JP2005163030A - Modified polyolefin resin composition and aqueous dispersion thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To have excellent adhesion to nonpolar substrates, particularly nonpolar substrates that are difficult to adhere or have not been surface-treated, have no tack, and are soluble in aromatic and non-aromatic solvents. Another object of the present invention is to provide a resin having a characteristic such as good compatibility with other resins and an aqueous dispersion thereof.
A resin composition (C) obtained by graft-copolymerizing one or more (meth) acrylamide derivatives (A) having a glass transition point (Tg) of a homopolymer of 100 ° C. or less to a polyolefin resin as a main component. Modified polyolefin resin composition.
[Selection figure] None

Description

  The present invention has excellent adhesion to non-polar sheets, films and molded articles such as polypropylene, polyethylene, ethylene-propylene copolymer, ethylene-propylene-diene copolymer, and ethylene-vinyl acetate copolymer. In addition, it has excellent adhesion to untreated polyethylene and polypropylene films, has no tack after coating and drying, and is excellent in solubility in solvents other than aromatic solvents. A novel modified polyolefin resin composition having good compatibility and an aqueous dispersion of a modified polyolefin resin composition excellent in blocking resistance, water resistance and gasohol resistance while further maintaining the characteristics of the resin Is.

JP-A-11-217537 JP 2002-173514 A Japanese Patent Publication No. 6-35572 JP-A-6-9832 JP 2000-302873 A JP 2000-327730 A Japanese Patent Application Laid-Open No. 2001-72724 JP 2002-37809 JP 2003-64111 A JP 2002-80686 JP 2002-80687 Japanese Patent Laid-Open No. 06-336568

Polyolefins such as polypropylene and polyethylene are widely used in recent years as sheets, films, molded articles and the like because they are inexpensive and have many excellent properties such as moldability, chemical resistance, water resistance, and electrical properties. However, unlike a polar resin such as a polyurethane resin, a polyamide resin, an acrylic resin, or a polyester resin, the polyolefin base material is nonpolar and crystalline, and thus is difficult to paint or bond.
In order to solve the above problems, an acid-modified polyolefin resin composition obtained by modifying a polyolefin resin with a plurality of unsaturated carboxylic acids and / or derivatives thereof has been proposed as a coating pretreatment agent or an adhesive (patents). Document 1 and Patent document 2). However, these acid-modified polyolefin resins have problems such as low adhesion to non-polar substrates, tackiness on the dried coating film, making winding after film coating difficult, and adhesion of dust. It was. Therefore, it was necessary to take new measures to reduce tack.
In addition, the acid-modified polyolefin resin has a drawback of low solvent solubility. For this reason, it is essential to use a non-polar aromatic solvent such as toluene or xylene as a solvent for dissolving it, and it is extremely difficult to dissolve it in a non-aromatic solvent while maintaining various physical properties such as adhesion. Met. However, in recent years, from the viewpoint of environmental problems, a resin that is soluble in a solvent that does not contain any aromatic solvent has been demanded. Furthermore, since the acid-modified polyolefin has poor compatibility with other resins, there are problems in that workability during coating is poor and other resins to be mixed are limited.

  [Patent Document 3] discloses graft polymerization of a (meth) acrylamide derivative to a chlorinated polyolefin for the purpose of improving adhesion, but unlike the present application, the polyolefin is chlorinated. Since chlorinated polyolefin itself has high solvent solubility, it is not aimed at improving the solvent solubility and compatibility with other resins, which are the purposes of the present application. In addition, chlorinated polyolefins have better adhesion to polyolefin substrates than acid-modified polyolefins, but their weather resistance is poor. May adversely affect the environment, which is not preferable from the viewpoint of environmental problems.

  [Patent Document 4] discloses a copolymer of an ethylene copolymer resin and a (meth) acrylamide derivative as an adhesive resin, but it is a hot melt used as a food packaging material, an industrial material packaging material, or the like. Because it is a mold resin, it has poor solvent solubility. Patent Document 4 is a copolymer of an olefin monomer and a (meth) acrylamide monomer, and a (meth) acrylamide unit is present in the main chain of the polymer, whereas in the present application, a (meth) acrylamide monomer is added to a polyolefin. Since the graft copolymer is a graft copolymer, the main chain is polyolefin and (meth) acrylamide is present in the side chain. Due to these structural differences, [Patent Document 4] requires an expensive production facility for high pressure in order to obtain a copolymer, which is economically problematic.

  [Patent Documents 5 to 9] disclose the inclusion of an olefin and an acrylic resin as a paint or primer for a polyolefin-based resin film or sheet, or a molded product. As monomers used for the synthesis of an acrylic resin, ( Examples are meth) acrylamide derivatives. However, in the methods of [Patent Documents 5 to 9], since a polymer such as an acrylic resin is grafted to a polyolefin, it is difficult to set reaction conditions, and (meth) acrylamide exemplified as a monomer of an acrylic resin. Derivatives are problematic in practice because they are highly toxic and must be handled with great care. In addition, the reaction is essential in the presence of an organic solvent, which is not preferable from the viewpoint of environmental problems.

On the other hand, from the viewpoint of environmental problems, an aqueous dispersion in which the solvent is changed from the solvent to water is also required. However, in order to disperse in water, various additives such as an emulsifier are required. These various additives remain in the resin-dried film, and there are problems that adhesion, water resistance, gasohol resistance, and blocking resistance are deteriorated. There was a need to improve.
As a method for improving the water resistance, gasohol resistance and blocking resistance of the aqueous dispersion, there is a method of crosslinking the resin. As the crosslinking agent, oxazoline-based, amine-based, hydrazide-based, epoxy-based crosslinking agents and the like are known. For example, in [Patent Document 10] and [Patent Document 11], an aqueous dispersion of a block copolymer of an olefin monomer and a vinyl monomer into which a crosslinkable functional group has been introduced, and a polyurethane or vinyl aqueous solution are used. A method of cross-linking a mixture of resins with an epoxy-based cross-linking agent, and [Patent Document 12] includes a mixture of a modified olefin-based aqueous resin and a polyurethane-based aqueous resin into which a crosslinkable functional group has been introduced. There is a method of crosslinking with a hydrazide-based or epoxy-based crosslinking agent. However, in these methods, since a polyurethane-based or vinyl-based aqueous resin is mixed, there is a problem in adhesion to a polyolefin substrate.

  As described above, until now, there is no tack, excellent adhesion to non-polar substrates, solvent solubility, compatibility with other resins, no adverse effects on the environment, and high safety properties are satisfied. There was no modified polyolefin resin composition. Moreover, the water dispersion of the modified polyolefin resin composition which has the said characteristic and was excellent in water resistance, body gasohol property, and blocking resistance did not exist.

  The object of the present invention is low in environmental problems, has excellent adhesion to nonpolar substrates, particularly nonpolar substrates that are difficult to adhere or are not surface-treated, has no tack, and is an aromatic solvent. In addition to exhibiting excellent solubility in non-aromatic solvents as well as a resin composition with good compatibility with other resins, and possessing the characteristics of the resin, in addition to blocking resistance, water resistance Another object is to provide an aqueous dispersion of a resin composition having excellent gasohol resistance.

As a result of intensive studies, the present inventors have found that the above problems can be solved by using as a main component a modified polyolefin resin obtained by graft polymerization using a (meth) acrylamide derivative having a glass transition point below a certain value. A satisfactory resin composition could be obtained. Moreover, the water dispersion which satisfies the said subject was also able to be obtained by disperse | distributing the said resin in water.
That is, the present invention
(1) Modification mainly composed of a resin composition (C) obtained by graft copolymerizing one or more (meth) acrylamide derivatives (A) having a glass transition point (Tg) of a homopolymer of 100 ° C. or less to a polyolefin resin Polyolefin resin composition.

(2) Grafting one or more (meth) acrylamide derivatives (A) having a glass transition point (Tg) of 100 ° C. or less and one or more unsaturated carboxylic acids and / or their derivatives (B) onto a polyolefin resin A modified polyolefin resin composition comprising a resin composition (D) obtained by copolymerization as a main component.

(3) The (meth) acrylamide derivative (A) having a glass transition point (Tg) of the homopolymer of 100 ° C. or lower is diacetone acrylamide and / or N, N, -diethylacrylamide (1) The modified polyolefin resin composition according to (2).

(4) A dispersion in which the modified polyolefin resin composition according to (1) to (3) is dispersed in water.

In the present invention, among (meth) acrylamide derivatives, (meth) acrylamide derivatives having a glass transition point of 100 ° C. or lower are graft-polymerized to polyolefin, thereby imparting useful properties to the modified polyolefin resin after graft modification. I was able to. In other words, even if the modified polyolefin resin has a high molecular weight, it has solubility in non-aromatic solvents, which has been difficult in the past, and solubility in various other polar and non-polar solvents, and compatibility with other resins. Became good.
Moreover, since the softening temperature of the modified polyolefin resin composition was improved by the graft polymerization, tack which was a problem disappeared.
Furthermore, compatibility with other resins could be further improved by using an unsaturated carboxylic acid and / or a derivative thereof together during graft polymerization.
According to the present invention, it was possible to obtain a useful modified polyolefin resin having characteristics that could not be achieved by conventional techniques.

  The aqueous dispersion of the modified polyolefin resin has high adhesion and compatibility with other resins, which are characteristics of the modified polyolefin resin. In addition, since the softening temperature of the resin composition is improved, excellent blocking resistance necessary for the aqueous dispersion is also exhibited. In addition, by adding a cross-linking agent that reacts with the functional groups present in the aqueous dispersion, the content of components other than the modified polyolefin resin, which causes a decrease in adhesion, is reduced, and water resistance and gasohol resistance are improved. I was able to.

  Each component in this invention is explained in full detail.

[Substrate]
Non-polar resins used as the adherend of the modified polyolefin resin composition of the present invention include polypropylene, polyethylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer sheet-like material, film-formed product, molded product, and the like. Say. The modified polyolefin resin composition of the present invention is characterized in that these adherends can be used even if they are difficult to adhere and are not surface-treated with plasma, corona, etc. Even an adherend that is present can be used similarly.

[Polyolefin resin]
The polyolefin resin used in the present invention is an ethylene, propylene, butene-1, pentene-2, hexene-1, heptene-1, octene-1,4-methyl-1-pentene, etc., having 2 to 20 carbon atoms, preferably Is an α-olefin of 2 to 6, or cyclopentene, cyclohexene, 1,4-hexadiene, 1,5-hexadiene, divinylbenzene, 1,3-cyclopentadiene, 1,3-cyclohexadiene, 5-vinyl-2- It is a linear or cyclic polyene such as norbornene, a polymer of the same monomer or a copolymer of different monomers having monomers such as styrene and substituted styrene.
The proportion of these monomers in the polymer can be arbitrarily selected. However, when polyethylene or polypropylene is used as the adherend, the proportion of propylene is preferably 50 mol% or more and 98 mol% or less, particularly ethylene-propylene. , Propylene-butene and ethylene-propylene-butene copolymers are preferred. When the proportion of propylene is less than 50 mol%, adhesion to the adherend is inferior, and when it is more than 98% mol, flexibility is insufficient.
The weight average molecular weight of the polyolefin resin used in the present invention can be freely selected so that the weight average molecular weight of the modified polyolefin resin composition obtained by graft modification is 15,000 to 500,000. For example, even a polymer having a weight average molecular weight of more than 500,000 may be adjusted to an appropriate range by a known method such as degradation in the presence of heat or radical. As the polyolefin resin, a plurality of (co) polymers may be used in combination from the above (co) polymers.

[(Meth) acrylamide derivatives]
The (meth) acrylamide derivative in the present invention refers to a compound in which one or two hydrogen atoms at the acrylamide or methacrylamide terminal are substituted with other substituents.
In the (meth) acrylamide derivative in the present invention, it is essential that the glass transition point (Tg) of the homopolymer is 100 ° C. or lower.
The glass transition point is a physical phenomenon peculiar to a polymer, and means a temperature at which the polymer exhibits flexibility at a molecular level. Therefore, when compared at a certain temperature, a polymer having a lower glass transition point has a higher flexibility, and a polymer having a higher glass transition point tends to have a lower flexibility and be hard and brittle. The glass transition point can be measured by differential scanning calorimetry (DSC) or the like.
In the present application, since it is considered that the graft-modified polyolefin resin is imparted with the physical properties of a homopolymer of a (meth) acrylamide derivative that is graft-polymerized as a result, the physical property value of the homopolymer was regarded as important.
The glass transition point of homopolymers of (meth) acrylamide derivatives is as wide as 80 to 180 ° C., and most of the (meth) acrylamide derivative homopolymers are 100 ° C. or higher. For example, homopolymers of acrylamide and N-isopropylacrylamide The glass transition points of are 180 ° C. and 135 ° C., respectively.
In the present invention, among the (meth) acrylamide derivatives, (meth) acrylamide derivatives having a glass transition point (Tg) of 100 ° C. or less are used. Examples thereof include, but are not limited to, diacetone acrylamide (glass transition point: about 85 ° C.) and N, N-diethyl (meth) acrylamide (glass transition point: about 80 ° C.). Moreover, they may be used independently or may be used in mixture of 2 or more types.
In the present invention, diacetone acrylamide and N, N-diethyl (meth) acrylamide are particularly preferably used.
When a (meth) acrylamide derivative having a glass transition point of 100 ° C. or lower is introduced by graft polymerization, a resin having both hardness and flexibility is obtained, whereas a resin having a glass transition point of 100 ° C. or higher has hardness and flexibility. It becomes a hard and brittle resin.
Further, the glass transition point is correlated with the polarity, and when the polarity is high, the glass transition point tends to be high. In order to improve the solubility in various solvents, which is the object of the present application, it is conceivable to increase the polarity of the modified polyolefin. As one of the means for that purpose, graft polymerization of a relatively high polarity monomer is possible. Can be considered.
Since the (meth) acrylamide derivative has an amide group and is generally highly polar and many of them are soluble in various polar solvents, it is expected to have a certain effect as a monomer that is polymerized into polyolefin. However, if the polarity of the monomer is too high, the target physical properties cannot be sufficiently satisfied. That is, since polyolefin is a nonpolar polymer, if the polarity of the monomer is too high, the compatibility with the polyolefin will be poor and the graft polymerization rate will be extremely low. Therefore, the unreacted monomer in the reaction system forms a homopolymer, and the resulting modified polyolefin resin composition has low adhesion and low solubility. If the polarity is too high, it will only dissolve in polar solvents.
For example, even a (meth) acrylamide derivative having a homopolymer having a glass transition point higher than 100 ° C. has a high polarity and therefore has a low solubility in a nonpolar solvent. The corresponding acrylamide is soluble only in water and methanol, and the homopolymer is soluble only in water.
However, a (meth) acrylamide derivative having a glass transition point of 100 ° C. or less of a homopolymer is not so high in polarity that it is soluble in a wide range of solvents including polar solvents and nonpolar solvents. These homopolymers also show similar properties.
Therefore, when a (meth) acrylamide derivative having a glass transition point of 100 ° C. or lower is introduced into polyolefin, the solubility in polar solvents other than conventionally used nonpolar aromatic solvents such as toluene and xylene is improved.
In addition, since the polarity also affects the compatibility with other resins, when the graft polymerization is performed using a (meth) acrylamide derivative having a glass transition point of 100 ° C. or lower as a monomer, the compatibility between the resulting modified polyolefin resin composition and the other resins is increased. Will improve.
Furthermore, since the (meth) acrylamide derivative has a hydrogen bond and has a melting point, when introduced into a polyolefin, the softening temperature rises. Thereby, tack is improved.
On the other hand, many (meth) acrylamide derivatives are highly toxic and care must be taken when handling them. However, among the (meth) acrylamide derivatives whose homopolymer has a glass transition point of 100 ° C. or less, diacetone acrylamide and N, N-diethylacrylamide have low toxicity unlike other (meth) acrylamide derivatives.
For example, when comparing the acute toxicity values (rat LD50) of diacetone acrylamide and acrylamide, the former is 1770 mg / Kg, while the latter is overwhelmingly toxic at 124 mg / Kg. It is designated as a deleterious substance by the Material Control Law and designated as a specified chemical substance that should be handled with care under the Industrial Safety and Health Law. Thus, diacetone acrylamide and N, N-diethylacrylamide have high safety, high workability, and low possibility of affecting the health of workers and the environment when discarded.
The content (% by weight) in the modified polyolefin resin composition of the (meth) acrylamide derivative (A) having a glass transition point (Tg) of the homopolymer of 100 ° C. or lower is preferable when graft modification is performed only with (A). Is 0.1 to 90% by weight, more preferably 0.1 to 80% by weight, and particularly preferably 0.1 to 70% by weight.

[Unsaturated carboxylic acid and / or derivative thereof]
Moreover, in this invention, an unsaturated carboxylic acid and / or its derivative (B) can be used together according to the objective. In the present invention, the unsaturated carboxylic acid refers to an unsaturated compound containing a carboxyl group, and the derivative refers to an acid anhydride, ester, amide, imide, metal salt, or the like of the compound.
Examples include fumaric acid, maleic acid, itaconic acid, citraconic acid, aconitic acid and their anhydrides, methyl fumarate, ethyl fumarate, propyl fumarate, butyl fumarate, dimethyl fumarate, diethyl fumarate, fumarate Dipropyl acid, dibutyl fumarate, methyl maleate, ethyl maleate, propyl maleate, butyl maleate, dimethyl maleate, diethyl maleate, dipropyl maleate, dibutyl maleate, and (meth) acrylate, methyl (meth) Acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, 2-hexyl (meth) acrylate, octyl (Meth) acrylate, stearyl (meth) acrylate, tridecyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (Meth) acrylate, hydroxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, acetoacetoxyethyl (meth) acrylate, and N-methyl (meth) acrylamide , N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-butyl (meth) acrylamide, N-isobutyl (meth) acryl Amide, Nt-butyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, N-methylenebis (meth) acrylamide, N-methylol (meth) It is at least one compound selected from the group of acrylamide, hydroxyethyl (meth) acrylamide, and (meth) acryloylmorpholine.
Preferably itaconic anhydride, maleic anhydride, methyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, octyl (meth) acrylate, hydroxyethyl (meth) acrylate, N-methylol ( (Meth) acrylamide.
By using together unsaturated carboxylic acid and / or its derivative (B), a specific functional group can be introduce | transduced and compatibility with another component improves.
When the (meth) acrylamide derivative (A) having a glass transition point (Tg) of the homopolymer of 100 ° C. or less and the unsaturated carboxylic acid and / or derivative (B) thereof are used in combination, (A) + (B) is preferably The content is 0.1 to 90% by weight, more preferably 0.1 to 80% by weight, and particularly preferably 0.1 to 70% by weight. However, the graft content (B) must be such that it does not adversely affect the physical properties of the graft-modified modified polyolefin resin composition, and the graft content must be changed according to the type of (B). is there.
In general, it is preferably 0.1 to 45% by weight, more preferably 0.1 to 40% by weight, and particularly preferably 1 to 40% by weight. In any case, if the graft content is less than the specified range, the solvent solubility of the modified polyolefin resin composition and the compatibility with other resins are lowered. On the other hand, if the amount is too large, the amount of homopolymer or copolymer that does not graft onto the polyolefin skeleton increases, and the adhesion is reduced.
In the present invention, maleimide, N-phenylmaleimide, isocyanate-containing (meth) acrylate, polyamide, N-vinylpyrrolidone, N-vinylacetamide, in combination with (A) and (B) depending on the use and purpose. N-vinylformamide or the like can also be used, but in order to obtain the target adhesion of the present invention, the amount of these compounds used does not exceed the total amount of the monomers (A) and (B). It is desirable.
The modified polyolefin resin composition of the present invention may contain a reaction aid for improving graft efficiency, a stabilizer for adjusting the stability of the resin composition, a radical initiator for promoting the reaction, and the like.
Examples of the reaction aid include styrene, o-, p-, α-methylstyrene, divinylbenzene, hexadiene, dicyclopentadiene and the like. Examples of the stabilizer include hydroquinone, benzoquinone, nitrosophenylhydroxy compound and the like. The radical initiator can be appropriately selected from known ones. For example, an organic peroxide such as benzoyl peroxide, dicumyl peroxide, lauroyl peroxide, di-t-butyl peroxide, cumene hydroperoxide, or the like can be used. preferable.

[Modified polyolefin resin composition]
A known method may be used to obtain a modified polyolefin resin composition by graft copolymerization using the above compound. For example, a polyolefin resin is dissolved by heating in a solvent such as toluene, and a (meth) acrylamide derivative (A), an unsaturated carboxylic acid and / or derivative (B) thereof having a homopolymer glass transition point (Tg) of 100 ° C. or lower is obtained. Examples include a solution method to be added and a melt method in which (A) and (B) are added to a polyolefin resin melted using a Banbury mixer, kneader, extruder, etc. No melting method is preferred. The addition method of (A) and (B) may be sequential or batch addition.
The reaction form of the above compound in the modified polyolefin resin composition is as follows: (meth) acrylamide derivative (A), unsaturated carboxylic acid and / or derivative thereof (Glass transition point (Tg) of homopolymer to 100 ° C. or less in the polyolefin skeleton) B) may be directly graft-polymerized, or the (homo) copolymer of (A) or (B) may be graft-polymerized to the polyolefin skeleton, and the reaction form is not particularly limited.
The weight average molecular weight of the modified polyolefin resin composition is 15,000 to 500,000, preferably 30,000 to 400,000. Especially preferably, it is 30,000-300,000. If it is less than 15,000, the adhesion and cohesion to nonpolar substrates are poor, and if it is greater than 500,000, workability decreases due to an increase in melt viscosity. Compatibility with resin decreases.
Moreover, a crosslinking | crosslinked component can also be added to the modified polyolefin resin composition of this invention as needed. The crosslinkable component means a compound that reacts with active hydrogen such as a hydroxyl group or a carbonyl group contained in the modified polyolefin resin composition of the present invention to form a crosslinked structure.
Crosslinkable components include polyisocyanates such as phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, polyamine, polyepoxy, polyepoxy. It is at least one compound selected from the group of hydrazide, carbodiimide resin, oxazoline resin and the like.
The weight average molecular weight can be determined by a known method such as a gel permeation chromatography method (GPC method), a light scattering method, or the like. The graft content of the (meth) acrylamide derivative is measured by elemental analysis, and the graft content of the unsaturated carboxylic acid and / or its derivative is determined by alkali titration, Fourier transform infrared spectroscopy (FT-IR), nuclear magnetic Measured by resonance analysis (NMR).

[Aqueous dispersion of modified polyolefin resin composition]
A method for obtaining an aqueous dispersion of the modified polyolefin resin composition in the present invention will be described in detail below.
The aqueous dispersion of the modified polyolefin resin composition is produced by adding an emulsifier and a basic substance to the modified polyolefin resin composition and emulsifying it, and then adding water such as ion exchange water.

〔emulsifier〕
As the emulsifier, an anionic surfactant or a nonionic surfactant can be used. Anionic surfactants include alkyl sulfates, polyoxyethylene alkyl ether sulfates, alkylbenzene sulfonates, alpha olefin sulfonates, methyl taurates, sulfosuccinates, ether sulfonates, ether carboxylates, fatty acids Salts, naphthalenesulfonic acid formalin condensates, alkylamine salts, quaternary ammonium salts, alkylbetaines, alkylamine oxides and the like.
Nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene alkylene alkyl ether, polyoxyethylene derivatives, polyoxyethylene fatty acid ester, polyoxyethylene polyhydric alcohol fatty acid ester, polyoxyethylene propylene polyol, sorbitan fatty acid ester, Examples include polyoxyethylene hydrogenated castor oil, polyoxyalkylalkylene polycyclic phenyl ether, polyoxyethylene alkylamine, alkylalkanolamide, polyalkylene glycol (meth) acrylate, and the like. Preferable examples include polyoxyethylene alkyl ether sulfate, sulfosuccinate, polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, and polyoxyethylene alkylamine.
The amount used is from 0 to 30 weights with respect to the modified polyolefin resin composition. When the amount is more than 30 parts by weight, an amount of emulsifier sufficient to form an aqueous dispersion is present in the system. , The adhesive force is remarkably reduced, and when a dry film is formed, a plastic effect and a bleeding phenomenon are caused, and blocking occurs.
The emulsification method may be any of the known forced emulsification method, phase inversion emulsification method, D phase emulsification method, gel emulsification method, etc., and the equipment used is a single agitation with a stirring blade, a disper, a homogenizer, etc. and a combination thereof. Combined stirring, sand mill, and multi-screw extruder can be used.

[Basic substance]
The basic substance is added for the purpose of neutralizing the acid component in the modified polyolefin resin composition and dispersing it in water.
In the present invention, the pH of the aqueous dispersion is desirably 6 or more, and particularly preferably 6 to 10. If the pH is 6 or less, neutralization is insufficient, so that the modified polyolefin resin does not disperse in water, or even if dispersed, precipitation / separation occurs with time and storage stability deteriorates, which is not preferable. In addition, when the pH is 10 or more, there is a problem in compatibility with other components and work safety.
As basic substances, sodium hydroxide, potassium hydroxide, ammonia, methylamine, propylamine, hexylamine, octylamine, ethanolamine, propanolamine, diethanolamine, N-methyldiethanolamine, dimethylamine, diethylamine, triethylamine, N, N -Dimethylethanolamine, 2-dimethylamino-2-methyl-1-propanol, 2-amino-2-methyl-1-propanol, morpholine and the like, preferably ammonia, triethylamine and morpholine.
The amount used can be arbitrarily added based on the amount of the acid component of the modified polyolefin resin composition, but it must be added so that the pH of the aqueous dispersion is 6 or more, preferably 6 to 10.

(Crosslinking component)
In the present invention, a crosslinkable component can be added to the aqueous dispersion depending on the application and purpose. The crosslinkable component is a compound that reacts with an active hydrogen such as a hydroxyl group, a carboxyl group, or an amino group derived from a modified polyolefin resin, an emulsifier, a basic substance, etc. present in an aqueous dispersion to form a crosslinked structure. Of course, it may be water-soluble or may be dispersed in water by some method.
Specific examples include blocked isocyanate compounds, aliphatic or aromatic epoxy compounds, amine compounds, amino resins, and the like.
When a blocked isocyanate compound is used as the crosslinkable component, not only can a film excellent in adhesion and water resistance be formed, but also the storage stability of the aqueous dispersion is excellent. When an aliphatic or aromatic epoxy compound is used, it not only has excellent water resistance and chemical resistance, but also has excellent cross-linking reactivity and can be cross-linked over a wide temperature range by adding a reaction catalyst, etc. Products that meet the conditions of use such as paints and adhesives produced using the can be prepared.
When an amine compound is used, it can be used as a room temperature dry composition having adhesion to a nonpolar substrate such as polyolefin. When an amino resin is used, the interlayer adhesion to the melamine-based top coat is excellent, and the water resistance is also excellent.
The addition method of a crosslinkable component is not specifically limited. For example, you may mix | blend in the middle of a water dispersion | distribution process, and may add after water dispersion | distribution.
Next, the crosslinkable component will be described in detail.

"Block isocyanate compounds"
The blocked isocyanate compound is an isocyanate compound having two or more isocyanate groups in one molecule, such as ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, decamethylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 2 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,5-naphthylene diisocyanate, 4,4 ', 4 "-triphenylmethane triisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'- Dimethyl-4,4'-diphenylene diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, isophorone diisocyanate, lysine Isocyanates such as socyanate and the above isocyanate compounds, for example, ethylene glycol, propylene glycol, 1,3-butylene glycol, neopentyl glycol, 2,2,4-trimethyl-1,3-pentanediol, hexamethylene glycol, cyclohexane A polyisocyanate having a bifunctional or higher functionality and a burette structure obtained by excessively blending the isocyanate compound in an addition reaction or addition polymerization reaction with a low molecular polyol such as dimethanol, trimethylolpropane, hexanetriol, glycerin, pentaerythritol, etc. It is an isocyanate compound obtained by blocking a polyisocyanate having an allophanate bond, an isocyanate having a nurate structure, or the like with a blocking agent.
Examples of the blocking agent include phenols such as phenol and cresol, alcohols such as methanol, benzyl alcohol and ethylene glycol monomethyl ether, active methylenes such as methyl acetoacetate and dimethyl malonate, and acid amides such as acetanilide and acetate amide. Other imides, amines, imidazoles, ureas, carbamates, imines, oximes such as acetoxime, methyl ethyl ketoxime, malonic esters such as diethyl malonate, mercaptans, sulfites, epsilon caprolactam, etc. There are lactams.
That is, the blocked isocyanate compound referred to in the present invention is generally a compound called blocked isocyanate, masked isocyanate, reactive urethane or the like.
As a ratio of the aqueous dispersion of the blocked isocyanate compound and the modified polyolefin resin composition, it is preferably used in the range of 1:20 to 10: 1. However, the isocyanate group contained in the blocked isocyanate compound and the coating film after the drying treatment are used. The optimum ratio can be determined by the amount of functional groups that react with isocyanate groups such as hydroxyl groups and carboxyl groups derived from the modified polyolefin resin composition and surfactant components contained in the remaining components.
When a film is formed using an aqueous dispersion to which a blocked isocyanate compound has been added, heat treatment is performed at 80 to 200 ° C. for 1 minute to 2 hours in order to proceed with the reaction between the isocyanate and other active hydrogen after blocking. About this process conditions, an optimal value is set with the deblocking conditions of the block isocyanate to be used, the kind and addition amount of a deblocking catalyst.

"Aliphatic or aromatic epoxy compounds"
An epoxy compound has one or more oxirane structures in its molecular structure and is liquid at room temperature, or solid at room temperature, itself water-soluble or water-dispersible, or water-soluble or water-dispersible It has been made water-based by some method such as addition of a surface active agent or formation of a hydrophilic protective colloid without the presence of water.
Typical examples include polyolefin epoxide, cycloalkene epoxide, epoxy acetal, glycidyl ether, glycidyl ester, glycidyl group derivatives such as glycidylamine and glycidylimine, and oxetane compounds.
Specifically, from bisphenol A diglycidyl ether represented by bisphenol A epoxy resin, novolac epoxy resin, polyphenol epoxy resin, polyhydroxybenzene epoxy resin, phenyl glycidyl ether, cresol monoglycidyl ether, etc. Epoxidized derivatives, copolymers of glycidyl methacrylate and other acrylic monomers, cyclohexene oxide epoxy resins, epoxy resins composed of aniline derivatives, triglycidyl isocyanurate, compounds having one or more oxetane rings, such as 3-ethyl-3 -Hydroxymethyloxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3- (phenoxymethyl) oxetane, 1,4-bis {[((3-ethyl-3-oxe Nyl) methoxy] methyl} benzene, di [1-ethyl (3-oxetanyl)] methyl ether, 1,4-bis [(1-ethyl-3-oxetanyl) methoxy] benzene, 1,3-bis [(1- Examples include ethyl-3-oxetanyl) methoxy] benzene, 4,4′-bis [(3-ethyl-3-oxetanyl) methoxy] biphenyl, phenol novolac oxetane and the like.
In the compounding of the epoxy compound, a curing agent or a curing catalyst can be blended depending on the use conditions of the aqueous dispersion, and a formulation suitable for the film forming conditions can be prepared.
Curing agents and curing catalysts include aliphatic polyamines typified by diethylenetriamine, aromatic polyamines typified by metaphenylenediamine, secondary amines typified by piperidine and pyrrolidine, triethanolamine, hexamethylenetetramine, and trisdiaminomethyl. Tertiary amines represented by phenol, acid anhydrides represented by phthalic anhydride, citraconic anhydride, pyromellitic anhydride, boron fluoride amine complex, phenol novolac resin, urea resin initial condensate, melamine resin Examples include initial condensates and dicyandiamide.
In the present invention, the epoxy compound is used in an amount of 2 to 500 parts by weight based on 100 parts by weight of the aqueous dispersion. When the amount used is less than 2 parts, the effect of addition does not appear, and when it is more than 500 parts, the adhesion to a nonpolar substrate decreases.

"Amine compounds"
As the amine curing agent, a polyamine compound having two or more active amino groups or imino groups in one molecule or a hydrazine compound having two or more hydrazine groups in one molecule can be used.
As the polyamine compound, those having an amine value in the range of 100 to 2000 are preferable. When the amine value is less than 100, the compound is highly toxic and difficult to use, and when the amine value exceeds 2000, sufficient coating curing can be obtained. Hateful.
Examples of the hydrazine-based compounds include carbodihydrazide, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutamic acid dihydrazide, adipic acid dihydrazide, azelaic acid dihydrazide, sebacic acid dihydrazide, undecanoic acid dihydrazide didicenediodic dihydradide Di (tri) hydrazides of di (tri) carboxylic acids such as phthalic acid dihydrazide, itaconic acid dihydrazide, isophthalic acid dihydrazide, terephthalic acid dihydrazide, glycolic acid dihydrazide, pentane-1,3,5-tricarboxylic acid (tri) hydrazide Aliphatic dihydrazides such as ethylene-1,2-dihydrazine, propylene-1,3-dihydrazine, butylene-1,4-dihydrazine, hexylene-1,6-dihydrazine S and the like.
Any polyhydrazide other than the above polyhydrazide may be used as long as it is water-soluble, self-emulsifiable, or dispersed in water by some method.
In the present invention, the amine compound is blended in an amount of 0.1 to 30 parts by weight with respect to 100 parts by weight of the aqueous dispersion. If it is less than 0.1 part, the improvement of blocking resistance is not observed, and if it exceeds 30 parts, the adhesion when an overcoat is applied is lowered.
An aqueous dispersion characterized by using an amine compound as a crosslinkable component can be used as a room temperature dry composition having adhesion to a nonpolar substrate such as polyolefin.

"Amino resin"
An amino resin means a thermosetting resin obtained by reacting an amino compound such as urea, melamine, benzoguanamine, and acetoguanamine with formaldehyde. As the amino resin used in the present invention, known resins can be used. Preferably, the amino resin is liquid at room temperature, or is it water-soluble or water-dispersible even when it is solid at room temperature? Alternatively, it is water-soluble by some method such as addition of a surfactant or formation of a hydrophilic protective colloid without water solubility or water dispersibility.
The amount of the amino resin used is 5 to 500 parts with respect to 100 parts of the aqueous dispersion. If it is less than 5 parts, the effect of addition does not appear, and if it is 500 parts or more, the adhesion to the polyolefin substrate is insufficient.
The modified polyolefin resin composition and aqueous dispersion thereof of the present invention can be used as an adhesive for non-polar substrates, a primer, a binder resin for paint, and a binder resin for ink. The modified polyolefin resin composition can be used in a form such as a solution, a powder, a sheet, or the like, but can be used as a solution using a solvent other than water as a medium at the coating stage. At that time, additives such as antioxidants, light stabilizers, ultraviolet absorbers, pigments, dyes, inorganic fillers and the like can be blended as necessary.
With respect to the aqueous dispersion, lower alcohols, lower ketones, lower esters, preservatives, leveling agents, metal salts, acids and the like can also be blended.
When using the modified polyolefin resin composition as a solution, aliphatic solvents such as cyclohexane, methylcyclohexane, ethylcyclohexane, n-heptane, n-nonane, n-decane, ester solvents such as ethyl acetate and butyl acetate, acetone, Various solvents such as ketone solvents such as methyl ethyl ketone and methyl butyl ketone, alcohol solvents such as methanol, ethanol, propanol and butanol, aromatic solvents such as toluene and xylene, or mixtures of the above solvents can be used. It is preferable to use a mixture of cyclohexane aliphatic solvent and ester or ketone solvent. In view of environmental problems, it is desirable not to use an aromatic solvent.
The heat treatment conditions when using the resin or aqueous dispersion of the present invention are as follows: laminating on a film at a high temperature of about 170 ° C. or 180 ° C., or applying the solution by spraying, brushing, bar coating, etc. It can also be used after drying and baking at a temperature of about ~ 100 ° C, or as it is dried at room temperature.
In adhesives and ink binder resins, not only nonpolar substrates such as polyethylene and polypropylene but also polar substrates such as polyester, polyurethane and polyamide are often used together. Since it has adhesion to a substrate, it is suitable for the same application.
Similarly, when used as a primer or a binder resin for paints, it is also suitable for the same application because of its excellent adhesion to top coats and clears.
When used as a binder for paints and inks, urethane resins, epoxy resins, acrylic resins, phenol resins, alkyd resins, polyamide resins, polyimide resins, silicone resins, nitrified cotton, and other resins and water dispersions are used as necessary. You may blend these water-based resins.
When using the modified polyolefin resin composition and its aqueous dispersion for various purposes, when the above additives and other resins are blended, the modified polyolefin resin of the present invention is used to maintain adhesion to nonpolar substrates. It is necessary to use the resin composition in a solid content of at least 5% by weight or more based on the total resin material.
In addition, the aqueous dispersion of the present invention includes an aqueous acrylic resin, an aqueous urethane resin, a lower alcohol, a lower ketone, a lower ester, an antiseptic, a leveling agent, an antioxidant, a light stabilizer, and an ultraviolet absorber. , Dyes, pigments, metal salts, acids and the like can be blended.

[Action]
The present invention provides a useful property to a modified polyolefin resin after graft modification by selecting a (meth) acrylamide derivative whose homopolymer has a glass transition point of 100 ° C. or less as a monomer to be graft polymerized to polyolefin. I was able to. That is, (meth) acrylamide derivatives having a glass transition point of 100 ° C. or lower are generally (meth) acrylamide derivatives having a high polarity, and have a certain degree of polarity, but are more polar than other (meth) acrylamide derivatives. Since it is low, it was possible to impart a good balance of solvent solubility, adhesion, compatibility with other resins, and resin rigidity to the polyolefin resin composition graft-modified using it as a monomer. The aqueous dispersion could also be dispersed in water without losing the useful properties of the modified resin.

EXAMPLES Next, although an Example demonstrates this invention still in detail, this invention is not limited to this. The physical properties shown in Examples and Comparative Examples were measured after washing the modified polyolefin resin composition with a large amount of methanol.
The weight average molecular weight is measured by GPC, the graft weight of the (meth) acrylamide derivative is measured by elemental analysis, and the graft weights of maleic anhydride and itaconic anhydride are measured by alkali titration method by lauryl methacrylate, methyl methacrylate. The graft weight of hydroxyethyl acrylate was measured by NMR.
The polymerization conditions and physical properties of the examples are summarized in Table 1, and the polymerization conditions and physical properties of the comparative examples are summarized in Table 2.

(Example of modified polyolefin resin composition)

[Example 1]
In a four-necked flask, 100 parts by weight of propylene-ethylene-α-olefin copolymer (propylene component 68 mol%, ethylene component 8 mol%, butene component 24 mol%, weight average molecular weight 60,000), N, N- 20 parts by weight of diethyl acrylamide and 1 part by weight of dicumyl peroxide were added and stirred at 180 ° C. for 2 hours for reaction.

[Example 2]
L / D = 40, the reaction part occupies 30% of the total length, the occupancy rate of the kneading disk in the reaction site is 50%, and the configuration is 17% kneading disk light, 17% kneading disk left, In the same direction twin screw extruder having a kneading disk neutral of 16%, 100 parts by weight of a propylene-ethylene-α-olefin copolymer (propylene component 95 mol%, ethylene component 5 mol%, weight average molecular weight 250,000), 500 parts by weight of diacetone acrylamide and 3 parts by weight of dicumyl peroxide were added. The residence time was 10 minutes, the temperature of the reaction part was 180 ° C., and devolatilization was performed in the final barrel to remove residual unreacted substances.

[Examples 3, 5, 6, 8, 11, 13]
Using the propylene-ethylene-α-olefin copolymer used in Example 1 and the (meth) acrylamide derivative and unsaturated carboxylic acid derivative shown in Table 1, a modified polyolefin resin composition was prepared in the same manner as in Example 1. Obtained.

[Examples 4, 7, and 12]
Using the propylene-ethylene-α-olefin copolymer used in Example 2 and the (meth) acrylamide derivative and unsaturated carboxylic acid derivative shown in Table 1, a modified polyolefin resin composition was prepared in the same manner as in Example 2. Obtained.

[Example 9]
To 100 parts by weight of the modified polyolefin resin composition obtained in Example 8, 1 part by weight of isophorone diisocyanate was added as a crosslinking agent.

[Example 10]
1 part by weight of Carbolite V-05 (manufactured by Nisshinbo Industries, Inc.) was added as a crosslinking agent to 100 parts by weight of the modified polyolefin resin composition obtained in Example 7.

(Example of water dispersion)
[Example 14]
L / D = 40, the reaction part occupies 30% of the total length, the occupancy rate of the kneading disk in the reaction site is 50%, and the configuration is 17% kneading disk light, 17% kneading disk left, A propylene-ethylene-α-olefin copolymer (propylene component: 68 mol%, ethylene component: 8 mol%, butene component: 24 mol%, weight average molecular weight: 60) , 000) 100 parts by weight, N, N-diethylacrylamide 500 parts by weight, itaconic anhydride 250 parts by weight, and dicumyl peroxide 3 parts by weight. The residence time was 10 minutes, the temperature of the reaction part was 180 ° C., and devolatilization was performed in the final barrel to remove residual unreacted substances.
After 100 parts by weight of the modified polyolefin obtained in a four-necked flask, 10 parts by weight of dimethylethanolamine, and 10 parts by weight of polyoxyethylene alkylamine were uniformly stirred at 100 ° C. for 2 hours with a stirring blade and dissolved, 90 ° C. An aqueous dispersion was obtained by adding 300 parts by weight of ion exchange water.

[Example 15]
In a four-necked flask, 100 parts by weight of the modified polyolefin obtained in Example 6 was melted at 110 ° C., 10 parts by weight of morpholine was added dropwise, and 10 parts by weight of polyoxyethylene alkyl ether sulfate was added. Thereafter, 300 parts by weight of 90 ° C. ion-exchanged water was added to obtain an aqueous dispersion.

[Example 16]
The aqueous dispersion obtained in Example 14 was mixed with aqueous blocked isocyanate (Elastolon BN-44, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) as a cross-linking agent at a solid content of 2: 1.

[Example 17]
20 parts by weight of adipic acid dihydrazide was added as a crosslinking agent to 100 parts by weight of the aqueous dispersion obtained in Example 15.

(Comparative example of modified polyolefin resin composition)

[Comparative Examples 1, 2, 4]
Using the propylene-ethylene-α-olefin copolymer used in Example 2 and the (meth) acrylamide derivative and unsaturated carboxylic acid derivative shown in Table 2, a modified polyolefin resin composition was prepared in the same manner as in Example 2. Obtained.

[Comparative Examples 3 and 5]
Using the propylene-ethylene-α-olefin copolymer used in Example 1 and the (meth) acrylamide derivative and unsaturated carboxylic acid derivative shown in Table 2, a modified polyolefin resin composition was prepared in the same manner as in Example 1. Obtained.

(Comparative example of water dispersion)
[Comparative Example 6]
In a four-necked flask, 100 parts by weight of the modified polyolefin obtained in Comparative Example 1 was melted at 110 ° C., 10 parts by weight of morpholine was added dropwise, and 10 parts by weight of polyoxyethylene alkyl ether sulfate was added. Thereafter, 300 parts by weight of 90 ° C. ion exchange water was added to obtain an aqueous dispersion.

[Comparative Example 7]
In a four-necked flask, 100 parts by weight of the modified polyolefin obtained in Comparative Example 3 was melted at 110 ° C., 10 parts by weight of morpholine was dropped, and 10 parts by weight of polyoxyethylene alkylamine was added. Thereafter, 300 parts by weight of 90 ° C. ion exchange water was added to obtain an aqueous dispersion.

(Test of modified polyolefin resin composition and aqueous dispersion)
The following tests were conducted on the modified polyolefin resin compositions obtained in Examples 1 to 13 and Comparative Examples 1 to 5, and the aqueous dispersions obtained in Examples 14 to 17 and Comparative Examples 6 to 7.

(1) Solvent solubility 10% by weight of the resulting modified polyolefin resin composition was dissolved in a methylcyclohexane / methyl ethyl ketone = 9/1 (w / w) solution, and the solvent solubility was evaluated.

(2) Tack test Using a # 20 Meyer bar, a solution prepared by dissolving the modified polyolefin resin composition in toluene was applied to high-density polyethylene film and polypropylene film that had not been surface-treated, and dried at room temperature for 15 hours. The aqueous dispersion was applied to an unsurface-treated polypropylene film using a # 7 Meyer bar, dried at room temperature for 15 hours, and then heat-treated at 120 to 130 ° C. for 2 to 15 minutes. About each, the test piece was bend | folded so that the film surface might overlap, and after peeling lightly with the finger | toe, it peeled off and tack was evaluated from the ease of the peeling.

(3) Film room temperature adhesion test Similar to the above tack test, a cellophane adhesive tape is closely adhered to the coated surface of the film coated with the modified polyolefin resin composition and the aqueous dispersion, and then peeled off in the 180-degree direction and remains. The state of the coating layer was observed.

(4) Adhesion test The toluene solution and aqueous dispersion of the modified polyolefin resin composition used in the tack test were spray-coated on an ultra-rigid polypropylene plate so that the dry film thickness was 10 μm or more and 15 μm or less. Was dried at 80 ° C. for 30 minutes, and the aqueous dispersion was dried at 120 to 130 ° C. for 2 to 15 minutes. After leaving the test piece at room temperature for 3 days, make a cut on the surface of the coating film with a cutter to make 100 grids at 1mm intervals, and adhere cellophane adhesive tape on it in the direction of 180 degrees After peeling off 5 times, the number of remaining grids was counted.

(5) Heat seal strength test About the modified polyolefin resin composition, the toluene solution of a tack test was apply | coated to the polypropylene film by which the corona surface treatment was carried out using # 20 Meyer bar, and it dried at room temperature for 15 hours. The aqueous dispersion was applied using a # 7 Meyer bar, dried at room temperature for 15 hours, and then heat-treated at 120 to 130 ° C. for 2 to 15 minutes. The coated surfaces are overlapped with each other. Heat sealing was performed using a 276 heat seal tester (Yasuda Seiki Seisakusho) under the conditions of 1.5 kg / cm 2, 90 ° C. and 1 second. Each test piece was cut to a width of 15 mm, peeled off using a tensile tester under conditions of 5 kg weight and 100 mm / min, and the peel strength was measured. The test was performed three times, and the average value was taken as the result.
Table 3 shows the test results from (1) to (5).

(6) Paint test A toluene solution in which 40% by weight of each modified polyolefin resin composition was dissolved in toluene was prepared, and this was used as a binder resin to prepare a paint with the following composition.
Binder resin (40% -containing toluene solution): 100 parts by weight Alkyd resin (Phthalkid V904 manufactured by Hitachi Chemical): 15 parts by weight TiO2: 5 parts by weight Carbon black: 1 part by weight Petal: 2 parts by weight Talc: 15 parts by weight Silica Matting agent: 5 parts by weight The above components were kneaded in a sand mill for about 1 hour, and then diluted with toluene so that the viscosity was 12 to 13 seconds / 20 ° C. in a Ford cup # 4 to prepare a paint. Each paint was spray-applied on an ultra-high rigidity polypropylene plate so that the dry film thickness was 30 μm to 35 μm, dried at room temperature for 30 minutes, and then baked at 80 ° C. for 30 minutes. The test piece was allowed to stand at room temperature for 2 days, and then the following test was performed.

-Adhesion test The test piece was subjected to the same cross cut test as described above.

-Warm water resistance test The test piece was immersed in warm water of 40 ° C for 240 hours, the state of the coating film was visually observed, and then an adhesion test by a cross-cut test was performed.

-Gasoline resistance test The test piece was immersed in gasoline for 2 hours, and the state of the coating film was visually observed.

-Gasohol resistance test The test piece was immersed in a solution in which gasoline and ethanol were mixed at 9/1 (w / w) for 2 hours, and the state of the coating film was visually observed.
The test results of (6) are shown in Table 4.

(7) Primer test For each modified polyolefin resin composition, a toluene solution having a solid content of 10% by weight was prepared and spray-coated on an ultra-high rigidity polypropylene plate so that the dry film thickness was 10 μm or more and 15 μm or less. Drying was performed for 30 minutes. Next, the two-pack type top coat white paint was spray-coated so that the dry film thickness was 45 μm or more and 50 μm or less, and allowed to stand at room temperature for 15 minutes, and then baked at 90 ° C. for 30 minutes. The aqueous dispersion was spray-coated under the same conditions as the modified polyolefin resin composition, allowed to stand at room temperature for 15 minutes, dried at 80 ° C. for 30 minutes, and then heat treated at 120 to 130 ° C. for 2 to 15 minutes. The test piece was allowed to stand at room temperature for 3 days, and then the same test as the paint test was performed. The results are shown in Table 5.

(8) Ink test / compatibility test 40% by weight of each solution prepared by dissolving the modified polyolefin resin composition in an ethylcyclohexane / butyl acetate = 7/3 (w / w) solution was used as a binder resin. The ink was adjusted with the following composition.
Binder resin (40% -containing solution): 100 parts by weight Urethane resin for ink: 50 parts by weight TiO2: 100 parts by weight Ethyl acetate: 100 parts by weight Isopropyl alcohol: 50 parts by weight The above components are kneaded with a paint shaker and white printing ink Adjusted. The compatibility with the ink component was judged visually from the separated state of the ink.
About the water dispersion obtained in Examples 11-14 and Comparative Examples 9-11, it mix | blends so that it may become 1: 1 by solid content ratio with the water-based polyurethane which is a typical thing of the other component of ink. The well-stirred one was stored at room temperature for 30 days, and the compatibility was confirmed.

-Adhesiveness The printing ink of the said composition containing the modified polyolefin resin composition obtained in Examples 1-10 and Comparative Examples 1-8 is polyester (PET), nylon (NY), stretched polypropylene (# 12 Meyer bar) It was applied to each film of OPP) and high density polyethylene (HDPE).
The adhesiveness was determined by visual observation of the state of the coated surface when a cellophane adhesive tape was applied to the coated surface and the cellophane adhesive tape was rapidly removed.
(8) Table 6 shows the test results.

Summary of test results [Modified polyolefin resin composition]
As shown in the examples, the modified polyolefin resin composition graft-polymerized using a (meth) acrylamide derivative having a glass transition point of 100 ° C. or lower is solvent-soluble, adhesive, compatible, tack-resistant, gasoline-resistant. Property, gasohol resistance, and warm water resistance were excellent. Furthermore, as shown in Examples 9 to 10, when a crosslinking agent was added, the heat seal strength was remarkably improved.
As shown in Comparative Example 1, unless the (meth) acrylamide derivative was graft-polymerized, satisfactory results were not obtained for all the tested items.
As shown in Comparative Examples 2 to 5, when graft polymerization was performed using a (meth) acrylamide derivative having a glass transition point of 100 ° C. or higher, adhesion, heat seal strength, gasoline resistance, gasohol resistance, and the like deteriorated.

[Water dispersion]
As shown in Examples 14 to 17, an aqueous dispersion of a modified polyolefin resin composition graft-polymerized using a (meth) acrylamide derivative having a glass transition point of 100 ° C. or lower has solvent solubility, adhesion, compatibility, Tack resistance, gasoline resistance, and warm water resistance were excellent. Furthermore, the addition of a crosslinking agent significantly improved the gasohol resistance.

Claims (4)

  Modified polyolefin resin composition comprising, as a main component, a resin composition (C) obtained by graft-copolymerizing one or more (meth) acrylamide derivatives (A) having a glass transition point (Tg) of a homopolymer of 100 ° C. or less to a polyolefin resin. Stuff.   One or more types of (meth) acrylamide derivatives (A) having a glass transition point (Tg) of the homopolymer of 100 ° C. or lower and one or more types of unsaturated carboxylic acids and / or derivatives (B) thereof are graft-copolymerized onto a polyolefin resin. The modified polyolefin resin composition which has as a main component the resin composition (D) obtained.   3. The (meth) acrylamide derivative (A) having a glass transition point (Tg) of the homopolymer of 100 ° C. or lower is diacetone acrylamide and / or N, N, -diethylacrylamide. Modified polyolefin resin composition.   The dispersion which disperse | distributed the modified polyolefin resin composition of any one of Claims 1-3 to water.