CZ2016231A3 - Water dispersion composition containing modified polyolefin - Google Patents

Abstract

A free dispersion composition comprising a modified polyolefin having excellent adhesion and water resistance and whose viscosity is constant in the range of 500 mPa.s to lower values. The aqueous dispersion comprises a modified polyolefin (A) and a base (B) and further comprises at least one member selected from the group consisting of a water-soluble polymer containing anionic groups having an acid number of 150 to 500 mg KOH / g resin (C) , and an electrolyte (D).

Description

Aqueous dispersion composition comprising a modified polyolefin

Field of technology

The present invention relates to an aqueous dispersion composition comprising a modified polyolefin. More specifically, the invention relates to an aqueous dispersion composition which is suitable for use in paints, inks, sealants, primers or adhesives. The aqueous dispersion composition comprises a modified polyolefin and a basic substance, and further comprises at least one member selected from the group consisting of a water-soluble polymer containing anionic groups and an electrolyte.

Prior art

Polypropylene and similar polyolefin-based resins have excellent properties and are inexpensive; therefore, they are used in large quantities in a variety of applications, including the manufacture of automobile parts, films, and molded products. However, polyolefin-based resins have a problem in that, because they are crystalline and have a non-polar surface, they are difficult to apply as coatings and do not adhere well.

For this reason, acid-modified polyolefins, chlorinated acid-modified polyolefins and similar modified polyolefins have been developed for coating, printing, laminating films and bonding polyolefin-based resins. In particular, an aqueous dispersion composition based on a modified polyolefin has been proposed, in which the requirements for ecology and hygiene have been taken into account (see, for example, patent literature 1 and 2). Since the aqueous dispersion composition based on the modified polyolefin contains substantially no emulsifying agent, the resulting coating film does not show any irregularities and the like. and has excellent physical properties such as gasohol resistance (mixture of gasoline and ethanol), water resistance and blocking resistance. Therefore, this method of producing an aqueous dispersion composition is considered excellent.

Citation

List of patent literature

PTL1: JP2009-079078A

PTL2: JP2004-018659A

The essence of the invention

Technical issue

However, in the above method, it is not possible to stabilize the viscosity of the aqueous dispersion composition. Unstable viscosity is problematic because it impairs handling during production and reduces production efficiency. Furthermore, there is another problem with improper handling in the preparation of paints, inks and the like, which, in addition to the aqueous dispersion composition containing the modified polyolefin, also contains various additives such as viscosity control agents.

The present invention has been developed in view of the above problems. The present inventors have conducted extensive research and found that when an aqueous dispersion composition containing a modified polyolefin contains a water-soluble polymer containing anionic groups and / or an electrolyte, it can be stabilized at low viscosity. This has achieved the object of the present invention.

Problem solving

To solve the identified problems, the present inventors conducted extensive research and came to the following inventions:

An aqueous dispersion composition comprising a modified polyolefin (A) and a basic substance (B), which composition further comprises at least one member selected from the group consisting of a water-soluble polymer containing anionic groups having an acid number of 150 to 500 mg KOH / g resin ( C), and the electrolyte (D).

The modified polyolefin (A) is preferably an acid-modified polyolefin (A1) and / or an acid-modified chlorinated polyolefin (A2).

In a preferred embodiment, the aqueous dispersion composition contains the basic substance (B) in an amount of from 0.5 to 10 parts by weight. per 100 parts by weight of modified polyolefin (A) a water-soluble polymer containing anionic groups (C) and / or an electrolyte (D) in a total amount of from 0.1 to 20 parts by weight. per 100 parts by weight modified polyolefin (A).

A coating material, paint, sealant, primer or adhesive comprising the aqueous dispersion composition.

A laminate comprising a polyolefin substrate and a resin substrate or a metal substrate, wherein the polyolefin substrate is adhered to the resin substrate or the metal substrate by the adhesive.

A polyolefin substrate coated with said coating material.

Advantageous effects of the invention

The aqueous dispersion composition of the present invention contains a water-soluble polymer containing anionic groups and / or an electrolyte, and when the dry matter content of the modified polyolefin in the aqueous dispersion composition is 30% by weight, its viscosity can be kept constant in the range of 500 mPa.s towards lower values. Furthermore, since the aqueous dispersion composition of the present invention contains substantially no emulsifying agent, the resulting coating film obtained from this aqueous dispersion composition does not show any irregularities and the like. and has excellent adhesion and water resistance.

Description of design

One embodiment of the present invention is described in detail below.

Modified polyolefin (A)

Although the modified polyolefin (A) used in the present invention is not particularly limited, it is preferably an acid-modified polyolefin (AI) and / or an acid-modified chlorinated polyolefin (A2).

Although the acid-modified polyolefin (AI) used in the present invention is not limited, it is preferably a product obtained by grafting at least one member selected from the group consisting of α, β-unsaturated carboxylic acids and their anhydrides to at least one member selected from the group consisting of polyethylene, polypropylene and propylene-α-olefin copolymers.

The propylene-α-olefin copolymer is obtained by copolymerizing propylene, which is used as the main component, and α-olefin. Examples of α-olefins include ethylene, 1-butene, 1-heptene, 1-octene, 4-methyl-1-pentene, vinyl acetate and the like. These α-olefins may be used singly or in combination of two or more substances. Of these α-olefins, ethylene and 1-butene are preferred. Although the ratio of the propylene component and the α-olefin component in the copolymers of propylene and the α-olefin is not limited, the propylene component preferably constitutes 50 mol% or more, and more preferably 70 mol% or more.

Examples of at least one member selected from the group consisting of α, β-unsaturated carboxylic acids and their anhydrides are maleic acid, itaconic acid, citraconic acid and anhydrides of these acids. Of these, acid anhydrides are preferred, and maleic anhydride is most preferred. Specific examples of acid-modified polyolefins include maleic anhydride-modified polypropylene, maleic anhydride-modified propylene-ethylene copolymer, maleic anhydride-modified propylene-butene copolymer, maleic anhydride-modified propylene-ethylene-butene copolymer, and the like. These acid-modified polyolefins may be used singly or in combination of two or more substances.

The method for producing the acid-modified (AI) polyolefins is not particularly limited. Examples of this method include a radical grafting reaction (specifically, a reaction in which a radical is generated on a polymer used as a backbone and an unsaturated carboxylic acid or its acid anhydride is polymerized by graft polymerization using a radical formed as a starting point for polymerization) and the like.

The radical-forming agent is not very limited and is preferably an organic peroxide. Examples of organic peroxides include, but are not limited to, di-tert-butyl peroxyphthalate, tert-butyl hydroperoxide, dicumyl peroxide, benzoyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxypivalate, methyl diethyl ketone peroxide tert-butyl peroxide, lauroyl peroxide and the like peroxides; azobisisobutyronitrile, azobisisopropionitrile and similar azonitriles; etc.

Although the chlorinated acid-modified polyolefin (A2) used in the present invention is not limited, it is preferably a product obtained by chlorinating the acid-modified polyolefin (AI).

The method for producing the chlorinated polyolefin modified with acid (A2) is not particularly limited. For example, a chlorinated acid-modified polyolefin (A2) can be obtained by dissolving an acid-modified polyolefin (A1) in a halogenated hydrocarbon such as chloroform and introducing chlorine.

The extent of modification of the acid-modified polyolefin (A) is preferably 0.1% by weight. or more, more preferably 0.3 wt. or more, even more preferably 0.5 wt. or more, particularly preferably 0.8 wt. or more and most preferably 1 or more wt. The extent of modification of the acid-modified polyolefin (A) is also preferably 10% by weight. or less, more preferably 8% by weight. or less, even more preferably 7 wt. or less, particularly preferably 6% by weight. or less and most preferably 5% by weight. or less. If the extent of acid modification in the modified polyolefin (A) is too small, it may be difficult to achieve sufficient dispersion. Too much acid modification in the modified polyolefin (A) may adversely affect the water resistance of the coating film.

When acid modification is performed using maleic anhydride, the extent of acid modification can be determined according to FT-IR (FT-IR8200PC manufactured by Shimadzu Corporation). First, maleic anhydride is dissolved in any concentration to prepare solutions for the calibration curve. Then the solutions for the calibration curve are measured by FT-IR. The calibration curve is constructed from data relating to the maximum absorbance (1780 cm- ¹ ) when stretching the carbonyl (C = O) bond of maleic anhydride. The modified polyolefin (A) was dissolved in chloroform, and FT-IR was measured to determine the extent of maleic anhydride modification based on the absorbance at maximum elongation (1780 cm ¹ ) of the maleic anhydride carbonyl bond using the above calibration curve.

The weight average molecular weight (Mw) of the modified polyolefin (A) is preferably in the range from 40,000 to 170,000, more preferably in the range from 50,000 to 160,000, even more preferably in the range from 60,000 to 150,000, especially in the range from 70,000 to 140,000 and most preferably in the range of 80,000 to 130,000. If the weight average molecular weight (Mw) of the modified polyolefin (A) is too low, the cohesiveness may be poor, resulting in poor adhesion. In case the weight average molecular weight (Mw) of the modified polyolefin (A) is too high, the solubility may be insufficient, which may cause problems in preparing the aqueous dispersion composition.

The weight average molecular weight given in the description of the present invention is a value measured in the atmosphere at 40 ° C by gel permeation chromatography (hereinafter also referred to as GPC; standard: polystyrene resin, mobile phase: tetrahydrofuran).

The modified polyolefin (A) is preferably crystalline. When the modified polyolefin (A) is crystalline, it is preferable in that it exhibits strong cohesion and excellent adhesion, water resistance, heat resistance, and chemical resistance as compared with being amorphous.

The term crystalline, as used herein, means that during a temperature rise in the range of -100 ° C to 250 ° C at a rate of 10 ° C / min in a differential scanning calorimeter (hereinafter also referred to as DSC, Q-2000, product TA Instruments Japan lne.), This polyolefin shows a clear melting peak. The melting point and melting point are determined from the maximum temperature and area of the melting peak obtained by increasing the sample temperature at a rate of 10 ° C / min until melting and cooling the resulting sample so that it solidifies and then reheats to melt by DSC.

The melting point (Tm) of the modified polyolefin (A) is preferably in the range of 50 ° C to 120 ° C, more preferably in the range of 60 ° C to 100 ° C, and most preferably in the range of 70 ° C to 90 ° C. If the melting point (Tm) of the modified polyolefin (A) is lower than the above-mentioned minimum value, the cohesion due to crystallization may be poor, resulting in poor adhesion, water resistance, heat resistance and chemical resistance. In the case where the melting point (Tm) of the modified polyolefin (A) is higher than the above-mentioned maximum value, the solubility may be low, which causes a problem in preparing the aqueous dispersion composition.

When the modified polyolefin (A) is a chlorinated acid-modified polyolefin (A2), the lower limit of the chlorine content of the chlorinated acid-modified polyolefin (A2) is preferably 5% with respect to solution stability and adhesion between the polyolefin substrate and the resin substrate or metal substrate. wt. or higher, more preferably 8%

»· · · •» ♦ • · · · · wt. or higher, even more preferably 10 wt. or higher, particularly preferably 12% by weight. or higher and most preferably 14% by weight. or higher. If the chlorine content of the chlorinated polyolefin modified with acid (A2) is lower than the above-mentioned minimum value, the stability of the solution may be low and emulsification may be impossible. The upper limit of the chlorine content in the chlorinated polyolefin modified with acid (A2) is preferably 40% by weight. or lower, more preferably 38 wt. or lower, even more preferably 35 wt. or lower, particularly preferably 32% by weight. or lower and most preferably 30 wt. or lower. If the chlorine content of the chlorinated acid-modified polyolefin (A2) exceeds the above-mentioned maximum value, the crystallinity of the chlorinated acid-modified polyolefin may be insufficient, resulting in low adhesion strength.

The chlorine content of the chlorinated polyolefin modified with acid (A2) can be determined by titration according to JIS K-7229-1995.

Alkaline substance (B)

The base (B) used in the present invention can neutralize the acidic groups (carboxyl groups) of the modified polyolefin (A) and improve its dispersibility.

The basic substance (B) is not particularly limited, and is preferably a volatile basic substance. In particular, ammonia and amines are preferred. Examples of amines include, but are not limited to, monomethylamine, dimethylamine, trimethylamine, monoethylamine, monon-propylamine, dimethyl-n-propylamine, monoethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, N-aminoethylethanolamine, N-methyldiethopropanolamine, , Β-dimethylethanolamine, N, N-dimethylpropanolamine and the like. Triethylamine and Ν, Ν-dimethylethanolamine are particularly preferred. These volatile amines may be used singly or in combination of two or more such substances.

The content of the basic substance (B) is preferably 0.5 part by weight. or higher, more preferably 1 part by weight. or higher, even more preferably 2 parts by weight. or higher and particularly preferably from 3 parts by weight. or higher, per 100 parts by weight. modified polyolefin (A). The content of basic substance (B) is also preferably 10 parts by weight. or lower, more preferably 9 parts by weight. or lower, even more preferably 8 parts by weight. or lower and particularly preferably 7 parts by weight. or less per 100 parts by weight. modified polyolefin (A). If the amount of the basic substance (B) is too small, the size of the dispersed particles in the resulting aqueous dispersion composition may be too large, leading to instability in storage. If the amount of the basic substance (B) is too large, the coating film may have insufficient water resistance.

Water-soluble polymer containing anionic groups (C)

The water-soluble polymer containing anionic groups (C) used in the present invention can reduce the surface charge of the modified polyolefin particles (A) in the aqueous dispersion composition. With its use, the solids content of the modified polyolefin in the aqueous dispersion composition is 30% by weight. the viscosity of this composition can be kept constant in the range from 500 mPa.s to lower values.

Furthermore, the use of a water-soluble polymer containing anionic groups (C) not only reduces the viscosity of the aqueous dispersion composition, but also provides an excellent effect in that the effect of the viscosity regulating agent is not impaired at the time of preparing the coating composition. Viscosity control agents impart the desired viscosity to the coating composition by hydrating and linking the polar groups present therein. However, when a low molecular weight compound such as an electrolyte is used as the charge reducing agent, hydration and association between polar groups may be inhibited, and therefore the viscosity regulating agent may not function. On the other hand, since the water-soluble polymer containing anionic groups (C) is a high molecular weight compound, its flow in the coating composition is suppressed, and its interaction with the viscosity regulating agent is small. Thus, the water-soluble polymer containing anionic groups (C) does not appear to affect the effect of the viscosity regulating agent. Specifically, in the preparation of the coating composition, paint, sealant, primer, adhesive, and the like. it must add not only an aqueous dispersion composition but also a viscosity regulating agent or similar additive to prevent dripping during application. Since the water-soluble polymer containing anionic groups (C) does not impair the effect of the viscosity regulating agent, it makes it possible to obtain an excellent coating composition, paint, sealant, primer, adhesive and the like which does not drip during application.

The term water-soluble polymer containing anionic groups (C) means a high molecular weight compound which is soluble in water and which reduces the surface charge of the modified polyolefin particles (A). Specific examples include, but are not limited to, acrylic resins, urethane resins, epoxy resins, and the like, which contain carboxyl groups, sulfonic acid groups, sulfatoester groups, and / or phosphoric acid ester groups. More specific examples include water-soluble polymers containing anionic groups which contain as a main component polystyrenesulfonic acid, polyacrylic acid, a copolymer of styrene with maleic anhydride, a copolymer of styrene with an acrylic monomer, a copolymer of styrene with a methacrylic monomer and the like. As the water-soluble polymer containing anionic groups (C), these polymers can be used singly or in combination of two or more components.

The acid number of the water-soluble polymer containing anionic groups (C) must be 150 mg KOH / g resin or higher. The acid number of the water-soluble polymer containing anionic groups (C) is preferably 160 mg KOH / g resin or higher, preferably 170 mg KOH / g resin or higher, even more preferably 180 mg KOH / g resin or higher, particularly preferably 190 mg KOH. / g resin or higher and most preferably 200 mg KOH / g resin or higher. If the acid number of the water-soluble polymer containing anionic groups (C) is too low, its effect on reducing the viscosity of the aqueous dispersion composition may be small. It is also required that the acid number of the water-soluble polymer containing anionic groups (C) be 500 mg KOH / g resin or less. The acid number of the water-soluble polymer containing anionic groups (C) is preferably 490 mg KOH / g resin or less, more preferably 480 mg KOH / g resin or less, even more preferably 470 mg KOH / g resin or less, particularly preferably 460 mg KOH. / g resin or less and most preferably 450 mg KOH / g resin or less. If the acid number of the water-soluble polymer containing anionic groups (C) is too high, the coating film may have insufficient water resistance, and the effect of the viscosity regulating agent may deteriorate at the time of preparing the coating composition. The acid number of the water-soluble polymer containing anionic groups (C) is preferably in the above-described range, since thus the excellent viscosity of the aqueous dispersion composition and the excellent physical properties of the coating film can be obtained. The acid number of a water-soluble polymer containing anionic groups (C) can be measured according to JIS K-0070-1992.

The weight average molecular weight (Mw) of the water-soluble polymer containing anionic groups (C) is preferably 1500 or more, more preferably 2000 or more.

higher, even more preferably 3000 or higher, even more preferably 5000 or higher, particularly preferably 7000 or higher and most preferably 9000 or higher. If the weight average molecular weight (Mw) of the water-soluble polymer containing anionic groups (C) is too low, the effect of the viscosity regulating agent controlling at the time of preparing the coating composition may deteriorate. The weight average molecular weight (Mw) of the water-soluble polymer containing anionic groups (C) is also preferably 30,000 or less, preferably 29,000 or less, even more preferably 28,000 or less, even more preferably 27,000 or less, particularly preferably 26,000 or less, and most preferably 25,000 or less. If the weight average molecular weight (Mw) of the water-soluble polymer containing anionic groups (C) is too high, its solubility in water may be insufficient, which may result in little effect on viscosity reduction. The weight average molecular weight (Mw) of the water-soluble polymer containing anionic groups (C) is preferably in the range described above, since excellent viscosity of the aqueous dispersion composition and excellent physical properties of the coating film can be obtained. The weight average molecular weight of the water-soluble polymer containing anionic groups (C) is a value measured in the atmosphere at 40 ° C by GPC.

The solubility of the water-soluble polymer containing anionic groups (C) in water (20 ° C) is preferably 5% or more by weight, more preferably 10% by weight. or higher, even more preferably 20 wt. or higher, even more preferably 30 or higher% by weight. Although the upper limit is not particularly limited, the solubility of the water-soluble polymer containing anionic groups (C) in water (20 ° C) should be practically 50% by weight. or lower.

The amount of the water-soluble polymer containing anionic groups (C) is preferably 0.1 part by weight. or higher, more preferably 1 part by weight. or higher, even more preferably 1.5 parts by weight. or higher, and particularly preferably 2 parts by weight. or higher, per 100 parts by weight. modified polyolefin (A). The amount of the water-soluble polymer containing anionic groups (C) is preferably 20 parts by weight. or lower, more preferably 19 parts by weight. or lower, even more preferably 18 parts by weight. or lower, and particularly preferably 17 parts by weight. or less, per 100 parts by weight. modified polyolefin (A). When the amount of the water-soluble polymer containing anionic groups (C) is too small, the viscosity reducing effect may be small. When the amount of the water-soluble polymer containing the anionic groups (C) is too large, the coating film may have insufficient water resistance and the effect of the viscosity regulating agent may be reduced at the time of preparing the coating composition.

Electrolyte (D)

The electrolyte (D) used in the present invention may be a substance that dissociates into cations and anions when dissolved in water, thereby providing conductivity. The use of an electrolyte makes it possible to reduce the charge on the surface of the modified polyolefin particles (A) in aqueous dispersion compositions and to keep the viscosity constant in the range from 500 mPa.s towards lower values, provided that the modified polyolefin content as dry matter in the aqueous dispersion composition is 30. % wt. The electrolyte (D) is not particularly limited. Examples include citric acid, isocitronic acid, malic acid, 2-hydroxyisocaproic acid (leucic acid), mevalonic acid, pantoic acid, ricinoleic acid, ricinelaidic acid, cerebronic acid, quinic acid, shikimic acid, tartaric acid, hydroxybutyric acid, glycolic acid, tartronic acid, glyceric acid and the like aliphatic hydroxy acids; salicylic acid, creosotic acid, vanillin acid, syringic acid, pyrocatechic acid, resorcylic acid, protocatechuic acid, gentisic acid, orsellinic acid, gallic acid, mandelic acid, benzyl acid, atromic acid, melilotic acid, florumic acid, umemic acid , caffeic acid, ferulic acid, sinapic acid and similar aromatic hydroxy acids; and lithium chloride, sodium chloride, potassium chloride, magnesium chloride, calcium chloride, sodium bromide, potassium bromide, magnesium bromide, calcium bromide, sodium iodide, calcium iodide, and similar alkali metal halide salts, as well as similar alkaline earth metal halide salts . Of these, citric acid, isocitric acid and sodium chloride are preferred. These electrolytes may be used singly or in combination of two or more as the electrolyte (D).

The amount of electrolyte (D) is preferably 0.1 part by weight. or more, more preferably 1 part by weight. or more, more preferably 1.5 parts by weight. or more and particularly preferably 2 parts by weight. or more, per 100 parts by weight. modified polyolefin (A). The amount of electrolyte (D) is preferably 20 parts by weight. or less, more preferably 19 parts by weight. or less, even more preferably 18 parts by weight. or less and particularly preferably 17 parts by weight. or less per 100 parts by weight. modified polyolefin (A). When the amount of electrolyte (D) is too small, the viscosity reducing effect may be small. When the amount of electrolyte (D) is too large, the coating film may have insufficient water resistance.

The total amount of the water-soluble polymer containing anionic groups (C) and the electrolyte (D) is preferably 0.1 part by weight. or more, more preferably 1 part by weight. or more, more preferably 1.5 parts by weight. or more and particularly preferably 2 parts by weight. or more, per 100 parts by weight. modified polyolefin (A). The total amount of the water-soluble polymer containing anionic groups (C) and the electrolyte (D) is preferably 20 parts by weight. or less, more preferably 5 parts by weight. or less, even more preferably 18 parts by weight. or less and especially preferably 17 parts by weight. or less per 100 parts by weight. modified polyolefin (A). If the total amount of the water-soluble polymer containing the anionic groups (C) and the electrolyte (D) is too small, the viscosity reduction effect may be small. If the total amount of the water-soluble polymer containing the anionic groups (C) and the electrolyte (D) is too large, the coating film may have insufficient water resistance, and the effect of the viscosity regulating agent may be impaired at the time of coating preparation.

Composition of aqueous dispersion

The aqueous dispersion composition of the present invention is a mixture comprising a modified polyolefin (A) and a basic substance (B), which further comprises at least one member selected from the group consisting of a water-soluble polymer containing anionic groups (C) and an electrolyte (D).

If the content of the modified polyolefin (A), expressed as dry matter content, is 30% by weight, the viscosity of the aqueous dispersion composition at 25 ° C measured by a Brookfield viscometer (rotor speed: 60 min ¹ ) is preferably 500 mPa.s or less. , more preferably 400 mPa.s or less, even more preferably 300 mPa.s or less, and most preferably 200 mPa.s or less. If the viscosity of the aqueous dispersion composition is too high, it may result in poor processability and the like. in the manufacture of an aqueous dispersion of the composition and preparation of the coating material. The lower the viscosity, the better the processability. Therefore, there is no special lower limit. However, the viscosity of the aqueous dispersion composition is practically 5 mPa.s or higher.

The content of the modified polyolefin (A), expressed as the dry matter content in the aqueous dispersion composition of the present invention, is preferably in the range of 5 to 50% by weight, more preferably 10 to 45% by weight, even more preferably 15 to 40% by weight. and most preferably 20 to 35 wt. If the content of the modified polyolefin (A), expressed as dry matter content, is too high, the viscosity may be high, which may tend to cause aggregation of the modified polyolefin particles, which may lead to a significant reduction in dispersion stability. Too low a content of modified polyolefin (A), expressed as dry matter content, is not practical from the point of view of production and application.

The modified polyolefin particles (A) contained in the aqueous dispersion composition preferably have a size of 5 to 500 nm, more preferably 10 to 400 nm, and even more preferably 15 to 300 nm. When the particle size of the modified polyolefin (A) is too small, it may lead to improved film-forming properties, however, the likelihood of undesired coalescence or aggregation of the dispersed increases, resulting in low dispersion stability. On the other hand, when the particle size of the modified polyolefin (A) is too large, it may not only result in low dispersion stability, but also film-forming properties may be insufficient, which impairs the appearance and properties of the resulting coating film.

The particle size of the modified polyolefin (A) contained in the aqueous dispersion composition can be measured using a particle size distribution diffraction analyzer (Zetasizer Nano manufactured by Malvem).

Since the aqueous dispersion composition of the present invention is substantially free of emulsifier, no irregularities and the like are formed in the coating film prepared using it, and the coating films are excellent in terms of adhesion and water resistance. The term is substantially free of emulsifier, in particular it means that the content of emulsifier is preferably 0.5 part by weight. or lower, more preferably 0.2 part by weight. or lower, more preferably 0.1 part by weight. or lower, and especially preferably 0 parts by weight. per 100 parts by weight modified polyolefin (A). In addition, the total content of the modified polyolefin (A), the basic substance (B), the water-soluble polymer containing anionic groups (C) and / or the electrolyte (D) and water in the aqueous dispersion composition is preferably 99.85% by weight. or higher, more preferably 99.94 wt. or higher, even more preferably 99.97 wt. or higher, and particularly preferably 100% by weight.

Examples of emulsifiers include cationic emulsifiers, anionic emulsifiers, nonionic emulsifiers and amphoteric emulsifiers. Examples of emulsifiers include not only emulsifiers commonly used in emulsion polymerization, but also surfactants. Examples of anionic emulsifiers include higher alcohol sulfuric acid ester salts, higher alkyl alkylsulfonic acid salts such as higher carboxylic acid salts, alkylbenzenesulfonate salts, polyoxyethylene alkyl sulfate salts, polyoxyethylene alkylphenyl ether sulfate salts, vinyl sulfosuccinates, and the like. Examples of nonionic emulsifiers include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, fatty acid polyethylene glycol esters, ethylene oxide-propylene oxide block copolymers, polyoxyethylene fatty acid amides, ethylene oxide-propylene oxide block copolymers, and the like having a polyoxyethylene structure; polyoxyethylene sorbitan fatty acid esters and similar sorbitan derivatives and the like. Examples of amphoteric emulsifiers include lauryl betaine, lauryldimethylamine oxide and the like.

The method for producing the aqueous dispersion composition is not particularly limited. Below is an example of a suitable procedure. Specifically, the aqueous dispersion composition can be prepared as follows. The modified polyolefin (A) is dissolved with heating in at least one solvent selected from the group consisting of ether-based solvents, alcohol-based solvents, aromatic solvents and water, a basic substance is added, and the resulting mixture is cooled. The at least one solvent is then removed. The time for which the water-soluble polymer containing anionic groups (C) and / or the electrolyte (D) is added is not particularly limited and may be selected as needed, for example during emulsification or before or after evaporation of the solvent.

Examples of ether-based solvents include, but are not limited to, tetrahydrofuran (hereinafter also THF), propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and the like. These solvents may be used singly or in combination of two or more solvents. Of these, tetrahydrofuran is preferred.

Examples of alcohol-based solvents include, but are not limited to, C 1-7 aliphatic alcohols, aromatic alcohols, alicyclic alcohols, and the like. These solvents may be used singly or in combination of two or more solvents. Of these, C3.5 aliphatic alcohols, especially isopropyl alcohol (hereinafter also IPA), are preferred.

Examples of aromatic solvents include benzene, toluene, xylene, ethylbenzene, isopropylbenzene, solvent naphtha, and the like. These solvents may be used singly or in combination of two or more solvents. Of these, toluene is preferred.

Although the amounts of solvent (s) and water used may be selected as needed, the weight ratio of modified polyolefin (A): water: solvent (s) is preferably 100: 50-800: 11-900 and more preferably 100: 200-400: 43-233. The large amount of water or solvent (s) allows the modified polyolefin to be more easily dispersed in water, but is economically disadvantageous and impractical because it prolongs the time required for concentration and results in low volumetric efficiency. When the amount of water is small, dispersion of the modified polyolefin may not occur. When the amount of solvent (s) is small, the viscosity when dissolved under heating may be too high; in this case, therefore, the modified polyolefin cannot be dissolved uniformly and, as a result, cannot be uniformly dispersed.

The dissolution temperature of the modified polyolefin with heating is not particularly limited, and is preferably 50 ° C or higher. The temperature for dissolving the modified polyolefin with heating is also preferably 75 ° C or lower, as this temperature is not higher than the boiling point of the organic solvent (s) used, so that dissolution with heating does not have to be performed in a pressure vessel. Although the dissolution time is not particularly limited, the modified polyolefin usually dissolves completely in 1 to 2 hours.

The aqueous dispersion composition of the present invention may contain not only a modified polyolefin (A), a basic substance (B) and a water-soluble polymer containing anionic groups (C) and / or an electrolyte (D), but also, if necessary, various additives in an amount range that does not degrade the performance parameters that are characteristic of the present invention. Examples of preferred additives include, but are not limited to, viscosity control agents, film-forming aids, wetting agents, flame retardants, pigments, antiblocking agents, and the like. Aqueous dispersion compositions containing such additives can be used for paints, varnishes, sealants, primers or adhesives.

Examples of viscosity control agents include, but are not limited to, viscosity control agents that swell in an alkaline environment, associative viscosity control agents that swell in an alkaline environment, urethane associative viscosity control agents, and the like. Specific examples of viscosity regulating agents that swell in an alkaline environment include, but are not limited to, Primal (registered trademark) ASE60. Specific examples of associative viscosity control agents that swell in an alkaline environment include, but are not limited to, Primal DR-72. Specific examples of urethane associative viscosity regulating agents include, but are not limited to, Adeka Nol (registered trademark) UH-752, and the like.

Laminate

The laminate of the present invention comprises a polyolefin substrate and a resin substrate, a metal substrate or a wood substrate, wherein the polyolefin substrate is adhered to the resin substrate, the metal substrate or the wood substrate with an adhesive of the present invention. Examples of resin substrates include, but are not limited to, sheets and films of polyvinyl chloride, polyester, polyolefin, polyamide, Poval, polyurethane, and the like resins. Examples of metal substrates include, but are not limited to, plates and foils or films of various metals, such as aluminum, stainless steel, copper, iron and zinc, their alloys, metallized articles, and the like.

Viscosity of the aqueous dispersion composition

If the content of the modified polyolefin, expressed as dry matter content in the aqueous dispersion composition of the invention, 30 wt.%, Measured viscosity at 25 ° C using a Brookfield viscometer (rotor speed: 60 min ^1).

Evaluation criteria

And (especially excellent for practical use): 200 mPa.s or less

B (excellent for practical use): higher than 200 mPa.s but 300 mPa.s or lower

C (applicable): above 300 mPa.s but 500 mPa.s or less

D (not applicable): above 500 mPa.s or with unmeasurable viscosity due to gelation

Evaluation of the effect of a viscosity regulating agent

If a coating material, ink, sealant, primer or adhesive containing an aqueous dispersion composition is to be applied to a substrate and the like, it is necessary that the coating material, ink, sealant, primer or adhesive contain a viscosity regulating agent to ensure a constant viscosity. However, in such a case, the effect of the viscosity regulating agent may be reduced by the action of a charge reducing agent such as an electrolyte. Therefore, it is necessary to evaluate the effect of the charge reducing agent on the viscosity regulating agent. Specifically, the viscosity control agent is added to the aqueous dispersion composition before and after the addition of the water-soluble polymer containing anionic groups and / or the electrolyte (charge reducing agent), and the viscosity is measured. The evaluation is performed according to the following formula:

Evaluation criteria r | a = viscosity after addition of a reducing agent / viscosity before addition of a reducing agent

A (especially excellent for practical use): pa = 0.9 or higher

B (excellent for practical use): η <ι = 0.7 or higher but less than 0.9

C (applicable): pa = 0,5 or more but less than 0,7

D (not applicable): pa less than 0.5

Evaluation as coating material, paint, sealing material or primer

The evaluation of the aqueous dispersion composition of the present invention as a coating material, paint, sealant or primer is performed by making a sample of the coating film and measuring its adhesion and water resistance.

Sample coating film preparation

To prepare a liquid simulating a basecoat material (a primer, also referred to as a flash primer, i.e., a primer that can be overlaid without pre-firing), a film-forming agent and a wetting agent are added to the aqueous dispersion composition. The flash primer is applied to the substrate (polypropylene plate) with a stretch ruler so that the film thickness after drying is 10 μm. The surface to which the primer is applied is pre - dried in a hot air oven at

At 80 ° C for 10 minutes and then a two-component urethane coating material was applied to the resulting substrate with a spray gun and the coating was dried in a hot air oven at about 80 ° C for about 35 minutes to obtain a coating film sample.

Evaluation of coating film adhesion

A sample of the coating film was allowed to stand in an atmosphere at 25 ° C for 36 hours. Then, 100 squares are marked with a cutting knife at a distance of 1 mm in the surface of the coating film. Cellophane adhesive tape is firmly pressed to the surface, which is then removed again at an angle of 60 °. This procedure is repeated ten times, each time using a new cellophane adhesive tape. The case where no change is observed on the surface of the paint film even after ten times the removal of the adhesive tape is assigned 10 points, the case where peeling is observed at the tenth removal of the adhesive tape is assigned 9 points, and so on, so the evaluation gradually assigns 8, 7 , 6 points, and so on, and the case where peeling is observed when the adhesive tape is first removed is evaluated at 0 points.

Evaluation criteria

B (excellent for practical use): 10 points

C (applicable): 9 points

D (not applicable): 8 points or less

Evaluation of water resistance of coating film

A sample of the coating film was allowed to stand in an atmosphere at 25 ° C for 36 hours and then immersed in warm water at 40 ° C for 10 days. After this time, a sample of the coating film is examined for any change and adhesion is evaluated. A sample of a coating film on which no change is observed is assigned 10 points and its adhesion is considered good, i.e., B. A coating film on which no change is observed and whose adhesion is rated 9 points is considered to be sample C and a coating sample. a film on which blisters have formed or whose adhesion is rated 8 points or less is considered bad, i.e., D.

Rating as glue

The evaluation of the adhesive containing the aqueous dispersion composition of the present invention is performed by making a sample of the laminate and measuring its adhesion.

Laminate sample production

The aqueous dispersion composition is applied to the polyolefin substrate with a stretch ruler so that the film thickness of the aqueous dispersion composition after drying is 3 μm. The surface to which the aqueous dispersion composition was applied was dried in a hot air oven at 80 ° C for about 10 minutes, and then a metal substrate was placed on the surface of the aqueous dispersion composition and thermocompression bonded at a temperature of about 120 ° C and a pressure of 0 ° C. , 1 MPa for about 2 minutes to obtain a laminate.

Evaluation of laminate adhesion

Peel strength at a tensile speed of 50 mm / min was measured in an atmosphere at 25 ° C using a Tensilon RTM-100 manufactured by Orientec Co., Ltd. in accordance with ASTM-D1876-61 test method. The peel strength (N / cm) between the metal substrate and the polyolefin substrate represents the average value of the five tests.

Evaluation criteria

A (especially excellent for practical use): 8 N / cm or higher

B (excellent for practical use): 7 N / cm or higher but less than 8 N / cm

C (applicable): 6 N / cm or higher but less than 7 N / cm

D (not applicable): less than 6 N / cm

The present invention is explained in detail below by means of exemplary embodiments. However, the present invention is not limited to these examples. The term parts in the examples and comparative examples means parts by weight.

Examples of embodiments of the invention

Production example 1

100 parts by weight of propylene-butene copolymer (Tafiner, / registered trademark / XM7080 manufactured by Mitsui Chemicals, Inc.), 300 parts by weight. of toluene and 25 parts by weight. maleic anhydride is placed in a 1 liter autoclave and the mixture is heated to 120 ° C. Then 8 parts by weight are added. di-tert-butyl peroxide and the mixture was stirred for 1 hour. Then, the resulting reaction liquid was cooled, poured into a vessel containing a large amount of methyl ethyl ketone to precipitate the resin. The resin-containing liquid is centrifuged to separate the acid-modified propylene butene copolymer with grafted maleic anhydride, ungrafted maleic anhydride, and low molecular weight substances, and the product is subsequently purified. After drying under reduced pressure at 70 ° C for 5 hours, a maleic anhydride-modified propylene-butene copolymer is obtained (PO-1, modifying maleic anhydride content: 2.0% by weight, weight average molecular weight 50,000).

Production example 2

Maleic anhydride-modified propylene-butene copolymer (PO-2, modifying maleic anhydride content: 1.0% by weight, weight average molecular weight 80,000) was obtained in the same manner as the product of Production Example 1 except that the amount of maleic anhydride was adjusted. to 15 parts by weight

Production example 3

The maleic anhydride-modified propylene-butene copolymer (PO-3, modifying maleic anhydride content: 1.5% by weight, weight average molecular weight 70,000) was obtained in the same manner as the product of Production Example 1 except that the amount of maleic anhydride was adjusts to 21 parts by weight.

Production example 4

100 parts by weight of propylene-ethylene copolymer (MFR in the atmosphere at 230 ° C = 5 g / 10 min), 150 parts by weight. of toluene, 20 parts by weight. of maleic anhydride and 5 parts by weight. di-tert-butyl peroxide was placed in a 1 liter autoclave equipped with a stirrer, and the mixture was heated to 140 ° C and stirred for 3 hours. The resulting reaction liquid was then cooled and poured into a vessel containing a large amount of methyl ethyl ketone to precipitate the resin. The resin-containing liquid is centrifuged to separate the acid-modified propylene ethylene copolymers grafted with maleic anhydride, polymaleic anhydride and low molecular weight substances, and the product is subsequently purified. After drying under reduced pressure at 70 ° C for 5 hours, maleic anhydride-modified propylene-ethylene copolymer is obtained. Subsequently, 100 parts by weight. to maleic anhydride-modified propylene-ethylene copolymers and 1700 parts by weight. chloroform is placed in a 2 liter glass lined reactor and the reactor is closed. The liquid in the reactor was heated with stirring to form a dispersion and the dissolution was performed at a reactor temperature of 120 ° C for 1 hour. After the temperature in the reactor is reduced to 110 DEG C., 0.5 part by weight is added. tert-butyl peroxy-2-ethylhexanoate and 70 parts by weight of chlorine. The temperature in the reactor is reduced to 60 DEG C. and 1400 parts by weight. chloroform is evaporated. Then 4 parts by weight are added as stabilizing agent. p-tert-butylphenylglycidyl ether. After drying, a chlorinated propylene ethylene copolymer modified with maleic anhydride is obtained (CPO-1, modifying maleic anhydride content: 2.5% by weight, chlorine content 20% by weight, weight average molecular weight 80,000).

Production example 5

The chlorinated propylene-ethylene copolymer modified with maleic anhydride (CPO-2, modifying maleic anhydride content: 0.8 wt.%, Chlorine content 40 wt.%, Weight average molecular weight 100,000) was obtained in the same manner as the product in Production Example 4 except that the amount of maleic anhydride is adjusted to 9 parts by weight, the amount of di-tert-butyl peroxide is changed to 3 parts by weight. and the amount of chlorine introduced is changed to 160 parts by weight.

Production example 6

Chlorinated propylene-ethylene copolymer modified with maleic anhydride (CPO-3, modifying maleic anhydride content: 3.0% by weight, chlorine content 15% by weight, weight average molecular weight 70,000) is obtained in the same manner as the product in Production Example 4 except that the amount of maleic anhydride is adjusted to 35 parts by weight, the amount of di-tert-butyl peroxide is changed to 6 parts by weight. and the amount of chlorine introduced is changed to 10 parts by weight.

Example 1

210 parts by weight ion-exchanged desalinated water, 100 parts by weight. of copolymer PO-1, 110 parts by weight. of tetrahydrofuran, 45 parts by weight. of isopropyl alcohol and 55 parts by weight. of toluene is placed in a flask equipped with a stirrer, the mixture is heated to 70 ° C and then dissolved with heating at the same temperature for 1 hour. Subsequently, 3.6 parts by weight of it are added. (2 chemical equivalents) of N, N-dimethylethanolamine. Then, the resulting mixture was gradually cooled to 40 ° C over 1 hour, and the organic solvents were evaporated under reduced pressure of about 10 kPa (absolute pressure) to obtain a white cloudy aqueous dispersion composition (a1-1). To the aqueous dispersion mixture, 5 parts by weight of (based on dry matter content) of JONCRYL (registered trademark) PDX-6137A to obtain an aqueous dispersion composition (a2-1). The aqueous dispersion composition (a2-1) has a dry matter content of 30% by weight, a viscosity of 64 mPa.s at 25 ° C, a pH of 9.0 and an average particle size of 92 nm.

Examples 2 to 22, Comparative Examples 1 to 6

Aqueous dispersion compositions (a1-1) to (a1-28) and (a2-1) to (a2-28) of the composition shown in Tables 1 to 4 are obtained in the same manner as aqueous dispersion compositions (a1-1) and (a2). -l). Tables 1 to 4 show their physical properties and the like.

Evaluation of the effect on the viscosity regulating agent (measuring the viscosity of aqueous dispersion compositions)

100 parts by weight of the aqueous dispersion composition (a1-1) is placed in a beaker and 8 parts by weight of viscosity regulating agents that swell in an alkaline environment, Primal (registered trademark) ASE60 (manufactured by Rohm and Haas). The mixture was stirred for 10 minutes. After stirring, the resulting mixture was allowed to stand in a thermostatic chamber at 25 ° C overnight and stirred again with a dispersion homogenizer and its viscosity was measured using a Brookfield viscometer. In the same manner as in (a-1), measurements are made in the case of the aqueous dispersion compositions (a1-2) to (a1-28) and (a2-1) to (a2-28). Tables 1 to 4 show the results.

Preparation of coating film samples * parts by weight film-forming excipients (butyl cellosolve) and 1 part by weight of a wetting agent (EnviroGem (registered trademark) AD01, a product of Nissin Chemical Industry Co., Ltd.) are added to 100 parts by weight of a wetting agent. aqueous dispersion compositions (a2-1) for the production of the Flash primer. The flash primer is applied to a polypropylene plate (manufactured by Yajima Corporation) using a ruler. The primed surface is pre-dried in a hot air oven at 80 ° C for 10 minutes and then a two-component urethane coating material is applied to the resulting substrate with a spray gun, which is then dried in a hot air oven at 80 ° C for for 35 minutes to obtain a coating film sample 1. Coating film samples 2-28 were prepared in the same manner as coating film sample 1 using aqueous dispersion compositions (a2-2) to (a2-28).

Adhesion of coating films

A sample of the coating film 1 was allowed to stand in an atmosphere at 25 ° C for 36 hours. Then, 100 squares are marked with a cutting knife at a distance of 1 mm in the surface of the coating film. Cellophane adhesive tape is firmly pressed to the surface and then removed again at an angle of 60 °. This procedure is repeated ten times, each time using a new cellophane adhesive tape. The case where no change is observed on the surface of the paint film even after ten times the removal of the adhesive tape is assigned 10 points, the case where peeling is observed at the tenth removal of the adhesive tape is assigned 9 points, and so on, so the evaluation gradually assigns 8, 7 , 6 points, and so on, and the case where peeling is observed when the adhesive tape is first removed is evaluated at 0 points. Measurements are also made on the coating film samples 2 to 28 in the same manner. Tables 1 to 4 show the results.

Water resistance of coating films

A sample of the coating film 1 was allowed to stand in an atmosphere at 25 ° C for 36 hours, and then immersed in warm water at 40 ° C for 10 days. After this time, a sample of the coating film is examined for any change and adhesion is evaluated. A sample of the coating film on which no change is observed is assigned 10 points and its adhesion is considered good, i.e., B. A coating film in which no change is observed and whose adhesion is evaluated 9 points is considered to be sample C and the sample A coating film on which blisters have formed or whose adhesion is rated at 8 points or less is considered bad, i.e., D. Measurements are also made on coating film samples 2 to 28 in the same manner. Tables 1 to 4 show the results.

Production of laminate samples of parts by weight film-forming excipient (butylcellosolve) and 1 part by weight of a wetting agent (EnviroGem (registered trademark) AD01, manufactured by Nissin Chemical Industry Co., Ltd.) is added to 100 parts by weight of a wetting agent. aqueous dispersion compositions (a2-1) for preparing the adhesive 1. The adhesive 1 is applied with a applicator ruler to an unstretched polypropylene film (Pylen (registered trademark) film CT, manufactured by Toyobo Co., Ltd., thickness: 40 μm) so that the film thickness of the adhesive layer after drying was 3 μm. The surface to which the adhesive 1 was applied was dried in a hot air oven at 80 ° C for 10 minutes. An aluminum foil (manufactured by Sumikei Aluminum Foil Co., Ltd, 8079-0, thickness: 40 μm) was placed on the surface of the adhesive layer, and the sandwich was hot-pressed at 120 ° C and 0.1 MPa for 2 minutes to obtain of the laminate sample 1. In the same manner as the laminate sample 1, samples of the laminate 2-28 are also produced using the aqueous dispersion compositions (a2-2) to (a2-28).

Evaluation of laminate adhesion

The peel strength of the laminate 1 sample was measured at a drawing speed of 50 mm / min in an atmosphere at 25 ° C using a Tensilon RTM-100 manufactured by Orientec Co., Ltd. in accordance with ASTM-D1876-61 test method. The peel strength (N / cm) between the metal substrate and the polyolefin substrate represents the average value of the five tests. In the same manner as for the laminate sample 1, measurements are also made on the laminate samples 2 to 28. Tables 1-4 show the results.

IT) abulka

ex 11 (a2-ll) 001 3.6 at m O 100 LO uo <C 1 CQ Φ CQ CQ Φ oo < pf. 10 (a2-10) 100 3.6 Sodium chloride uo about what Φ < φ ’ Q Φ CQ CQ 00 CQ Ex 9 (a2-9) Φ o 3.6 'and- m about what 125 co CM < Q Φ CQ CQ oo < Ex 8 (a2-8) 1 o o 3.6 O uo es about what Φ LO < lO φ O Φ m O 00 CQ Ex 7 (a2-7) o o 3.6 O LO about what LO Φ oo < φ CQ Φ CQ CQ Φ oo < O o • U CN a o o 3.6 O 0.5 about what CO 154 < Φ o ' < φ CQ CQ oo < lO ÍĎ a g o o 3.6 ύ iO about what 120 LO co < 0.8 Φ CQ CQ co oo < O. g o o 3.6 O LO about what 150 Φ es < 0.8 Φ CQ CQ 1 8.5 < Ex 3 (a2-3) Φ o WHAT £ -3 m about what uo 150 < Φ φ < Φ CQ CQ oo < CN O] > U CM P- o o 3.6 c-2 m Φ co 103 < φ CQ Φ CQ CQ oo < Ex 1 (a2-1) 100 I 3.6 O ΙΌ Φ co es φ with < οθ φ CQ CQ CQ oo < (Part wt. L PO-1 PO-2 PO-3 N, N- dimethylethanolamine 2-amino-2-methyl-1- propanol P. Amount P. Amount i% wt. nm (0 CX S Evaluation π σ Evaluation Body Evaluation Rated N / cm | Evaluation Acid modified polyolefin (AI) Alkaline substance (B) Water-soluble polymer containing anionic groups (C) Electrolyte (D) 1 Dry matter content Avg. particle size Viscosity aqueous dispersion compositions Effect on the reagent viscosity regulating Coating film adhesion Water resistance of the coating film Laminate adhesion

Table 2

a 3 O o <0 H ΜΊ Ο ΗΊ s < co o what O what what what < Q 3 O O CD i— Ε ΟΌ ι— Ο -Ε <Λ U ιη Ο m Ο LT> what < O and O what what what what Q O CsJ > L O. O O what γ ΙΛ ο £ < O O O what what 00 < cn ^M σ>CM> L Q. O O what m rH rxi Ο ΙΛ The < O at O what CD what Ex 18 (a2-18) o o what Η ο Γ * Ί m what < O what O what what O 00 < 17 (a2-17) o o what ύ ΙΛ Ο Ο s what < σ> O < O what Π) m 00 < with > L O O what m ύ 1 ΓΗ ΓΗ 3 m < what about 00 O what what O 00 < u-> > L · Q. O O what rd Lfl Ο co ΙΟ O < co o what O what what CD what a £ o o what m τ ΙΛ ο CM O < CD O < O what what O oo < £) 1 5 o o CO m ύ ΙΛ ο Μ fNJ m < O what 3 what it oo < ™ 5 l 'š O. 5 o o it rH ΙΛ the m ο £ < what O what O what cn TO < (Parts by weight) O at rsi O m O 0. AT C E O E Φ r— 1 Φ Z E Z Ό _E φ E <N O η © E E • i- ω E O. ft O 1 L · (N Q. Η The Ν Ο Ε Σ Ο. Π > <Λ • Ν Ο Ε Σ Ε Ο Ε £ Ε Ε <Λ ft E E Φ O E o I E Φ u o E o z about what E Φ O E or X E Φ O E or X E z E Φ O E O X σ < > E C 3 d e o> · (- c OM-T U Φγ— Or- φ i— O ω -E O> U CU * rt5 r— fO l / l> Co5 co N * >> 'υ> -> β β «2 S. a ~ a ο- ® ·“ £ .2 »£ Ο« Φ -Η ο Ε c > ^ .2 ο β η > Ρ-ι Λ ct Q Ο ί_ ϊ Φ ω β > ω β GO X <c co 0 ω ο £ * φ > 'Λ β 8 · 5 »3 co c- -cC Q-> υ d „φ C ^u N £ NS 'S« ° 44 C _α a <n T3 ® E - o “o>> T3 Ji § .2 > υ a o 2 Ji '7 N c J. c β 0 Sr; β 6 o Λ 'Φ > φ s Ν ’* φ w Ό o <a s ε *.with Q W O o > ex β 2 S 3 = β <

Table 3

(Part by weight) Cf. př. 1 ía2-23) Cf. př. 2 ía2-24) Cf. př. 3 (a2-25) Acid modified polyolefin (AI) PO-1 100 PO-2 PO-3 100 100 Alkaline substance (B) N, N-dimethylethanolamine 3.6 3.6 3.6 2-amino-2-methyl-1-propanol Water-soluble polymer containing anionic skunin in C Type c-5 Amount 0 0 5 Electrolyte (D) Type Amount Dry matter content % wt. 30 30 30 Avg. particle size nm 92 120 116 Viscosity of the aqueous dispersion composition mPa.s 1320 1152 727 Evaluation D D D Effect on viscosity regulating agent Ha 1.0 1.0 0.9 Rated AND AND AND Coating film adhesion Body 10 10 10 Evaluation B B B Water resistance of the coating film Evaluation B B B Laminate adhesion N / cm 8.1 8.1 8.3 Evaluation AND AND AND

Table 4

(Part no Cf. ex 4 (a2-26) Cf. Ex 5 (a2-271 Cf. Ex 6 (a2-28) _____ Chlorinated polyolefin modified with acid CPO-1 100 CPO-2 CPO-3 100 100 Alkaline substance (B) N, N-dimethylethanolamine 3.6 3.6 3.6 2-amino-2-methyl-1- propanol Water-soluble polymer containing anionic groups C Type c-5 Amount D 0 5 Electrolyte (D) Type Amount Dry matter content % wt. 30 30 30 Avg. particle size nm 131 156 154 Viscosity of the aqueous dispersion composition mPa.s 1440 1105 840 Evaluation D D D Effect on viscosity regulating agent hd 1.0 1.0 0.9 Evaluation AND AND AND Coating film adhesion Body 10 10 10 Evaluation B B B Water resistance of the coating film Evaluation B B B Laminate adhesion N / cm 8.0 8.1 8.3 Evaluation AND AND

The water-soluble polymers containing anionic groups C listed in Tables 1 to 4 are as follows:

Water-soluble polymer containing anionic groups (c-1): Joncryl (registered trademark) PDX-6137A (copolymer of styrene and acrylic monomer), non-volatile content 28.0% by weight, dry acid number 240 mg KOH / g resin, weight average molecular weight 16500, a product of BASF;

Water-soluble polymer containing anionic groups (c-2): Joncryl (registered trademark), 57J (copolymer of styrene and acrylic monomer), non-volatile content 37.0% by weight, dry acid number 215 mg KOH / g resin, weight average molecular weight 4900, product of BASF;

Water-soluble polymer containing anionic groups (c-3): Joncryl (registered trademark) HPD-196 (copolymer of styrene and acrylic monomer), non-volatile content 36.0% by weight, dry acid number 200 mg KOH / g resin, weight average molecular weight 9200, a product of BASF;

Water-soluble polymer containing anionic groups (c-4): Joncryl (registered trademark) S2J (copolymer of styrene and acrylic monomer), non-volatile content 60.0% by weight, dry acid number 238 mg KOH / g resin, weight average molecular weight weight 1700, BASF product;

Water-soluble polymer containing anionic groups (C-5): Joncryl (registered trademark) JDX-6500 (copolymer of styrene and acrylic monomer), non-volatile content 29.5% by weight, dry acid number 85 mg KOH / g resin, weight average molecular weight 10,000, product of BASF.

Industrial applicability]

Since the aqueous dispersion composition of the present invention contains a modified polyolefin and a basic substance, and a water-soluble polymer containing anionic groups and / or an electrolyte, its viscosity can be kept constant in the range of 500 mPa.s to lower values if dry matter content of modified polyolefin in aqueous dispersion composition 30 wt. Furthermore, the effect of the additive used in the preparation of the coating material, in particular the viscosity control agent, is not impaired by the water-soluble polymer containing anionic groups. The aqueous dispersion composition of the present invention is therefore suitable for such applications as automotive exterior coatings, automotive interior coatings and adhesives for household electrical appliances.

Claims (6)

PATENT CLAIMS An aqueous dispersion composition comprising a modified polyolefin (A) and a basic substance (B), said composition further comprising at least one member selected from the group consisting of a water-soluble polymer containing anionic groups having an acid number 150 to 500 mg KOH / g resin (C), and electrolyte (D). Aqueous dispersion composition according to Claim 1, characterized in that the modified polyolefin (A) is an acid-modified polyolefin (A1) and / or an acid-modified chlorinated polyolefin (A2). Aqueous dispersion composition according to claim 1, characterized in that the aqueous dispersion composition contains the basic substance (B) in an amount of from 0.5 to 10 parts by weight. per 100 parts by weight of modified polyolefin (A) and a water-soluble polymer containing anionic groups (C) and / or an electrolyte (D) in a total amount of from 0.1 to 20 parts by weight. per 100 parts by weight modified polyolefin (A). Coating material, paint, sealant, primer or adhesive, characterized in that it comprises an aqueous dispersion composition according to any one of claims 1 to 3. A laminate comprising a polyolefin substrate and a resin substrate or a metal substrate, characterized in that the polyolefin substrate is adhered thereto to the resin substrate or the metal substrate by means of an adhesive according to claim 4. Polyolefin substrate, characterized in that it is coated with a coating material according to claim 4.