Method for producing acid-modified chlorinated polyolefin resin

Abstract

To provide a production method of an acid-modified chlorinated polyolefin resin, capable of suppressing hue of an acid-modified chlorinated polyolefin resin to be obtained.SOLUTION: A production method of an acid-modified chlorinated polyolefin resin includes an acid-modifying chlorination step of continuously performing acid-modifying reaction by acid components and chlorination reaction relative to a polyolefin resin in the same reaction tank in an arbitrary order. In the production method of the acid-modified chlorinated polyolefin resin, a graft amount of acid components of the acid-modified chlorinated polyolefin resin is 0.1 wt.%-10 wt.%, and a graft amount of chlorine is 10 wt.%-70 wt.%.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a method for producing an acid-modified chlorinated polyolefin resin using a polyolefin resin as a raw material. [Background technology]

[0002] In the past, when polyolefin resins were acid-modified and chlorinated, the acid modification was generally carried out using a melting method in which an acid component and a radical reaction initiator were added to a kneader such as an extruder and kneaded, and then the resulting mixture was transferred to a reaction tank for chlorination.

[0003] However, the melting method has a problem that the resin produced becomes strongly colored during kneading due to an increase in double bonds (unsaturated parts) inside the polyolefin resin, oligomerization of residual monomers, etc. If the resin obtained is strongly colored in this way, a problem may arise in that the range of application of the resin is narrowed, for example, it cannot be used in white paints or white inks.

[0004] In order to suppress coloration, it is possible to use methods other than the melting method, but due to concerns about a decrease in grafting efficiency, this method has not been studied much up to now. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] International Publication No. 2005 / 116093 Summary of the Invention [Problem to be solved by the invention]

[0006] An object of the present invention is to provide a method for producing an acid-modified chlorinated polyolefin resin, which can suppress the color of the resulting acid-modified chlorinated polyolefin resin. [Means for solving the problem]

[0007] As a result of intensive research into the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by continuously carrying out an acid modification reaction with an acid component and a chlorination reaction in any order on a polyolefin resin in the same reaction tank, and have completed the present invention. That is, the present inventors provide the following [1] to [6]. [1] A method for producing an acid-modified chlorinated polyolefin resin, comprising an acid-modified chlorination step in which an acid modification reaction with an acid component and a chlorination reaction are continuously carried out in any order on a polyolefin resin in the same reaction tank, A method for producing an acid-modified chlorinated polyolefin resin, in which the graft amount of an acid component in the acid-modified chlorinated polyolefin resin is 0.1% by weight to 10% by weight, and the graft amount of chlorine is 10% by weight to 70% by weight. [2] The method for producing an acid-modified chlorinated polyolefin resin according to the above item [1], wherein the acid-modified chlorination step is an acid-modified chlorination step in which an acid modification reaction with an acid component and a chlorination reaction are continuously carried out in this order on a polyolefin resin in the same reaction tank. [3] The method for producing an acid-modified chlorinated polyolefin resin according to the above [2], wherein a radical reaction initiator is added after the addition of an acid component in the acid-modified chlorination step. [4] The method for producing an acid-modified chlorinated polyolefin resin according to any one of the above [1] to [3], wherein the amount of the acid component added is 10 parts by weight or less per 100 parts by weight of the polyolefin resin. [5] The method includes adding a radical reaction initiator in the acid-modified chlorination step, The method for producing an acid-modified chlorinated polyolefin resin according to any one of the above [1] to [4], wherein the amount of the radical reaction initiator added is 0.1 part by weight or more per part by weight of the acid component. [6] The method includes adding a radical reaction initiator in the acid-modified chlorination step, The method for producing an acid-modified chlorinated polyolefin resin according to any one of the above [1] to [5], wherein the amount of the radical reaction initiator added is 2 parts by weight or less per part by weight of the acid component. Effect of the Invention

[0008] According to the present invention, an acid-modified chlorinated polyolefin resin having reduced color can be produced. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] Hereinafter, the present invention will be described in detail based on preferred embodiments thereof. Note that the notation "AA to BB%" indicates AA% or more and BB% or less.

[0010] [1. Method for producing acid-modified chlorinated polyolefin resin] The method for producing an acid-modified chlorinated polyolefin resin of the present invention is characterized by comprising an acid-modified chlorination step in which an acid modification reaction by adding an acid component and a chlorination reaction are carried out continuously in any order on a polyolefin resin in the same reaction tank. "Continuously" means that a reaction is carried out from one reaction to another without transferring the reaction tank for each reaction.

[0011] The acid-modified chlorination step may be a step in which the acid modification reaction is continuously carried out in the order of chlorination reaction (production method B or production method C), or a step in which the chlorination reaction is continuously carried out in the order of acid modification reaction (production method A), but from the viewpoint of further suppressing color, a step in which the acid modification reaction is continuously carried out in the order of chlorination reaction is preferred. Therefore, the acid-modified chlorination step is preferably an acid-modified chlorination step in which the acid modification reaction by adding an acid component and the chlorination reaction are continuously carried out in this order in the same reaction tank for the polyolefin resin.

[0012] The acid modification reaction is carried out by adding an acid component to a reaction tank and reacting the polyolefin resin with the acid component. When the acid modification reaction and the chlorination reaction are carried out successively, in one embodiment, the acid component is usually added to the reaction tank simultaneously with the addition of the polyolefin resin or after the addition of the resin.

[0013] The acid component is, for example, an α,β-unsaturated carboxylic acid and its derivative (for example, an α,β-unsaturated carboxylic acid ester, an α,β-unsaturated carboxylic acid anhydride), and specifically includes maleic acid, maleic anhydride, fumaric acid, citraconic acid, citraconic anhydride, mesaconic acid, itaconic acid, itaconic anhydride, aconitic acid, aconitic anhydride, hymic anhydride, (meth)acrylic acid, and (meth)acrylic acid ester. The (meth)acrylic acid ester is preferably an ester consisting of a (meth)acrylic acid group and a hydrocarbon group, and examples thereof include lauryl (meth)acrylate, tridecyl (meth)acrylate, octyl (meth)acrylate, and isodecyl (meth)acrylate. The acid component may be one or more compounds, or a combination of two or more compounds. Such an acid component can be introduced into the main chain of a polyolefin resin by graft copolymerization. In consideration of the graftability to a polyolefin resin, the acid component is preferably maleic anhydride.

[0014] The amount of the acid component added is preferably 0.05 parts by weight or more, more preferably 0.1 parts by weight or more, even more preferably 0.3 parts by weight or more, and particularly preferably 0.5 parts by weight or more, relative to 100 parts by weight of the polyolefin resin. By adding an amount of 0.05 parts by weight or more, the adhesion of the acid-modified chlorinated polyolefin resin to the metal adherend can be maintained. The upper limit of the amount of the acid component added is preferably 15 parts by weight or less, more preferably 10 parts by weight or less, even more preferably 7 parts by weight or less, and particularly preferably 5 parts by weight or less, relative to 100 parts by weight of the polyolefin resin. By adding an amount of 15 parts by weight or less, sufficient adhesion to the resin adherend can be obtained. By adding an amount of 10 parts by weight or less, better graft efficiency can be achieved.

[0015] The chlorination reaction can be carried out by using a known method for introducing chlorine into a polyolefin resin, for example, by blowing chlorine gas into a reaction tank.

[0016] In the chlorination reaction, the amount of chlorine grafted depends on factors such as the type of polyolefin resin, the reaction scale, and the reaction apparatus, and therefore the amount of chlorine grafted can be adjusted, for example, by monitoring the amount of chlorine blown in and the time of the chlorination reaction.

[0017] When the chlorination reaction is carried out by blowing in chlorine gas, it is desirable to remove the by-produced hydrogen chloride after the chlorination reaction by blowing in an inert gas such as nitrogen gas.

[0018] The acid modification reaction and the chlorination reaction are preferably carried out in the presence of a radical reaction initiator by introducing the radical reaction initiator into a reaction tank.

[0019] Examples of the radical reaction initiator include organic peroxide compounds and azonitriles. Examples of the organic peroxide compounds include di-tert-butyl peroxide, dicumyl peroxide, tert-butyl cumyl peroxide, benzoyl peroxide, dilauryl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, cumene hydroperoxide, tert-butyl hydroperoxide, 1,1-bis(tert-butylperoxy)-3,5,5-trimethylcyclohexane, 1,1-bis(tert-butylperoxy)-cyclohexane, cyclohexanone peroxide, tert-butyl peroxybenzoate, tert-butyl peroxy isobutyrate, tert-butyl peroxy-3,5,5-trimethylhexanoate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxy isopropyl carbonate, and cumyl peroxy octoate. Examples of 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). As the radical reaction initiator, organic peroxide compounds are preferable, and tert-butylperoxy-2-ethylhexanoate is particularly preferable.

[0020] The amount of radical reaction initiator added to the acid component is preferably 0.01 parts by weight or more, more preferably 0.1 parts by weight or more, and even more preferably 0.5 parts by weight or more, per 1 part by weight of the acid component. By adding an amount of 0.1 parts by weight or more, it is possible to maintain even more sufficient graft efficiency. The upper limit of the amount of radical reaction initiator added to the acid component is preferably 5 parts by weight or less, more preferably 2 parts by weight or less, and even more preferably 1.5 parts by weight or less, per 1 part by weight of the acid component. By adding an amount of 2 parts by weight or less, it is possible to keep the molecular weight of the acid-modified chlorinated polyolefin resin low. If the molecular weight increases, problems such as a decrease in solvent solubility and a tendency to form aggregates may occur.

[0021] The amount of radical reaction initiator added to the polyolefin resin is preferably 0.05 parts by weight or more, more preferably 0.1 parts by weight or more, and even more preferably 0.5 parts by weight or more, relative to 100 parts by weight of the polyolefin resin. By adding an amount of 0.5 parts by weight or more, it is possible to maintain even more sufficient graft efficiency. The upper limit of the amount of radical reaction initiator added to the polyolefin resin is preferably 20 parts by weight or less, more preferably 10 parts by weight or less, and even more preferably 5 parts by weight or less, relative to 100 parts by weight of the polyolefin resin. By adding an amount of 5 parts by weight or less, it is possible to maintain the graft efficiency and to keep the molecular weight of the acid-modified chlorinated polyolefin resin low.

[0022] In the case where a polyolefin resin is subjected to an acid modification reaction using an acid component and a chlorination reaction in the same reaction tank in that order, when a radical reaction initiator is used, the radical reaction initiator may be added to the reaction tank after the acid component is added (production method C), or the acid component may be added to the reaction tank after the radical reaction initiator is added (production method B). However, from the viewpoint of further improving the grafting efficiency, it is preferable to add the radical reaction initiator to the reaction tank after the acid component.

[0023] The acid modification reaction and the chlorination reaction may be carried out according to a known method such as a solution method. According to the solution method, a uniform acid modification product can be obtained with few side reactions. The solution method may be, for example, a method in which a polyolefin resin is dissolved in an organic solvent, and then the acid modification reaction and the chlorination reaction are carried out.

[0024] Examples of the organic solvent include chlorine-based solvents such as chloroform and methylene chloride, and aromatic solvents such as benzene, toluene, xylene, ethylbenzene and trimethylbenzene. Among these, chlorine-based solvents are preferred, and chloroform is more preferred.

[0025] In the acid modification reaction, the pressure in the reaction tank may be normal pressure or may be increased. In the chlorination reaction, the pressure may be normal pressure or may be increased, but it is preferable to carry out the reaction under increased pressure, for example, at 1 MPa or less, particularly preferably 0.25 MPa or less.

[0026] The acid modification reaction and the chlorination reaction are preferably carried out by heating, and the temperature range is, for example, 50 to 140° C., preferably 60 to 130° C., more preferably 70 to 120° C., and further preferably 80 to 110° C. The acid modification reaction and the chlorination reaction may be carried out at the same temperature or at different temperatures within the above range. When using a solution method, for example, a polyolefin resin is heated to a temperature within the above range to be dissolved in an organic solvent, and then the acid modification reaction and the chlorination reaction are carried out at a temperature within the above range.

[0027] The method for producing the acid-modified chlorinated polyolefin resin of the present invention may further include a concentration step of concentrating the solution containing the acid-modified chlorinated polyolefin resin when a solution method is used, etc. As the concentration method, for example, a heat concentration method, a reduced pressure concentration method, etc. can be used.

[0028] [1-1. Polyolefin resin] The polyolefin resin is not particularly limited, and may be a homopolymer of one type of olefin, or a copolymer of two or more types of olefin. In addition, in the case of a copolymer, it may be a random copolymer or a block copolymer. As the olefin, α-olefin is preferably used. Examples of the α-olefin include ethylene, propylene, and 1-butene.

[0029] Examples of polyolefin resins include propylene homopolymers, ethylene-propylene copolymers, hydrogenated polybutadiene, ethylene-butene copolymers, ethylene-octene copolymers, propylene-butene copolymers, ethylene-propylene-butene copolymers, and α-olefin derivatives. These may be commercially available products. The polyolefin resin may be one type alone or two or more types may be used in combination. Among them, the polyolefin resin is preferably a propylene homopolymer, an ethylene-propylene copolymer, a propylene-butene copolymer, or an ethylene-propylene-butene copolymer.

[0030] Propylene homopolymer refers to a polymer consisting of structural units derived from propylene. Ethylene-propylene copolymer refers to a copolymer whose structural units are structural units derived from ethylene and structural units derived from propylene. Propylene-butene copolymer refers to a copolymer whose structural units are structural units derived from propylene and structural units derived from 1-butene. Ethylene-propylene-butene copolymer refers to a copolymer whose base unit is a structural unit derived from ethylene, whose structural units are structural units derived from propylene and structural units derived from 1-butene. Propylene homopolymer, ethylene-propylene copolymer, propylene-butene copolymer, and ethylene-propylene-butene copolymer may each contain a small amount of structural units derived from other olefins other than the above structural units. This content may be an amount that does not significantly impair the inherent performance of the resin.

[0031] The polyolefin resin preferably contains a propylene-derived structural unit (propylene content), and the content ratio of the propylene-derived structural unit (propylene content) of the polyolefin resin is preferably 50 mol% or more, more preferably 60 mol% or more, in 100 mol% of all structural units. When the propylene-derived structural unit is contained within the above range, adhesion to a substrate or molded product such as a non-polar resin (e.g., propylene resin) can be ensured. The upper limit of the content ratio of the propylene-derived structural unit (propylene content) of the polyolefin resin is not particularly limited, but may be, for example, 100 mol% (i.e., in the case of a propylene homopolymer) or 95 mol% or less (e.g., in the case of an ethylene-propylene copolymer, a propylene-butene copolymer, and an ethylene-propylene-butene copolymer, etc.) in 100 mol% of all structural units.

[0032] As the polyolefin resin, a polyolefin resin obtained using a metallocene catalyst as a polymerization catalyst is preferred because it has the following characteristics. The polyolefin resin obtained using a metallocene catalyst has a narrow molecular weight distribution. When the polyolefin resin is a copolymer, it has excellent random copolymerization properties, a narrow composition distribution, and a wide range of comonomers that can be copolymerized. As the metallocene catalyst, a known one can be used. The metallocene catalyst is preferably obtained by combining the following components (1) and (2), and, if necessary, (3). Component (1): A metallocene complex which is a transition metal compound of Groups 4 to 6 of the periodic table having at least one conjugated five-membered ring ligand. Ingredient (2): Ion-exchange layered silicate Ingredient (3): Organoaluminum compounds

[0033] The structure of the polyolefin resin may be any of the isotactic structure, atactic structure, syndiotactic structure, etc., which can be taken by ordinary polymer compounds. Among these structures, in consideration of the adhesion to the polyolefin substrate, particularly the adhesion during low-temperature drying, a polyolefin resin having an isotactic structure, which can be taken when a metallocene catalyst is used, is preferred.

[0034] The lower limit of the weight average molecular weight of the polyolefin resin is preferably 10,000 or more, more preferably 20,000 or more. This allows the resin to exert cohesive force, so that the resin composition can better exhibit adhesion to the substrate. The upper limit of the weight average molecular weight is preferably 300,000 or less, more preferably 250,000 or less. This allows the resin composition to have better compatibility with other resins and better solubility in solvents. The weight average molecular weight can be determined from a standard polystyrene calibration curve by gel permeation chromatography (GPC).

[0035] [1-2. Acid-modified chlorinated polyolefin resin] The graft amount of the acid component of the acid-modified chlorinated polyolefin resin (the amount of the acid component introduced) is 0.1% by weight to 10% by weight, preferably 0.3% by weight to 7% by weight, and more preferably 0.5% by weight to 5% by weight, based on 100% by weight of the raw material polyolefin resin. By setting the graft amount of the acid component to 0.1% by weight or more, the adhesiveness of the acid-modified chlorinated polyolefin resin to a metal adherend can be maintained. By setting the graft amount of the acid component to 10% by weight or less, sufficient adhesiveness to a resin adherend can be obtained.

[0036] The graft amount of the acid component means the weight (% by weight) of the acid component introduced to the polyolefin resin when the raw material polyolefin resin is taken as 100% by weight. The graft amount of the acid component can be, for example, 1 It can be determined by a method using H-NMR, alkali titration, Fourier transform infrared spectroscopy, or the like.

[0037] The graft efficiency of the acid component of the acid-modified chlorinated polyolefin resin is preferably 50% or more, more preferably 70% or more, and particularly preferably 80% or more, from the viewpoint of reducing production costs.

[0038] The grafting efficiency of the acid component indicates the weight percentage (%) of the acid component grafted to the polyolefin resin out of the total acid component added, and can be calculated by dividing the numerical value (weight %) of the graft amount of the acid component of the acid-modified chlorinated polyolefin resin by the numerical value (parts by weight) of the amount of the acid component added per 100 parts by weight of the raw material polyolefin resin, and then multiplying the resulting numerical value by 100.

[0039] The graft amount of chlorine (chlorine content) of the acid-modified chlorinated polyolefin resin is 10% by weight to 70% by weight, preferably 15% by weight to 55% by weight, and more preferably 20% by weight to 45% by weight, based on 100% by weight of the acid-modified chlorinated polyolefin resin. By setting the graft amount of chlorine within the above range, the polarity of the acid-modified chlorinated polyolefin resin can be adjusted to a certain range. This improves the compatibility with other resins in the coating material, and further provides sufficient adhesion to non-polar substrates such as polyolefin substrates.

[0040] The graft amount of chlorine means the weight (wt%) of chlorine introduced into the acid-modified chlorinated polyolefin resin by the chlorination reaction when the acid-modified chlorinated polyolefin resin is taken as 100 wt%. The graft amount of chlorine may be, for example, a value measured based on JIS-K7229.

[0041] The lower limit of the weight average molecular weight of the acid-modified chlorinated polyolefin resin is preferably 2,000 or more, more preferably 10,000 or more, and even more preferably 20,000 or more. This can improve the cohesive force of the acid-modified chlorinated polyolefin resin and can exhibit adhesion to the substrate. The upper limit is preferably 250,000 or less, more preferably 200,000 or less, even more preferably 100,000 or less, and particularly preferably 80,000 or less. This can improve compatibility with other resins and solubility in solvents.

[0042] [2. Uses of acid-modified chlorinated polyolefin resin] The acid-modified chlorinated polyolefin resin can also be used as a composition in combination with other components. In addition to the acid-modified chlorination step, the method for producing such a composition can include, for example, a step of mixing the acid-modified chlorinated polyolefin resin with other components.

[0043] Examples of other components include water, organic solvents, curing agents, adhesive components, stabilizers, basic substances, emulsifiers, crosslinking agents, diluents, antioxidants, light stabilizers, ultraviolet absorbers, pigments, dyes, inorganic fillers, other polyolefin resins, and the like, and can be selected according to the application.

[0044] Examples of the curing agent include polyisocyanate compounds, epoxy compounds, polyamine compounds, polyol compounds, etc. The content of the curing agent may be appropriately selected depending on the content of the acid-modified chlorinated polyolefin resin. When using a curing agent, a catalyst such as an organic tin compound or a tertiary amine compound may be used in combination as a curing catalyst depending on the purpose.

[0045] Examples of the adhesive component include known adhesive components such as polyester adhesives, polyurethane adhesives, and acrylic adhesives.

[0046] Examples of the stabilizer include compounds containing an epoxy ring, such as epoxy-based stabilizers. Examples of the epoxy-based stabilizer include 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 the epoxy stabilizer include 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 such as epoxidized tetrahydrophthalate; monoepoxy compounds such as bisphenol A glycidyl ether, ethylene glycol glycidyl ether, propylene glycol glycidyl ether, glycerol polyglycidyl ether, and sorbitol polyglycidyl ether obtained by condensing bisphenol A or polyhydric alcohol with epichlorohydrin; and monoepoxy compounds such as butyl glycidyl ether, 2-ethylhexyl glycidyl ether, decyl glycidyl ether, stearyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, sec-butylphenyl glycidyl ether, tert-butylphenyl glycidyl ether, and phenol polyethylene oxide glycidyl ether. The stabilizer may be a compound that does not contain an epoxy ring, and examples of the stabilizer include 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.

[0047] The content of the stabilizer is preferably 0.1% by weight or more, more preferably 1% by weight or more, and even more preferably 2% by weight or more, based on 100% by weight of the acid-modified chlorinated polyolefin resin. This allows the stabilizing effect to be exhibited well. The upper limit is preferably 15% by weight or less, more preferably 12% by weight or less, and even more preferably 10% by weight or less. This allows the adhesiveness to the substrate such as polyolefin to be exhibited well.

[0048] Examples of organic solvents include aromatic 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 solvents such as cyclohexane, methylcyclohexane, and ethylcyclohexane; aliphatic solvents such as pentane and hexane; glycol solvents such as ethylene glycol, ethyl cellosolve, and butyl cellosolve; alcohol solvents such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, tert-butyl alcohol, and 2-ethyl-hexanol; 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. These organic solvents may be used alone or may be included in the resin composition as a mixed solvent of two or more kinds. From the viewpoint of environmental issues, it is preferable to select a solvent other than an aromatic solvent, and more preferable is a mixed solvent of an alicyclic solvent and an ester solvent or a ketone solvent. When using an organic solvent, it is preferable to use an alcohol-based solvent (for example, the above-mentioned aliphatic alcohol-based solvent or glycol monoether-based solvent) in order to improve the storage stability of the composition. In this case, the content of the alcohol-based solvent is preferably 1 to 20% by weight relative to 100% by weight of the organic solvent.

[0049] When water or a hydrophilic organic solvent (e.g., an alcohol-based solvent, a glycol-based solvent, a ketone-based solvent, or an ester-based solvent) is used as a component of the composition, the composition preferably contains a basic substance. This can further increase the dispersibility of the resin in the 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, and dimethylethanolamine, and preferably ammonia, triethylamine, 2-amino-2-methyl-1-propanol, morpholine, and dimethylethanolamine. The content of the basic substance can be adjusted to any amount depending on the amount of the acidic component in the acid-modified chlorinated polyolefin resin. The amount is such that the pH of the acid-modified chlorinated polyolefin resin composition is usually 5 or more, and preferably 6 or more. This allows sufficient neutralization and stable dispersibility to be maintained. The upper limit is usually an amount that results in a pH of 10 or less. This allows compatibility with other components and operational safety to be maintained well.

[0050] When water or a hydrophilic organic solvent is used as a component of the composition, the composition preferably contains an emulsifier. This allows the particle size of the resin component to be adjusted when the acid-modified chlorinated polyolefin resin is made aqueous to form an aqueous dispersion, and the dispersibility can be stabilized to improve the performance related to stability such as moisture resistance. Examples of the emulsifier include surfactants such as nonionic surfactants and anionic surfactants, and nonionic surfactants are preferred.

[0051] 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, alkyl alkanolamides, polyalkylene glycol (meth)acrylates, etc. Preferred are polyoxyethylene alkyl ethers, polyoxyethylene fatty acid esters, polyoxyethylene sorbitan fatty acid esters, and polyoxyethylene alkylamines.

[0052] Examples of anionic surfactants include alkyl sulfates, polyoxyethylene alkyl ether sulfates, alkylbenzene sulfonates, α-olefin sulfonates, methyl tauryl salts, sulfosuccinates, ether sulfonates, ether carboxylates, fatty acid salts, naphthalenesulfonic acid-formalin condensates, alkylamine salts, quaternary ammonium salts, alkyl betaines, alkylamine oxides, etc. Polyoxyethylene alkyl ether sulfates and sulfosuccinates are preferred.

[0053] When water or a hydrophilic organic solvent is used as a component of the composition, the composition preferably contains a crosslinking agent. The crosslinking agent may be any compound capable of reacting with groups such as hydroxyl groups, carboxyl groups, and amino groups present in the composition 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 the crosslinking agent include blocked isocyanate compounds, aliphatic or aromatic epoxy compounds, amine compounds, and amino resins. The crosslinking agent may be used alone or in combination of two or more types. The method of adding the crosslinking agent is not particularly limited, and the crosslinking agent may be added during or after the aqueous conversion process.

[0054] When a hydrophobic organic solvent (e.g., aromatic solvent, alicyclic solvent, aliphatic solvent) is used as a component of the composition, the composition preferably contains a diluent. This can improve storage stability. Examples of the diluent include alcohol and propylene glycol ether. Examples of the alcohol include methanol, ethanol, propanol, isopropanol, and butanol. Examples of the propylene glycol ether include propylene glycol methyl ether, propylene glycol ethyl ether, and propylene glycol-tert-butyl ether.

[0055] Acid-modified chlorinated polyolefin resins and compositions have excellent adhesion between non-polar resins such as polyolefin substrates and between non-polar resins and metals, and can be used in a variety of applications such as primers, adhesives, paint binders, and ink binders.

[0056] The acid-modified chlorinated polyolefin resin and the composition can be used as a material for layers constituting a laminate. The laminate may include a layer containing an acid-modified chlorinated polyolefin resin or composition, a metal layer, and a resin layer. Examples of metals include aluminum, aluminum alloys, nickel, and stainless steel. Examples of resins include non-polar resins such as polyolefin resins (e.g., polyethylene resins such as low-density polyethylene resins, linear low-density polyethylene resins, and high-density polyethylene resins; polypropylene resins such as non-oriented polypropylene resins), polyurethane resins, polyamide resins, acrylic resins, and polyester resins. The arrangement of layers in the laminate is not particularly limited, but examples include an embodiment in which a metal layer and a resin layer are positioned with a layer containing an acid-modified chlorinated polyolefin resin or composition sandwiched therebetween, and an embodiment in which a first resin layer and a second resin layer are present with a metal layer sandwiched therebetween, and a layer containing an acid-modified chlorinated polyolefin resin composition is sandwiched between the metal layer and each resin layer. Examples of uses of the laminate include refill pouches for toiletries. EXAMPLES

[0057] The present invention will be described in detail below with reference to examples. The following examples are provided to better explain the present invention, and are not intended to limit the present invention. The methods for measuring physical properties and the like are the same as those described above unless otherwise specified. Furthermore, "parts" refers to parts by weight unless otherwise specified. Furthermore, unless otherwise specified, the temperature conditions are normal temperature (25°C), and unless otherwise specified, the pressure conditions are normal pressure (0.1 MPa).

[0058] (Example 1: Production of polyolefin resin by production method A (sequential chlorination → acid modification)) 4 kg of ethylene-propylene copolymer (molecular weight 60,000, ethylene content 10%) as polyolefin resin and 24 L of chloroform as reaction solvent were charged into a glass-lined reaction vessel, and after fully melting at a temperature of 95°C, stirring was started. 160 g of tert-butylperoxy-2-ethylhexanoate was added as a radical reaction initiator, and while controlling the pressure inside the vessel to between normal pressure and 0.25 MPa, chlorine gas was blown in, followed by nitrogen gas, to remove the by-product hydrogen chloride, thereby chlorinating the polyolefin resin.

[0059] Next, 4 g of tert-butylperoxy-2-ethylhexanoate was added, and 120 g of maleic anhydride was added as an acid component. The mixture was kept at an internal temperature of 85°C and an internal pressure of 0.2 MPa for 4 hours to acid-modify the chlorinated polyolefin resin, thereby obtaining an acid-modified chlorinated polyolefin resin with a weight average molecular weight of 68,000.

[0060] (Example 2: Production of polyolefin resin by production method B (sequential acid modification (adding acid after) → chlorination)) 4 kg of ethylene-propylene copolymer (molecular weight 60,000, ethylene content 10%) as polyolefin resin and 24 L of chloroform as reaction solvent were charged into a glass-lined reaction vessel, and stirring was started after sufficient melting at a temperature of 95°C. 160 g of tert-butylperoxy-2-ethylhexanoate as a radical reaction initiator and 120 g of maleic anhydride as an acid component were charged, and the internal temperature was kept at 85°C and the internal pressure was kept at 0.2 MPa for 4 hours to perform acid modification of the polyolefin resin.

[0061] Next, while controlling the internal temperature at 95°C and the internal pressure of the vessel to between normal pressure and 0.25 MPa, chlorine gas was blown in, followed by nitrogen gas, to remove the by-product hydrogen chloride and chlorinate the acid-modified polyolefin resin, thereby obtaining an acid-modified chlorinated polyolefin resin having a weight average molecular weight of 64,000.

[0062] (Example 3: Production of polyolefin resin by production method C (sequential acid modification (acid first charged) → chlorination)) 4 kg of ethylene-propylene copolymer (molecular weight 60,000, ethylene content 10%) as polyolefin resin, 120 g of maleic anhydride as acid component, and 24 L of chloroform as reaction solvent were charged into a glass-lined reaction vessel, and stirring was started after sufficient melting at a temperature of 95°C. 160 g of tert-butylperoxy-2-ethylhexanoate was charged as a radical reaction initiator, and the internal temperature was kept at 85°C and the internal pressure was kept at 0.2 MPa for 4 hours to perform acid modification of the polyolefin resin.

[0063] Next, while controlling the internal temperature at 95°C and the internal pressure of the vessel to between normal pressure and 0.25 MPa, chlorine gas was blown in, followed by nitrogen gas, to remove the by-product hydrogen chloride and chlorinate the acid-modified polyolefin resin, thereby obtaining an acid-modified chlorinated polyolefin resin having a weight average molecular weight of 64,000.

[0064] (Example 4: Production of polyolefin resin by production method C (acid modification (acid first charged) → chlorination in succession)) An acid-modified chlorinated polyolefin resin having a weight average molecular weight of 64,000 was obtained in the same manner as in Example 3, except that the amount of maleic anhydride (MAH) added was changed from 120 g to 40 g and the amount of tert-butylperoxy-2-ethylhexanoate added was changed from 160 g to 52 g.

[0065] (Example 5: Production of polyolefin resin by production method C (acid modification (acid first) → chlorination in succession)) An acid-modified chlorinated polyolefin resin having a weight average molecular weight of 60,000 was obtained in the same manner as in Example 3, except that the amount of tert-butylperoxy-2-ethylhexanoate added was changed from 160 g to 6 g.

[0066] (Example 6: Production of polyolefin resin by production method C (sequential acid modification (acid first charged) → chlorination)) An acid-modified chlorinated polyolefin resin having a weight average molecular weight of 150,000 was obtained in the same manner as in Example 3, except that the amount of tert-butylperoxy-2-ethylhexanoate added was changed from 160 g to 360 g.

[0067] (Example 7: Production of polyolefin resin by production method C (sequential acid modification (acid first charged) → chlorination)) Except for changing the amount of maleic anhydride added from 120 g to 600 g and the amount of tert-butylperoxy-2-ethylhexanoate added from 160 g to 600 g, an acid-modified chlorinated polyolefin resin having a weight average molecular weight of 60,000 was obtained in the same manner as in Example 3.

[0068] (Example 8: Production of polyolefin resin by production method C (sequential acid modification (acid first charged) → chlorination)) An acid-modified chlorinated polyolefin resin having a weight average molecular weight of 20,000 was obtained in the same manner as in Example 3, except that the polyolefin resin used was changed to an ethylene-propylene copolymer (molecular weight 20,000, ethylene content 10%).

[0069] (Comparative Example 1: Production of polyolefin resin by production method D (acid modification (extrusion) → discontinuous chlorination)) As a polyolefin resin, 100 parts of ethylene-propylene copolymer (molecular weight 60,000, ethylene content 10%) was added with 3.5 parts by weight of maleic anhydride and 3 parts of dicumyl peroxide, and the mixture was fed into a twin-screw extruder with the reaction zone temperature set at 300°C to carry out thermal degradation, thereby obtaining acid-modified polyolefin A.

[0070] 4 kg of the obtained acid-modified polyolefin A and 24 L of chloroform as a reaction solvent were placed in a glass-lined reaction vessel, and stirring was started after sufficient melting at a temperature of 95° C. 4 g of tert-butylperoxy-2-ethylhexanoate was added as a radical reaction initiator, and while controlling the pressure inside the vessel to be between normal pressure and 0.25 MPa, chlorine gas was blown in, followed by nitrogen gas to remove the by-product hydrogen chloride, yielding an acid-modified chlorinated polyolefin resin with a weight-average molecular weight of 60,000.

[0071] (Comparative Example 2: Production of polyolefin resin by production method E (discontinuous acid modification (melting) → chlorination)) In a four-neck flask equipped with a stirrer, a cooling tube, and a dropping funnel, 100 parts of an ethylene-propylene copolymer (molecular weight 60,000, ethylene content 10%) was completely dissolved in an oil bath at 180°C as a polyolefin resin. After nitrogen replacement in the flask for about 10 minutes, 4.7 parts of maleic anhydride were added over about 5 minutes while stirring, and 16 parts of di-tert-butyl peroxide dissolved in 16 parts of heptane were added from the dropping funnel over about 30 minutes. After that, the system was kept at 180°C and the reaction was continued for another hour, and then the unreacted maleic anhydride was removed over about 1 hour while reducing the pressure in the flask with an aspirator, to obtain an acid-modified polyolefin B.

[0072] 4 kg of the obtained acid-modified polyolefin B and 24 L of chloroform as a reaction solvent were placed in a glass-lined reaction vessel, and stirring was started after sufficient melting at a temperature of 95° C. 4 g of tert-butylperoxy-2-ethylhexanoate was added as a radical reaction initiator, and while controlling the pressure inside the vessel to normal pressure or higher and 0.25 MPa or lower, chlorine gas was blown in, followed by nitrogen gas to remove the by-product hydrogen chloride, thereby obtaining an acid-modified chlorinated polyolefin resin with a weight average molecular weight of 60,000.

[0073] (Comparative Example 3: Production of polyolefin resin by production method D (acid modification (extrusion) → discontinuous chlorination)) As a polyolefin resin, 100 parts of ethylene-propylene copolymer (molecular weight 60,000, ethylene content 10%) was added with 1 part by weight of maleic anhydride and 3 parts of dicumyl peroxide, and the mixture was fed into a twin-screw extruder with the reaction zone temperature set at 300°C to carry out thermal degradation, thereby obtaining acid-modified polyolefin C.

[0074] 4 kg of the obtained acid-modified polyolefin C and 24 L of chloroform as a reaction solvent were placed in a glass-lined reaction vessel, and stirring was started after sufficient melting at a temperature of 95°C. 4 g of tert-butylperoxy-2-ethylhexanoate was added as a radical reaction initiator, and while controlling the pressure inside the vessel to between normal pressure and 0.25 MPa, chlorine gas was blown in, followed by nitrogen gas to remove the by-product hydrogen chloride, yielding an acid-modified chlorinated polyolefin resin with a weight-average molecular weight of 90,000.

[0075] (Test Example 1: Evaluation of coloration of acid-modified chlorinated polyolefin resin) The acid-modified chlorinated polyolefin and toluene were placed in a glass bottle to prepare a 20% toluene solution.Then, the color of the solution was visually evaluated against a white paper background. The evaluation criteria are as follows: A: Almost no coloring is observed B: A very slight red color is observed. C: The solution is colored red, but remains transparent. D: The solution is cloudy due to red coloring.

[0076] (Weight average molecular weight (Mw)) The resins produced in the Production Examples were measured by GPC under the following conditions. Equipment: HLC-8320GPC (Tosoh Corporation) Column: TSK-gel G-6000HXL, G-5000HXL, G-4000HXL, G-3000HXL, G-2000HXL (manufactured by Tosoh Corporation) Eluent: Tetrahydrofuran Flow rate: 1mL / min Temperature: Pump oven, column oven 40℃ Injection volume: 100μL Standard material: Polystyrene EasiCal PS-1 (Agilent Technology, Inc.)

[0077] (Amount of grafted acid component (wt%) and grafting efficiency (%)) Measurements were carried out using the alkali titration method in accordance with JIS-K0070:1992, and calculations were made.

[0078] (Grafted amount of chlorine (wt%)) The measurements were carried out according to JIS-K7229:1995.

[0079] The amounts of acid component and radical reaction initiator added in the examples and comparative examples, the weight average molecular weight (Mw) of the resulting acid-modified chlorinated polyolefin resin, the graft amount of chlorine, the graft amount of acid component, the graft efficiency of the acid component, and the results of coloration evaluation are shown in Table 1 below.

[0080] [Table 1]

[0081] ·Manufacturing method Manufacturing method A: Manufacturing method of the present invention (chlorination → acid modification in succession) Manufacturing method B: Manufacturing method of the present invention (acid modification (adding acid after) → chlorination in succession) Manufacturing method C: Manufacturing method of the present invention (acid modification (acid first) → chlorination in succession) Manufacturing method D: Conventional manufacturing method (acid modification (extrusion) → discontinuous chlorination) Manufacturing method E: Conventional manufacturing method (acid modification (melting) → discontinuous chlorination)

[0082] From Table 1, it can be seen that the acid-modified chlorinated polyolefin resins (Examples 1 to 8) produced by continuously carrying out the acid modification reaction and the chlorination reaction in the same reaction tank have a less pronounced color than those produced by the conventional melting method (Comparative Examples 1 to 3).

[0083] Therefore, the chlorinated polyolefin resin produced by the production method of the present invention has a subdued color and can be used in a wider range of applications than ever before, including white paints and white inks.

Claims

1. A method for producing an acid-modified chlorinated polyolefin resin, comprising an acid-modified chlorination step in which a polyolefin resin is subjected to an acid modification reaction with an acid component in the presence of a chloroform solvent and a chlorination reaction in the presence of a chloroform solvent in the same reaction tank in this order, the graft amount of the acid component of the acid-modified chlorinated polyolefin resin is 0.1% by weight to 10% by weight, and the graft amount of the chlorine is 10% by weight to 70% by weight; In the acid-modified chlorination step, a radical reaction initiator is added after the acid component is added. A method for producing an acid-modified chlorinated polyolefin resin.

2. A method for producing an acid-modified chlorinated polyolefin resin as described in claim 1, wherein the acid modification reaction in the acid modification chlorination step is carried out at 50°C to 110°C.

3. A method for producing an acid-modified chlorinated polyolefin resin as described in claim 1 or 2, wherein the acid modification reaction in the acid modification chlorination step is carried out at 50°C to 85°C.

4. The method for producing an acid-modified chlorinated polyolefin resin according to any one of claims 1 to 3, wherein the amount of the acid component added is 10 parts by weight or less per 100 parts by weight of the polyolefin resin.

5. The method for producing an acid-modified chlorinated polyolefin resin according to any one of claims 1 to 4, wherein the amount of the radical reaction initiator added is 0.1 parts by weight or more per 1 part by weight of the acid component.

6. The method for producing an acid-modified chlorinated polyolefin resin according to any one of claims 1 to 5, wherein the amount of the radical reaction initiator added is 2 parts by weight or less per 1 part by weight of the acid component.

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