Method for producing chlorinated polyolefin resin composition

Abstract

To provide a novel method for producing a chlorinated polyolefin resin composition in which the content of a volatile chlorine-based compound such as chloroform can be further reduced without using a high-temperature condition while suppressing coloration.SOLUTION: A method for producing a chlorinated polyolefin resin composition in which the content of a volatile chlorine-based compound is less than 0.2 wt.% for 100 wt.% of a chlorinated polyolefin resin composition includes the following processes 1 to 3. Process 1: a process of supplying a solid-state chlorinated polyolefin resin composition, in which the content of a volatile chlorine-based compound is 0.2 wt.% or more for 100 wt.% of a chlorinated polyolefin resin composition, to a twin-screw extruder. Process 2: a process of feeding water to the chlorinated polyolefin resin composition and then degassing at reduced pressure in the twin-screw extruder. Process 3: a process of recovering the chlorinated polyolefin resin composition in which the content of a volatile chlorine-based compound is less than 0.2 wt.% for 100 wt.% of the chlorinated polyolefin resin composition from the twin-screw extruder.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a method for producing a resin composition containing a chlorinated polyolefin resin. [Background technology]

[0002] Polyolefin resins have many excellent properties, such as excellent mechanical properties such as tensile strength, tear strength, and impact strength, as well as excellent water resistance and chemical resistance, and are also lightweight, inexpensive, and easy to mold, and therefore are used in a variety of applications such as sheets, films, molded products, etc. However, polyolefin resins have the disadvantage of being poor in paintability and adhesiveness because they are non-polar and have good crystallinity compared to acrylic resins and polyester resins.

[0003] On the other hand, chlorinated polyolefin resins obtained by chlorinating polyolefin resins are known to have excellent coating properties and adhesion to non-polar resin substrates (see Patent Document 1). However, because volatile chlorine-based compounds such as chloroform are generally used in the production of chlorinated polyolefin resins, volatile chlorine-based compounds such as chloroform have inevitably remained in relatively high concentrations in chlorinated polyolefin resin products to date.

[0004] However, in recent years, there has been growing concern about the environmental toxicity of volatile chlorine compounds contained in products, and there is a demand for products with even lower levels of volatile chlorine compounds than ever before.

[0005] For example, it is possible to reduce the content of volatile chlorine-based compounds by degassing a chlorinated polyolefin resin composition under reduced pressure at a higher temperature, but it is known that treatment at a high temperature significantly reduces the quality of the product due to discoloration, etc. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Patent No. 4420314 Summary of the Invention [Problem to be solved by the invention]

[0007] An object of the present invention is to provide a novel method for producing a chlorinated polyolefin resin composition, which can further reduce the content of volatile chlorine-based compounds such as chloroform while suppressing discoloration without using high-temperature conditions. [Means for solving the problem]

[0008] Means for Solving the Problems of the Invention The present inventors have conducted extensive research to achieve the objects of the present invention, and as a result have found that the content of volatile chlorine-based compounds can be significantly reduced by injecting water into a chlorinated polyolefin resin composition charged into a twin-screw extruder and then subjecting it to reduced-pressure devolatilization, thereby completing the present invention.

[0009] Thus, the present invention provides the following: [1] A method for producing a chlorinated polyolefin resin composition, the method comprising the following steps 1 to 3, wherein the content of volatile chlorine-based compounds is less than 0.2% by weight based on 100% by weight of the chlorinated polyolefin resin composition: Step 1: A step of supplying a solid chlorinated polyolefin resin composition having a volatile chlorine-based compound content of 0.2% by weight or more relative to 100% by weight of the chlorinated polyolefin resin composition to a twin-screw extruder. Step 2: A step of pouring water into the chlorinated polyolefin resin composition in the twin-screw extruder, and then devolatilizing the composition under reduced pressure. Step 3: A step of recovering a chlorinated polyolefin resin composition having a content of volatile chlorine-based compounds of less than 0.2% by weight based on 100% by weight of the chlorinated polyolefin resin composition from the twin-screw extruder. [2] The method for producing a chlorinated polyolefin resin composition according to the above [1], wherein the chlorinated polyolefin resin composition recovered in step 3 has a content of volatile chlorine-based compounds of less than 0.1% by weight based on 100% by weight of the chlorinated polyolefin resin composition. [3] The method for producing a chlorinated polyolefin resin composition according to the above [1] or [2], wherein step 2 is repeated two or more times in succession. [4] The method for producing a chlorinated polyolefin resin composition according to any one of [1] to [3] above, wherein the amount of water injected per step in step 2 is 0.5 to 20% by weight based on 100% by weight of the chlorinated polyolefin resin composition. [5] The method for producing a chlorinated polyolefin resin composition according to any one of the above [1] to [4], wherein the internal temperature of the cylinder of the twin-screw extruder is 150°C or lower. [6] The method for producing a chlorinated polyolefin resin composition according to any one of the above [1] to [5], wherein the content of volatile chlorine-based compounds in the solid chlorinated polyolefin resin composition supplied in step 1 is 3% by weight or less, based on 100% by weight of the chlorinated polyolefin resin composition. [7] The method for producing a chlorinated polyolefin resin composition according to any one of the above [1] to [6], wherein the volatile chlorine-based compound comprises chloroform. [8] A method for producing an ink, primer, adhesive, or paint, comprising the following steps 1 to 3: Step 1: A step of supplying a solid chlorinated polyolefin resin composition having a volatile chlorine-based compound content of 0.2% by weight or more relative to 100% by weight of the chlorinated polyolefin resin composition to a twin-screw extruder. Step 2: A step of pouring water into the chlorinated polyolefin resin composition in the twin-screw extruder, and then devolatilizing the composition under reduced pressure. Step 3: A step of recovering a chlorinated polyolefin resin composition having a content of volatile chlorine-based compounds of less than 0.2% by weight based on 100% by weight of the chlorinated polyolefin resin composition from the twin-screw extruder. [Effects of the Invention]

[0010] According to the present invention, it is possible to produce a chlorinated polyolefin resin composition having a reduced content of volatile chlorine-based compounds such as chloroform while suppressing coloration without using high-temperature conditions. [Brief explanation of the drawings]

[0011] [Figure 1] FIG. 1 is a schematic view showing an example of a twin-screw extruder used in the production method of the present invention in an embodiment in which step 2 is repeated twice consecutively. DETAILED DESCRIPTION OF THE INVENTION

[0012] The present invention provides a method for producing a chlorinated polyolefin resin composition having a volatile chlorine-based compound content of less than 0.2% by weight based on 100% by weight of the chlorinated polyolefin resin composition, comprising the following steps 1 to 3: Step 1: A step of supplying a solid chlorinated polyolefin resin composition having a volatile chlorine-based compound content of 0.2% by weight or more relative to 100% by weight of the chlorinated polyolefin resin composition to a twin-screw extruder. Step 2: A step of pouring water into the chlorinated polyolefin resin composition in the twin-screw extruder, and then devolatilizing the composition under reduced pressure. Step 3: A step of recovering a chlorinated polyolefin resin composition having a content of volatile chlorine-based compounds of less than 0.2% by weight based on 100% by weight of the chlorinated polyolefin resin composition from the twin-screw extruder.

[0013] Step 1 in the production method of the present invention is a step of supplying a solid chlorinated polyolefin resin composition having a volatile chlorine-based compound content of 0.2% by weight or more relative to 100% by weight of the chlorinated polyolefin resin composition to a twin-screw extruder.

[0014] The solid chlorinated polyolefin resin composition supplied in step 1 contains a volatile chlorine-based compound and a chlorinated polyolefin resin, and may further contain other components.

[0015] The solid content of the solid chlorinated polyolefin resin composition supplied in step 1 is preferably 95% by weight or more, more preferably 97% by weight or more, even more preferably 98% by weight or more, and particularly preferably 99% by weight or more.

[0016] Step 2 in the production method of the present invention is a step of pouring water into the chlorinated polyolefin resin composition in a twin-screw extruder, followed by devolatilization under reduced pressure.

[0017] Step 2 does not necessarily have to be repeated, but is preferably repeated two or more times in succession, more preferably two to five times in succession, and particularly preferably two times in succession. That is, step 2 may be performed in such a manner that water injection and devolatilization under reduced pressure are each performed once after step 1, but is preferably performed in such a manner that water injection and devolatilization under reduced pressure are each performed alternately two or more times in succession after step 1, more preferably performed in such a manner that water injection and devolatilization under reduced pressure are each performed alternately two to five times in succession after step 1, and particularly preferably performed in such a manner that water injection and devolatilization under reduced pressure are each performed alternately two times in succession after step 1.

[0018] The amount of water injected per step in step 2 is preferably 0.1 to 30% by weight, more preferably 0.5 to 20% by weight, even more preferably 0.8 to 15% by weight, and particularly preferably 1 to 10% by weight, relative to 100% by weight of the chlorinated polyolefin resin composition.

[0019] The maximum degree of vacuum during reduced pressure devolatilization in step 2 is preferably 50 kPa or less, more preferably 30 kPa or less. The lower limit of the maximum degree of vacuum during reduced pressure devolatilization in step 2 is not particularly limited, but may be, for example, 1 kPa or more.

[0020] The temperature condition during the reduced pressure devolatilization in step 2 is preferably 150°C or lower, more preferably 140°C or lower, and the lower limit is preferably 70°C or higher, more preferably 80°C or higher.

[0021] The production method of the present invention may further include a step of devolatilizing the chlorinated polyolefin resin composition fed in step 1 in a twin-screw extruder under reduced pressure after step 1 and before step 2. Such a step may be repeated two or more times in succession.

[0022] The production method of the present invention may further include, after step 1 and before step 2, a step of heating and kneading the chlorinated polyolefin resin composition supplied in step 1 in a twin-screw extruder.

[0023] Step 3 in the production method of the present invention is a step of recovering from the twin-screw extruder a chlorinated polyolefin resin composition having a volatile chlorine-based compound content of less than 0.2% by weight relative to 100% by weight of the chlorinated polyolefin resin composition.

[0024] The volatile chlorine-based compounds in the chlorinated polyolefin resin composition recovered in step 3 contain chlorinated polyolefin resin, and may further contain volatile chlorine-based compounds and other components.

[0025] The color number of the chlorinated polyolefin resin composition recovered in step 3 (a toluene solution with a solid content of 30% by weight) is preferably less than 7, more preferably less than 6, and even more preferably less than 5, as measured by a Gardner color meter.

[0026] (1. Twin-screw extruder) The twin-screw extruder used in the production method of the present invention will be described with reference to Fig. 1. Fig. 1 is a schematic diagram showing an example of a twin-screw extruder 100 used in the production method of the present invention in an embodiment in which step 2 is repeated twice consecutively. Note that the present invention is not limited to the embodiment in which step 2 is repeated twice consecutively as performed by the twin-screw extruder shown in Fig. 1, and can be implemented with any modifications within the scope of the claims of the present invention and their equivalents.

[0027] In this embodiment, as shown in FIG. 1 , the twin-screw extruder 100 includes a motor section 110, a cylinder 101 provided adjacent to the motor section 110, a screw 102 disposed within the cylinder 101 and connected to the motor section 110, a supply section 120 provided with a hopper 121 for supplying a solid chlorinated polyolefin resin composition, and, in this order from the supply section 120 toward the downstream extrusion direction, a first kneading section 130, a first water injection section 140 provided with a first water injection port 141 for carrying out a first water injection, and a second water injection section 150 provided with a first water injection port 151 for carrying out a first water injection. The apparatus comprises a first devolatilization section 150 having a first vent port 151 for carrying out the second reduced pressure devolatilization, a second water injection section 160 having a second water injection port 161 for carrying out the second water injection, a second devolatilization section 170 having a second vent port 171 for carrying out the second reduced pressure devolatilization, a second kneading section 180, and a die section 190 having a discharge die 191 for recovering the chlorinated polyolefin resin composition, and a cylinder 101 and a screw 102 arranged within the cylinder 101 run from the supply section 120 to the die section 190.

[0028] The screw 102 is configured by appropriately combining screw elements. The shape and configuration of the screw are not particularly limited as long as the water injected from the first water inlet 141 and the second water inlet 161 is uniformly dispersed within the cylinder 101. The ratio L / D of the length L (mm) of the screw 102 to the diameter D (mm) of the screw 102 is preferably 15 to 80, and more preferably 20 to 60. The diameter D of the screw 102 is preferably 15 to 150 mm, and more preferably 40 to 135 mm.

[0029] The peripheral speed of the screw 102 is preferably 27 m / s or less, more preferably 25 m / s or less, and more preferably 23 m / s or less. The lower limit of the peripheral speed of the screw 102 is not particularly limited, but is preferably 5 m / s or more.

[0030] A solid chlorinated polyolefin resin composition is supplied from a hopper 121 in a supply section 120 and kneaded in a first kneading section 130 while being heated.

[0031] The internal temperature of the cylinder 101 is preferably 150°C or lower, and more preferably 140°C or lower, with the lower limit being preferably 70°C or higher, and more preferably 80°C or higher.

[0032] After kneading in first kneading section 130, water is injected into the chlorinated polyolefin resin composition via a water injection pump (not shown) through first water inlet 141 in first water injection section 140 and kneaded, and then in first volatilization section 150, at least a portion of volatile components such as water and volatile chlorine-based compounds are volatilized under reduced pressure through first vent port 151. After volatilization under reduced pressure in first volatilization section 150, water is again injected into the chlorinated polyolefin resin composition via a water injection pump (not shown) through second water inlet 161 in second water injection section 160 and kneaded, and then in second volatilization section 170, at least a portion of volatile components such as water and volatile chlorine-based compounds are volatilized under reduced pressure through second vent port 171. As the water injection pump, a plunger-type liquid addition pump or the like can be used.

[0033] The water injected from the first water inlet 141 and the second water inlet 161 may contain any additive components or impurities such as hydrophilic solvents, as long as it is primarily composed of water (for example, 90% by weight or more, preferably 99% by weight or more, and more preferably 99.9% by weight or more), but it is preferable to use pure water.

[0034] The amount of water poured from the first water pouring port 141 and the amount of water poured from the second water pouring port 161 are each preferably 0.1 wt % to 30 wt %, more preferably 0.5 wt % to 20 wt %, even more preferably 0.8 wt % to 15 wt %, and particularly preferably 1 wt % to 10 wt %, relative to 100 wt % of the chlorinated polyolefin resin composition.

[0035] The volatilization method in the first volatilization section 150 and the second volatilization section 170 may be, for example, a decompression vent method in which a decompression pump is connected to the first vent port 151 and the second vent port 171 to reduce the pressure.

[0036] The degree of vacuum in second devolatilization section 170 is preferably higher than the degree of vacuum in first devolatilization section 150. The degree of vacuum in first devolatilization section 150 is preferably 60 kPa or less, and more preferably 40 kPa or less. The degree of vacuum in second devolatilization section 170 is preferably 50 kPa or less, and more preferably 30 kPa or less. The lower limits of the degree of vacuum in first devolatilization section 150 and second devolatilization section 170 are not particularly limited, but may be, for example, 1 kPa or more.

[0037] 1, two sets of combinations of a water injection section with a water inlet and a devolatilization section with a vent port are installed consecutively from first water injection section 140 to second devolatilization section 170. However, in the present invention, the number of these combinations installed is not limited to two, and three or more sets may be installed consecutively, or only one set may be installed, but two or more sets are preferably installed consecutively. Furthermore, the number of water injection ports per combination is not limited to one, and may be two or more, and the number of vent ports is not limited to one, and may be two or more.

[0038] Furthermore, a devolatilization unit equipped with a vent port may be optionally installed upstream of the first water injection unit 140, separate from the first devolatilization unit 150 and the second devolatilization unit 170. A plurality of such devolatilization units may be installed.

[0039] After devolatilization under reduced pressure in the second devolatilization section 170, the chlorinated polyolefin resin composition is kneaded in the second kneading section 180, and recovered from a discharge die 191 in a die section 190 that communicates with the cylinder 101. In one embodiment, the recovered chlorinated polyolefin resin composition is passed directly from the discharge die 191 through a cooling bath to be cooled, and then processed with a cutter to form pellets.

[0040] (2. Volatile chlorine compounds) The solid chlorinated polyolefin resin composition supplied in step 1 contains volatile chlorine-based compounds. The chlorinated polyolefin resin composition recovered in step 3 may contain volatile chlorine-based compounds.

[0041] Volatile chlorine-based compounds are, for example, chlorine atom-containing compounds having a boiling point of 150°C or less under normal pressure (760 mmHg), and specific examples include chloroform, dichloromethane, 1,2-dichloroethane, 1,1-dichloroethane, 1,1,2-trichloroethane, chloroethylene, 1,1-dichloroethylene, 1,2-dichloroethylene, trichloroethylene, tetrachloroethylene, etc. The volatile chlorine-based compound preferably includes chloroform.

[0042] The content of volatile chlorine-based compounds in the solid chlorinated polyolefin resin composition supplied in step 1 is 0.2% by weight or more, and may be 0.3% by weight or more, 0.4% by weight or more, or 0.5% by weight or more, relative to 100% by weight of the chlorinated polyolefin resin composition. On the other hand, the upper limit is not particularly limited, but is preferably 5% by weight or less, more preferably 3% by weight or less, even more preferably 2% by weight or less, and particularly preferably 1% by weight or less.

[0043] The content of volatile chlorine-based compounds in the chlorinated polyolefin resin composition recovered in step 3 is not particularly limited, but is preferably less than 0.2% by weight, more preferably less than 0.15% by weight, more preferably less than 0.1% by weight, even more preferably less than 0.05% by weight, particularly preferably less than 0.02% by weight, and especially preferably less than 0.01% by weight, relative to 100% by weight of the chlorinated polyolefin resin composition.

[0044] (3. Chlorinated polyolefin resin) The solid chlorinated polyolefin resin composition supplied in step 1 and the chlorinated polyolefin resin composition recovered in step 3 both contain a chlorinated polyolefin resin.

[0045] The chlorinated polyolefin resin is a resin obtained by chlorinating at least a portion of a polyolefin resin.

[0046] Polyolefin resins are polymers of olefins (α-olefins), such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, and 1-octene.

[0047] The polyolefin resin may be a polymer of one type of olefin (α-olefin) or a copolymer of two or more types of olefins (α-olefins). When the polyolefin resin is a copolymer, the polyolefin resin may be a random copolymer or a block copolymer.

[0048] From the viewpoint of exhibiting sufficient adhesion to non-polar resin substrates such as polypropylene substrates, polypropylene (propylene homopolymer), ethylene-propylene copolymer, propylene-1-butene copolymer, and ethylene-propylene-1-butene copolymer are preferred as polyolefin resins.

[0049] Here, "polypropylene" refers to a polymer whose structural units are propylene-derived structural units. "Ethylene-propylene copolymer" refers to a copolymer containing ethylene-derived structural units and propylene-derived structural units as structural units. "Propylene-1-butene copolymer" refers to a copolymer containing propylene-derived structural units and butene-derived structural units as structural units. "Ethylene-propylene-1-butene copolymer" refers to a copolymer containing ethylene-derived structural units, propylene-derived structural units, and butene-derived structural units as structural units. These (co)polymers may contain small amounts of other olefin-derived structural units as structural units, as long as the amount does not significantly impair the inherent performance of the resin.

[0050] The polyolefin resin preferably contains 50 mol % or more of propylene-derived structural units out of 100 mol % of all structural units. When the propylene-derived structural units are contained in the above range, adhesion to non-polar resin substrates such as propylene resins can be maintained.

[0051] When the ethylene-propylene copolymer or propylene-1-butene copolymer is a random copolymer, preferably, out of 100 mol% of all structural units, ethylene-derived structural units or butene-derived structural units account for 3 to 50 mol% and propylene-derived structural units account for 50 to 97 mol%.

[0052] The lower limit of the melting point of the polyolefin resin is preferably 50°C or higher, more preferably 60°C or higher. When the melting point of the polyolefin resin is 50°C or higher, sufficient coating film strength can be exhibited when the chlorinated polyolefin resin obtained by chlorination is used for applications such as inks and paints. Therefore, adhesion to substrates can be sufficiently exhibited. Furthermore, when used as an ink, blocking during printing can be suppressed. The upper limit of the melting point of the polyolefin resin is preferably 180°C or lower, more preferably 170°C or lower, and even more preferably 165°C or lower. When the melting point of the polyolefin resin is 180°C or lower, the coating film can be prevented from becoming too hard when the chlorinated polyolefin resin obtained by chlorination is used for applications such as inks and paints. Therefore, the coating film can exhibit appropriate flexibility.

[0053] The weight average molecular weight (Mw) of the polyolefin resin is preferably 5,000 or more, more preferably 10,000 or more, even more preferably 15,000 or more, and particularly preferably 20,000 or more. The upper limit of the weight average molecular weight of the chlorinated polyolefin resin is preferably 500,000 or less, more preferably 400,000 or less, even more preferably 300,000 or less, and particularly preferably 250,000 or less. The weight average molecular weight (Mw) can be measured by GPC using polystyrene as a standard substance.

[0054] The chlorinated polyolefin resin is a resin obtained by chlorinating a polyolefin resin by a known method, for example, by blowing chlorine gas into the polyolefin resin.

[0055] The chlorination degree (chlorine content) of the chlorinated polyolefin resin is preferably 60% by weight or less, more preferably 55% by weight or less, even more preferably 50% by weight or less, and particularly preferably 45% by weight or less, based on 100% by weight of the chlorinated polyolefin resin. The lower limit of the chlorination degree (chlorine content) of the chlorinated polyolefin resin is preferably 5% by weight or more, more preferably 10% by weight or more, even more preferably 15% by weight or more, and particularly preferably 20% by weight or more, based on 100% by weight of the chlorinated polyolefin resin. This allows the polarity to be kept below a certain level, thereby achieving sufficient adhesion to non-polar substrates such as polyolefin substrates. The chlorination degree can be measured in accordance with JIS-K7229. Specifically, it can be measured using the "oxygen flask combustion method," in which a chlorine-containing resin is burned in an oxygen atmosphere, the generated chlorine gas is absorbed with water, and the amount is quantified by titration.

[0056] In one embodiment, the chlorinated polyolefin resin may be further modified with an acid component. Examples of the acid component include α,β-unsaturated carboxylic acids and their derivatives. Examples of the derivatives include α,β-unsaturated carboxylic acid anhydrides and α,β-unsaturated carboxylic acid esters.

[0057] Examples of α,β-unsaturated carboxylic acids and derivatives thereof include maleic acid, maleic anhydride, fumaric acid, citraconic acid, citraconic anhydride, mesaconic acid, itaconic acid, itaconic anhydride, aconitic acid, aconitic anhydride, himic anhydride, (meth)acrylic acid, (meth)acrylic acid esters, etc. Among these, maleic anhydride is preferred.

[0058] The total graft weight (modification degree) of acid components in the chlorinated polyolefin resin is preferably 20% by weight or less, more preferably 10% by weight or less, based on 100% by weight of the raw material unmodified polyolefin resin. The lower limit of the total graft weight (modification degree) of acid components is not particularly limited, but may be, for example, 0% by weight or more, 1% by weight or more. The graft weight (% by weight) can be determined, for example, by alkali titration or Fourier transform infrared spectroscopy.

[0059] The weight-average molecular weight (Mw) of the chlorinated polyolefin resin is preferably 2,000 or more, more preferably 10,000 or more, even more preferably 15,000 or more, and particularly preferably 50,000 or more. The upper limit of the weight-average molecular weight of the chlorinated polyolefin resin is preferably 250,000 or less, more preferably 200,000 or less, even more preferably 150,000 or less, and particularly preferably 120,000 or less.

[0060] (4. Method for producing chlorinated polyolefin resin) The chlorinated polyolefin resin can be produced by chlorinating a polyolefin resin.

[0061] Therefore, the method for producing a chlorinated polyolefin resin may include steps A and B in this order. Step A: preparing polyolefin resin Step B: Chlorination step

[0062] The chlorination in step B is usually carried out after dissolving the raw resin in a chlorine-based solvent (a volatile chlorine-based compound) such as chloroform in advance. Chlorination is carried out, for example, by blowing chlorine gas into the solution of the raw resin. The pressure when blowing chlorine gas is not limited, and may be normal pressure or under pressure. The pressure when blowing chlorine gas is not particularly limited, but is, for example, 0.1 MPa to 0.5 MPa. The temperature when blowing chlorine gas is not particularly limited, but is, for example, 50 to 140°C.

[0063] The chlorine gas may be blown in under irradiation with ultraviolet light or in the presence of a radical reaction initiator, but is preferably blown in the presence of a radical reaction initiator.

[0064] The radical reaction initiator may be, for example, a thermal polymerization initiator that generates free radicals when heated, such as organic peroxide compounds and azonitriles. Examples of the organic peroxide compounds include di-tert-butyl peroxide, dicumyl peroxide, tert-butylcumyl peroxide, dibenzoyl peroxide, benzoyl m-tolyl peroxide, di(m-tolyl)benzoyl, dilauryl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, cumene hydroperoxide, tert-butyl hydroperoxide, 1,1-bis(tert-butylperoxy)-3,5,5-trimethyl ... Examples of the azonitriles include methylcyclohexane, 1,1-bis(tert-butylperoxy)cyclohexane, cyclohexanone peroxide, tert-butylperoxybenzoate, tert-butylperoxyisobutyrate, tert-butylperoxy-3,5,5-trimethylhexanoate, tert-butylperoxy-2-ethylhexanoate, tert-butylperoxyisopropyl carbonate, tert-butylperoxyoctoate, and cumylperoxyoctoate. Examples of the azonitriles include 2,2-azobis(2-methylbutyronitrile), 2,2-azobisisobutyronitrile, 2,2-azobis(2,4-dimethylvaleronitrile), and 2,2-azobis(4-methoxy-2,4-dimethylvaleronitrile).

[0065] The amount of the radical reaction initiator used in step B is preferably 0.001 to 1% by weight, more preferably 0.01 to 0.1% by weight, relative to 100% by weight of the raw material resin.

[0066] If the chlorinated polyolefin resin is further modified with an acid component, step C may be included at any time after step A. Step C: Modification with an acid component

[0067] Step C can be carried out at any time after step A, but is preferably carried out before step B.

[0068] In step C, for example, a method of introducing an acid component into a polyolefin chain by graft copolymerization can be used. The graft copolymerization is not particularly limited, and can be carried out using known methods such as a melt method or a solution method. When using the melt method, the operation is simple and the reaction can be carried out in a shorter time. When using the solution method, side reactions are reduced and a more uniform graft polymer can be obtained.

[0069] When step C is carried out by a melting method, for example, the raw material resin is heated and melted (heat-melted) in the presence of a radical reaction initiator to cause a reaction. The heat-melting temperature may be equal to or higher than the melting point, and is preferably equal to or higher than the melting point and equal to or lower than 300°C. Equipment such as a Banbury mixer, kneader, or extruder can be used for the heat-melting.

[0070] When step C is carried out by a melting method, it is preferably carried out using an extruder (extrusion modification). Examples of extrusion modification methods include blending raw material resins, feeding them into the feed section of an extruder (e.g., a co-rotating multi-screw extruder, a twin-screw extruder), sequentially carrying out the steps of raw material mixing, melt kneading, reaction, and devolatilization cooling in the extruder, and cooling the resin emerging from the tip die (e.g., immersed in a water bath) to obtain a polyolefin resin modified with an acid component. The progress of the reaction can be controlled by adjusting the temperature of each part of the barrel and the screw rotation speed.

[0071] When step C is carried out by a solution method, for example, the raw material resin is dissolved in a hydrophobic solvent and then reacted by heating and stirring in the presence of a radical reaction initiator. The temperature during the reaction is preferably 100 to 180° C. After step C, the hydrophobic solvent in the system may be distilled off under reduced pressure, or the hydrophobic solvent may be removed using an extruder.

[0072] When step C is carried out by a solution method, the hydrophobic solvent to be used is preferably an aromatic hydrocarbon solvent such as toluene, o-xylene, m-xylene, p-xylene, or ethylbenzene; or an aliphatic hydrocarbon solvent such as n-pentane, cyclopentane, n-hexane, isohexane, cyclohexane, n-heptane, methylcyclohexane, n-octane, ethylcyclohexane, n-nonane, or n-decane.

[0073] (5. Other Ingredients) The solid chlorinated polyolefin resin composition supplied in step 1 and the chlorinated polyolefin resin composition recovered in step 3 may further contain other components. Examples of the other components include a stabilizer and an antioxidant.

[0074] Examples of the stabilizer include epoxy-based stabilizers (stabilizers containing an epoxy structure), such as epoxy compounds having an epoxy equivalent of about 100 to 500 and containing one or more epoxy groups in one molecule. More specifically, examples of such compounds include the following: epoxidized soybean oil and linseed oil obtained by epoxidizing vegetable oils having natural unsaturated groups with peracids such as peracetic acid; epoxidized fatty acid esters obtained by epoxidizing unsaturated fatty acids such as oleic acid, tall oil fatty acid, and soybean oil fatty acid; epoxidized alicyclic compounds typified by epoxidized tetrahydrophthalate; polyglycidyl ether compounds such as bisphenol A diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, glycerol polyglycidyl ether, sorbitol polyglycidyl ether, and trimethylolpropane polyglycidyl ether; and monoglycidyl ether compounds typified by butyl glycidyl ether, 2-ethylhexyl glycidyl ether, decyl glycidyl ether, stearyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, p-sec-butylphenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, and phenol polyethylene oxide glycidyl ether. The stabilizer may be a stabilizer other than an epoxy-based stabilizer, and examples thereof include oxetane compounds; metal soaps such as calcium stearate and lead stearate, which are used as stabilizers for polyvinyl chloride resins; organometallic compounds such as dibutyltin dilaurate and dibutyl maleate; and hydrotalcite compounds. The stabilizers may be used alone or in combination of two or more.

[0075] The antioxidant may suitably be a compound that functions as a radical scavenger. Examples of the antioxidant include phenol-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants. The antioxidant may be used alone or in combination of two or more.

[0076] (6. Uses of Chlorinated Polyolefin Resin Composition) In addition to the steps 1 to 3 described above, the chlorinated polyolefin resin composition can be subjected to a step of adding an additive to form a resin composition in the form of, for example, a resin solution, an aqueous dispersion, a solid, or the like, and can be used as a primer, an adhesive, a paint, or an ink.

[0077] Therefore, the present invention provides a method for producing a primer, adhesive, paint, or ink, which includes the above-described steps 1 to 3. In one embodiment, the primer, adhesive, paint, or ink produced using such a production method may be characterized by reduced coloration and a lower content of volatile chlorine-based compounds.

[0078] The content of volatile chlorine-based compounds in the primer, adhesive, paint or ink produced using such a production method may be less than 0.2% by weight, preferably less than 0.15% by weight, more preferably less than 0.1% by weight, even more preferably less than 0.05% by weight, particularly preferably less than 0.02% by weight, and especially preferably less than 0.01% by weight, based on 100% by weight of the total amount of the primer, adhesive, paint or ink.

[0079] The manufacturing method of the primer, adhesive, paint or ink may include the step of adding the additive.

[0080] Examples of additives include the stabilizers and antioxidants described above, as well as non-chlorine-based solvents, curing agents, adhesive components, basic substances, crosslinking agents, emulsifiers, diluents, light stabilizers, ultraviolet absorbers, pigments, dyes, inorganic fillers, etc., and these can be selected appropriately depending on the application.

[0081] The non-chlorine-based solvent may be either a non-chlorine-based hydrophobic solvent or a non-chlorine-based hydrophilic solvent.

[0082] Examples of non-chlorine-based hydrophobic solvents include aromatic hydrocarbon solvents such as toluene and xylene; ester solvents such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, and butyl acetate; ketone solvents such as acetone, methyl ethyl ketone, and methyl butyl ketone; alicyclic hydrocarbon solvents such as cyclohexane, methylcyclohexane, and ethylcyclohexane; and aliphatic hydrocarbon solvents such as nonane and decane.

[0083] Examples of non-chlorine hydrophilic solvents include water; glycol solvents such as ethylene glycol, ethyl cellosolve, and butyl cellosolve; aliphatic alcohol solvents such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, tert-butyl alcohol, and 2-ethylhexanol; and glycol monoether solvents such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monoisopropyl ether, and propylene glycol monobutyl ether. The solvents may be used alone or in combination of two or more.

[0084] Examples of curing agents include polyisocyanate compounds, epoxy compounds, polyamine compounds, polyol compounds, crosslinking agents in which the functional groups of these compounds are blocked with protecting groups, and combinations of two or more of these. The content of the curing agent may be appropriately selected depending on the content of the modified polyolefin resin. When using a curing agent, a catalyst such as an organotin compound or a tertiary amine compound may be used in combination depending on the purpose. One type of curing agent may be used alone, or two or more types may be used in combination.

[0085] Examples of adhesive components include known adhesive components such as polyester adhesives, polyurethane adhesives, acrylic adhesives, etc. The adhesive components may be used alone or in combination of two or more.

[0086] When using a non-chlorine-based solvent such as water, an alcohol-based solvent, a glycol-based solvent, a ketone-based solvent, or an ester-based solvent, the resin composition preferably contains a basic substance. This allows for appropriate adjustment of the pH and improves the dispersibility and storage stability of the resin in the non-chlorine-based solvent. Examples of basic substances include sodium hydroxide, potassium hydroxide, ammonia, methylamine, propylamine, hexylamine, octylamine, ethanolamine, propanolamine, diethanolamine, N-methyldiethanolamine, dimethylamine, diethylamine, triethylamine, N,N-dimethylethanolamine, 2-dimethylamino-2-methyl-1-propanol, 2-amino-2-methyl-1-propanol, morpholine, dimethylethanolamine, and 2-amino-2-ethyl-1,3-propanediol. Preferred examples include ammonia, triethylamine, 2-amino-2-methyl-1-propanol, morpholine, dimethylethanolamine, and 2-amino-2-ethyl-1,3-propanediol. The basic substance may be used alone or in combination of two or more kinds.

[0087] When a non-chlorine-based hydrophobic solvent is used as the non-chlorine-based solvent, the resin composition preferably contains a diluent. This can improve storage stability. Examples of the diluent include alcohol and propylene-based glycol ether. Examples of the alcohol include methanol, ethanol, propanol, isopropanol, and butanol. Examples of the propylene-based glycol ether include propylene glycol methyl ether, propylene glycol ethyl ether, and propylene glycol tert-butyl ether. The diluent may be used alone or in combination of two or more.

[0088] When a non-chlorine-based hydrophobic solvent is used as the non-chlorine-based solvent, the resin composition preferably contains a crosslinking agent. The crosslinking agent may be any compound capable of reacting with groups present in the composition, such as hydroxyl groups, carboxyl groups, and amino groups, to form a crosslinked structure, and may be either a water-soluble crosslinking agent or an aqueous dispersion of a crosslinking agent (a crosslinking agent dispersed in water by some method). Examples of crosslinking agents include blocked isocyanate compounds, aliphatic or aromatic epoxy compounds, amine compounds, and amino resins. The crosslinking agents may be used alone or in combination of two or more.

[0089] When a non-chlorine-based hydrophilic solvent is used as the non-chlorine-based solvent, the resin composition preferably contains an emulsifier. Examples of the emulsifier include surfactants such as nonionic surfactants and anionic surfactants, and nonionic surfactants are preferred.

[0090] Examples of nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene derivatives, polyoxyethylene fatty acid esters, polyoxyethylene polyhydric alcohol fatty acid esters, polyoxyethylene polyoxypropylene polyols, sorbitan fatty acid esters, polyoxyethylene hydrogenated castor oil, polyoxyalkylene polycyclic phenyl ethers, polyoxyethylene alkylamines, alkylalkanolamides, polyalkylene glycol (meth)acrylates, etc. Preferred are polyoxyethylene alkyl ethers, polyoxyethylene fatty acid esters, polyoxyethylene sorbitan fatty acid esters, and polyoxyethylene alkylamines.

[0091] Examples of anionic surfactants include alkyl sulfates, polyoxyethylene alkyl ether sulfates, alkylbenzene sulfonates, α-olefin sulfonates, methyl taurates, sulfosuccinates, ether sulfonates, ether carboxylates, fatty acid salts, naphthalene sulfonate-formalin condensates, alkylamine salts, quaternary ammonium salts, alkyl betaines, and alkylamine oxides. Polyoxyethylene alkyl ether sulfates and sulfosuccinates are preferred. The emulsifiers may be used singly or in combination of two or more. [Example]

[0092] The present invention will be described in detail below using examples, but the present invention is not limited to these examples. In the following description, unless a specific temperature condition is specified, the temperature condition is assumed to be room temperature (25°C), and unless a specific pressure condition is specified, the pressure condition is assumed to be normal pressure (760 mmHg).

[0093] [Example 1] 960 kg of polypropylene with a melting point of 150°C and a weight-average molecular weight (Mw) of 20,000 was placed in a glass-lined reactor, and 5,000 L of chloroform was added. The reactor was pressurized with air to a gauge pressure of 0.4 MPa, and the mixture was thoroughly dissolved at a temperature of 115°C. 670 g of tert-butyl peroxyoctoate (radical reaction initiator) was then added, and chlorine gas and oxygen gas were blown in while maintaining the reactor pressure at 0.35 MPa, yielding a chloroform solution of chlorinated polyolefin resin with a chlorine content of 42.0 wt% and a weight-average molecular weight of 20,000.

[0094] The resulting chloroform solution was concentrated to a solids content of 30-40 wt%, and an epoxy compound (component name: epoxidized soybean oil) dissolved in chloroform (4.0 wt% relative to the chlorinated polyolefin resin) was added. In the first chloroform removal step, the chloroform was removed using a vented twin-screw extruder equipped with a vent port for distilling off the reaction solvent under reduced pressure. The chlorinated polypropylene resin was extruded into strands and cooled with water. The resulting mixture was then pelletized using a water-cooled pelletizer to obtain a solid chlorinated polyolefin resin composition (A) containing 0.65 wt% chloroform.

[0095] The resulting solid chlorinated polyolefin resin composition (A) was fed through a resin inlet (hopper) into a twin-screw extruder (internal temperature of the cylinder: 120°C; peripheral speed: 10 m / s; throughput: 10 kg / h; screw diameter: 32 mm; L / D: 28) equipped with two vents for vacuum distillation and two water inlets for water supply, as shown in Figure 1. Water was fed through the water inlets (7.0 wt% of the chlorinated polyolefin resin composition per inlet) and vacuum devolatilized through a vent (vacuum degree: 10 kPa) twice to remove chloroform and water, yielding a solid chlorinated polyolefin resin composition (1) containing 41.0 wt% chlorine, a weight-average molecular weight of 20,000, and 0.02 wt% residual chloroform. The color number was 4.

[0096] [Example 2] A solid chlorinated polyolefin resin composition (2) containing chlorine content of 41.0 wt%, chlorinated polyolefin resin having a weight average molecular weight of 20,000, residual chloroform of 0.04 wt%, and color number of 4 was obtained in the same manner as in Example 1, except that the amount of water injected per water injection port was changed from 7.0 wt% to 4.0 wt% relative to the chlorinated polyolefin resin composition.

[0097] [Example 3] A solid chlorinated polyolefin resin composition (3) having a chlorine content of 41.0 wt%, a residual chloroform content of 0.07 wt%, and a color number of 4, containing a chlorinated polyolefin resin having a weight average molecular weight of 20,000, was obtained in the same manner as in Example 1, except that the amount of water injected per water inlet was changed from 7.0 wt% to 2.4 wt% (first water inlet) and 2.5 wt% (second water inlet) relative to the chlorinated polyolefin resin composition.

[0098] [Example 4] A solid chlorinated polyolefin resin composition (4) having a chlorine content of 41.0% by weight, a residual chloroform content of 0.13% by weight, and a color number of 4, containing a chlorinated polyolefin resin having a weight average molecular weight of 20,000, was obtained in the same manner as in Example 1, except that the amount of water injected per water inlet was changed from 7.0% by weight to 1.5% by weight (first water inlet) and 1.3% by weight (second water inlet) relative to the chlorinated polyolefin resin composition.

[0099] [Example 5] A solid chlorinated polyolefin resin composition (5) having a chlorine content of 41.0% by weight, a residual chloroform content of 0.15% by weight, and a color number of 4, containing a chlorinated polyolefin resin having a weight average molecular weight of 20,000, was obtained in the same manner as in Example 1, except that the amount of water injected per water inlet was changed from 7.0% by weight to 0% by weight (first water inlet) and 4.0% by weight (second water inlet) relative to the chlorinated polyolefin resin composition, and that the pressure was not reduced through the first vent port.

[0100] [Example 6] 800 kg of polypropylene with a melting point of 163°C and a weight-average molecular weight (Mw) of 200,000 was placed in a glass-lined reactor, and 8,000 L of chloroform was added. The reactor was pressurized with air to a gauge pressure of 0.4 MPa, and the mixture was thoroughly dissolved at a temperature of 115°C. 600 g of tert-butyl peroxyoctoate (radical reaction initiator) was then added, and chlorine gas and oxygen gas were blown in while maintaining the reactor pressure at 0.35 MPa, yielding a chloroform solution of chlorinated polyolefin resin with a chlorine content of 37.0 wt% and a weight-average molecular weight of 30,000.

[0101] The resulting chloroform solution was concentrated to a solids content of 30-40 wt%, and an epoxy compound (component name: trimethylolpropane polyglycidyl ether) dissolved in chloroform (4.0 wt% relative to the chlorinated polyolefin resin) was added. In the first chloroform removal step, the chloroform was removed using a vented twin-screw extruder equipped with a vent port for distilling off the reaction solvent under reduced pressure. The chlorinated polypropylene resin was extruded into strands and cooled with water. The resulting mixture was then pelletized using a water-cooled pelletizer to obtain a solid chlorinated polyolefin resin composition (B) containing 0.54 wt% chloroform.

[0102] The resulting solid chlorinated polyolefin resin composition (B) was fed through a resin inlet (hopper) into a twin-screw extruder for water injection and vacuum devolatilization (internal temperature of the cylinder: 120°C; peripheral speed: 10 m / s; throughput: 10 kg / h; screw diameter: 32 mm; L / D: 28) equipped with two vents for vacuum distillation and two water inlets for water supply, as shown in Figure 1. The process of feeding water through the water inlets (4.0 wt% of the chlorinated polyolefin resin composition per inlet) and vacuum devolatilization through the vent (vacuum degree: 10 kPa) was repeated twice to remove chloroform and water, yielding a solid chlorinated polyolefin resin composition (6) containing chlorine content 36.0 wt%, weight-average molecular weight 30,000, residual chloroform 0.01 wt%, and having a color number of 5.

[0103] [Example 7] 850 kg of polypropylene with a melting point of 158°C and a weight-average molecular weight (Mw) of 110,000 was placed in a glass-lined reactor, and 8,000 L of chloroform was added. The reactor was pressurized with air to a gauge pressure of 0.4 MPa, and the mixture was thoroughly dissolved at a temperature of 115°C. 820 g of tert-butyl peroxyoctoate (radical reaction initiator) was then added, and chlorine gas and oxygen gas were blown in while maintaining the reactor pressure at 0.35 MPa, yielding a chloroform solution of chlorinated polyolefin resin with a chlorine content of 29.0 wt% and a weight-average molecular weight of 110,000.

[0104] The resulting chloroform solution was concentrated to a solids content of 30-40 wt%, and an epoxy compound (component name: p-tert-butylphenyl glycidyl ether) dissolved in chloroform (4.0 wt% relative to the chlorinated polyolefin resin) was added. In the first chloroform removal step, the chloroform was removed using a vented twin-screw extruder equipped with a vent port for distilling off the reaction solvent under reduced pressure. The chlorinated polypropylene resin was extruded into strands and cooled with water. The resulting mixture was then pelletized using a water-cooled pelletizer to obtain a solid chlorinated polyolefin resin composition (C) containing 0.75 wt% chloroform.

[0105] The resulting solid chlorinated polyolefin resin composition (C) was fed through a resin inlet (hopper) into a twin-screw extruder (internal temperature of the cylinder: 120°C; peripheral speed: 10 m / s; throughput: 10 kg / h; screw diameter: 32 mm; L / D: 28) equipped with two vents for vacuum distillation and two water inlets for water supply, as shown in Figure 1. The process of feeding water through the water inlets (4.0 wt% of the chlorinated polyolefin resin composition per inlet) and vacuum devolatilization through the vent (vacuum degree: 10 kPa) was repeated twice to remove chloroform and water, yielding a solid chlorinated polyolefin resin composition (7) containing 28.0 wt% chlorine and a weight-average molecular weight of 110,000, with less than 0.01 wt% residual chloroform and a color number of 4.

[0106] [Example 8] 1,000 kg of maleic anhydride-modified polypropylene with a melting point of 125°C and a weight-average molecular weight (Mw) of 80,000 was placed in a glass-lined reactor, and 7,000 L of chloroform was added. The reactor was pressurized with air to a gauge pressure of 0.4 MPa, and the mixture was thoroughly dissolved at a temperature of 115°C. 820 g of tert-butyl peroxyoctoate (radical reaction initiator) was then added, and chlorine gas and oxygen gas were blown in while maintaining the reactor pressure at 0.35 MPa, yielding a chloroform solution of chlorinated polyolefin resin with a chlorine content of 22.0 wt% and a weight-average molecular weight of 80,000.

[0107] The resulting chloroform solution was concentrated to a solids content of 30-40 wt%, and an epoxy compound (component name: p-tert-butylphenyl glycidyl ether) dissolved in chloroform (4.0 wt% relative to the chlorinated polyolefin resin) was added. In the first chloroform removal step, the chloroform was removed using a vented twin-screw extruder equipped with a vent port for distilling off the reaction solvent under reduced pressure. The chlorinated polypropylene resin was extruded into strands and cooled with water. The resulting mixture was then pelletized using a water-cooled pelletizer to obtain a solid chlorinated polyolefin resin composition (D) containing 0.44 wt% chloroform.

[0108] The resulting solid chlorinated polyolefin resin composition (D) was fed through a resin inlet (hopper) into a twin-screw extruder for water injection and vacuum devolatilization (internal temperature of the cylinder: 120°C; peripheral speed: 10 m / s; throughput: 10 kg / h; screw diameter: 32 mm; L / D: 28) equipped with two vents for vacuum distillation and two water inlets for water supply, as shown in Figure 1. Water was fed through the water inlets (4.0 wt% of the chlorinated polyolefin resin composition per inlet) and vacuum devolatilization was performed through a vent (vacuum degree: 10 kPa) twice to remove chloroform and water, yielding a solid chlorinated polyolefin resin composition (8) containing 21.0 wt% chlorine and a weight-average molecular weight of 80,000, with less than 0.01 wt% residual chloroform and a color index of 2.

[0109] [Example 9] A solid chlorinated polyolefin resin composition (9) having a chlorine content of 41.0 wt%, a residual chloroform content of 0.07 wt%, a color number of 4, and a weight average molecular weight of 20,000, was obtained in the same manner as in Example 1, except that the chloroform content of the solid chlorinated polyolefin resin composition (A) was 2.61 wt%.

[0110] [Comparative Example 1] A solid chlorinated polyolefin resin composition (1') containing a chlorine content of 41.0 wt%, a chlorinated polyolefin resin having a weight average molecular weight of 20,000, a residual chloroform content of 0.40 wt%, and a color number of 4 was obtained in the same manner as in Example 1, except that water was not poured from the water inlet.

[0111] Comparative Example 2 A solid chlorinated polyolefin resin composition (2') containing a chlorinated polyolefin resin having a chlorine content of 41.0 wt%, a weight average molecular weight of 20,000, a residual chloroform content of 0.15 wt%, and a color number of 8 was obtained in the same manner as in Example 1, except that water was not injected from the water inlet and the internal temperature of the cylinder of the water-injection vacuum devolatilization twin-screw extruder was changed from 120°C to 160°C.

[0112] Comparative Example 3 A solid chlorinated polyolefin resin composition (3') containing a chlorine content of 28.0 wt%, a chlorinated polyolefin resin having a weight average molecular weight of 110,000, a residual chloroform content of 0.53 wt%, and a color number of 4 was obtained in the same manner as in Example 7, except that water was not poured from the water inlet.

[0113] Comparative Example 4 A solid chlorinated polyolefin resin composition (4') containing a chlorine content of 21.0 wt%, a chlorinated polyolefin resin having a weight average molecular weight of 80,000, a residual chloroform content of 0.37 wt%, and a color number of 2 was obtained in the same manner as in Example 8, except that water was not poured from the water inlet.

[0114] (Measurement of weight average molecular weight (Mw) of resin) The weight average molecular weight (Mw) of the chlorinated polyolefin resin was measured by GPC under the following conditions. Apparatus: HLC-8320GPC (manufactured by Tosoh Corporation) Column: TSK-gel G-6000 HXL, G-5000 HXL, G-4000 HXL, G-3000 HXL, G-2000 HXL (manufactured by Tosoh Corporation) Eluent:THF Flow rate: 1mL / min Temperature: Pump oven, column oven 40℃ Injection volume: 100μL Standard material: Polystyrene EasiCal PS-1 (Agilent Technology)

[0115] (Measurement of chlorine content in resin) The chlorine content was measured in accordance with JIS-K7229.

[0116] (Measurement of chloroform content in resin composition) Analysis was performed using a Shimadzu gas chromatograph GC-2010plus Tracera (using a BID detector), carrier gas: helium (linear flow rate: 40 cm / sec), capillary column (Restek Rtx-624 (inner diameter: 0.32 mm, film thickness: 1.8 μm, length: 30 m), sample injection temperature (injection temperature): 160°C, column temperature: 60°C), and chlorinated polyolefin resin adjusted to a concentration of 5 wt% in p-xylene solvent was introduced into the instrument.

[0117] (Measurement of color number of resin composition) The color number of the resin composition was measured using a Gardner color meter in accordance with JIS K 0071-2.

[0118] The amount of chloroform in the supplied resin composition, the amount of water injected from the first water inlet (upstream side) and the second water inlet (downstream side), the weight average molecular weight (Mw) of the chlorinated polyolefin resin contained in the recovered resin composition, the degree of chlorination, the amount of residual chloroform in the resin composition, and the color of the resin composition in the examples and comparative examples are summarized in Table 1 below.

[0119] [Table 1] [Explanation of symbols]

[0120] 100 Twin-screw extruder 101 cylinder 102 Screw 110 Motor section 120 Supply section 121 Hopper 130 First kneading section 140 First water injection part 141 First water inlet 150 First devolatilization section 151 First Vent 160 Second water injection part 161 Second water inlet 170 Second devolatilization section 171 Second Vent 180 Second kneading section 190 Dice Section 191 Discharge Die

Claims

1. A method for producing a chlorinated polyolefin resin composition having a volatile chlorine-based compound content of less than 0.2% by weight, based on 100% by weight of the chlorinated polyolefin resin composition, comprising the following steps 1 to 3, wherein step 2 is repeated two or more times in succession: Step 1: A step of supplying a solid chlorinated polyolefin resin composition having a volatile chlorine-based compound content of 0.2% by weight or more relative to 100% by weight of the chlorinated polyolefin resin composition to a twin-screw extruder having an internal temperature of the cylinder of 150°C or less. Step 2: A step of pouring water into the chlorinated polyolefin resin composition in the twin-screw extruder in which the internal temperature of the cylinder is 150°C or less, and then devolatilizing the composition under reduced pressure. Step 3: A step of recovering a chlorinated polyolefin resin composition having a volatile chlorine-based compound content of less than 0.2% by weight based on 100% by weight of the chlorinated polyolefin resin composition from the twin-screw extruder.

2. 2. The method for producing a chlorinated polyolefin resin composition according to claim 1, wherein the chlorinated polyolefin resin composition recovered in step 3 has a content of volatile chlorine-based compounds of less than 0.1% by weight based on 100% by weight of the chlorinated polyolefin resin composition.

3. A method for producing a chlorinated polyolefin resin composition according to claim 1 or 2, wherein the chlorine content of the chlorinated polyolefin resin is 41.0% by weight or more.

4. 4. The method for producing a chlorinated polyolefin resin composition according to claim 1, wherein the amount of water added per step in step 2 is 0.5 to 20% by weight based on 100% by weight of the chlorinated polyolefin resin composition.

5. A method for producing a chlorinated polyolefin resin composition as described in Claim 4, wherein the amount of water injected per step of step 2 is 4 wt% or more relative to 100 wt% of the chlorinated polyolefin resin composition.

6. The method for producing a chlorinated polyolefin resin composition according to any one of claims 1 to 5, wherein the content of volatile chlorine-based compounds in the solid chlorinated polyolefin resin composition supplied in step 1 is 3% by weight or less, based on 100% by weight of the chlorinated polyolefin resin composition.

7. The method for producing a chlorinated polyolefin resin composition according to any one of claims 1 to 6, wherein the volatile chlorine-based compound comprises chloroform.

8. A method for producing an ink, primer, adhesive, or paint, comprising the following steps 1 to 3, wherein step 2 is repeated two or more times in succession: Step 1: A step of supplying a solid chlorinated polyolefin resin composition having a volatile chlorine-based compound content of 0.2% by weight or more relative to 100% by weight of the chlorinated polyolefin resin composition to a twin-screw extruder having an internal temperature of the cylinder of 150°C or less. Step 2: A step of pouring water into the chlorinated polyolefin resin composition in the twin-screw extruder in which the internal temperature of the cylinder is 150°C or less, and then devolatilizing the composition under reduced pressure. Step 3: A step of recovering a chlorinated polyolefin resin composition having a volatile chlorine-based compound content of less than 0.2% by weight based on 100% by weight of the chlorinated polyolefin resin composition from the twin-screw extruder.

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