Dispersion resin composition

Abstract

The present invention aims to provide a dispersion resin composition of chlorinated polyolefin which can exert adhesiveness and emulsifiability in balance. A dispersion resin composition is provided, which contains at least component (A): acid-unmodified chlorinated polyolefin having a degree of chlorination of 28 to 41%, component (B): surfactant, component (C): fatty acid ester containing an epoxy group, and component (D): aqueous medium, and the component (B) contains at least a surfactant represented by general formula (I): R1-(OA) n -OH (in the formula, R1 represents an aliphatic hydrocarbon group of C13 or more. OA represents an oxyalkylene group of 2 to 18 carbon atoms which can be the same or different. n represents an integer of 10 to 50.), and the weight average value of the HLB value of the component (B) is 14 to 16.

Description

Technical Field

[0001] This invention relates to dispersion resin compositions, and more particularly to dispersion resin compositions containing acid-unmodified chlorinated polyolefins and their uses. Background Technology

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

[0003] Existing technical documents

[0004] Patent documents

[0005] Patent document 1: Japanese Patent Application Publication No. 1-256556. Summary of the Invention

[0006] The problem that the invention aims to solve

[0007] However, the method of adding emulsifiers requires a large amount of emulsifier and also suffers from reduced adhesion. In addition, the acid modification method has problems such as difficulty in bringing out the original properties of chlorinated polyolefins and time-consuming manufacturing process.

[0008] The object of the present invention is to provide a dispersion resin composition of chlorinated polyolefins that can exert a balanced adhesion and emulsifying effect.

[0009] Methods for solving problems

[0010] In order to solve the above-mentioned problems, the inventors have repeatedly conducted in-depth research and found that by combining a specified surfactant and stabilizer in chlorinated polyolefins, a dispersion that can exert both adhesion and emulsification properties in a balanced manner can be obtained.

[0011] This invention provides the following content.

[0012] [1] A dispersion resin composition, wherein at least:

[0013] Component (A): Unmodified chlorinated polyolefin with a chlorination degree of 28-38%,

[0014] Component (B): Surfactant,

[0015] Ingredient (C): Epoxy-containing fatty acid esters, and

[0016] Component (D): Aqueous medium;

[0017] Component (B) contains at least the following: R1-(OA) using the general formula (I): n -OH represents a surfactant.

[0018] In the formula, R1 represents an aliphatic hydrocarbon group with 13 or more carbon atoms, OA represents an oxidized alkenyl group with 2 to 18 carbon atoms that may be the same or different, and n represents an integer from 10 to 50;

[0019] The average weight of HLB values ​​for component (B) is 14–16.

[0020] [2] The dispersion resin composition according to [1], wherein the weight average molecular weight of component (A) is 2,000 to 40,000.

[0021] [3] The dispersion resin composition according to [1] or [2], wherein the glass transition temperature (Tg) of the component (A) is 10 to 60 °C.

[0022] [4] The dispersion resin composition according to any one of [1] to [3], wherein the softening point of the component (A) is 0 to 60°C.

[0023] [5] The dispersion resin composition according to any one of [1] to [4], wherein the content of the component (B) is more than 0% by weight and less than 25% by weight relative to the content of the component (A).

[0024] [6] The dispersion resin composition according to any one of [1] to [5] further contains an alkaline substance.

[0025] [7] The dispersion resin composition according to [6], wherein the alkaline substance is an alkaline substance having nitrogen atoms and oxygen atoms.

[0026] [8] A primer, wherein it contains a dispersion resin composition according to any one of [1] to [7].

[0027] [9] An adhesive, wherein it contains a dispersion resin composition according to any one of [1] to [7].

[0028]

[10] A binder for coatings, wherein the binder contains a dispersion resin composition according to any one of [1] to [7].

[0029]

[11] An ink binder, wherein it contains a dispersion resin composition according to any one of [1] to [7].

[0030] [1. Composition]

[0031] The composition of the present invention contains components (A) to (D).

[0032] [(A) Acid-unmodified chlorinated polyolefin]

[0033] Component (A) is an acid-unmodified chlorinated polyolefin. In this specification, "acid-unmodified" means substantially ungrafted polymerized with α,β-unsaturated carboxylic acids or their anhydrides (e.g., graft weight less than 0.1 wt%, preferably below the detection limit), and preferably refers to being manufactured by ungrafted polymerization. Examples of α,β-unsaturated carboxylic acids and their anhydrides include, for example, maleic acid, maleic anhydride, fumaric acid, citracic acid, citracic anhydride, succinic acid, itaconic acid, itaconic anhydride, aconitic acid, aconitic anhydride, nadic anhydride, (meth)acrylic acid, and (meth)acrylate. The graft weight of the α,β-unsaturated carboxylic acid or its anhydride can be determined by alkaline titration or... 1 Obtained by H-NMR.

[0034] -Polyolefin resin-

[0035] Polyolefin resins are generally polymers containing olefin (α-olefin) structural units. In this specification, olefin structural units refer to structural units derived from olefins (α-olefins). Examples of α-olefins include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, styrene, and norbornene.

[0036] Polyolefin resins can be a single olefin polymer or a copolymer of two or more olefin polymers. When the polyolefin resin is a copolymer, it can be a random copolymer or a block copolymer.

[0037] From the viewpoint of exhibiting sufficient adhesion to non-polar resin substrates such as polypropylene substrates, polyolefin resins are preferably polypropylene (propylene homopolymer), ethylene-propylene copolymer, propylene-1-butene copolymer, and ethylene-propylene-1-butene copolymer.

[0038] Here, "polypropylene" refers to a polymer whose basic unit is a structural unit derived from propylene. "Ethylene-propylene copolymer" refers to a copolymer whose basic unit is a structural unit derived from ethylene and propylene. "Propylene-1-butene copolymer" refers to a copolymer whose basic unit is a structural unit derived from propylene and butene. "Ethylene-propylene-1-butene copolymer" refers to a copolymer whose basic unit is a structural unit derived from ethylene, propylene, and butene. These (co)polymers may contain small amounts of structural units derived from other olefins besides the basic unit, provided that it does not significantly impair the inherent properties of the resin.

[0039] The polyolefin resin preferably contains at least 50 mol% of propylene-derived structural units in 100 mol% of structural units. If propylene-derived structural units are present within the above range, adhesion to non-polar resin substrates such as propylene resins can be maintained.

[0040] When the ethylene-propylene copolymer or propylene-1-butene copolymer is a random copolymer, it is preferred that in 100 mol% of the structural units, the structural units derived from ethylene or the structural units derived from butene are 1 to 50 mol%, and the structural units derived from propylene are 50 to 99 mol%.

[0041] The lower limit of the melting point of the polyolefin resin is preferably 100°C or higher, more preferably 120°C or higher. Furthermore, the upper limit is preferably 160°C or lower. As one embodiment of the melting point of the polyolefin resin, 100–160°C is preferred, more preferably 120–160°C.

[0042] The weight-average molecular weight of the polyolefin resin is preferably 200,000 or less, more preferably 180,000 or less, and even more preferably 150,000 or less. The lower limit is typically 10,000 or more, preferably 20,000 or more. The weight-average molecular weight can be determined by gel permeation chromatography (GPC) from a standard curve of standard polystyrene.

[0043] -chlorination-

[0044] Acid-unmodified chlorinated polyolefins are polyolefin resins obtained by introducing chlorine into the aforementioned polyolefin resins. When introducing chlorine, the polyolefin resin can be dissolved in a chlorine-based solvent such as chloroform beforehand. The introduction of chlorine is usually carried out by blowing chlorine gas into the reaction system. The blowing of chlorine gas can be carried out under ultraviolet light irradiation, or in the presence or absence of a free radical reaction initiator.

[0045] Examples of free radical reaction initiators include organic peroxide compounds and azonitrs. Examples of organic peroxide compounds include di-tert-butyl peroxide, dicumyl peroxide, tert-butylcumyl 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, and cumyl peroxyoctanoate. Examples of azonitrile compounds include 2,2-azobis(2-methylbutyronitrile), 2,2-azobisisobutyronitrile, 2,2-azobis(2,4-dimethylpentanitrile), and 2,2-azobis(4-methoxy-2,4-dimethylpentanitrile).

[0046] There are no restrictions on the pressure when chlorine gas is introduced; it can be at atmospheric pressure or under pressure. There are no particular restrictions on the temperature when chlorine gas is introduced; it is usually between 50 and 140°C.

[0047] - Chlorination degree-

[0048] The degree of chlorination of the acid-unmodified chlorinated polyolefin is preferably 28-38% by weight, more preferably 30-35% by weight. This allows it to improve the adhesion and emulsifying properties of the composition when used with other components.

[0049] The degree of chlorination is the amount of chlorine relative to the solid component of the chlorinated resin, and can be determined according to JIS-K7229. That is, it can be determined by the "oxygen flask combustion method", in which the acid-unmodified chlorinated polyolefin (usually the solidified product after solvent removal) is burned in an oxygen atmosphere, the generated gaseous chlorine is absorbed by water, and the result is quantified by titration.

[0050] -Softening point-

[0051] The softening point of acid-unmodified chlorinated polyolefins is typically below 60°C, preferably below 55°C, and more preferably below 50°C. This allows them to easily maintain a molten state at low temperatures, thus exhibiting good low-temperature adhesion. The lower limit is typically above 0°C, preferably above 10°C, and more preferably above 15°C. This suppresses adhesion during solidification.

[0052] -Glass transition temperature-

[0053] The glass transition temperature of acid-unmodified chlorinated polyolefins is typically below 60°C, preferably below 55°C, and more preferably below 50°C. This allows them to easily maintain a molten state at low temperatures, thus exhibiting good low-temperature adhesion. The lower limit is typically above 10°C, preferably above 15°C, and more preferably above 20°C. This suppresses adhesion during solidification.

[0054] -weight-average molecular weight-

[0055] The weight-average molecular weight of the acid-unmodified chlorinated polyolefin is preferably 40,000 or less, more preferably 35,000 or less, and even more preferably 30,000 or less. The lower limit is typically 2,000 or more, preferably 5,000 or more, and more preferably 8,000 or more. The weight-average molecular weight can be obtained by gel permeation chromatography (GPC) from a standard curve of standard polystyrene; the weight-average molecular weight of the examples is the value obtained by this method.

[0056] Acid-unmodified chlorinated polyolefins can be solidified products obtained by desolventizing chlorinated solvents such as chloroform and molding as needed. In this specification, a solidified product refers to a product that substantially does not contain liquid components such as solvents. Desolventizing can be performed by concentration, vacuum distillation, etc., using equipment such as evaporators. A stabilizer may be added during desolventizing. Examples of stabilizers include components (C) and stabilizers other than component (C) described later. The amount of stabilizer used can be determined from the viewpoint of stabilizing the product by inhibiting the removal of chlorine; preferably, it is 0.1% by weight or more, more preferably 1% by weight or more, and even more preferably 2% by weight or more, relative to 100% by weight of the acid-unmodified chlorinated polyolefin (solid component). The upper limit is preferably 10% by weight or less, more preferably 8% by weight or less, and even more preferably 7% by weight or less. Molding methods include, for example, extruders and water-cooled granulators. By using an extruder (e.g., a twin-screw extruder), vacuum distillation and molding can be performed simultaneously.

[0057] Component (A) can be a single acid-unmodified chlorinated polyolefin or a combination of two or more acid-unmodified chlorinated polyolefins.

[0058] [(B) Surfactant]

[0059] Component (B) is a surfactant. Component (B) may be a single surfactant or a combination of two or more surfactants, and preferably contains at least a surfactant represented by general formula (I).

[0060] - Surfactants represented by general formula (I) -

[0061] General formula (I) is expressed as follows:

[0062] R1-(OA) n -OH···(I)

[0063] In general formula (I), R1 represents an aliphatic hydrocarbon group with 13 or more carbon atoms, which can be saturated or unsaturated, and can 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 generally 50 or less, preferably 40 or less, more preferably 30 or less, further preferably 25 or less, and even more preferably 20 or less. Examples of R1 include tridecyl, myristyl, cetyl, oleyl, stearyl, behenyl, and octyldodecyl.

[0064] OA represents an oxidized alkenyl group with 2 to 18 carbon atoms. Examples of oxidized alkenyl groups with 2 to 18 carbon atoms include oxyvinyl, oxypropenyl, and oxybutenyl, with oxyvinyl being preferred. When there are multiple OAs, each OA may be the same or different, but it is preferable to contain at least an oxyvinyl group.

[0065] n is an integer, with a lower limit of 10 or more, more preferably 11 or more, and even more preferably 12 or more. The upper limit is 50 or less, preferably 45 or less, more preferably 40 or less, even more preferably 35 or less, and even more preferably 33 or less, 32 or less, 31 or less, or 30 or less.

[0066] Examples of surfactants represented by general formula (I) include polyoxyethylene myristyl ether, polyoxyethylene oil-based ether, polyoxyethylene cetyl ether, polyoxyethylene behenyl ether, polyoxyethylene octyl dodecyl ether, and other branched alkyl ethers of polyoxyethylene C13 or higher, and alkyl ethers of polyoxyethylene oxypropylene C13 or higher.

[0067] -HLB value-

[0068] The weight-average HLB (hydrophilic-lipophilic balance) value of component (B) is 14–16. The weight-average HLB value is the sum of the products of the weight fraction of each surfactant and its HLB number. The HLB of each surfactant can be calculated using the Griffin formula shown below.

[0069] HLB = [{(molecular weight of hydrophilic group) / (molecular weight of total mass)} × 100] / 5

[0070] For component (B), one or more surfactants can be selected such that the average weight of their HLB values ​​is 14 to 16. Examples include one surfactant represented by general formula (I), a combination of a surfactant represented by general formula (I) and other surfactants, and a combination of two or more surfactants represented by general formula (I), preferably a combination of two or more surfactants represented by general formula (I). The HLB value of each surfactant constituting component (B) is preferably 9 or higher, more preferably 10 or higher. The upper limit is preferably 25 or lower, more preferably 20 or lower, and even more preferably 18 or lower. When component (B) is a combination of two or more surfactants, the range of HLB values ​​(the difference between the highest and lowest values) of each surfactant is preferably 4.0 or lower, 3.5 or lower, or 3.0 or lower. The lower limit is not particularly limited and is 0.5 or higher, 0.6 or higher, or 0.7 or higher.

[0071] -Other surfactants-

[0072] Surfactants other than those represented by general formula (1) can be listed as, for example, surfactants selected from nonionic surfactants and anionic surfactants, with nonionic surfactants being preferred.

[0073] Examples of nonionic surfactants include polyoxyethylene fatty acid esters, polyoxyethylene polyol fatty acid esters, polyoxyethylene polyoxypropylene polyols, sorbitol fatty acid esters, polyoxyethylene hydrogenated castor oil, polyoxyethylene polycyclic phenyl ethers, polyoxyethylene alkylamines, alkyl alkanolamides, and polyalkylene glycol (meth)acrylates. Examples of anionic surfactants include alkyl sulfate salts, polyoxyethylene alkyl ether sulfates, alkylbenzene sulfonates, α-olefin sulfonates, methyl taurate, sulfosuccinates, ether sulfonates, ether carboxylates, fatty acid salts, naphthalene sulfonic acid formaldehyde condensates, alkylamine salts, quaternary ammonium salts, alkyl betaines, and alkyl amine oxides. Polyoxyethylene alkyl ether sulfates and sulfosuccinates are preferred.

[0074] The content of component (B) is preferably 25% by weight or less, more preferably 23% by weight or less, and even more preferably 20% by weight or less, relative to 100% by weight of component (A). This provides a good stabilizing effect. The lower limit is acceptable as long as it exceeds 0% by weight, typically 0.1% by weight or more, preferably 1% by weight or more, but there is no particular limitation.

[0075] [(C) Stabilizer]

[0076] Component (C) is an epoxy-containing fatty acid ester. The epoxy-containing fatty acid ester only needs to have an epoxy equivalent of approximately 100-500 and contain at least one epoxy group per molecule. Examples include epoxidized soybean oil or epoxidized linseed oil oleic acid obtained by epoxidizing natural unsaturated vegetable oils with peracids such as peracetic acid, and epoxidized fatty acid esters (epoxidized fatty acid esters containing epoxy groups) obtained by epoxidizing unsaturated fatty acids such as tall oil fatty acids and soybean oil fatty acids. Epoxidized soybean oil is preferred. Component (C) can be a single component or a combination of two or more components.

[0077] The content of component (C) relative to 100% by weight of component (A) is preferably 0.1% by weight or more, more preferably 1% by weight or more, and even more preferably 2% by weight or more. This provides a good stabilizing effect. 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 provides good adhesion of the composition to the substrate.

[0078] [(D) Aqueous medium]

[0079] Component (D) is an aqueous medium. By containing component (D), it can take the form of a dispersion in which at least component (A) is dispersed. Examples of aqueous media include water and hydrophilic substances. Examples of hydrophilic substances include alcohols, ketones, and esters, with methanol, ethanol, isopropanol, and acetone being preferred. Component (D) can be one aqueous medium or a combination of two or more aqueous media, but preferably contains at least water.

[0080] [Optional Ingredients]

[0081] The composition may contain other components besides components (A) to (D). Examples of other components include unmodified polyolefin resins, modified polyolefin resins other than component (A), alkyd resins, waterborne acrylic resins, waterborne urethane resins, alkaline 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.

[0082] -Alkaline substances-

[0083] The composition, by containing an alkaline substance, can further improve the dispersibility of the resin in a solvent. Examples of alkaline substances include substances with hydroxyl groups such as sodium hydroxide and potassium hydroxide; substances with amino groups such as ammonia, methylamine, propylamine, hexylamine, octylamine, dimethylamine, diethylamine, and triethylamine; and substances with both nitrogen and oxygen atoms 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. Ammonia, triethylamine, and substances with both nitrogen and oxygen atoms are preferred, and substances with both nitrogen and oxygen atoms (e.g., triethanolamine, 2-amino-2-methyl-1-propanol, morpholine, and dimethylethanolamine) are more preferred. The alkaline substance can be one type or a combination of two or more. The amount of alkaline substance is such that the pH of the composition after addition is typically 5 or higher, preferably 6 or higher. Therefore, it can be fully neutralized and maintain stable dispersibility. The upper limit is usually the amount reaching below pH 10. This ensures good compatibility with other components and operational safety.

[0084] -Crosslinking agent-

[0085] A crosslinking agent can be any compound that can react with hydroxyl, carboxyl, amino, or other groups present in the composition to form a crosslinked structure. Both water-soluble crosslinking agents and aqueous dispersions of crosslinking agents (crosslinking agents dispersed in water by a certain method) are acceptable. Examples of crosslinking agents include end-capped isocyanate compounds, aliphatic or aromatic epoxy compounds, amine compounds, and amino resins. A single crosslinking agent or a combination of two or more can be used. There are no particular limitations on the method of adding the crosslinking agent; it can be added during or after the water-based treatment process.

[0086] -Stabilizers (other than ingredient (C)-

[0087] As stabilizers other than component (C), examples include: epoxidized epoxide esters and other epoxidized epoxide esters; monoepoxide compounds formed by the condensation of bisphenol A or polyols with epichlorohydrin, such as bisphenol A glycidyl ether, ethylene glycol glycidyl ether, propylene glycol glycidyl ether, glyceryl polyglycidyl ether, sorbitol polyglycidyl ether, 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 phenolic polyethylene oxide glycidyl ether. Additionally, compounds that do not contain epoxy groups can also be listed as examples, such as calcium stearate, lead stearate, and other metal soaps used as stabilizers for polyvinyl chloride resins; organometallic compounds such as dibutyltin dilaurate and dibutyl malate; and hydrotalcite compounds.

[0088] [Morphology of the composition]

[0089] The composition can typically be in the form of a dispersion, for example, in which resin components (A) are dispersed in component (D). The average particle size of the dispersed resin components is typically 50 nm or more, without particular limitation. The upper limit is typically 500 nm or less, without particular limitation. The average particle size can be appropriately adjusted by the composition, manufacturing conditions (e.g., stirring conditions), etc.

[0090] [Method for manufacturing the composition]

[0091] As a method for manufacturing the composition, examples include adding components (A) to (D) and other components as needed to the reaction system together or sequentially. As a method of sequential addition, examples include adding a solvent to components (A) to (C) and other components as needed, mixing them, adding a basic substance as needed, then adding component (D), and removing the previously added solvent (e.g., by vacuum treatment). The series of reactions is preferably carried out at high temperatures (e.g., 70°C or higher, preferably 80°C or higher). Examples of solvents include aliphatic solvents (e.g., n-hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, heptane, nonane, decane) and glycol solvents (e.g., ethylene glycol, ethyl cellosolve, butyl cellosolve). After removing the solvent, stirring can be performed using stirring equipment such as stirring blades, dispersers, homogenizers, sand mills, or multi-spindle extruders. This allows adjustment of the particle size of the resin component in the dispersion.

[0092] [Uses of the resin composition]

[0093] The resin composition exhibits excellent adhesion to non-polar resins such as polyolefins and substrates such as metals, thus it can be used in various applications such as primers, adhesives, coating adhesives, and ink adhesives. Example

[0094] (1) Chlorination

[0095] [Example 1: Preparation of Chlorinated Polypropylene Solution A]

[0096] 5 kg of polypropylene resin (melting point 132℃, weight average molecular weight 60,000) was added to a 50 L glass-lined reactor, along with 16 L of chloroform. After the resin was fully dissolved at 110℃ under a pressure of 0.2 MPa, 5 g of tert-butyl peroxide-2-ethylhexanoate initiator was added. While maintaining the pressure inside the reactor at 0.2 MPa, gaseous chlorine was blown into the reactor to carry out the chlorination reaction. At the same time, gaseous oxygen was blown in to reduce the molecular weight, resulting in a chlorinated polypropylene solution A (solid content approximately 13%: component (A)) with a chlorination degree of 33.5% and a weight average molecular weight of 10,000.

[0097] [Example 2: Preparation of Chlorinated Polypropylene Solution B]

[0098] Perform the same procedure as in Chlorination Example 1 to obtain a chlorinated polypropylene solution B (solid content approximately 13%) with a chlorination degree of 29.5% and a weight-average molecular weight of 20,000.

[0099] [Example 3: Preparation of Chlorinated Polypropylene Solution C]

[0100] Perform the same procedure as in Chlorination Example 1 to obtain a chlorinated polypropylene solution C (solid content approximately 13%) with a chlorination degree of 39.5% and a weight-average molecular weight of 15,000.

[0101] [Example 4: Preparation of Chlorinated Polypropylene Solution D]

[0102] Perform the same procedure as in Chlorination Example 1 to obtain a chlorinated polypropylene solution D (solid content approximately 13%) with a chlorination degree of 26.5% and a weight-average molecular weight of 10,000.

[0103] [Example 5: Preparation of Chlorinated Polypropylene Solution E]

[0104] Perform the same procedure as in Chlorination Example 1 to obtain a chlorinated polypropylene solution E (solid content approximately 13%) with a chlorination degree of 42% and a weight-average molecular weight of 10,000.

[0105] [Example 6: Preparation of Chlorinated Polypropylene Solution F]

[0106] Except that the polypropylene resin used in the chlorination process was maleic anhydride modified polypropylene resin, the same operation as in chlorination example 2 was performed to obtain an acid-modified chlorinated polypropylene solution (solid content about 13%) with a chlorination degree of 29.5% and a weight average molecular weight of 40,000.

[0107] (2) Solidification

[0108] [Solidation Example 1]

[0109] After concentrating solution A obtained in chlorination Example 1 to approximately 40% solids using an evaporator, 5.1 parts by weight of component (C) were added relative to 100 parts by weight of component (A): NEWCIZER (registered trademark) 510R (epoxidized soybean oil, manufactured by Nippon Oil Company). Chloroform was removed using a vented twin-screw extruder equipped with a vent for vacuum distillation to remove the reaction solvent, and the chlorinated polypropylene was extruded to obtain chlorinated polyolefin A (chlorinated polypropylene, chlorination degree 32%, weight average molecular weight 10,000, Tg approximately 35°C, softening point approximately 35°C).

[0110] [Solidation Example 2]

[0111] Except for using solution B obtained in chlorination example 2, the same operation as in solidification example 1 was performed to obtain chlorinated polyolefin B (chlorinated polypropylene, chlorination degree 28%, weight average molecular weight 20,000, Tg about 25°C, softening point about 38°C).

[0112] [Solidation Example 3]

[0113] Except for using solution C obtained in chlorination Example 3, the same operation as in solidification Example 1 was performed to obtain chlorinated polyolefin C (chlorinated polypropylene, chlorination degree 38%, weight average molecular weight 15,000, Tg about 50°C, softening point about 50°C).

[0114] [Solidation Example 4]

[0115] Except for using solution D obtained in chlorination example 4, the same operation as in solidification example 1 was performed to obtain chlorinated polyolefin D (chlorinated polypropylene, chlorination degree 25%, weight average molecular weight 10,000, Tg about 20°C, softening point about 20°C).

[0116] [Solidation Example 5]

[0117] Except for using solution E obtained in chlorination Example 5, the same operation as in solidification Example 1 was performed to obtain chlorinated polyolefin E (chlorinated polypropylene, chlorination degree 40%, weight average molecular weight 10,000, Tg about 55°C, softening point about 55°C).

[0118] [Solidation Example 6]

[0119] Except for using solution F obtained in chlorination example 6, the same operation as in solidification example 1 was performed 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).

[0120] (3) Emulsification

[0121] [Example 1]

[0122] In a 3L four-necked flask equipped with a stirrer, cooling tube, and dropping funnel, 200g of component (A) obtained in Solidification Example 1 (chlorinated resin A), 20g of pure water, 40g of component (B) (surfactants (polyoxyethylene oil-based ethers a and b), 10g (5 parts by weight relative to 100 parts by weight of component (A)) of component (C) (stabilizer NEWCIZER510R (an epoxy-containing fatty acid ester, manufactured by Nippon Oil Co., Ltd.), and 50g of methylcyclohexane) were added, and the mixture was kneaded at 85°C for 1 hour. Next, 25g of triethanolamine as an alkaline substance was added, and after maintaining the mixture for 1 hour, 590g of 90°C warm water was added over approximately 2 hours. Then, the mixture was subjected to reduced pressure to remove the methylcyclohexane, and cooled to room temperature while stirred to obtain an aqueous dispersion composition of chlorinated polypropylene.

[0123] [Examples 2-3]

[0124] Except for changing the component (B) added in the emulsification process to the surfactant (polyoxyethylene oil-based ether) listed in Table 1, the same procedure as in Example 1 was followed to obtain the aqueous dispersion compositions of chlorinated polypropylene in Examples 2 and 3.

[0125] [Example 4]

[0126] Except for changing component (A) used in the emulsification process to chlorinated resin B obtained in solidification example 2, the same operation as in example 1 was performed to obtain the aqueous dispersion composition of chlorinated polypropylene of example 4.

[0127] [Example 5]

[0128] Except for changing component (A) used in the emulsification process to chlorinated resin C obtained in solidification example 3, the same operation as in example 1 was performed to obtain the aqueous dispersion composition of chlorinated polypropylene of example 5.

[0129] [Example 6]

[0130] Except for changing the alkaline substance added in the emulsification process to dimethylethanolamine, the same operation as in Example 2 was performed to obtain the aqueous dispersion composition of chlorinated polypropylene of Example 6.

[0131] [Example 7]

[0132] Except for changing the alkaline substance added in the emulsification process to 2-amino-2-methyl-1-propanol, the same operation as in Example 2 was performed to obtain the aqueous dispersion composition of chlorinated polypropylene of Example 7.

[0133] [Comparative Example 1]

[0134] Except for changing component (A) used in the emulsification process to chlorinated resin D obtained in solidification example 4, the same operation as in example 1 was performed to obtain the aqueous dispersion composition of chlorinated polypropylene of comparative example 1.

[0135] [Comparative Example 2]

[0136] Except for changing the component (A) used in the emulsification process to the chlorinated resin E obtained in solidification example 5, the same operation as in example 1 was performed to obtain the aqueous dispersion composition of chlorinated polypropylene of comparative example 2, but the emulsification was poor.

[0137] [Comparative Examples 3-5]

[0138] Except for changing the component (B) added in the emulsification process to the surfactant (polyoxyethylene oil-based ether) listed in Table 1, the same procedure as in Example 1 was followed to obtain the aqueous dispersion compositions of chlorinated polypropylene of Comparative Examples 3-5, but the emulsification was poor.

[0139] [Comparative Example 6]

[0140] Except for changing the component (C) added in the emulsification process to DENACOL EX-212 (1,6-hexanediol glycidyl ether, manufactured by Nagase ChemteX Corporation) as listed in Table 1, the same operation as in Example 1 was performed in order to obtain the aqueous dispersion composition of chlorinated polypropylene of Comparative Example 6, but the emulsification was poor.

[0141] [Comparative Example 7]

[0142] Except for changing component (A) used in the emulsification process to acid-modified chlorinated resin F obtained in solidification example 6, the same operation as in example 1 was performed to obtain the acid-modified chlorinated polypropylene aqueous dispersion composition of comparative example 7.

[0143] <Average particle size>

[0144] For the resin compositions obtained in the examples and comparative examples, the average particle size (μm) was determined by dynamic light scattering using a "Zetasizer" manufactured by Malvern.

[0145] Viscosity

[0146] For the resin compositions obtained in the examples and comparative examples, the B-type viscosity (mPa·s) was measured using a "BII type viscometer" manufactured by Toki Sangyo Co., Ltd.

[0147] <Adhesion>

[0148] The resin compositions obtained in the examples and comparative examples were adjusted to 30% by weight of solids and coated onto a biaxially stretched polypropylene film (corona-treated surface) that had been wiped with isopropanol. The films were then dried at 55°C for 30 seconds to prepare test pieces. Cellophane tape was applied tightly to the coating of the test piece and slowly peeled off in a 180° direction (approximately 5 mm / s). Adhesion (tack) was evaluated immediately after coating and after one day of rest according to the following criteria.

[0149] A: No coating peeling was observed.

[0150] B: The area of ​​the peeled coating is 1-49%, but it is at a usable level in practical applications.

[0151] C: The area of ​​the peeled coating exceeds 50%.

[0152] [Table 1]

[0153] Table 1 Formula

[0154]

[0155] The ingredients (B) used in this study are summarized in Table 2.

[0156] [Table 2]

[0157] Table 2 Types of Surfactants

[0158] surfactants HLB <![CDATA[R1]]> n a 14.2 C18 15 b 15.3 C18 20 C 13.6 C18 13 d 16.6 C18 30 e 14.5 C13 12 f 15.4 C13 15 g 10.9 C12 5 h 14.8 C12 12

[0159] [Footnotes to Table 2]

[0160] C18: Oil-based

[0161] C13: Tridecyl group

[0162] C12: Laurel base

[0163] For the examples in Table 1 that can form emulsions, an adhesion test was performed (Table 3).

[0164] [Table 3]

[0165] Table 3 Adhesion Test

[0166] freshly applied After letting it sit for a day Example 1 A A Example 2 A A Example 3 A A Example 4 B A Example 5 B A Example 6 A A Example 7 A A Comparative Example 1 C C Comparative Example 7 C C

[0167] Comparative Examples 1 and 2, using chlorinated resins D or E with a chlorination degree of 25% or 40% (Table 1), and Comparative Example 7, using an acid-modified chlorinated resin, could not obtain satisfactory adhesion or emulsions (Tables 1 and 3). Furthermore, Comparative Examples 3 and 4, using surfactants with an average HLB weight of less than 14 or more than 16 (Table 2), Comparative Example 5, using surfactants with an aliphatic hydrocarbon group of C12 or less (Table 2), and Comparative Example 6, not using an epoxy-containing fatty acid ester, all failed to obtain emulsions (Table 1). On the other hand, Examples 1 to 7, using chlorinated polyolefins with a chlorination degree of 28-38% (Table 1) and surfactants with an average HLB weight of 14-16 (Table 2), all obtained emulsions and exhibited good adhesion (Table 3). These results show that, for the dispersion resin composition of the present invention, a dispersion resin composition that can balance emulsification and adhesion can be obtained.

Claims

1. A dispersion resin composition, wherein, It contains at least: Component (A): Unmodified chlorinated polyolefin with a chlorination degree of 28-32%. Component (B): Surfactant, Ingredient (C): Epoxy-containing fatty acid esters, and Component (D): Aqueous medium; The weight-average molecular weight of component (A) is 2,000 to 40,000. Component (B) contains at least two or more components using the general formula (I): R1-(OA) n -OH represents a surfactant. In the formula, R1 represents an aliphatic hydrocarbon group with 13 to 18 carbon atoms, OA represents an oxidized alkenyl group with 2 to 18 carbon atoms that may be the same or different, and n represents an integer from 12 to 30. The average weight of HLB values ​​for component (B) is 14–16.

2. The dispersion resin composition according to claim 1, wherein, The glass transition temperature (Tg) of the component (A) is 10–60 °C.

3. The dispersion resin composition according to claim 1 or 2, wherein, The softening point of component (A) is 0–60°C.

4. The dispersion resin composition according to claim 1 or 2, wherein, The content of component (B) is more than 0% by weight and less than 25% by weight relative to the content of component (A).

5. Primer, of which, A dispersion resin composition containing any one of claims 1 to 4.

6. Adhesive, wherein, A dispersion resin composition containing any one of claims 1 to 4.

7. Adhesives for coatings, wherein, A dispersion resin composition containing any one of claims 1 to 4.

8. Binders for inks, wherein, A dispersion resin composition containing any one of claims 1 to 4.

Images