Dispersion resin composition

Abstract

The purpose of the present invention is to provide a dispersion resin composition of a chlorinated polyolefin capable of exhibiting adhesive properties and emulsification properties in a well-balanced manner. Provided is a dispersion resin composition that at least contains: an acid-unmodified chlorinated polyolefin having a chlorination degree of 28-41% as component (A); a surfactant as component (B); an epoxy group-containing fatty acid ester as component (C); and an aqueous medium as component (D). Said component (B) at least contains a surfactant represented by general formula (I): R1-(OA)n-OH (in the formula, R1 represents an aliphatic hydrocarbon group having C13 or more, OA may be the same or different in each instance and represents an oxyalkylene group having 2-18 carbon atoms, and n represents an integer of 10-50). The weight-average of the HLB value of component (B) is 14-16.

Description

Technical Field

[0001] The present invention relates to a dispersion resin composition, and more particularly to a dispersion resin composition containing an acid-unmodified chlorinated polyolefin and its uses.

Background Art

[0002] Chlorinated polyolefins have low stability in water. Therefore, when obtaining a dispersion of chlorinated polyolefin in an aqueous solvent, there were methods such as adding an emulsifier and a method of acid-modifying the chlorinated polyolefin and then using it as an aqueous dispersion (see, for example, Patent Document 1).

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] However, in the method of adding an emulsifier, it was necessary to add a large amount of the emulsifier, and there was also a problem that the adhesiveness decreased. Further, in the method of acid-modifying, there were problems such as difficulty in exhibiting the original characteristics of the chlorinated polyolefin and the manufacturing process being laborious.

[0005] An object of the present invention is to provide a dispersion resin composition of a chlorinated polyolefin that can balance the adhesiveness and emulsifying properties.

Means for Solving the Problems

[0006] As a result of intensive studies to solve the above problems, the present inventors have found that by combining a predetermined surfactant and stabilizer with the chlorinated polyolefin, a dispersion capable of balancing the adhesiveness and emulsifying properties can be obtained.

[0007] The present invention provides the following. 〔1〕Component (A): An acid-unchanged chlorinated polyolefin having a chlorine content of 28 to 38%, Component (B): A surfactant, Component (C): An epoxy group-containing fatty acid ester, Component (D): An aqueous medium, and at least containing Component (B) is a surfactant represented by the general formula (I): R1-(OA) n -OH (In the formula, R1 represents an aliphatic hydrocarbon group having 13 or more carbon atoms. OA represents an oxyalkylene group having 2 to 18 carbon atoms, which may be the same or different. n represents an integer of 10 to 50.) and at least containing The weight average of the HLB value of component (B) is 14 .0 ~16 .0 and is a dispersion resin composition. 〔2〕The dispersion resin composition according to [1], wherein the weight average molecular weight of component (A) is 2,000 to 40,000. 〔3〕The dispersion resin composition according to [1] or [2], wherein the glass transition temperature (Tg) of component (A) is 10 to 60 °C. 〔4〕The dispersion resin composition according to any one of [1] to [3], wherein the softening point of component (A) is 0 to 60 °C. 〔5〕The dispersion resin composition according to any one of [1] to [4], wherein the content of component (B) is more than 0% by weight and 25% by weight or less based on the content of component (A). 〔6〕The dispersion resin composition according to any one of [1] to [5], further containing a basic substance. 〔7〕The dispersion resin composition according to [6], wherein the basic substance is a basic substance having a nitrogen atom and an oxygen atom. 〔8〕A primer containing the dispersion resin composition according to any one of [1] to [7]. 〔9〕An adhesive containing the dispersion resin composition according to any one of [1] to [7]. 〔10〕A binder for paints containing the dispersion resin composition according to any one of [1] to [7]. A binder for ink containing the dispersion resin composition according to any one of

[11] [1] to [7].

[0008] 〔1. Composition〕 The composition of the present invention contains components (A) to (D).

[0009] 〔(A) Acid-unchanged chlorinated polyolefin〕 Component (A) is an acid-unchanged chlorinated polyolefin. In this specification, acid-unchanged means that α,β-unsaturated carboxylic acid or its anhydride is not substantially graft-polymerized (for example, the graft weight is less than 0.1% by weight, preferably below the measurement limit), and preferably, it means that it is produced without graft polymerization. Examples of the α,β-unsaturated carboxylic acid and its anhydride include 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 graft weight of the α,β-unsaturated carboxylic acid or its anhydride can be determined by an alkali titration method or 1 1H-NMR.

[0010] - Polyolefin resin - The polyolefin resin is usually a polymer containing olefin (α-olefin) structural units. In this specification, the olefin structural unit means a structural unit derived from olefin (α-olefin). Examples of the α-olefin include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, styrene, and norbornene.

[0011] The polyolefin resin may be a single olefin polymer or a copolymer of two or more olefin polymers. When the polyolefin resin is a copolymer, the polyolefin resin may be a random copolymer or a block copolymer.

[0012] From the viewpoint of exhibiting sufficient adhesiveness to a non-polar resin substrate such as a polypropylene substrate, polypropylene (propylene homopolymer), ethylene-propylene copolymer, propylene-1-butene copolymer, and ethylene-propylene-1-butene copolymer are preferred for the polyolefin resin.

[0013] Here, "polypropylene" represents a polymer whose basic unit is a structural unit derived from propylene. "Ethylene-propylene copolymer" represents a copolymer whose basic units are structural units derived from ethylene and propylene. "Propylene-1-butene copolymer" represents a copolymer whose basic units are structural units derived from propylene and butene. "Ethylene-propylene-1-butene copolymer" represents a copolymer whose basic units are structural units derived from ethylene, propylene, and butene. As long as the amount does not significantly impair the original performance of the resin, these (co)polymers may contain a small amount of structural units derived from other olefins in addition to the basic units.

[0014] The polyolefin resin preferably contains 50 mol% or more of the structural units derived from propylene in 100 mol% of the structural units. When the structural units derived from propylene are included in the above range, the adhesiveness to a non-polar resin substrate such as a propylene resin can be maintained.

[0015] When the ethylene-propylene copolymer or propylene-1-butene copolymer is a random copolymer, preferably, in 100 mol% of the structural units, the structural units derived from ethylene or butene are 1 to 50 mol%, and the structural units derived from propylene are 50 to 99 mol%.

[0016] The lower limit of the melting point of the polyolefin resin is preferably 100°C or higher, more preferably 120°C or higher. Also, the upper limit is preferably 160°C or lower. As one embodiment of the melting point of the polyolefin resin, 100 to 160°C is preferable, and 120 to 160°C is more preferable.

[0017] The weight-average molecular weight of the polyolefin resin is preferably 200,000 or less, more preferably 180,000 or less, and still more preferably 150,000 or less. The lower limit is usually 10,000 or more, preferably 20,000 or more. The weight-average molecular weight can be determined from a standard polystyrene calibration curve by gel permeation chromatography (GPC).

[0018] -Chlorination- The acid-unchanged chlorinated polyolefin is a polyolefin resin in which chlorine is introduced into the above-mentioned polyolefin resin. When introducing chlorine, the polyolefin resin may be dissolved in a chlorine-based solvent such as chloroform in advance. The introduction of chlorine is usually carried out by blowing chlorine gas into the reaction system. The blowing of chlorine gas may be carried out under ultraviolet irradiation or in the presence or absence of a radical reaction initiator.

[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 peroxyisobutyrate, tert-butyl peroxy-3,5,5-trimethylhexanoate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxyisopropyl carbonate, cumyl peroxy octoate, and the like. Examples of the azonitriles include 2,2-azobis(2-methylbutyronitrile), 2,2-azobisisobutyronitrile, 2,2-azobis(2,4-dimethylvaleronitrile), 2,2-azobis(4-methoxy-2,4-dimethylvaleronitrile).

[0020] The pressure during the blowing of chlorine gas is not limited and may be normal pressure or under pressure. The temperature during the blowing of chlorine gas is not particularly limited, but is usually 50 to 140 °C.

[0021] -Degree of chlorination- The degree of chlorination of the acid-unmodified chlorinated polyolefin is preferably 28 to 38% by weight, more preferably 30 to 35% by weight. Thereby, the adhesiveness and emulsifiability of the composition can be improved together with other components.

[0022] The degree of chlorination is the amount of chlorine relative to the solid content of the chlorinated resin and can be measured in accordance with JIS-K7229. That is, it can be measured using the "oxygen flask combustion method" in which an acid-unmodified chlorinated polyolefin (usually the solidified product after removing the solvent) is burned in an oxygen atmosphere, the generated gaseous chlorine is absorbed by water, and quantified by titration.

[0023] -Softening point- The softening point of the acid-unmodified chlorinated polyolefin is usually 60°C or lower, preferably 55°C or lower, more preferably 50°C or lower. As a result, it is easy to maintain a molten state at low temperatures, and thus good low-temperature adhesion can be exhibited. The lower limit is usually 0°C or higher, preferably 10°C or higher, more preferably 15°C or higher. Thereby, blocking can be suppressed when solidified.

[0024] -Glass transition point- The glass transition point of the acid-unmodified chlorinated polyolefin is usually 60°C or lower, preferably 55°C or lower, more preferably 50°C or lower. As a result, it is easy to maintain a molten state at low temperatures, and thus good low-temperature adhesion can be exhibited. The lower limit is usually 10°C or higher, preferably 15°C or higher, more preferably 20°C or higher. Thereby, blocking can be suppressed when solidified.

[0025] -Weight average molecular weight- The weight average molecular weight of the acid-unmodified chlorinated polyolefin is preferably 40,000 or lower, more preferably 35,000 or lower, still more preferably 30,000 or lower. The lower limit is usually 2,000 or higher, preferably 5,000 or higher, more preferably 8,000 or higher. The weight average molecular weight can be determined from a standard polystyrene calibration curve by gel permeation chromatography (GPC) method, and the weight average molecular weight in the examples is the value determined by this method.

[0026] The acid non-modified chlorinated polyolefin may be a solid obtained by removing the solvent from a chlorinated solvent such as chloroform and, if necessary, molding it. In this specification, the solid means that it substantially does not contain liquid components such as solvents. The solvent removal can be carried out by concentration, distillation under reduced pressure, etc., and equipment such as an evaporator may be used. When removing the solvent, a stabilizer may be added. Examples of the stabilizer include the component (C) described later and stabilizers other than the component (C). The amount of the stabilizer used may be determined from the viewpoint of suppressing the release of chlorine and achieving stabilization. It is preferably 0.1% by weight or more, more preferably 1% by weight or more, still more preferably 2% by weight or more, based on 100% by weight of the acid non-modified chlorinated polyolefin (solid content). The upper limit is preferably 10% by weight or less, more preferably 8% by weight or less, still more preferably 7% by weight or less. Examples of the molding means include equipment such as an extruder and a water-cooled pelletizer. By using an extruder (for example, a twin-screw extruder), distillation under reduced pressure and molding can be carried out simultaneously.

[0027] Component (A) may be a single acid non-modified chlorinated polyolefin or a combination of two or more thereof.

[0028] [(B) Surfactant] Component (B) is a surfactant. Component (B) may be a single surfactant or a combination of two or more surfactants, but it preferably contains at least a surfactant represented by the general formula (I).

[0029] -Surfactant represented by the general formula (I)- The general formula (I) is represented as follows: R1―(OA) n ―OH···(I)

[0030] In general formula (I), R1 represents an aliphatic hydrocarbon group having 13 or more carbon atoms, which may be either saturated or unsaturated, and may be linear, branched, or cyclic. The number of carbon atoms is 13 or more, preferably 14 or more, more preferably 15 or more. The upper limit is usually 50 or less, preferably 40 or less, more preferably 30 or less, still more preferably 25 or less, and even more preferably 20 or less. Examples of R1 include a tridecyl group, a myristyl group, a cetyl group, an oleyl group, a stearyl group, a behenyl group, and an octyldodecyl group.

[0031] OA represents an oxyalkylene group having 2 to 18 carbon atoms. Examples of the oxyalkylene group having 2 to 18 carbon atoms include an oxyethylene group, an oxypropylene group, and an oxybutylene group, and an oxyethylene group is preferred. When there are a plurality of OAs, each OA may be the same or different, and it is preferably at least an oxyethylene group.

[0032] n is an integer, and the lower limit is 10 or more, more preferably 11 or more, still more preferably 12 or more. The upper limit is 50 or less, preferably 45 or less, more preferably 40 or less, still more preferably 35 or less, even more preferably 33 or less, 32 or less, 31 or less, or 30 or less.

[0033] Examples of the surfactant represented by general formula (I) include polyoxyethylene-C13 or more branched alkyl ethers such as polyoxyethylene myristyl ether, polyoxyethylene oleyl ether, polyoxyethylene cetyl ether, polyoxyethylene behenyl ether, and polyoxyethylene octyldodecyl ether, and polyoxyethylene oxypropylene-C13 or more alkyl ethers.

[0034] -HLB value- Component (B) has a weight average HLB (Hydrophilic-Lipophilic Balance) value of 14 .0 ~16 .0The weight average of the HLB value is the sum of the products of the weight fraction and the HLB number of each surfactant. The HLB of each surfactant can be calculated using the Griffin formula shown below. HLB = [{(molecular weight of hydrophilic group) / (total molecular weight)} × 100] / 5

[0035] Component (B) has a weight average HLB value of 14 .0 ~16 .0 One or more surfactants may be selected so that the HLB value of each of the surfactants constituting component (B) is 9 or more. For example, one surfactant represented by general formula (I), a combination of a surfactant represented by general formula (I) and another surfactant, or a combination of two or more surfactants represented by general formula (I) may be used, and a combination of two or more surfactants represented by general formula (I) is preferred. The HLB value of each of the surfactants constituting component (B) is 9 or more. .0 More than 10 is preferable. .0 More preferably, the upper limit is 25 .0 Less than 20 is preferred .0 The following is more preferable: 18 .0 More preferably, component (B) is 2 .0 In the case of the combination of the above surfactants, the HLB value of each surfactant is preferably in the range of 4.0 or less, 3.5 or less, or 3.0 or less (difference between the maximum and minimum values). The lower limit is not particularly limited, but is preferably 0.5 or more, 0.6 or more, or 0.7 or more.

[0036] -Other surfactants- Examples of surfactants other than those represented by formula (1) include surfactants selected from nonionic surfactants and anionic surfactants, with nonionic surfactants being preferred.

[0037] Examples of nonionic surfactants include 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, and the like. Examples of anionic surfactants include alkyl sulfate esters, polyoxyethylene alkyl ether sulfates, alkylbenzene sulfonates, α-olefin sulfonates, methyl taurates, sulfosuccinates, ether sulfonates, ether carboxylates, fatty acid salts, naphthalene sulfonic acid formalin condensates, alkylamine salts, quaternary ammonium salts, alkyl betaines, alkylamine oxides, and the like. Preferably, they are polyoxyethylene alkyl ether sulfates and sulfosuccinates.

[0038] The content of component (B) is preferably 25% by weight or less, more preferably 23% by weight or less, still more preferably 20% by weight or less, based on 100% by weight of component (A). Thereby, the stabilizing effect can be exhibited well. The lower limit only needs to exceed 0% by weight, and is usually 0.1% by weight or more, preferably 1% by weight or more, and is not particularly limited.

[0039] [(C) Stabilizer] Component (C) is an epoxy group-containing fatty acid ester. The epoxy group-containing fatty acid ester may be a fatty acid ester having an epoxy equivalent of about 100 to 500 and containing at least one epoxy group in one molecule. For example, epoxidized soybean oil obtained by epoxidizing a vegetable oil having a natural unsaturated group with a peracid such as peracetic acid, or epoxidized fatty acid esters (epoxy group-containing fatty acid esters) obtained by epoxidizing unsaturated fatty acids such as epoxidized linseed oil oleic acid, tall oil fatty acid, and soybean oil fatty acid. Among these, epoxidized soybean oil is preferred. Component (C) may be used alone or in combination of two or more.

[0040] The content of component (C) is preferably 0.1% by weight or more, more preferably 1% by weight or more, still more preferably 2% by weight or more, based on 100% by weight of component (A). Thereby, the stabilizing effect can be exhibited well. The upper limit is preferably 15% by weight or less, more preferably 12% by weight or less, still more preferably 10% by weight or less. Thereby, the adhesiveness to the base material of the composition can be exhibited well.

[0041] 〔(D) Aqueous medium〕 Component (D) is an aqueous medium. By containing component (D), at least component (A) can be in the form of a dispersion. Examples of the aqueous medium include water and hydrophilic substances. Examples of the hydrophilic substances include hydrophilic substances of alcohol-based, ketone-based, and ester-based, and methanol, ethanol, isopropyl alcohol, and acetone are preferred. Component (D) may be one type of aqueous medium or a combination of two or more types of aqueous media, and it is preferably to contain at least water.

[0042] 〔Optional components〕 The composition may contain other components other than components (A) to (D). Examples of the other components include resin components such as unmodified polyolefin resins, modified polyolefin resins other than component (A), alkyd resins, aqueous acrylic resins, and aqueous urethane resins, basic substances, crosslinking agents, stabilizers other than component (C), lower alcohols, lower ketones, lower esters, preservatives, leveling agents, antioxidants, light stabilizers, ultraviolet absorbers, dyes, pigments, metal salts, and acids.

[0043] - Basic substance - When the composition contains a basic substance, the dispersibility of the resin in the solvent can be further enhanced. Examples of the basic substance include those having a hydroxyl group such as sodium hydroxide and potassium hydroxide; those having an amino group such as ammonia, methylamine, propylamine, hexylamine, octylamine, dimethylamine, diethylamine, and triethylamine; those having a nitrogen atom and an oxygen atom such as ethanolamine, propanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N,N-dimethylethanolamine, 2-dimethylamino-2-methyl-1-propanol, 2-amino-2-methyl-1-propanol, morpholine, and dimethylethanolamine. Preferably, they are ammonia, triethylamine, those having a nitrogen atom and an oxygen atom, and more preferably those having a nitrogen atom and an oxygen atom (for example, triethanolamine, 2-amino-2-methyl-1-propanol, morpholine, dimethylethanolamine). The basic substance may be of one kind or a combination of two or more kinds. The content of the basic substance is an amount such that the pH of the composition after addition is usually 5 or more, preferably 6 or more. Thereby, sufficient neutralization can be achieved and stable dispersibility can be maintained. The upper limit is usually an amount such that the pH is 10 or less. Thereby, the compatibility with other components and the working safety can be maintained well.

[0044] -Crosslinking agent- The crosslinking agent may be any compound that can react 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 the crosslinking agent (a crosslinking agent in a state of being 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. The addition method of the crosslinking agent is not particularly limited, and at the time of addition, it may be either during the aqueous conversion process or after the aqueous conversion.

[0045] -Stabilizer (other than component (C))- Examples of stabilizers other than component (C) include, for example, the following: Epoxidized alicyclic compounds such as epoxidized tetrahydrophthalate; for example, bisphenol A glycidyl ether, ethylene glycol glycidyl ether, propylene glycol glycidyl ether, glycerol polyglycidyl ether, sorbitol polyglycidyl ether; monoepoxy compounds formed by condensing bisphenol A, polyhydric alcohols, and epichlorohydrin, 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, phenol polyethylene oxide glycidyl ether. Further examples include compounds not containing an epoxy group, such as metal soaps like 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.

[0046] 〔Form of the composition〕 The composition can usually take the form of a dispersion, for example, a form in which a resin component such as component (A) is dispersed in component (D). The average particle size of the dispersed resin component is usually 50 nm or more and is not particularly limited. The upper limit is usually 500 nm or less and is not particularly limited. The average particle size can be appropriately adjusted according to the composition, manufacturing conditions (e.g., stirring conditions), etc.

[0047] 〔Method for producing the composition〕 Examples of the method for producing the composition include a method of adding components (A) to (D) and other components used as necessary all at once or sequentially into the reaction system. Examples of the sequential addition method include adding a solvent to components (A) to (C) and other components used as necessary, kneading them, then adding a basic substance used as necessary, subsequently adding component (D), and removing the previously added solvent (for example, by vacuum treatment). It is preferable to conduct the series of reactions at a high temperature (for example, 70 °C or higher, preferably 80 °C or higher). Examples of the solvent include aliphatic solvents (for example, n-hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, heptane, nonane, decane), glycol solvents (for example, ethylene glycol, ethyl cellosolve, butyl cellosolve). After removing the solvent, a stirring treatment may be performed using stirring equipment such as stirring blades, a disper, a homogenizer, a sand mill, a multi-screw extruder, etc. Thereby, the particle diameter of the resin component in the dispersion can be adjusted.

[0048] 〔Use of the resin composition〕 Since the resin composition is excellent in adhesion to non-polar resins such as polyolefin and substrates such as metals, it can be used in various applications such as primers, adhesives, paint binders, and ink binders.

Examples

[0049] (1) Chlorination [Example of chlorination 1: Production of chlorinated polypropylene solution A] 5 kg of polypropylene resin (melting point 132 °C, weight average molecular weight 60,000) was charged into a 50 L glass-lined reaction kettle, 16 L of chloroform was added, and after being sufficiently dissolved at a temperature of 110 °C under a pressure of 0.2 MPa, 5 g of the initiator t-butylperoxy-2-ethylhexanoate was added. While controlling the pressure in the kettle at 0.2 MPa, gaseous chlorine was blown into the reaction kettle to conduct the chlorination reaction, and gaseous oxygen was blown in to reduce the molecular weight, obtaining chlorinated polypropylene solution A (solid content of about 13%: component (A)) with a chlorination degree of 33.5% and a weight average molecular weight of 10,000.

[0050] [Example of Chlorination 2: Production of Chlorinated Polypropylene Solution B] The same operation as in Chlorination Example 1 was carried out to obtain a chlorinated polypropylene solution B with a chlorine content of 29.5% and a weight-average molecular weight of 20,000 (solid content: about 13%).

[0051] [Example of Chlorination 3: Production of Chlorinated Polypropylene Solution C] The same operation as in Chlorination Example 1 was carried out to obtain a chlorinated polypropylene solution C with a chlorine content of 39.5% and a weight-average molecular weight of 15,000 (solid content: about 13%).

[0052] [Example of Chlorination 4: Production of Chlorinated Polypropylene Solution D] The same operation as in Chlorination Example 1 was carried out to obtain a chlorinated polypropylene solution D with a chlorine content of 26.5% and a weight-average molecular weight of 10,000 (solid content: about 13%).

[0053] [Example of Chlorination 5: Production of Chlorinated Polypropylene Solution E] The same operation as in Chlorination Example 1 was carried out to obtain a chlorinated polypropylene solution E with a chlorine content of 42% and a weight-average molecular weight of 10,000 (solid content: about 13%).

[0054] [Example of Chlorination 6: Production of Chlorinated Polypropylene Solution F] The same operation as in Chlorination Example 2 was carried out except that the polypropylene resin used in the chlorination step was a maleic anhydride-modified polypropylene resin, to obtain a maleic anhydride-modified chlorinated polypropylene solution with a chlorine content of 29.5% and a weight-average molecular weight of 40,000 (solid content: about 13%).

[0055] (2) Solidification [Example of Solidification 1] The solution A obtained in Chlorination Example 1 was concentrated to about 40% solids content using an evaporator, and then Component (C): Nusizer (registered trademark) 510R (epoxidized soybean oil, manufactured by NOF Corporation) was added in an amount of 5.1 parts by weight per 100 parts by weight of Component (A). Chloroform was removed using a twin-screw extruder with a vent for distilling off the reaction solvent under reduced pressure, and the chlorinated polypropylene was extruded to obtain Chlorinated Polyolefin A (chlorinated polypropylene, chlorine content 32%, weight average molecular weight 10,000, Tg about 35°C, softening point about 35°C).

[0056] [Solidification Example 2] The same operations as in Solidification Example 1 were carried out except that the solution B obtained in Chlorination Example 2 was used, to obtain Chlorinated Polyolefin B (chlorinated polypropylene, chlorine content 28%, weight average molecular weight 20,000, Tg about 25°C, softening point about 38°C).

[0057] [Solidification Example 3] The same operations as in Solidification Example 1 were carried out except that the solution C obtained in Chlorination Example 3 was used, to obtain Chlorinated Polyolefin C (chlorinated polypropylene, chlorine content 38%, weight average molecular weight 15,000, Tg about 50°C, softening point about 50°C).

[0058] [Solidification Example 4] The same operations as in Solidification Example 1 were carried out except that the solution D obtained in Chlorination Example 4 was used, to obtain Chlorinated Polyolefin D (chlorinated polypropylene, chlorine content 25%, weight average molecular weight 10,000, Tg about 20°C, softening point about 20°C).

[0059] [Solidification Example 5] The same operations as in Solidification Example 1 were carried out except that the solution E obtained in Chlorination Example 5 was used, to obtain Chlorinated Polyolefin E (chlorinated polypropylene, chlorine content 40%, weight average molecular weight 10,000, Tg about 55°C, softening point about 55°C).

[0060] [Solidification Example 6] The same operation as in Solidification Example 1 was carried out except that Solution F obtained in Chlorination Example 6 was used, to obtain acid-modified chlorinated polyolefin F (acid-modified chlorinated polypropylene, chlorination degree 28%, weight average molecular weight 40,000, Tg about 25°C, softening point about 55°C).

[0061] (3) Emulsification [Example 1] In a 3 L scale four-neck flask equipped with a stirrer, a condenser, and a dropping funnel, the solidification example 1 was added. Sodium salt 200 g of fluorinated resin A, 20 g of pure water, 40 g of component (B): surfactant (polyoxyethylene oleyl ether a and b), 10 g of component (C): stabilizer Newcizer 510R (epoxy group-containing fatty acid ester, manufactured by NOF Corporation) Chlorinated resin A The mixture was mixed at 85° C. for 1 hour, and then 50 g of methylcyclohexane was added (5 parts by weight per 100 parts by weight). Next, 25 g of triethanolamine was added as a basic substance, and the mixture was held for 1 hour, after which 590 g of hot water at 90° C. was added over about 2 hours. After that, the mixture was subjected to a reduced pressure treatment to remove the methylcyclohexane, and then cooled to room temperature while being stirred, to obtain an aqueous dispersion composition of chlorinated polypropylene.

[0062] [Examples 2 to 3] Water dispersion compositions of chlorinated polypropylene of Examples 2 and 3 were obtained in the same manner as in Example 1, except that the component (B) added in the emulsification step was changed to a surfactant (polyoxyethylene oleyl ether) shown in Table 1.

[0063] [Example 4] The same procedure as in Example 1 was carried out except that the component (A) used in the emulsification step was changed to the chlorinated resin B obtained in Solidification Example 2, to obtain a water dispersion composition of a chlorinated polypropylene of Example 4.

[0064] [Example 5] The same procedure as in Example 1 was carried out except that the component (A) used in the emulsification step was changed to the chlorinated resin C obtained in Solidification Example 3, to obtain a water dispersion composition of a chlorinated polypropylene of Example 5.

[0065] [Example 6] The same operations as in Example 2 were carried out except that the basic substance added in the emulsification step was changed to dimethylethanolamine, and an aqueous dispersion composition of chlorinated polypropylene of Example 6 was obtained.

[0066] [Example 7] The same operations as in Example 2 were carried out except that the basic substance added in the emulsification step was changed to 2-amino-2-methyl-1-propanol, and an aqueous dispersion composition of chlorinated polypropylene of Example 7 was obtained.

[0067] [Comparative Example 1] The same operations as in Example 1 were carried out except that component (A) used in the emulsification step was changed to the chlorinated resin D obtained in Solidification Example 4, and an aqueous dispersion composition of chlorinated polypropylene of Comparative Example 1 was obtained.

[0068] [Comparative Example 2] The same operations as in Example 1 were carried out except that component (A) used in the emulsification step was changed to the chlorinated resin E obtained in Solidification Example 5, and an attempt was made to obtain an aqueous dispersion composition of chlorinated polypropylene of Comparative Example 2, but poor emulsification occurred.

[0069] [Comparative Examples 3 to 5] The same operations as in Example 1 were carried out except that component (B) added in the emulsification step was changed to the surfactant (polyoxyethylene oleyl ether) shown in Table 1, and an attempt was made to obtain an aqueous dispersion composition of chlorinated polypropylene of Comparative Examples 3 to 5, but poor emulsification occurred.

[0070] [Comparative Example 6] The same operations as in Example 1 were carried out except that component (C) added in the emulsification step was changed to Denacol EX-212 (1,6-hexanediol glycidyl ether, manufactured by Nagase ChemteX Corporation) shown in Table 1, and an attempt was made to obtain an aqueous dispersion composition of chlorinated polypropylene of Comparative Example 6, but poor emulsification occurred.

[0071] [Comparative Example 7] The same operations as in Example 1 were carried out except that the component (A) used in the emulsification step was changed to the acid-modified chlorinated resin F obtained in Solidification Example 6, and an aqueous dispersion composition of the acid-modified chlorinated polypropylene of Comparative Example 7 was obtained.

[0072] <Average particle diameter> Regarding the resin compositions obtained in the examples and comparative examples, the average particle diameter (μm) was measured by the dynamic light scattering method using a "Zetasizer" manufactured by Malvern.

[0073] <Viscosity> Regarding the resin compositions obtained in the examples and comparative examples, the B-type viscosity (mPa·s) was measured using a "BII viscometer" manufactured by Toki Sangyo Co., Ltd.

[0074] <Adhesion> Regarding the resin compositions obtained in the examples and comparative examples, they were adjusted to a solid content of 30% by weight and applied to a biaxially oriented polypropylene film (corona-treated surface) whose surface was wiped with isopropanol, and dried at 55°C for 30 seconds to prepare test pieces respectively. A cellophane adhesive tape was adhered onto the coating film of the test piece and slowly peeled off in the 180° direction (at a speed of about 5 mm / s), and the adhesion (adhesiveness) immediately after coating and after standing for one day was evaluated according to the following criteria. A: No peeling of the coating film was observed. B: The area of the peeled coating film is 1 - 49%, but it is at a level that can be used in practice. C: The area of the peeled coating film exceeds 50%.

[0075]

Table 1

[0076] Regarding the component (B) used this time, it is summarized in Table 2 below.

[0077]

Table 2

[0078] 〔Footnote to Table 2〕 C18: Oleyl group C13: Tridecyl group C12: Lauryl group

[0079] For those that could form emulsions among those in Table 1, an adhesion test was carried out (Table 3).

[0080]

Table 3

[0081] In Comparative Examples 1 and 2 using chlorinated resin D or E with a chlorination degree of 25% or 40% (Table 1), and Comparative Example 7 using an acid-modified chlorinated resin, satisfactory adhesion could not be obtained, or an emulsion could not be obtained (Tables 1 and 3). Also, in Comparative Examples 3 to 4 using a surfactant with a weight-average HLB of less than 14 .0 or more than 16 .0 (Table 2), Comparative Example 5 using a surfactant with an aliphatic hydrocarbon group of C12 or less (Table 2), and Comparative Example 6 not using an epoxy group-containing fatty acid ester, in all cases, an emulsion could not be obtained (Table 1). On the other hand, in Examples 1 to 7 using a chlorinated polyolefin with a chlorination degree of 28 to 38% (Table 1) and a surfactant with a weight-average HLB of 14 .0 ~16 .0 (Table 2), in all cases, an emulsion could be obtained and good adhesion was shown (Table 3). These results indicate that the dispersion resin composition of the present invention can obtain a dispersion resin composition that can achieve good balance between emulsifying property and adhesion property.

Claims

1. Component (A): an acid-unchanged chlorinated polyolefin having a chlorination degree of 28 to 38%, and Component (B): a surfactant, and Component (C): an epoxy group-containing fatty acid ester, and Component (D): an aqueous medium, and containing at least, Component (B) is represented by the general formula (I): R1-(OA)n-OH (wherein, R1 represents an aliphatic hydrocarbon group having 13 or more carbon atoms. OA represents an oxyalkylene group having 2 to 18 carbon atoms, which may be the same or different. n represents an integer of 10 to 50). contains at least a surfactant represented by, the weight average of the HLB value of Component (B) is 14.0 to 16.0, a dispersion resin composition.

2. The dispersion resin composition according to Claim 1, wherein the weight average molecular weight of the said Component (A) is 2,000 to 40,000.

3. The dispersion resin composition according to Claim 1 or 2, wherein the glass transition temperature (Tg) of the said Component (A) is 10 to 60°C.

4. The dispersion resin composition according to any one of Claims 1 to 3, wherein the softening point of the said Component (A) is 0 to 60°C.

5. The dispersion resin composition according to any one of Claims 1 to 4, wherein the content of the said Component (B) is more than 0% by weight and 25% by weight or less with respect to the content of the said Component (A).

6. The dispersion resin composition according to any one of Claims 1 to 5, further containing a basic substance.

7. The dispersion resin composition according to Claim 6, wherein the basic substance is a basic substance having a nitrogen atom and an oxygen atom.

8. A primer containing the dispersion resin composition according to any one of Claims 1 to 7.

9. An adhesive containing the dispersion resin composition according to any one of Claims 1 to 7.

10. A binder for paints containing the dispersion resin composition according to any one of Claims 1 to 7.

11. A binder for inks containing the dispersion resin composition according to any one of Claims 1 to 7.

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