains a large amount of impurities of chlorinated polar components and low-molecular-weight oxidation-modified chlorinated polypropylene due to the chlorination reaction. Coloring is likely to occur, resulting in poor adhesion and blocking resistance necessary for ink applications (for example, Patent Document 2).
特開昭４８－８８５６号（特に上記１））JP-A-48-8856 (particularly the above 1)) 特開平１－３０１７０３号（特に上記２））JP-A-1-301703 (particularly 2)
　よって、酸化変性度や塩素含有量を容易にコントロールし、さらに効率的に極性成分の不純物や低分子量成分を除去した酸化変性塩素化プロピレン含有重合体組成物およびその製造方法の開発が望まれている。 Therefore, it is desired to develop an oxidatively modified chlorinated propylene-containing polymer composition that easily controls the degree of oxidative modification and chlorine content, and more efficiently removes impurities and low molecular weight components, and a method for producing the same. Yes.
　本発明は、酸化変性プロピレン含有重合体をクロロホルムと水との混合溶媒で塩素化する工程を有することにより、着色の少ない、極性成分の不純物や低分子量成分を除去した、ポリウレタン樹脂との相溶性に優れ、ポリウレタンに配合したインキ用バインダーの各種素材（特にOPP）への接着性に優れた酸化変性塩素化プロピレン含有重合体組成物を得ること、および従来よりも効率的に目的物を得ることが出来る製造方法を提供することを目的とする。 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. To obtain an oxidation-modified chlorinated propylene-containing polymer composition excellent in adhesion to various materials (especially OPP) of an ink binder blended in polyurethane, and to obtain the target product more efficiently than before. It aims at providing the manufacturing method which can be performed.
　本発明者らは上記目的を達成すべく鋭意研究を重ねた結果、下記の酸化変性塩素化プロピレン含有重合体組成物を採用する場合には上記目的を達成できることを見出し、本発明を完成するに至った。 As a result of intensive studies to achieve the above object, 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.
　即ち、本発明は、下記の酸化変性塩素化プロピレン含有重合体組成物、およびその製造方法に関する。
１．　酸化変性ポリプロピレン及び酸化変性プロピレン－α－オレフィン共重合体の少なくとも１種の酸化変性プロピレン含有重合体をクロロホルム及び水を含む混合物に分散させて、１３０℃以下の温度で塩素化することにより得られる酸化変性塩素化プロピレン含有重合体組成物。
２．　前記酸化変性ポリプロピレン及び酸化変性プロピレン－α－オレフィン共重合体は、アイソタクチック重合体である、上記項１記載の組成物。
３．　前記酸化変性ポリプロピレン及び酸化変性プロピレン－α－オレフィン共重合体は、メタロセン系触媒を用いて合成される、上記項１又は２に記載の組成物。
４．　前記酸化変性ポリプロピレン及び酸化変性プロピレン－α－オレフィン共重合体の酸化変性度は酸価５ｍｇＫＯＨ／ｇ以上である、上記項１～３のいずれかに記載の組成物。
５．　前記酸化変性塩素化ポリプロピレン及び酸化変性塩素化プロピレン－α－オレフィン共重合体の塩素含有量が、２５～４５重量％である、上記項１～４のいずれかに記載の組成物。
６．　前記酸化変性プロピレン含有重合体を塩素化した後、得られた塩素化反応液に水不溶のエポキシ基含有化合物を添加する上記項１～５のいずれかに記載の組成物。
７．　上記項１～６のいずれかに記載の組成物を主成分とする印刷インキ用バインダー。
８．　酸化変性ポリプロピレン及び酸化変性プロピレン－α－オレフィン共重合体の少なくとも１種の酸化変性プロピレン含有重合体をクロロホルム及び水を含む混合物に分散させて、１３０℃以下の温度で塩素化する酸化変性塩素化プロピレン含有重合体組成物の製造方法。 That is, 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-α-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. The composition according to Item 1, wherein the oxidation-modified polypropylene and the oxidation-modified propylene-α-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-α-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-α-olefin copolymer is an acid value of 5 mgKOH / g or more.
5. Item 5. The composition according to any one of Items 1 to 4, wherein the chlorine content of the oxidation-modified chlorinated polypropylene and the oxidation-modified chlorinated propylene-α-olefin copolymer is 25 to 45% by weight.
6). 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-α-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.
　本発明は、酸化変性プロピレン含有重合体を塩素化するにあたり、クロロホルム及び水の混合溶媒を使用することによって、塩素化された極性成分の不純物や低分子量成分を水相及び乳化相に除去することができ、低着色かつ高品質の酸化変性塩素化プロピレン含有共重合体を得ることができる。本発明で得られた酸化変性塩素化プロピレン含有共重合体は、ポリウレタン樹脂との相溶性に優れ、ポリウレタンに配合したインキ用バインダーの各種素材（特にOPP）への密着性に優れており、また、目的物を効率的に製造することができる。 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. Thus, 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.
　以下、本発明について詳細に説明する。 Hereinafter, the present invention will be described in detail.
　本発明は、酸化変性ポリプロピレン及び酸化変性プロピレン－α－オレフィン共重合体の少なくとも１種の酸化変性プロピレン含有重合体をクロロホルム及び水を含む混合物に分散させて分散液を得た後、密閉下において、前記分散液を１３０℃以下の温度で加温しながら、前記分散液に塩素ガスを導入することにより前記酸化変性プロピレン含有重合体を塩素化することが好ましい。溶媒にクロロホルムと水を使用しているため酸化変性塩素化プロピレン含有重合体はクロロホルム含有相に溶解し、副生する塩化水素は水に溶解して塩酸含有相となる。塩素化後、反応液を静置し、塩酸含有相を分液除去する。このときクロロホルム含有相と塩酸含有相の界面に極性成分の不純物や低分子量の酸化変性塩素化プロピレンが含まれた乳化相が生じることがあるので、塩酸含有相とともに除去することが好ましい。 In the present invention, at least one oxidation-modified propylene-containing polymer of oxidation-modified polypropylene and an oxidation-modified propylene-α-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. Since chloroform and water are used as the solvent, 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. After chlorination, the reaction solution is allowed to stand to separate and remove the hydrochloric acid-containing phase. At this time, since 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.
　また、塩素化後の反応液に、水不溶性のエポキシ基含有化合物を添加すると、クロロホルム含有相と塩酸含有相とは短時間で相分離することができるので好ましい。塩酸含有相及び乳化相を除去してクロロホルム含有相を得た後、そのクロロホルム含有相からクロロホルムを留去することにより得られる酸化変性塩素化プロピレン含有重合体組成物およびその製造方法を特徴とする。 Further, it is preferable to add 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 .
　上記特徴を有する本発明の組成物は、塩酸含有相と乳化相を除いたクロロホルム含有相のみを分取することにより、極性成分の不純物や低分子量成分を含まない低着色かつ高品質の酸化変性塩素化プロピレン含有重合体組成物を得ることが出来る。 The 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.
　本発明では、プロピレン含有重合体としては、ポリプロピレン及びプロピレン－α－オレフィン共重合体の少なくとも１種を用いる。 In the present invention, as the propylene-containing polymer, at least one of polypropylene and a propylene-α-olefin copolymer is used.
　プロピレン－α－オレフィン共重合体は、プロピレンを主体としてこれにα－オレフィンを共重合したものである。α－オレフィンとしては、例えば、エチレン、１－ブテン、１－ヘプテン、１－オクテンなどを１種類又は数種類用いることができる。これらのα－オレフィンの中では、エチレン、１－ブテンが好ましい。プロピレン－α－オレフィン共重合体のプロピレン成分とα－オレフィン成分との比率は限定されないが、プロピレン成分が６０モル％以上であることが好ましく、９０モル％以上であることがより好ましい。 The propylene-α-olefin copolymer is a copolymer in which α-olefin is copolymerized mainly with propylene. As the α-olefin, for example, one kind or several kinds of ethylene, 1-butene, 1-heptene, 1-octene and the like can be used. Of these α-olefins, ethylene and 1-butene are preferred. The ratio of the propylene component to the α-olefin component of the propylene-α-olefin copolymer is not limited, but the propylene component is preferably 60 mol% or more, and more preferably 90 mol% or more.
　ポリプロピレン及びプロピレン－α－オレフィン共重合体は、いずれもアイソタクチック重合体であることが好ましい。アイソタクチック重合体は比較的高い結晶化度を示し、塩素化することにより結晶性をコントロールすることができる。例えば、プロピレン含有重合体に様々な有機溶剤への溶解性を付与する場合には、塩素含有量を高めることにより低結晶化することができる。他方、プロピレン含有重合体の塗膜に凝集力を付与する場合には、有機溶剤への溶解性は低下するが、塩素含有量を低く設定することにより高結晶性を維持することができる。塩素含有量はかかる範囲に限定されないが、本発明では２５～４５重量％が好ましく、３０～４０重量％がより好ましい。塩素含有量が２５重量％未満では、印刷インキ用溶剤として使われるエステル系溶剤やケトン系溶剤への溶解性が乏しくなり、塩素含有量が４５重量％を超えると、ＯＰＰフィルムなどのポリプロピレン基材に対する接着性が乏しいものとなる。また、ポリプロピレン及びプロピレン－α－オレフィン共重合体は、メタロセン触媒を用いて合成されたものが、均一な結晶性を有しており、溶剤に対する溶解性もすぐれている点で好ましい。 Both the polypropylene and the propylene-α-olefin copolymer are preferably isotactic polymers. Isotactic polymers exhibit a relatively high degree of crystallinity, and crystallinity can be controlled by chlorination. For example, when the propylene-containing polymer is provided with solubility in various organic solvents, it can be crystallized by increasing the chlorine content. On the other hand, when the cohesive force is imparted to the coating film of the propylene-containing polymer, 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. If the chlorine content is less than 25% by weight, 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-α-olefin copolymers synthesized using a metallocene catalyst are preferable because they have uniform crystallinity and excellent solubility in solvents.
　本発明では塩素化反応を行う原料として、酸化変性ポリプロピレン及び酸化変性プロピレン－α－オレフィン共重合体の少なくとも１種の酸化変性プロピレン含有重合体を使用する。酸化変性は公知の方法により、上記ポリプロピレン及びプロピレン－α－オレフィン共重合体の少なくとも１種のプロピレン含有重合体に熱溶融または溶媒に溶解し、酸素を導入しながら熱減成を行い、プロピレンまたはα－オレフィン分子内に酸素含有基を導入する。酸化変性により、プロピレンまたはα－オレフィン分子内にはカルボニル基、カルボキシル基、水酸基等の酸素含有基が混在する状態となる。これにより、インキ用ポリウレタンとの相溶性が良好となる。酸化変性時にラジカル発生剤を使用する場合、ベンゾイルパーオキシド、ジクミルパーオキサイド、ジ－tert－ブチルパーオキサイド、tert－ブチルヒドロパーオキサイドのようなパーオキサイド類やアゾビスイソブチロニトリル、アゾビスイソプロピオニトリルなどのアゾ系類の使用より速やかな変性が可能である。酸化変性ポリプロピレン及び酸化変性プロピレン－α－オレフィン共重合体は、市販品を使用することもできる。酸化変性度はかかる範囲に限定されないが、本発明ではASTM D-1386による酸価を指標とし、その値は5mgKOH／g以上が好ましく、１０mgKOH／g以上がより好ましい。 In the present invention, at least one oxidation-modified propylene-containing polymer of oxidation-modified polypropylene and an oxidation-modified propylene-α-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-α-olefin copolymer, and performing thermal degradation while introducing oxygen. An oxygen-containing group is introduced into the α-olefin molecule. By oxidative modification, the oxygen-containing groups such as carbonyl group, carboxyl group, and hydroxyl group are mixed in the propylene or α-olefin molecule. Thereby, compatibility with the polyurethane for ink becomes good. When using radical generators during oxidative modification, 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. Commercially available products may be used as the oxidation-modified polypropylene and the oxidation-modified propylene-α-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.
　本発明では、上記酸化変性プロピレン含有重合体をクロロホルム及び水を含む混合物に分散して分散液を得る。水の主な使用目的は、塩素化の際に副生する塩化水素を吸収すること及び目的物の製造工程を簡略化すること、さらには塩素化後の極性成分の不純物や低分子量の酸化変性塩素化プロピレンの多くを溶解させて除去することであり、水の使用量は副生する塩化水素の量に応じて設定すれば良いが、望ましくは反応終了後の塩酸含有相の塩酸濃度が１０～３０重量％となるように設定する。これらを考慮し、分散液中の酸化変性プロピレン含有重合体とクロロホルムと水との重量比は限定的ではないが、１：８～２０：０．８～２が好ましく、１：９～１５：０．９～１．８がより好ましい。 In the present invention, 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. Preferably, the hydrochloric acid concentration in the hydrochloric acid-containing phase after the reaction is 10 Set to ˜30% by weight. In consideration of these, 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.
　前記分散液を、密閉下において、１３０℃以下の温度で加温しながら、前記分散液に塩素ガスを導入することにより上記酸化変性プロピレン含有重合体を塩素化する。 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.
　塩素化の際は、密閉下において分散液を１３０℃以下の温度で加温する。温度は前記の範囲内であれば限定されないが、酸化変性プロピレン含有重合体が溶解性を確保する点で、塩素化中における最高到達温度は１１０～１３０℃が好ましく、１１５～１２５℃がより好ましい。 During chlorination, 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. .
　本発明では、分散液が水を含有しているため、塩素を導入することにより、下記の反応により反応系で連続的に酸素ラジカル（Ｏ・）が生成するため、安定的且つ効率的に酸化変性プロピレン含有重合体を塩素化することができる。具体的には、先ず水又は水酸化物イオンと塩素が反応することにより次亜塩素酸が生成し、次いで次亜塩素酸が分解することで酸素ラジカルが生じる。 In the present invention, since 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.
　Ｈ２Ｏ＋Ｃｌ２→ＨＣｌＯ＋ＨＣｌ
　ＯＨ－＋Ｃｌ２→ＨＣｌＯ＋Ｃｌ－
　ＨＣｌＯ→ＨＣｌ＋Ｏ・
　従って、本発明の反応系では酸素ラジカルが連続的に生成されるため、公知のラジカル発生剤（例えば、紫外線、有機過酸化物、アゾ系化合物等）を用いる必要がなく、ラジカル発生剤を用いることによる従来の課題（専用装置、温度管理、圧力管理等）を回避して目的物を製造することができる。 H 2 O + Cl 2 → HClO + HCl
OH − + Cl 2 → HClO + Cl −
HClO → HCl + O.
Therefore, since oxygen radicals are continuously generated in the reaction system of the present invention, it is not necessary to use known radical generators (for example, ultraviolet rays, organic peroxides, azo compounds, etc.), and radical generators are used. Therefore, the object can be manufactured while avoiding the conventional problems (dedicated device, temperature management, pressure management, etc.).
　反応系に塩素ガスを導入する際は、密閉状態を確保しつつ塩素ガスを吹き込めばよい。塩素ガスの導入量は限定されないが、塩素化された酸化変性プロピレン含有重合体の塩素含有量が好ましくは２５～４５重量％となる量とすればよい。塩素含有量はかかる範囲に限定されないが、本発明では２５～４５重量％が好ましく、３０～４０重量％がより好ましい。塩素ガスの導入により塩化水素が副生するが、塩化水素はその殆どが水に溶存するため、過度な圧力管理等は本発明の製造方法では不要である。また、密閉下において塩素化を行うため、従来の塩素系溶剤のみ使用する塩素化と比べて塩素利用率を多く確保できる点で好ましい。 When introducing chlorine gas into the reaction system, it is only necessary to blow in chlorine gas while ensuring a sealed state. 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. In addition, since 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.
　本発明で得られる塩素化された酸化変性プロピレン含有重合体の重量平均分子量は、限定的ではないが３０００～１０００００が好ましい。３０００未満の場合には凝集力が弱くなりポリプロピレン基材に対する密着性が劣る場合がある。他方、１０００００を超えると、ポリウレタンとの相溶性及び溶剤への溶解状態が悪くなる場合がある。より好ましい重量平均分子量は１００００～５００００である。 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.
　得られた塩素化反応液は静置した後、クロロホルム含有相を分取する。水相（塩酸含有相）および界面付近の乳化相には、塩素化された極性成分の不純物や低分子量の酸化変性塩素化ポリプロピレンを含んでいる。塩素化された極性成分の不純物や低分子量の酸化変性塩素化ポリプロピレンの含有量が多くなると、着色が起こりやすくなり、インキ用途に必要な接着性や耐ブロッキング性等が不良になる。よって、塩酸含有相および界面の乳化相を除き、クロロホルム含有相のみを分取することにより、効率的に、着色の少ない目的物を得ることができる。 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. When 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.
　さらに、塩素化後の反応液に、水不溶性のエポキシ基含有化合物を添加すると、クロロホルム含有相と塩酸含有相とは短時間で相分離することができる。水不溶性のエポキシ基含有化合物は、反応液中の微細な水粒子を凝集させる作用（エマルションブレーカーとしての作用）を有するものが好ましく、例えば、フェニルグリシジルエーテル、２－メチルフェニルグリシジルエーテル、p－tert－ブチルフェニルグリシジルエーテル、４－クロロフェニルグリシジルエーテル、４－メトキシフェニルグリシジルエーテル、２－ビフェニルグリシジルエーテル、１－ナフチルグリシジルエーテル、２－エチルヘキシルグリシジルエーテル、アリルグリシジルエーテル等のモノエポキシ化合物が例示される。その他、ビスフェノールＡとエピクロルヒドリンとを各種の割合で重縮合反応させて得られるビスフェノールＡ型エポキシ化合物、ビスフェノールＦとエピクロルヒドリンとを各種の割合で重縮合反応させて得られるビスフェノールＦ型エポキシ化合物、不飽和基を有する植物油を過酢酸などの過酸と反応させて得られるエポキシ化大豆油、エポキシ化アマニ油などが例示される。また、水添ビスフェノールＡジグリシジルエーテル、ジクリシジルo－フタレート、１,６－ヘキサンジオールジグリシジルエーテル、トリメチロールプロパントリグリシジルエーテル等の多官能エポキシ化合物も例示される。この中でも、特にp－tert－ブチルフェニルグリシジルエーテル、ビスフェノールＡ型エポキシ化合物等が好ましい。水不溶性のエポキシ基含有化合物の添加量は限定的ではないが、反応液中の塩素化された酸化変性プロピレン含有重合体１００重量部に対して０．１～５重量部が好ましく、０．３～２重量部がより好ましい。 Furthermore, when a water-insoluble epoxy group-containing compound is added to the reaction solution after chlorination, 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). For example, phenyl glycidyl ether, 2-methylphenyl glycidyl ether, p-tert 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. In addition, 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. Further, 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. Among these, p-tert-butylphenyl glycidyl ether, bisphenol A type epoxy compound and the like are particularly preferable. 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.
　エポキシ基含有化合物を添加後の静置時間は相分離が十分に行える限り限定されないが、本発明では２時間以下が好ましく、１時間以下がより好ましい。このように、水不溶性のエポキシ基含有化合物を添加すると、有意に短時間で相分離することができるため、効率的に目的物を製造することができる。 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.
　本発明ではクロロホルム含有相に塩素化された酸化変性プロピレン含有重合体が含まれており、分取方法は公知の分取方法が利用できる。 In the present invention, 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.
　前記クロロホルム含有相からクロロホルムを留去することにより、塩素化された酸化変性プロピレン含有重合体を得る。 Chlorinated oxidatively modified propylene-containing polymer is obtained by distilling off chloroform from the chloroform-containing phase.
　クロロホルム含有相からクロロホルムを留去する際の温度条件及び圧力条件は限定的ではないが、クロロホルムの沸点（６１℃）以上の状態から徐々に減圧状態にするのが効率上好ましく、温度は１５～７０℃が好ましく、２５～６５℃がより好ましい。また、圧力条件は－０．０９～０．０８ＭＰａが好ましく、－０．０８～０．０５ＭＰａがより好ましい。また、本発明では、減圧留去により大部分のクロロホルムを留去した後、公知である次の工程１または工程２により目的の組成物を得ることができる。 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. Moreover, in this invention, after most chloroform is distilled off by depressurizing distillation, the target composition can be obtained by the following following process 1 or process 2.
　《工程１》
工程１は塩素化された酸化変性プロピレン含有重合体の高濃度クロロホルム溶液を押出し機にフィードし、残留したクロロホルムを留去しつつ塩素化された酸化変性プロピレン含有重合体を造粒して取り出す工程である。押出し時の温度条件及び圧力条件も限定的ではないが、高温低真空状態から徐々に低温高真空状態にフィードするのが製造方法の効率上好ましく、押出機温度は５０～１５０℃が好ましく、６０～１４０℃がより好ましい。また、押出機圧力条件は－０．０９９～－０．０８０ＭＰａが好ましく、－０．０９９～－０．０９０ＭＰａがより好ましい。得られた酸化変性塩素化プロピレン含有重合体の固形物は、所望の溶剤に溶解して使用することができる。 << Process 1 >>
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.
　《工程２》
工程２は塩素化された酸化変性プロピレン含有重合体の高濃度クロロホルム溶液に所望の溶剤を添加後、溶解し、クロロホルムと溶剤を、上記のクロロホルム留去条件と同様に留去する工程である。クロロホルム残量が実質上なくなるまで同様の操作を繰り返した後、所望の溶剤に溶解し、酸化変性塩素化プロピレン含有共重合体溶液を得ることができる。 << Process 2 >>
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.
　工程１、２共に所望の溶剤としては、溶解性の良いトルエンやキシレンのような芳香族炭化水素が好都合であるが、インキ用途においてはノントルエン化が求められる傾向にあり、酢酸エチルや酢酸ｎ－プロピル、酢酸イソプロピルなどのエステル系溶剤、アセトン、メチルエチルケトンなどのケトン系溶剤、シクロヘキサン、メチルシクロヘキサンなどの脂環式炭化水素を使用することができる。この中でも、酢酸エチル、酢酸ｎ－プロピル、メチルエチルケトン、メチルシクロヘキサンが好ましい。 As the desired solvent in both steps 1 and 2, 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, and alicyclic hydrocarbons such as cyclohexane and methylcyclohexane can be used. Of these, ethyl acetate, n-propyl acetate, methyl ethyl ketone, and methylcyclohexane are preferable.
　上記により得られる酸化変性塩素化プロピレン含有重合体は、着色が少なく、また極性成分の不純物や低分子量成分の含有量も少ない。そのため、ポリウレタン樹脂との相溶性に優れ、ポリウレタンに配合したインキ用バインダーの各種素材（特にOPP）への接着性に優れた組成物として利用できる。 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.
　以下に実施例及び比較例を示して本発明を具体的に説明する。但し、本発明は以下の実施例に限定されるものでなく、上記・下記の趣旨に適合し得る範囲で適当に変更を加えて実施することも勿論可能であり、それらはいずれも本発明の技術的範囲に包含される。 Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples. However, the present invention is not limited to the following examples, and can of course be carried out with appropriate modifications within a range that can be adapted to the above and the following purposes. Included in the technical scope.
　実施例１
　5Lのグラスライニング製反応缶中に、酸化変性アイソタクチックポリプロピレンであるGMT-2520（Gong Myoung Technologies Co.製、180℃における溶融粘度90mPa・s、酸価20KOHmg/g、融点157℃）400g、クロロホルム3900g、脱イオン水630ｇを入れ密閉し、反応缶中の液を攪拌して分散しながら反応缶内を加温した。缶内温度が110℃に到達した時点で塩素を180g/時間の速度で導入し、缶内温度を100～120℃で保持した。反応缶内の圧力は最大0.6MPaになった。塩素導入開始から2時間40分経過時の塩素485g導入した段階において塩素の導入を止め、10分間液の攪拌を続けた後に、攪拌を止めた。缶内温度を80～100℃で保持し３時間静置したところ、上相の塩酸含有相と下相のクロロホルム溶液に分離し、わずかに上相と下相の間に乳化相が見られた。上相および乳化相には塩素化された極性成分の不純物が含まれていた。下相のクロロホルム溶液のみを4Lのグラスライニング製反応缶に移送し、缶内温度35～75℃、缶内圧力-0.08～0.08MPaの条件下でクロロホルム3500gを留去した。続いて酢酸エチル800gを添加し、缶内温度55～75℃で溶解後、缶内温度35～75℃、缶内圧力-0.08～0.08MPaの条件下でクロロホルムと酢酸エチルの混合溶液を留去した。酢酸エチルを添加し、溶解後、クロロホルムと酢酸エチルの混合溶液を留去するという同様の工程を２回繰り返した後、固形分が２９重量％となるよう酢酸エチルを添加、溶解し、安定剤としてp－tert－ブチルフェニルグリシジルエーテルを16g添加することにより、酸化変性塩素化ポリプロピレンの固形分３０重量％の酢酸エチル溶液を得た。得られた酸化変性塩素化ポリプロピレンの塩素含有量は34.5重量％、酸価は15 KOHmg/g、重量平均分子量は16000、溶液のガードナー色数は２であった。 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. The pressure inside the reaction can reached a maximum of 0.6 MPa. 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. When 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. Only the chloroform solution of the lower phase was transferred to a 4 L glass-lined reaction can, and 3500 g of chloroform 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. Subsequently, 800 g of ethyl acetate was added and dissolved at a can internal temperature of 55 to 75 ° C. Then, 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. 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. As a result, 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.
　実施例２
　実施例１において、脱イオン水の仕込み量を820ｇとし、塩素を3時間40分かけて635g導入し、安定剤のp－tert－ブチルフェニルグリシジルエーテルの添加量を18gにした以外は実施例１と同じ操作を行った。得られた酸化変性塩素化ポリプロピレンの塩素含有量は44.8重量％、酸価は14 KOHmg/g、重量平均分子量は17000、溶液のガードナー色数は２であった。 Example 2
Example 1 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.
　実施例３
　実施例１において、脱イオン水の仕込み量を450ｇとし、塩素を2時間かけて350g導入し、安定剤のp－tert－ブチルフェニルグリシジルエーテルの添加量を15gにした以外は実施例１と同じ操作を行った。得られた酸化変性塩素化ポリプロピレンの塩素含有量は25.4重量％、酸価は16KOHmg/g、重量平均分子量は15000、溶液のガードナー色数は２であった。 Example 3
Example 1 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.
　試作例１
　２ＬのＳＵＳ３１６製反応缶中に、メタロセン触媒を用いて合成されたアイソタクチックプロピレンエチレン共重合体（プロピレン：エチレン＝98：2 モル比、180℃における溶融粘度１１00mPa・s、融点1３５℃）500gを入れ密閉し、反応缶を加温した。缶内温度が160℃に到達した時点で、ジ－tert－ブチルパーオキサイド5gを添加し、攪拌を開始し、酸素を０．３Ｌ／分で反応缶中に導入した。酸素を導入しながら、缶内温度160℃、缶内圧力0.60MPaに保持し、３時間後に反応を終了した。得られた酸化変性プロピレンエチレン共重合体の180℃における溶融粘度220mPa・s、酸価7KOHmg/g、融点134℃であった。 Prototype example 1
500 g of isotactic propylene ethylene copolymer (propylene: ethylene = 98: 2 molar ratio, melt viscosity 1180 mPa · s at 180 ° C., melting point 135 ° C.) synthesized using a metallocene catalyst in a 2 L SUS316 reaction vessel Was sealed and the reaction vessel was warmed. When the temperature in the can reached 160 ° C., 5 g of di-tert-butyl peroxide was added, stirring was started, and oxygen was introduced into the reaction can at 0.3 L / min. While introducing oxygen, the inside temperature of the can was maintained at 160 ° C. and the inside pressure of the can was 0.60 MPa, and the reaction was terminated after 3 hours. 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.
　実施例４
　実施例１において、試作例１により合成した酸化変性プロピレンエチレン共重合体を使用した以外は実施例１と同じ操作を行った。得られた酸化変性塩素化ポリプロピレンの塩素含有量は34.7重量％、酸価は5KOHmg/g、重量平均分子量は21000、溶液のガードナー色数は２であった。 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.
　実施例５
　実施例２において、試作例１により合成した酸化変性プロピレンエチレン共重合体を使用した以外は実施例２と同じ操作を行った。得られた酸化変性塩素化ポリプロピレンの塩素含有量は44.9重量％、酸価は5KOHmg/g、重量平均分子量は22000、溶液のガードナー色数は２であった。 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.
　実施例６
　実施例１において、塩素導入後、10分間液の攪拌を続けた後に、水不溶性エポキシ基含有化合部であるp－tert－ブチルフェニルグリシジルエーテルを２．４ｇ添加した。攪拌停止後、缶内温度を80～100℃で保持し１時間静置したところ、上相の塩酸含有相と下相のクロロホルム含有相に明確に分離した。その他は、実施例１と同じ操作を行った。得られた酸化変性塩素化ポリプロピレンの塩素含有量は34.5重量％、酸価は15 KOHmg/g、重量平均分子量は16000、溶液のガードナー色数は２であった。 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.
　比較例１
　5Lのグラスライニング製反応缶中に、実施例１～３で使用したGMT-2520を400g、クロロホルム4600gを入れ密閉し、反応缶中の液を攪拌しながら反応缶内を加温した。缶内温度が110℃に到達した時点で塩素を180g/時間の速度で導入し、缶内温度を100～120℃で保持した。反応缶内の圧力は制御しながら、0.6MPaを超えるたびに反応缶内の圧力を放圧し、0.5MPaまで下げた。放圧したガスは1Lの19重量％の水酸化ナトリウム水溶液に吸収させた。塩素導入開始から2時間50分経過時の塩素515g導入した段階において塩素の導入を止め、10分間液の攪拌を続けた後に、攪拌を止めた。反応液を4Lのグラスライニング製反応缶に移送し、缶内温度35～75℃、缶内圧力-0.08～0.08MPaの条件下でクロロホルム3600gを留去した。続いて酢酸エチル800gを添加し、缶内温度55～75℃で溶解後、缶内温度35～75℃、缶内圧力-0.08～0.08MPaの条件下でクロロホルムと酢酸エチルの混合溶液を留去した。酢酸エチルを添加し、溶解後、クロロホルムと酢酸エチルの混合溶液を留去するという同様の工程を２回繰り返した後、固形分が２９重量％となるよう酢酸エチルを添加、溶解し、安定剤としてp－tert－ブチルフェニルグリシジルエーテルを16g添加することにより、酸化変性塩素化ポリプロピレンの固形分３０重量％の酢酸エチル溶液を得た。得られた酸化変性塩素化ポリプロピレンの塩素含有量は34.6重量％、酸価は15 KOHmg/g、重量平均分子量は15000、溶液のガードナー色数は６であった。 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. Then, 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. 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. As a result, 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 a Gardner color number of the solution of 6.
　比較例２
　比較例１において、試作例１により合成した酸化変性プロピレンエチレン共重合体を使用した以外は比較例１と同じ操作を行った。得られた酸化変性塩素化ポリプロピレンの塩素含有量は34.8重量％、酸価は5KOHmg/g、重量平均分子量は20000、溶液のガードナー色数は６であった。 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.
　比較例３
　比較例１において、試作例１で使用した、酸化変性を行っていないプロピレンエチレン共重合体を使用した以外は比較例１と同じ操作を行った。得られた酸化変性塩素化ポリプロピレンの塩素含有量は34.7重量％、重量平均分子量は45000、溶液のガードナー色数は６であった。 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.
　比較例４
　実施例１において、試作例１で使用した、酸化変性を行っていないプロピレンエチレン共重合体を使用した以外は実施例１と同じ操作を行った。得られた酸化変性塩素化ポリプロピレンの塩素含有量は34.7重量％、重量平均分子量は45000、溶液のガードナー色数は２であった。 Comparative 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.
　試験方法 Test method
　相溶性試験
　実施例１～５、比較例１～３で得られた酸化変性塩素化プロピレン含有重合体に印刷インキ用ポリウレタン樹脂（サンプレンＩＢ－５０１とサンプレンＩＢ－９１１、共に固形分３０重量％、三洋化成工業株式会社製）を固形分重量比５／９５ で混合し、バーコーターNo.8でガラス板に塗布し、２５℃において２４時間乾燥させた塗膜の状態を観察した。評価基準は、○澄明、△僅かに濁り、Ｘ白濁　である。結果を表１に示す。 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, Δ slightly cloudy, and X cloudiness. The results are shown in Table 1.
　接着性試験
　相溶性試験に使用した、酸化変性塩素化プロピレン含有重合体と印刷インキ用ポリウレタン樹脂の混合溶液（固形分３０重量％溶液）を下記の配合にて混合し、インキを調合した。なお、白色顔料には石原産業株式会社製ルチル型酸化チタン　タイペークPF-742　を使用した。
実施例または比較例の樹脂溶液　　　３５重量部
白色顔料　　　　　　　　　　　　　　　　　　３０重量部
酢酸ｎ－プロピル　　　　　　　　　　　　　１５重量部
酢酸エチル　　　　　　　　　　　　　　　　　１０重量部
イソプロピルアルコール　　　　　　　　　 １０重量部
上記組成のインキ用混合物をそれぞれボールミルで練肉し、白色印刷インキを調合した。得られた白色インキを＃８バーコーターで、ＯＰＰフィルム（二軸延伸ポリプロピレン、コロナ処理面、東洋紡パイレンフィルム-OT P2161）、ＰＥＴフィルム（二軸延伸ポリエステルフィルム、コロナ処理面、東洋紡エステルフィルム　T6140）、ＯＮＹフィルム（二軸延伸ナイロンフィルム、コロナ処理面、東洋紡ハーデンフィルム N1102）に塗工した。塗工面に、セロファンテープ（ニチバン製セロテープ）を貼り付け、これを急速に剥がした時の塗工面の状態を観察した。評価基準は、○剥がれなし、△僅かに剥がれあり、Ｘ大部分剥がれあり、とした。結果を表１に示す。 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. As the 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 Each ink mixture having the above composition was kneaded with a ball mill to obtain white printing ink. Was formulated. 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, Δ slight peeling, and most X peeling. The results are shown in Table 1.
　色数
　ＪＩＳ　Ｋ　５６００－２－１に準拠して測定した。 The number of colors was measured according to JIS K 5600-2-1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　本発明によれば、低着色かつ高品質の酸化変性塩素化プロピレン含有共重合体を得ることができる。本発明で得られた酸化変性塩素化プロピレン含有共重合体は、ポリウレタン樹脂との相溶性に優れ、ポリウレタンに配合したインキ用バインダーの各種素材（特にOPP）への密着性に優れており、また、目的物を効率的に製造することができる。 According to the present invention, 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.

Claims (8)

  1. 　酸化変性ポリプロピレン及び酸化変性プロピレン－α－オレフィン共重合体の少なくとも１種の酸化変性プロピレン含有重合体をクロロホルム及び水を含む混合物に分散させて、１３０℃以下の温度で塩素化することにより得られる酸化変性塩素化プロピレン含有重合体組成物。 Obtained by dispersing at least one oxidation-modified propylene-containing polymer of oxidation-modified polypropylene and an oxidation-modified propylene-α-olefin copolymer in a mixture containing chloroform and water and chlorinating at a temperature of 130 ° C. or lower. Oxidation-modified chlorinated propylene-containing polymer composition.
  2. 　前記酸化変性ポリプロピレン及び酸化変性プロピレン－α－オレフィン共重合体は、アイソタクチック重合体である、請求項１記載の組成物。 The composition according to claim 1, wherein the oxidation-modified polypropylene and the oxidation-modified propylene-α-olefin copolymer are isotactic polymers.
  3. 　前記酸化変性ポリプロピレン及び酸化変性プロピレン－α－オレフィン共重合体は、メタロセン系触媒を用いて合成される、請求項１又は２に記載の組成物。 The composition according to claim 1 or 2, wherein the oxidation-modified polypropylene and the oxidation-modified propylene-α-olefin copolymer are synthesized using a metallocene catalyst.
  4. 　前記酸化変性ポリプロピレン及び酸化変性プロピレン－α－オレフィン共重合体の酸化変性度は酸価5mgKOH／g以上である、請求項１～３のいずれかに記載の組成物。 4. The composition according to claim 1, wherein the oxidation-modified degree of the oxidation-modified polypropylene and the oxidation-modified propylene-α-olefin copolymer is an acid value of 5 mgKOH / g or more.
  5. 　前記酸化変性塩素化ポリプロピレン及び酸化変性塩素化プロピレン－α－オレフィン共重合体の塩素含有量が、２５～４５重量％である、請求項１～４のいずれかに記載の組成物。 The composition according to any one of claims 1 to 4, wherein the chlorine content of the oxidation-modified chlorinated polypropylene and the oxidation-modified chlorinated propylene-α-olefin copolymer is 25 to 45 wt%.
  6. 　前記酸化変性プロピレン含有重合体を塩素化した後、得られた塩素化反応液に水不溶のエポキシ基含有化合物を添加する請求項１～５のいずれかに記載の組成物。 The composition according to any one of claims 1 to 5, wherein a water-insoluble epoxy group-containing compound is added to the obtained chlorination reaction solution after chlorination of the oxidation-modified propylene-containing polymer.
  7. 　請求項１～６のいずれかに記載の組成物を主成分とする印刷インキ用バインダー。 A binder for printing ink comprising the composition according to any one of claims 1 to 6 as a main component.
  8. 　酸化変性ポリプロピレン及び酸化変性プロピレン－α－オレフィン共重合体の少なくとも１種の酸化変性プロピレン含有重合体をクロロホルム及び水を含む混合物に分散させて、１３０℃以下の温度で塩素化する酸化変性塩素化プロピレン含有重合体組成物の製造方法。 Oxidation-modified chlorination in which at least one oxidation-modified propylene-containing polymer of oxidation-modified polypropylene and an oxidation-modified propylene-α-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.
PCT/JP2013/051814 2012-02-17 2013-01-29 Polymer composition containing oxidation-modifiable chlorinated propylene and method for producing same WO2013121871A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
KR1020147015728A KR20140125347A (en) 2012-02-17 2013-01-29 Polymer composition containing oxidation-modifiable chlorinated propylene and method for producing same
CN201380004636.7A CN104024282A (en) 2012-02-17 2013-01-29 Polymer composition containing oxidation-modifiable chlorinated propylene and method for producing same

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2012-032448 2012-02-17
JP2012032448 2012-02-17

Publications (1)

Publication Number Publication Date
WO2013121871A1 true WO2013121871A1 (en) 2013-08-22

Family

ID=48983987

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2013/051814 WO2013121871A1 (en) 2012-02-17 2013-01-29 Polymer composition containing oxidation-modifiable chlorinated propylene and method for producing same

Country Status (4)

Country Link
JP (1) JPWO2013121871A1 (en)
KR (1) KR20140125347A (en)
CN (1) CN104024282A (en)
WO (1) WO2013121871A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014148576A1 (en) * 2013-03-22 2014-09-25 日本製紙株式会社 Chlorinated polyolefin resin

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS50117839A (en) * 1974-03-01 1975-09-16
JPH01301703A (en) * 1988-05-31 1989-12-05 Sanyo Kokusaku Pulp Co Ltd Novel chlorinated polyolefin containing hydroxyl group, production thereof and composition containing said polymer
JPH0673362A (en) * 1992-08-18 1994-03-15 Nippon Paper Ind Co Ltd Binder resin composition
JPH07258335A (en) * 1994-03-22 1995-10-09 Nippon Paper Ind Co Ltd Ink composition
JPH11323236A (en) * 1998-05-22 1999-11-26 Nippon Paper Industries Co Ltd Resin composition for printing ink and its production
WO2013046846A1 (en) * 2011-09-30 2013-04-04 東洋紡株式会社 Method for producing chlorinated propylene-containing polymer

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101012295B (en) * 2007-02-06 2010-12-22 泸州北方化学工业有限公司 Method of producing chlorinated polypropylene
CN100569809C (en) * 2007-08-27 2009-12-16 东莞市金成化工有限公司 Continuous large-devolatilization double screw extruder drying method during Chlorinated Polypropylene III is produced
CN101555301B (en) * 2009-05-19 2011-05-04 中山大学 Method for preparing solid phase of chlorinated polypropylene or chlorinated maleic anhydride inoculated polypropylene
CN101759823A (en) * 2010-03-09 2010-06-30 华东理工大学 Photo-initiation preparation method for chlorinated polypropylene
CN101831020B (en) * 2010-05-14 2012-06-13 泸州北方塑料化工有限公司 Method for producing chlorinated polypropylene with mixed solvent

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS50117839A (en) * 1974-03-01 1975-09-16
JPH01301703A (en) * 1988-05-31 1989-12-05 Sanyo Kokusaku Pulp Co Ltd Novel chlorinated polyolefin containing hydroxyl group, production thereof and composition containing said polymer
JPH0673362A (en) * 1992-08-18 1994-03-15 Nippon Paper Ind Co Ltd Binder resin composition
JPH07258335A (en) * 1994-03-22 1995-10-09 Nippon Paper Ind Co Ltd Ink composition
JPH11323236A (en) * 1998-05-22 1999-11-26 Nippon Paper Industries Co Ltd Resin composition for printing ink and its production
WO2013046846A1 (en) * 2011-09-30 2013-04-04 東洋紡株式会社 Method for producing chlorinated propylene-containing polymer

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014148576A1 (en) * 2013-03-22 2014-09-25 日本製紙株式会社 Chlorinated polyolefin resin
JP5703423B2 (en) * 2013-03-22 2015-04-22 日本製紙株式会社 Chlorinated polyolefin resin
US9458267B2 (en) 2013-03-22 2016-10-04 Nippon Paper Industries Co., Ltd. Chlorinated polyolefin resin

Also Published As

Publication number Publication date
KR20140125347A (en) 2014-10-28
CN104024282A (en) 2014-09-03
JPWO2013121871A1 (en) 2015-05-11

Similar Documents

Publication Publication Date Title
JP6660517B1 (en) Method for producing chlorinated polyolefin resin
JP5484642B2 (en) Chlorinated polyolefin resin composition
JP6976260B2 (en) Modified polyolefin resin
WO2000026310A1 (en) Binder resin for polyolefin resin, process for producing the same, and uses thereof
JP6943882B2 (en) Modified polyolefin resin
TWI542607B (en) Production method of propylene chloride-containing polymer
JP5703423B2 (en) Chlorinated polyolefin resin
WO2013121871A1 (en) Polymer composition containing oxidation-modifiable chlorinated propylene and method for producing same
JP6166564B2 (en) Chlorinated polyolefin resin composition
JP4240882B2 (en) Resin composition for printing ink and method for producing the same
JP3965697B2 (en) Chlorinated polyolefin binder resin composition with good solvent resistance
CN114945603A (en) Chlorinated polyolefin resin, primer, adhesive, laminate, food packaging material, and method for producing the resin
JP2022117819A (en) Production method of acid-modified chlorinated polyolefin resin
JP2015209450A (en) Chlorinated polyolefin resin composition
WO2020213528A1 (en) Modified polyolefin resin composition
JP2015067719A (en) Chlorinated polyolefin resin composition
JP2010059273A (en) Aqueous dispersion liquid and method for manufacturing coating film

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 13749957

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2014500155

Country of ref document: JP

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 20147015728

Country of ref document: KR

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 13749957

Country of ref document: EP

Kind code of ref document: A1