JP5003218B2 - Process for producing modified polyolefin resin and aqueous dispersion composition of modified polyolefin resin - Google Patents

Description

  The present invention relates to a novel method for producing a modified polyolefin resin in which unsaturated carboxylic acid and / or a derivative thereof are added to polyolefin to suppress the generation of by-products and efficiently added, and the modified polyolefin resin thus obtained is added to water. The present invention relates to an aqueous dispersion composition of a dispersed polyolefin resin. More specifically, (meth) acrylic acid alkyl esters and unsaturated carboxylic acids (excluding (meth) acrylic acid alkyl esters) are efficiently added to polyolefins using organic peroxides to suppress the generation of by-products. The present invention relates to a novel method for producing a modified polyolefin resin, and a modified polyolefin resin aqueous dispersion composition obtained by dispersing a modified polyolefin resin thus obtained in water.

  Homopolymers of olefins such as polyethylene, polypropylene and polybutene and copolymers with other copolymerizable monomers based on these olefins (hereinafter collectively referred to as “polyolefins”) It is relatively inexpensive and has good moldability, heat resistance, water resistance, solvent resistance, mechanical properties, appearance, etc., and is copolymerized or blended with different polymers to form various alloys. It is a material that can be combined with an inorganic material to form a composite material, or laminated on a metal to exhibit superior characteristics, and is therefore processed into various molded products and used in various fields. However, since polyolefin resins are composed of saturated hydrocarbons and have poor chemical reactivity and low polarity, they are different types of polymers having polar groups, especially so-called engineering plastics such as polyester, polyamide, polyphenylene sulfide, and polyphenylene oxide. A polymer alloy having poor compatibility and simply blending both has a problem that the impact resistance, mechanical strength, etc. are low, and surface peeling occurs in a molded product. Moreover, when only a polyolefin is used, since the dispersibility and adhesiveness of inorganic materials are insufficient, when it is a composite material, impact resistance and mechanical strength are reduced. The adhesion between the polyolefin and the metal is also insufficient, and when the metal surface is covered with polyolefin, there is a problem that peeling from the adhesive surface occurs. In addition, various molded products using these polyolefins adhere to other materials, and are coated or printed on the surface of molded products. Polyolefins have low polarity and poor chemical reactivity. Property, paintability, printability, etc. were insufficient.

In order to solve these problems, it is effective to impart a polar group to a part or all of the polyolefin. A method of treating the polyolefin resin with radiation such as an electron beam or ozone, a method of chlorination, or an organic peroxide. A method is known in which an ethylenically unsaturated compound such as an unsaturated carboxylic acid, an unsaturated carboxylic acid anhydride, or a derivative thereof is modified by graft reaction in the presence of a radical generator such as an oxide (for example, Patent Documents). 1-3).
JP 49-010890 A Japanese Patent Application Laid-Open No. 64-087611 Japanese Patent Laid-Open No. 01-282207

  Polyolefins that have been acid-modified by graft reaction of ethylenically unsaturated compounds such as unsaturated carboxylic acids or their anhydrides are used as compatibilizers and adhesives for polyolefins and other resins, dispersants and adhesives for inorganic materials, and metals. It can be used as an adhesive, a primer such as a polyolefin substrate, an additive for ink and paint, and the like. However, chlorinated polyolefin aromatic hydrocarbon varnishes have often been used as primers for polyolefin base materials, and additives for inks and paints in view of performance. In recent years, due to environmental problems due to organic halogens and aromatics, the use of high-performance acid-modified polyolefin aqueous dispersions instead of chlorinated polyolefin varnishes has been studied.

  A method of continuously producing acid-modified polyolefin using a kneading extruder without using a solvent and a method of performing a batch reaction in the presence of a solvent are known. However, since the reaction is performed by mixing unsaturated carboxylic acids and organic peroxides, by-products such as molecular weight reduction due to radical decomposition of the polyolefin main chain, residual unreacted unsaturated carboxylic acid and black foreign matter are generated, The molecular weight of the polyolefin main chain is reduced, the performance of the modified polyolefin is reduced due to the mixture of unreacted products and by-products, and there are problems such as black foreign objects causing defects in films and highly transparent moldings. It was.

Continuous production using a kneading extruder is a general modification reaction method, but the reaction ripening time is limited to a short time, so unreacted products are likely to remain and suppress the generation of by-products. Not a thing. Therefore, removal of unreacted substances and by-products can be achieved by purifying the modified polyolefin by dissolving it in a solvent and reprecipitating it (for example, see Patent Document 4), or by reheating the resulting modified polyolefin. A method for reducing the amount of reactants (see, for example, Patent Document 5) has been proposed. However, there are problems such as requiring a complicated process such as separating a large amount of organic solvent by filtration, and lowering the molecular weight of polyolefin by reheating. If the batch reaction is performed in the presence of a solvent, the reaction can be sufficiently matured, so it is easy to suppress unreacted residues. However, since the reaction is performed in a low-concentration solution, the grafting efficiency is low and the by-product is low. (See, for example, Patent Documents 6 and 7). Therefore, in order to obtain a high-performance modified polyolefin by a simple production process, a technique for suppressing the decrease in molecular weight during the modification reaction, improving the reaction efficiency, and suppressing the generation of by-products has been demanded. .
JP-A-54-99193 JP-A-56-95914 Japanese Patent Laid-Open No. 06-199967 JP 2006-249340 A

As a technique for improving the reaction efficiency of unsaturated carboxylic acids, a technique is known in which unsaturated carboxylic acids such as maleic anhydride are used in combination with unsaturated compounds such as styrenes and methacrylic esters, and the decrease in molecular weight is also suppressed. It is known that it is easy (see, for example, Patent Documents 8 to 15).
Japanese Patent Laid-Open No. 07-173229 JP-T-08-505181 JP 2001-139642 A JP 2002-173514 A JP 2002-234919 A JP 2004-277619 A JP 2006-083294 A JP 2006-219627 A

  However, when a kneader is used, the remaining of unreacted substances is not sufficiently suppressed, and black foreign matter is easily generated. When batch reaction is performed in the presence of a solvent, a large amount of aromatic hydrocarbon such as toluene or xylene is used. Since the reaction was performed with the low concentration solution used in the above, the grafting efficiency was low. In recent years, due to environmental problems, a production process that does not use aromatic hydrocarbons such as toluene and xylene is required.

  In view of the above situation, the present invention is a modified polyolefin resin that maintains good physical properties and functions by suppressing the generation of by-products, has few defects in the resin due to black foreign matter, and does not contain an aromatic solvent. And a modified polyolefin resin aqueous dispersion composition in which the modified polyolefin resin thus obtained is dispersed in water.

  In order to solve the above problems, the present inventor added (meth) acrylic acid alkyl ester and unsaturated carboxylic acid with an organic peroxide in the presence of sorbitols and an organic solvent to polyolefin. It was found that the reaction can be carried out efficiently and the generation of unreacted residues and by-products can be suppressed.

  Specifically, the present invention can be solved as follows.

  That is, the present invention provides the polyolefin (A) having at least ethylene and propylene as structural units, at least one selected from sorbitols (B) and alkyl alkylates, alkylene glycol alkyl ether alkylates, dialkylene glycol alkyl ether alkylates. (Meth) acrylic acid alkyl ester (D) and unsaturated carboxylic acids (E) ((meth) acrylic acid alkyl ester ( It is a method for producing a modified polyolefin resin, characterized in that it is obtained by adding an organic peroxide (F) except for (D) (Invention 1).

  In the method for producing a modified polyolefin resin according to the first aspect of the present invention, 100 parts by mass of the polyolefin (A), 0.01 parts by mass to 2 parts by mass of the sorbitol (B), and 5 parts by mass of the organic solvent (C). In the presence of not less than 50 parts by mass and not more than 50 parts by mass of (meth) acrylic acid alkyl ester (D) 0.5 parts by mass to 30 parts by mass and unsaturated carboxylic acids (E) 0.5 parts by mass to 30 parts by mass. A method for producing a modified polyolefin resin, which is obtained by adding 0.1 to 10 parts by mass of an organic peroxide (F) (Invention 2).

  In the method for producing a modified polyolefin resin according to the first or second aspect of the present invention, the molar ratio of the (meth) acrylic acid alkyl ester (D) and the unsaturated carboxylic acid (E) is a (meth) acrylic acid alkyl ester. (D) / Unsaturated carboxylic acid (E) = A method for producing a modified polyolefin resin in which 0.5 to 2.0 (Invention 3).

In the method for producing a modified polyolefin resin according to any one of Inventions 1 to 3, the present invention provides the polyolefin (A) having a weight average molecular weight of 10,000 to 200,000 and a density of 0.85 g / cm ^{3 to} 0. It is a manufacturing method of the modified polyolefin resin which is .89 g / cm ³ or less (Invention 4).

  The present invention also provides a modified polyolefin resin aqueous dispersion composition obtained by dispersing a modified polyolefin obtained by the method for producing a modified polyolefin resin according to any one of the first to fourth inventions in water (Invention 5). .

  According to the present invention, the modified polyolefin or the modified polyolefin resin aqueous dispersion that suppresses by-products and unreacted products, which have good adhesion to the olefin substrate and also have fewer black foreign matters, resulting in fewer defects in the molded product. A body composition can be provided.

  Furthermore, the modified polyolefin resin produced by the method for producing a modified polyolefin according to the present invention has a modified polyolefin resin produced by suppressing the residual unreacted substances and by-products as compared with the modified polyolefin produced by the conventional production method. There is little degradation in the performance of polyolefins, and the modification reaction proceeds efficiently, so the modification rate is easy to increase. Therefore, high performance can be exhibited as an additive for inks and paints, a primer and an adhesive for polyolefin base materials, a compatibilizer for polyolefin base materials and other resins, and a modifier for polyolefin base materials. The aqueous dispersion of the modified polyolefin resin can exhibit high performance as an additive for water-based inks and paints, a water-based primer and an adhesive.

  The configuration of the present invention will be described in more detail as follows.

  The polyolefin (A) that can be used in the present invention is an α-olefin copolymer containing at least ethylene and propylene. As the α-olefin, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1 -Heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-dodecadecene, 4-methyl-1-pentene and the like. Examples of the copolymer include a random copolymer, a block copolymer, a graft copolymer, and a mixture thereof.

The density of the polyolefin (A) used in the present invention is 0.85 g / cm ³ or more and 0.89 g / cm ³ or less. Polyolefin resins having a density of less than 0.85 g / cm ³ are not common and only polyolefins having insufficient strength can be obtained. Therefore, the density is preferably 0.85 g / cm ³ or more. When the density is 0.89 g / cm ³ or less, the crystallinity of the polyolefin is low, and the (meth) acrylic acid alkyl ester (D) and the unsaturated carboxylic acid (E) are easily compatible with the polyolefin. It is preferable because efficiency is improved and generation of unreacted substances and by-products can be suppressed.

  The molecular weight of the polyolefin (A) is preferably a weight average molecular weight of 10,000 or more and 200,000 or less. Compared with the case where the weight average molecular weight is smaller than 10,000, the case where the weight average molecular weight is 10,000 or more and 200,000 or less is preferable because the cohesive force is increased and the effect is improved when adhesion, surface modification, and the like are performed. Compared with the case where the weight average molecular weight is larger than 200,000, when the weight average molecular weight is 10,000 or more and 200,000 or less, the fluidity is improved. Therefore, the (meth) acrylic acid alkyl ester (D) and the unsaturated carboxylic acids (E) are uniformly used. It is preferable because it is easy to disperse in the solution, the efficiency of the reaction is improved, and residual unreacted products and generation of by-products can be suppressed. Further, even when the weight average molecular weight is larger than 200,000, the molecular weight is adjusted to 10,000 or more and 200,000 or less by a known method such as degrading in the presence of heat or radical to adjust the molecular weight to an appropriate range. It can be used as a preferred polyolefin (A).

In the case of a high molecular weight polyolefin (A) having a density exceeding 0.89 g / cm ³ and a weight average molecular weight exceeding 200,000, the crystallinity is high, the softening point is high, and the high molecular weight makes the melt viscosity extremely high. In some cases, the polyolefin (A) tends to be less soluble in the organic solvent (C), so that it may not be sufficiently soluble in the organic solvent (C), so the addition reaction is made uniform. Tend to be difficult to do.

  Sorbitols (B) are sorbitol and sorbitol derivatives, specifically, sorbitol, sorbitol monofatty acid ester, sorbitol difatty acid ester, sorbitol trifatty acid ester, sorbitol monounsaturated fatty acid ester, sorbitol diunsaturated fatty acid ester, Examples include sorbitol triunsaturated fatty acid esters, sorbitol monoalkyl ethers, sorbitol dialkyl ethers, and sorbitol trialkyl ethers, and at least one compound selected from these can be used. Among these, sorbitol is preferable from the viewpoint of preventing coloring and black foreign matter generation.

  The amount of sorbitol (B) used is preferably 0.01 parts by mass or more and 2 parts by mass or less, and particularly 0.03 parts by mass or more and 0.5 parts by mass or less with respect to 100 parts by mass of the polyolefin (A). It is more preferable. Compared to the case where the content is less than 0.01 parts by mass, when the content is 0.01 parts by mass or more and 2 parts by mass or less, the generation of polymers and oligomers as a by-product and black foreign matters can be suppressed. In the case of 0.03 parts by mass or more and 0.5 parts by mass or less, it is preferable because the compatibility, adhesion, adhesion, paintability, printability, and dispersibility in the resin and the base material are good. Is preferable because generation of by-products can be further suppressed. In addition, the purity of the modified polyolefin is improved when it is 0.01 parts by mass or more and 2 parts by mass or less as compared with the case where the content is more than 2 parts by mass. In addition, the adhesiveness, adhesiveness, paintability, printability, and dispersibility are preferable because they do not decrease, and the case of 0.03 parts by mass or more and 0.5 parts by mass or less is preferable because the purity of the modified polyolefin is further improved.

  The organic solvent (C) is at least one selected from alkyl alkylates, alkylene glycol alkyl ether alkylates, dialkylene glycol alkyl ether alkylates, and may be any organic solvent having a boiling point of 250 ° C. or lower. Are alkyl alkylates such as ethyl acetate, propyl acetate, butyl acetate, ethyl propionate, propyl propionate, butyl propionate, ethyl butyrate, propyl butyrate, butyl butyrate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate , Alkylene glycol alkyl ether alkylates such as propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol There may be mentioned di-alkylene glycol alkyl ether alkylate such as Bruno butyl ether acetate, it can be used at least one compound selected from these. Among these, butyl propionate, butyl butyrate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate having boiling points of 130 ° C. or more and 250 ° C. or less are It is preferable because a reaction at a high temperature can be performed to facilitate the grafting reaction by hydrogen abstraction. Further, butyl propionate and propylene glycol monomethyl ether acetate having a boiling point of 130 ° C. or higher and 150 ° C. or lower are easily removed by distillation. Therefore, it is preferable.

  The amount of the organic solvent (C) used is preferably 5 to 50 parts by mass, more preferably 10 to 30 parts by mass, with respect to 100 parts by mass of the polyolefin (A). Compared with the case where the content is less than 5 parts by mass, when the content is 5 parts by mass or more, the viscosity of the polyolefin (A) due to the organic solvent (C) can be suppressed. D) Uniform dispersion of unsaturated carboxylic acids (E) and organic peroxide (F) is facilitated. In addition, (meth) acrylic acid alkyl ester (D), unsaturated carboxylic acids (E), and organic peroxide (F) condensed on the ceiling and walls of the reaction tank are washed by refluxing the organic solvent (C). This can be quickly returned to the polyolefin being modified. Because of these effects, it is possible to suppress the generation of by-products generated by homopolymerization of (meth) acrylic acid alkyl ester (D) and unsaturated carboxylic acids (E). The compatibility, adhesiveness, adhesiveness, paintability, printability, and dispersibility are preferable, and when it is 10 parts by mass or more, more uniform dispersion is facilitated and cleaning can be easily performed. Since generation | occurrence | production of a by-product can be suppressed, it is preferable. Moreover, when it is 50 mass parts or less compared with the case where there are more than 50 mass parts, polyolefin (A), methacrylic acid alkyl ester (D), unsaturated carboxylic acids (E), organic peroxide (F) This is preferable because the grafting reaction easily proceeds, and the amount of 30 parts by mass or less is preferable because the concentration during the reaction can be further increased.

  The (meth) acrylic acid alkyl ester (D) is an acrylic acid alkyl ester and a methacrylic acid alkyl ester, preferably an acrylic acid which is an ester with a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms. Methyl, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, i-propyl acrylate, i-propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, I-butyl acrylate, i-butyl methacrylate, 2-butyl acrylate, 2-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, It is at least one compound selected from n-octyl crylate, n-octyl methacrylate, n-dodecyl acrylate, n-dodecyl methacrylate, n-octadecyl acrylate, n-octadecyl methacrylate and the like at high temperature In order to carry out the reaction, the alcohol having a linear, branched, or cyclic alkyl group having a boiling point of 150 ° C. or higher and a linear alkyl group and acrylic acid or methacrylic acid ester n-butyl acrylate, methacrylate n -Butyl, i-butyl acrylate, i-butyl methacrylate, 2-butyl acrylate, 2-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, acrylic acid 2 -Ethylhexyl, 2-ethylhexyl methacrylate, Le acid n- octyl, methacrylic acid n- octyl, acrylic acid n- dodecyl, methacrylic acid n- dodecyl, acrylic acid n- octadecyl, preferably from the reaction of methacrylic acid n- octadecyl and the like to be added to the polyolefin easily proceeds.

  The amount of the (meth) acrylic acid alkyl ester (D) used is preferably 0.5 parts by mass or more and 30 parts by mass or less, particularly 1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the polyolefin (A). More preferably. Compared with the case where the content is less than 0.5 parts by mass, when the content is 0.5 parts by mass or more, the copolymerization with the grafted unsaturated carboxylic acid (E) proceeds, and the by-product It is preferable because the generation is easily suppressed. When the amount is 1 part by mass or more, copolymerization of the graft chain further proceeds, and generation of a by-product is suppressed, which is preferable. In addition, when the amount is 30 parts by mass or less, the amount of by-products such as a homopolymer of (meth) acrylic acid alkyl ester (D) decreases, compared to the case where the amount is more than 30 parts by mass, preferably 20 parts by mass. When the amount is less than or equal to parts, the amount of by-products is further reduced, which is preferable.

  Unsaturated carboxylic acids (E) are unsaturated carboxylic acids and their derivatives except (meth) acrylic acid alkyl ester (D), preferably unsaturated such as acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, etc. Monobasic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, unsaturated dibasic acid such as citraconic anhydride, and unsaturated dibasic acid and methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, 2-butanol, t-butanol, cyclohexanol, 2-ethylhexanol, n-octanol, n-dodecyl alcohol, n-octadecyl alcohol, ethylene glycol monoethyl ether, ethylene glycol Mono-i-propyl ether, ethylene glycol Groups of monoesters with monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, tritylene glycol monoethyl ether, tritylene glycol monobutyl ether and the like and methylamine, dimethylamine, ethylamine, diethylamine, n-propylamine, i-propyl At least one compound selected from the group of amides and imides with amine, n-butylamine, cyclohexylamine, 2-ethylhexylamine, n-octylamine, n-dodecylamine, n-octadecylamine, aniline, benzylamine, etc. It is. Maleic anhydride and / or its derivatives are particularly preferred because they have poor homopolymerization and the grafting reaction tends to proceed.

  The amount of the unsaturated carboxylic acid (E) used is preferably 0.5 parts by mass or more and 30 parts by mass or less, particularly 1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the polyolefin (A). More preferred. Compared with the case where the content is less than 0.5 parts by mass, when the content is 0.5 parts by mass or more and 30 parts by mass or less, sufficient polarity can be imparted to the modified polyolefin. It is preferable because the compatibility, adhesiveness, and adhesiveness are better, and when it is 1 part by mass or more and 20 parts by mass or less, the compatibility, adhesiveness, and adhesiveness are further improved. Moreover, compared with the case where there are more than 30 mass parts, when it is 0.5 mass part or more and 30 mass parts or less, since the efficiency of reaction which adds unsaturated carboxylic acid (E) improves, byproduct of The amount is preferably 1 to 20 parts by mass because the generation is easily suppressed, and the reaction efficiency is further improved, and the generation of by-products is suppressed.

  The molar ratio of (meth) acrylic acid alkyl ester (D) to unsaturated carboxylic acid (E) is (meth) acrylic acid as the ratio of use of (meth) acrylic acid alkyl ester (D) and unsaturated carboxylic acid (E). The alkyl ester (D) / unsaturated carboxylic acid (E) is preferably 0.5 to 2.0. Compared with the case where the molar ratio is less than 0.5, when the molar ratio is 0.5 to 2.0, the (meth) acrylic acid alkyl ester (D) and the unsaturated carboxylic acids (E) Since both copolymerization and grafting occur efficiently, the compatibility with the polyolefin-based resin and the base material, adhesion, and adhesion are preferable, and ungrafted unsaturated carboxylic acids (E) Therefore, the generation of by-products such as unreacted substances and black foreign matters derived from the unsaturated carboxylic acids (E) can be suppressed, which is preferable. Moreover, compared with the case where the said molar ratio is larger than 2.0, when the said molar ratio is 0.5-2.0, (meth) acrylic-acid alkylester (D) and unsaturated carboxylic acids (E ) And ungrafted copolymers are reduced, the grafting efficiency is improved, the polyolefin-based resin, the compatibility with the base material, the adhesiveness, and the adhesion are preferable, Generation of by-products such as unreacted products derived from (meth) acrylic acid alkyl ester (D), ungrafted polymer, and black foreign matter due to reduction of ungrafted (meth) acrylic acid alkyl ester (D) Can be suppressed.

  The organic peroxide (F) may be a peroxide having a carbon atom in the skeleton of the compound, and is preferably a peroxide capable of generating a radical having a hydrogen abstracting effect, such as ketone peroxide, peroxyketal, hydroper Oxides, dialkyl peroxides, diacyl peroxides, peroxyesters, peroxydicarbonates, alkylperoxycarbonates, and specific examples include diisobutyryl peroxide, cumyl peroxyneodecanate, di-n-propyl peroxy Dicarbonate, diisopropyl peroxydicarbonate, di-sec-butyl peroxydicarbonate, 1,1,3,3-tetramethylbutyl peroxyneodecanate, di (4-t-butylcyclohexyl) peroxydicarbonate 1-cyclohexyl-1-methylethyl peroxyneodecanate, di (2-ethoxyethyl) peroxydicarbonate, di (2-ethylhexyl) peroxydicarbonate, t-hexyl peroxyneodecanate, dimethoxybutyl per Oxydicarbonate, t-butyl peroxyneodecanate, t-hexyl peroxypivalate, t-butyl peroxypivalate, di (3,3,5-trimethylhexanoyl) peroxide, di-n-octanoyl peroxide , Dilauroyl peroxide, distearoyl peroxide, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanate, disuccinic acid peroxide, 2,5-dimethyl-2,5-di (2-ethylhexanoyl) Paoki ) Hexane, t-hexyl peroxy-2-ethylhexanate, di (4-methylbenzoyl) peroxide, t-butyl peroxy-2-ethylhexanate, dibenzoyl peroxide, t-butyl peroxyisobutyrate, 1,1 -Di (t-butylperoxy) -2-methylcyclohexanate, 1,1-di (t-butylperoxy) -3,3,5-trimethylcyclohexanate, 1,1-di (t-butyl) Peroxy) cyclohexane, 1,1-di (t-hexylperoxy) cyclohexane, 2,2-di (4,4-di- (t-butylperoxy) cyclohexane) propane, t-hexyl peroxyisopropyl monocarbonate, t-Butyl peroxy maleic acid, t-butyl peroxy-3,3 5-trimethylhexanate, t-butyl peroxylaurate, 2,5-dimethyl-2,5-di (3-methylbenzoylperoxy) hexane, t-butylperoxyisopropyl monocarbonate, t-butyl peroxy-2 -Ethylhexyl monocarbonate, t-hexyl peroxybenzoate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxyacetate, 2,2-di- (t-butylperoxy) Butane, t-butyl peroxybenzoate, n-butyl 4,4-di- (t-butylperoxy) valerate, di (2-t-butylperoxyisopropyl) benzene, dicumyl peroxide, di-t-hexyl par Oxide, 2,5-dimethyl-2,5-di (t-butyl para -Oxy) hexane, t-butyl cumyl peroxide, di-t-butyl peroxide, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroper Examples thereof include oxide and t-butyl hydroperoxide. These may be used individually by 1 type, and may be used in combination of 2 or more types.

  The organic peroxide (F) preferably has a structure that does not contain a hydroxyl group and an aromatic ring. When an organic peroxide having a structure that does not contain a hydroxyl group and an aromatic ring is used, The generation of products is suppressed, and the resulting modified polyolefin is preferably less colored. The reaction of adding the (meth) acrylic acid alkyl ester (D) and the unsaturated carboxylic acid (E) to the polyolefin (A) is carried out by reacting the (meth) acrylic acid alkyl ester (D) and the unsaturated carboxylic acid (E) with an organic solvent. In order to make the oxide (F) compatible with the polyolefin (A), it is necessary to carry out at a temperature higher than the softening point of the softening and melting of the polyolefin (A). Since it is preferable to suppress degradation of the polyolefin (A) by peroxide as much as possible, a temperature range as low as possible is preferable. For this reason, it is preferable that the 1-hour half-life decomposition temperature of an organic peroxide (C) is the range of 110-160 degreeC. In particular, t-butylperoxy 2-ethylhexyl monocarbonate, di-t-hexyl peroxide, di-t-butyl peroxide and the like are organic peroxides having a one-hour half-life decomposition temperature in the range of 110 to 160 ° C. Is preferred.

  The amount of the organic peroxide (F) used is preferably 0.1 parts by mass or more and 10 parts by mass or less, particularly 0.2 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the polyolefin (A). It is more preferable. When the content is 0.1 parts by mass or more and 10 parts by mass or less compared to the case where the content is less than 0.1 parts by mass, (meth) acrylic acid alkyl ester (D) and unsaturated carboxylic acids (E) are added. It is preferable because the efficiency of the reaction to be added is improved, and when it is 0.2 parts by mass or more and 5 parts by mass or less, the efficiency of the reaction is further improved, which is preferable. In addition, when the amount is 0.1 parts by mass or more and 10 parts by mass or less compared to the case where the amount is more than 10 parts by mass, since the cleavage of the polyolefin chain by radicals generated by the organic peroxide is suppressed, the low molecular weight component And the compatibility, adhesiveness, and adhesion are improved, and the amount of 0.2 parts by mass or more and 5 parts by mass or less is more preferable because the generation of low molecular weight components is further suppressed.

  In the modified polyolefin of the present invention, a stabilizer for adjusting the stability can be added during production according to the purpose of use. Stabilizers include hydroquinone, benzoquinone, nitrosophenylhydroxy compounds, phosphite compounds such as tris (2,4-di-t-butylphenyl) phosphite, pentaerythrityl-tetrakis [3- (3,5-di- Known compounds such as pentaerythritol esters such as t-butyl-4-hydroxyphenyl) propionate].

  In the present invention, an ethylenically unsaturated compound other than the (meth) acrylic acid alkyl ester (D) and the unsaturated carboxylic acid (E) is converted into a (meth) acrylic acid alkyl ester (D ) And unsaturated carboxylic acids (E). Examples of the ethylenically unsaturated compound include styrene monomers such as styrene, α-methylstyrene, and divinylbenzene, olefins such as ethylene, propylene, and butene, alkadienes such as butadiene and isoprene, vinyl acetate, and vinyl propionate. And vinyl ethers such as vinyl ester, isobutyl vinyl ether, dodecyl vinyl ether, cyclohexyl vinyl ether, diethylene glycol monovinyl ether, and 4-hydroxybutyl vinyl ether. These ethylenically unsaturated compounds may be used alone or in combination of two or more. The amount of the ethylenically unsaturated compound used is 15 when the total amount of the (meth) acrylic acid alkyl ester (D) and the unsaturated carboxylic acid (E) is 100 parts by mass so as not to inhibit the effects of the present invention. It is preferable that it is below mass parts.

  The graft reaction of the (meth) acrylic acid alkyl ester (D) and the unsaturated carboxylic acid (E) to the polyolefin (A) is carried out by bringing the polyolefin (A) to a temperature higher than the softening point. And alkyl alkylate, alkylene glycol alkyl ether alkylate, dialkylene glycol alkyl ether alkylate, and at least one organic solvent (C) having a boiling point of 250 ° C. or lower is dissolved, and (meth) acrylic acid alkyl ester ( D), unsaturated carboxylic acids (E) (excluding (meth) acrylic acid alkyl ester (D)) and organic peroxide (F) can be added and reacted. The grafting reaction may be performed at a temperature higher than the temperature at which the polyolefin melts, but is preferably performed at 130 ° C. or higher so that the hydrogen abstraction reaction proceeds easily, in order to suppress a decrease in the molecular weight of the polyolefin due to peroxide. It is desirable to carry out at 200 degrees C or less. The addition method of (meth) acrylic acid alkyl ester (D), unsaturated carboxylic acid (E) and organic peroxide (F) is as follows: batch addition, addition after diluting into solution, divided addition, continuous method by dropping The addition method can be selected as appropriate, and the order of addition can also be selected as appropriate. In addition, a decompression step is provided at the end of the reaction, and the organic solvent (C), residual (meth) acrylic acid alkyl ester (D), unsaturated carboxylic acids (E), organic peroxide (F), organic peroxide The decomposition product of (F) can also be removed.

  The modified polyolefin resin can be dispersed in water using an emulsifier or a protective colloid to obtain a modified polyolefin resin aqueous dispersion composition. As an emulsification method, a solution in which a modified polyolefin resin is dissolved in an oil-soluble solvent, an emulsifier, a protective colloid and water are mixed, and after homogenizer treatment, the solvent is distilled off to produce an oil-in-water emulsion, Mixing the molten polyolefin resin and emulsifier, protective colloid and water under high temperature, so-called mechanical method to produce oil-in-water emulsion through a homogenizer, mixing the molten polyolefin resin and emulsifier, protective colloid and some water under high temperature, A so-called phase inversion method is used in which a water-in-oil emulsion is formed, and then inverted water is added to cause phase transition to an oil-in-water emulsion. Moreover, the mechanical method which forms an oil-in-water-type emulsion using a high shear type | mold rotary emulsification disperser can also be used.

  When the modified polyolefin resin is dispersed in water, the carboxyl group derived from the unsaturated carboxylic acid (E) can be neutralized with a basic substance. Basic substances include alkali metals such as sodium hydroxide and potassium hydroxide, alkaline earth metals such as calcium hydroxide, ammonium, methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, ethanolamine, isopropylamine Organic amine compounds such as propanolamine, 2-methyl-2-aminopropanol, diethanolamine, N, N-dimethylethanolamine, N-methyldiethanolamine, dimethylamine, triethylamine, morpholine, N-methylmorpholine, N-ethylmorpholine 1 type or 2 types or more can be used.

  The reason why the basic substance is added is to neutralize and ionize the carboxyl group to improve the dispersion in water. The electric repulsion between the carboxyl anions generated by the neutralization prevents aggregation between the fine particles and imparts the stability of the aqueous dispersion.

  As an emulsifier for the modified polyolefin resin, polyoxyethylene lauryl ether, polyoxyethylene octylphenyl ether, polyoxyethylene alkyl ether such as polyoxyethylene nonylphenyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene sorbitan monolaurate, Nonionic surfactants such as polyoxyethylene sorbitan monooleate such as polyoxyethylene sorbitan monooleate, lauryl sulfate and lauryl sulfate (hereinafter sometimes abbreviated as lauryl sulfate (salt)), dodecylbenzenesulfone Acid (salt), dialkylsulfosuccinic acid (salt), polyoxyethylene alkyl ether sulfuric acid (salt), polyoxyethylene alkyl phenyl ether sulfuric acid (salt), fatty acid (salt) , Anionic surfactants such as alkenyl succinic acid (salts), also include surfactants of the cationic and amphoteric. Here, the salt represents an alkali metal salt such as sodium salt or potassium salt, an alkaline earth metal salt such as calcium salt, an ammonium salt, or an amine salt such as triethylamine salt.

Examples of the protective colloid of the modified polyolefin resin include polyvinyl alcohol, polyethylene glycol, polyacrylamide, starch, and carboxymethyl cellulose. These emulsifiers and protective colloids can be used alone or in combination of two or more.

  The pH of the aqueous dispersion is not particularly limited, but is preferably 6 to 11, and more preferably 7 to 9. When the pH of the aqueous dispersion is 6 to 11, since the carboxyl group in the modified polyolefin is neutralized and ionized to improve the dispersion in water, the storage stability of the aqueous dispersion is good, and the pH is preferable. 7 to 9 is more preferable because neutralization of the carboxyl group in the modified polyolefin proceeds and the storage stability of the aqueous dispersion becomes good. On the other hand, when the pH of the aqueous dispersion is 6 to 11, it is preferable because the free basic substance is not excessively present in the aqueous dispersion, so that the adhesion and water resistance of the coating film are improved, and the pH is 7 In the case of -9, since a free basic substance further reduces in an aqueous dispersion and the adhesiveness of a coating film and water resistance become favorable, it is more preferable. It is. In addition, when an organic amine is used, amine odor can be suppressed by suppressing the free base, and this is preferable because there is less restriction due to odor when used in applications such as paints and inks such as aqueous coating compositions.

  The aqueous dispersion of the present invention may contain an organic solvent as another component. When an organic solvent is contained, workability is improved, and dispersibility of the above-mentioned other components such as pigments is increased. However, it is preferable not to contain an organic solvent because the emulsion has a high storage stability and conforms to recent VOC regulations. Examples of organic solvents include aliphatic hydrocarbons such as hexane, heptane, and octane, alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, and cycloheptane, ethyl acetate, n-butyl acetate, isobutyl acetate, and amine acetate Esters, ethers such as n-butyl ether, isobutyl ether, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methanol, ethanol, isopropanol, n-butanol, 2-butanol, isobutanol, t-butanol, n-propylene glycol, alcohols such as isopropylene glycol, cellosolves such as ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, di Carbitols such as tylene glycol monoethyl ether, propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, dioxane, N-methylpyrrolidone, dimethylformamide, diacetone alcohol, etc. And the like.

  When the aqueous dispersion is prepared by the solvent method, aromatic hydrocarbons such as toluene and xylene can be used as a solvent for dissolving the modified polyolefin and as other components of the aqueous dispersion. . However, the use of aromatic hydrocarbons should be avoided as much as possible due to recent environmental problems.

  The solid content concentration of the modified polyolefin resin aqueous dispersion composition is not particularly limited, but as a dispersion that is easy to handle, the solid content concentration is preferably 1% by weight to 60% by weight, and preferably 10% by weight to 50% by weight. It is more preferable to make it below.

  The modified polyolefin resin aqueous dispersion composition may contain a stabilizer, an additive, a pigment, a filler, an organic solvent, etc. In this case, the stabilizer, the additive, the pigment, the filler, an organic solvent, etc. It may be dissolved or dispersed in water.

  The modified polyolefin and the modified polyolefin aqueous dispersion thus obtained can be used as, for example, a paint binder, an ink binder, and a primer, and are particularly excellent in adhesion, paintability, and the like when applied to polyolefin resins and composite materials. . Further, it can be used as a heat sealant, an adhesive, and an adhesive modifier, and is particularly excellent in adhesion between a polyolefin resin or composite material and another resin, metal, glass or the like. In addition, when making polyolefin resins and composite materials such as films, sheets, structural materials, building materials, automobile parts, electrical / electronic products, packaging materials, etc., compatibilizers between polyolefin resins and other resins It can also be used as a modifier such as a dispersing agent or a glass fiber sizing agent that facilitates dispersing the composite material into the polyolefin.

  The modified polyolefin of the present invention can function as a paint binder, an ink binder, a primer, an adhesive, a compatibilizer, a dispersant, or a modifier as it is, but various additives may be added depending on the purpose of use. You can also. Additives include stabilizers such as phenol stabilizers, phosphite stabilizers, amine stabilizers, amide stabilizers, antioxidants, weathering stabilizers, antioxidants, heat stabilizers, light stabilizers, Thixotropic agents, thickeners, antifoaming agents, surface conditioners, weathering agents, pigments, pigment dispersants, antistatic agents, lubricants, nucleating agents, flame retardants, oils, dyes, additives, titanium oxide, zinc oxide Transition metal compounds such as, pigments such as carbon black, glass fiber, carbon fiber, potassium titanate fiber, wollastonite, calcium carbonate, calcium sulfate, talc, glass flake, barium sulfate, clay, kaolin, finely divided silica, mica , Inorganic and organic fillers such as calcium silicate, aluminum hydroxide, magnesium hydroxide, aluminum oxide, magnesium oxide, alumina, and celite.

  Since the modified polyolefin of the present invention is also excellent in compatibility with other resins, urethane resin, epoxy resin, acrylic resin, phenol resin, alkyd resin, silicon resin, polyacetal resin, polyester resin, polyamide resin, polyimide as required Other resins such as resin and nitrified cotton may be blended.

  Since the modified polyolefin resin of the present invention is in a solid state at room temperature, it can be obtained as a modified polyolefin having a block shape, a plate shape, a rod shape, a pellet shape or a strand shape, but it can also be obtained as a dissolved or dispersed state in an organic solvent. it can.

  When the modified polyolefin of the present invention is obtained as a dissolved or dispersed state in an organic solvent, saturated aliphatic hydrocarbons such as hexane, heptane, and octane, cyclohexane, methylcyclohexane, ethylcyclohexane, cycloheptane, methylcycloheptane, etc. Esters that do not contain ethylenic double bonds such as saturated alicyclic hydrocarbons, ethyl acetate, n-butyl acetate, and isobutyl acetate, and ethylenic double bonds such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. No ketones, n-butyl ether, isobutyl ether, tetrahydrofuran, diethyl ether, ethylene glycol dialkyl ether, ethers not containing ethylenic double bond such as dioxane, methanol, isopropyl alcohol, ethyl Glycol, and alcohols such free of ethylenic double bonds, such as propylene glycol may be used. The solid content concentration of the modified polyolefin is not particularly limited, but it is desirable that the solid content concentration is about 1% by weight to 50% by weight as an easy-to-handle liquid. The modified polyolefin solution or dispersion may contain stabilizers, additives, pigments, fillers, etc. In this case, the stabilizers, additives, pigments, fillers, etc. are dissolved in the solvent. May also be dispersed.

  In addition, when the modified polyolefin is obtained in a state dissolved or dispersed in an organic solvent, aromatic hydrocarbons such as toluene and xylene can also be used. However, the use of aromatic hydrocarbons is not preferred due to recent environmental problems.

  The method for producing the modified polyolefin of the present invention will be specifically described below.

  Prior to describing the present invention more specifically with reference to Examples and Comparative Examples, the polyolefin (A), sorbitols (B), alkyl alkylates, alkylene glycol alkyl ether alkylates, dialkyls used in the Examples and Comparative Examples were used. An alkylene glycol alkyl ether alkylate having a boiling point of 250 ° C. or lower, at least one organic solvent (C), (meth) acrylic acid alkyl ester (D), unsaturated carboxylic acid (E), organic solvent The oxide (F) will be described.

  In the following, “part” and “%” are all based on weight unless otherwise specified.

Polyolefin (A-1) for Examples and Comparative Examples.
A density of 0.87 g / cm ³ , a weight average molecular weight of 92,000, a softening point of 107 ° C., and a copolymer of ethylene, propylene and 1-butene, VESTOPLAST750 (manufactured by Degussa Japan Co., Ltd.), polyolefin (A- 1). The molecular weight was measured using gel permeation chromatography (manufactured by Tosoh Corporation: HLC-8120GPC, standard material polystyrene), and the softening point was measured by the ring and ball method based on JIS K 6863. The measured values are shown in Table 1.

Polyolefin (A-2) for Examples and Comparative Examples.
A density of 0.87 g / cm ³ , a weight average molecular weight of 118,000, a softening point of 108 ° C., a copolymer of ethylene, propylene and 1-butene, VESTOPLAST 792 (manufactured by Degussa Japan Co., Ltd.), polyolefin (A- 2).

Polyolefin (A-3) for Examples and Comparative Examples.
The density is 0.88 g / cm ³ , the weight average molecular weight is 56,000, the softening point is 85 ° C., and LICOCENE PP 1602 (manufactured by Clariant Japan Co., Ltd.), which is a copolymer of ethylene and propylene, is polyolefin (A-3). It was. The molecular weight was measured using gel permeation chromatography (supra), and the softening point was measured by the ring and ball method based on JIS K 6863. The measured values are shown in Table 1.

Polyolefin (A-4) for Examples and Comparative Examples.
The density is 0.89 g / cm ³ , the weight average molecular weight is 58,000, the softening point is 100 ° C., and LICOCENE PP 2602 (made by Clariant Japan Co., Ltd.), which is a copolymer of ethylene and propylene, is polyolefin (A-4). It was. The molecular weight was measured using gel permeation chromatography (supra), and the softening point was measured by the ring and ball method based on JIS K 6863. The measured values are shown in Table 1.

Polyolefin (A-5) for a comparative example.
The density is 0.89 g / cm ³ , the weight average molecular weight is 8,000, the softening point is 120 ° C., and LICOCENE PP 4202 (manufactured by Clariant Japan Co., Ltd.), which is a copolymer of ethylene and propylene, is polyolefin (A-5). It was. The molecular weight was measured using gel permeation chromatography (supra), and the softening point was measured by the ring and ball method based on JIS K 6863. The measured values are shown in Table 1.

Polyolefin (A-6) for a comparative example.
A high wax 720P (manufactured by Mitsui Chemicals, Inc.) having a density of 0.92 g / cm ³ , a weight average molecular weight of 8,200, a softening point of 118 ° C., and an ethylene polymer was defined as polyolefin (A-6). The molecular weight was measured using gel permeation chromatography (supra), and the softening point was measured by the ring and ball method based on JIS K 2207. The measured values are shown in Table 1.

Sorbitols (B) for Examples and Comparative Examples.
Sorbitol was designated as (B-1) and sorbitan laurate as (B-2).

Organic solvent (C) for Examples and Comparative Examples.
Alkyl alkylate, alkylene glycol alkyl ether alkylate, dialkylene glycol alkyl ether alkylate, and at least one organic solvent (C) having a boiling point of 250 ° C. or lower, propylene glycol monomethyl ether acetate having a boiling point of 146 ° C. ( C-1), diethylene glycol monoethyl ether acetate having a boiling point of 210 ° C. (C-2), butyl acetate having a boiling point of 127 ° C. (C-3), butyl propionate having a boiling point of 145 ° C. (C-4), boiling point 188 (C-5) was ethylene glycol monobutyl ether acetate at 0 ° C., and (C-6) was butyl butyrate having a boiling point of 164 ° C. Xylene having a boiling point of 138 ° C. was used as the organic solvent for the comparative example.

(Meth) acrylic acid alkyl ester (D) for Examples and Comparative Examples.
Lauryl methacrylate (D-1), 2-ethylhexyl acrylate (D-2), methyl methacrylate (D-3), cyclohexyl methacrylate (D-4), n-butyl methacrylate (D-5) did.

Unsaturated carboxylic acids (E) for Examples and Comparative Examples.
Maleic anhydride (E-1), itaconic acid (E-2), methacrylic acid (E-3), phenylmaleimide (E-4), maleic acid i-butanol half ester (E-5) It was.

Organic peroxide (F) for Examples and Comparative Examples.
Di-t-butyl peroxide (Nippon Yushi Co., Ltd .: Perbutyl D) (F-1), 1,1,3,3-tetramethylbutyl hydroperoxide (Nippon Yushi Co., Ltd .: Perocta H) (F-2), t-butyl peroxybenzoate (Nippon Yushi Co., Ltd .: Perbutyl Z) (F-3), di-t-hexyl peroxide (Nippon Yushi Co., Ltd .: Perhexyl D) (F-4) ), T-butylperoxy 2-ethylhexyl monocarbonate (Nippon Yushi Co., Ltd .: Perbutyl E) was defined as (F-5). Table 1 shows the 1-hour half-life decomposition temperature of organic peroxide (F) (cited from Nippon Oil & Fats Co., Ltd., Organic Peroxide Catalog (9th edition)).

<Graft ratio of modified polyolefin>
5 g of the modified polyolefins of Examples and Comparative Examples were dissolved in 100 g of xylene by heating and then added to 500 g of acetone, and the precipitate was filtered and dried to obtain a purified product of the modified polyolefin. The purified product of the modified polyolefin was subjected to ¹ H-NMR measurement, and the graft amount of the (meth) acrylic acid alkyl ester (D) and the graft amount of the unsaturated dicarboxylic acid (E) were determined. The graft ratio of the (meth) acrylic acid alkyl ester (D) and the graft ratio of the unsaturated dicarboxylic acids (E) were values obtained by the formulas (1) and (2).
(D) Graft ratio = ((D) Graft amount) / ((D) Charge amount) × 100 Formula (1)
(E) Graft ratio = ((E) graft amount) / ((E) charge amount) × 100 Formula (2)

<Melt viscosity of modified polyolefin>
The melt viscosity of the modified polyolefins of Examples and Comparative Examples was measured using a flow tester (manufactured by Shimadzu Corporation: CFT-500D) and measured at 190 ° C. except for Example 16. Example 16 was 140 ° C. It is the value obtained by measuring with. The load was 0.49 MPa, and the die was measured with an inner diameter × length = 1 mm × 10 mm.

<Softening point of modified polyolefin>
The softening points of the examples and comparative examples were values obtained by a T1 / 2 method using a flow tester (manufactured by Shimadzu Corporation: CFT-500D) with a weight of 0.49 MPa, a die having an inner diameter × length = 1 mm × 10 mm. It is.

<Molecular weight of modified polyolefin>
The molecular weights of the modified polyolefins of Examples and Comparative Examples are values obtained by measurement using gel permeation chromatography (manufactured by Tosoh Corporation: HLC-8120GPC, standard material polystyrene).

<Black foreign substance of modified polyolefin>
The black foreign substances of the modified polyolefins of Examples and Comparative Examples were melted 1000 g of the modified polyolefin and poured into a 24 cm × 35 cm vat, and the size and number of the black foreign substances were visually confirmed.

(Example 1) Production of modified polyolefin (G-1) for Examples.
In a 3000 ml Separa flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet tube, 1000 g of polyolefin (A-1), 30 g of sorbitol (B-1), and 200 g of propylene glycol monomethyl ether acetate (C-1) are placed. Then, melting was performed in an oil bath maintained at 170 ° C. in a nitrogen atmosphere, and the temperature of the oil bath was adjusted so that the temperature in the system was 160 ° C. while stirring. After the inside of the system was melted, 20 g of lauryl methacrylate (D-1) and 12 g of maleic anhydride (E-1) were added, and 2 g of perbutyl D (F-1) was added while stirring to obtain a uniform state. The reaction was continued for 30 minutes while maintaining the system at 200 ° C., 20 g of lauryl methacrylate (D-1) and 12 g of maleic anhydride (E-1) were added, and 2 g of perbutyl D (F-1) was added. did. Similarly, addition of lauryl methacrylate (D-1), maleic anhydride (E-1) and perbutyl D (F-1) is performed 5 times every 30 minutes, and the amount of lauryl methacrylate (D-1) added is adjusted. The total amount was 100 g, the total amount of maleic anhydride (E-1) added was 60 g, and the total amount of perbutyl D (F-1) added was 10 g.
After completion of the addition, the reaction was performed at 160 ° C. for 2 hours, and then the pressure in the flask was reduced with an aspirator while propylene glycol monomethyl ether acetate (C-1), unreacted lauryl methacrylate (D-1) and maleic anhydride ( E-1), perbutyl D (F-1), and low molecular weight compound in which perbutyl D (F-1) is decomposed are removed for 2 hours. After completion of the pressure reduction, the reaction product is taken out and cooled to give a pale yellow color. A solid product of modified polyolefin (G-1) modified with (meth) acrylic acid alkyl ester and unsaturated carboxylic acids was obtained.
The obtained modified polyolefin (G-1) had a melt viscosity (190 ° C.) of 11.3 Pa · s, a softening point of 102 ° C., and a weight average molecular weight of 83,000. 85% by weight of lauryl methacrylate (D-1) and 79% by weight of maleic anhydride (E-1) were graft-reacted, and 7 black foreign substances having a size of 1 mm or less were observed. Table 3 shows the materials used, equivalence ratio, and reaction temperature. Graft ratio, melt viscosity, measured molecular weight, softening point, black foreign material of (meth) acrylic acid alkyl ester (D) and unsaturated carboxylic acids (E) Table 4 shows the size and number.

(Example 2) Production of modified polyolefin (G-2) for Examples.
In a 3000 ml Separa flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet tube, 1000 g of polyolefin (A-1), 10 g of sorbitan laurate (B-2), 30 g of diethylene glycol monoethyl ether acetate (C-2) The mixture was melted in an oil bath maintained at 180 ° C. under a nitrogen atmosphere, and the temperature of the oil bath was adjusted so that the temperature in the system was 200 ° C. while stirring. After the inside of the system is melted, 10 g of 2-ethylhexyl acrylate (D-2) and 10 g of maleic anhydride (E-1) are added while stirring to obtain a uniform state, and then 2 g of perocta H (F-2) is added. did. The reaction was continued for 30 minutes while maintaining the system at 200 ° C., 10 g of 2-ethylhexyl acrylate (D-2) and 10 g of maleic anhydride (E-1) were added, and then 2 g of perocta H (F-2). Was added. In the same manner, lauryl methacrylate (D-1), maleic anhydride (E-1) and perocta H (F-2) were added five times every 30 minutes, and 2-ethylhexyl acrylate (D-2) was added. The total amount was 50 g, the total addition amount of maleic anhydride (E-1) was 50 g, and the total addition amount of Perocta H (F-2) was 10 g.
After completion of the addition, the reaction was carried out at 200 ° C. for 2 hours, and then diethylene glycol monoethyl ether acetate (C-2), unreacted 2-ethylhexyl acrylate (D-2), and anhydrous maleate while reducing the pressure in the flask with an aspirator. The removal of the low molecular weight compound in which the acid (E-1), perocta H (F-2) and perocta H (F-2) were decomposed was performed for 2 hours, and after completion of the decompression, the reaction product was taken out and cooled, A solid product of modified polyolefin (G-2) modified with black-brown (meth) acrylic acid alkyl ester and unsaturated carboxylic acids was obtained.
The obtained modified polyolefin (G-2) had a melt viscosity (190 ° C.) of 4.3 Pa · s, a softening point of 99 ° C., and a weight average molecular weight of 57,000. 82% by weight of 2-ethylhexyl acrylate (D-2) and 81% by weight of maleic anhydride (E-1) had undergone a graft reaction, and 10 black foreign matters having a size of 1 mm or less were observed. Table 3 shows the materials used, equivalence ratio, and reaction temperature. Graft ratio, melt viscosity, measured molecular weight, softening point, black foreign material of (meth) acrylic acid alkyl ester (D) and unsaturated carboxylic acids (E) Table 4 shows the size and number.

(Example 3) Production of modified polyolefin (G-3) for Examples.
In a 5000 ml Separa flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas introduction tube, 1000 g of polyolefin (A-2), 0.1 g of sorbitan laurate (B-2), and 200 g of butyl acetate (C-3) were added. The mixture was melted in an oil bath maintained at 140 ° C. under a nitrogen atmosphere, and the temperature of the oil bath was adjusted so that the temperature in the system became 130 ° C. while stirring. After the inside of the system melts, stirring to make it uniform, 30 g of methyl methacrylate (D-3), 30 g of maleic anhydride (E-1), 5 g of Perbutyl Z (F-3) manufactured by NOF Corporation Was added dropwise over 1.5 hours to a monomer solution prepared by dissolving benzene acetate in 800 g of butyl acetate (C-3).
The reaction was carried out for 3 hours while maintaining the system at 130 ° C., and then the temperature of the oil bath was increased to 180 ° C., and the pressure in the flask was reduced with an aspirator while butyl acetate (C-3) and unreacted methacrylic acid were used. Removal of low molecular weight compounds in which methyl (D-3), maleic anhydride (E-1), perbutyl Z (F-3) and perbutyl Z (F-3) were decomposed was carried out for 1 hour. The product was taken out and cooled to obtain a solid product of modified polyolefin (G-3) modified with brown alkyl (meth) acrylate and unsaturated carboxylic acids.
The obtained modified polyolefin (G-3) had a melt viscosity (190 ° C.) of 43.2 Pa · s, a softening point of 122 ° C., and a weight average molecular weight of 103,000. 59% by weight of methyl methacrylate (D-3) and 52% by weight of maleic anhydride (E-1) were graft-reacted, and three black foreign objects of 1 mm or less were observed. Table 3 shows the materials used, equivalence ratio, and reaction temperature. Graft ratio, melt viscosity, measured molecular weight, softening point, black foreign material of (meth) acrylic acid alkyl ester (D) and unsaturated carboxylic acids (E) Table 4 shows the size and number.

(Example 4) Production of modified polyolefin (G-4) for Examples.
A 3000 ml Separa flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet tube was charged with 1000 g of polyolefin (A-3), 1 g of sorbitol (B-1), and 50 g of butyl propionate (C-4). Melting was performed in an oil bath maintained at 170 ° C. under an atmosphere, and the temperature of the oil bath was adjusted so that the temperature in the system was 160 ° C. while stirring. After the inside of the system melts, while stirring to make it uniform, 60 g of cyclohexyl methacrylate (D-4), 60 g of maleic anhydride (E-1), 10 g of Perhexyl D (F-4) manufactured by NOF Corporation are added. A monomer solution dissolved in 150 g of butyl propionate (C-4) was added dropwise over 1.5 hours.
After completion of the dropwise addition, the reaction was carried out for 2 hours while keeping the system at 160 ° C., and then the temperature of the oil bath was raised to 180 ° C., and while reducing the pressure in the flask with an aspirator, butyl propionate (C-4) and Removal of low-molecular compounds in which unreacted cyclohexyl methacrylate (D-4), maleic anhydride (E-1), perhexyl D (F-4) and perhexyl D (F-4) were decomposed was performed for 1 hour, and the pressure was reduced. After completion, the reaction product was taken out and cooled to obtain a solid product of modified polyolefin (G-4) modified with pale yellow (meth) acrylic acid alkyl ester and unsaturated carboxylic acids.
The obtained modified polyolefin (G-4) had a melt viscosity (190 ° C.) of 8.6 Pa · s, a softening point of 96 ° C., and a weight average molecular weight of 68,000. 93% by weight of cyclohexyl methacrylate (D-4) and 91% by weight of maleic anhydride (E-1) were graft-reacted, and one black foreign substance of 1 mm or less was observed. Table 3 shows the materials used, equivalence ratio, and reaction temperature. Graft ratio, melt viscosity, measured molecular weight, softening point, black foreign material of (meth) acrylic acid alkyl ester (D) and unsaturated carboxylic acids (E) Table 4 shows the size and number.

(Example 5) Production of modified polyolefin (G-5) for Example.
In a 3000 ml Separa flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet tube, polyolefin (A-4) 1000 g, sorbitol (B-1) 0.5 g, ethylene glycol monobutyl ether acetate (C-5) 50 g The mixture was melted in an oil bath maintained at 160 ° C. in a nitrogen atmosphere, and the temperature of the oil bath was adjusted so that the temperature in the system was 150 ° C. while stirring. After the inside of the system melts, stirring to make it uniform, 60 g of n-butyl methacrylate (D-5), 60 g of maleic anhydride (E-1), and 20 g of perbutyl E (F-5) are added to ethylene glycol monobutyl ether. A monomer solution dissolved in 150 g of acetate (C-5) was added dropwise over 2 hours, and after completion of the addition, 5 g of styrene was added.
After completion of the addition, the reaction was carried out at 150 ° C. for 3 hours, and then the pressure in the flask was reduced with an aspirator while ethylene glycol monobutyl ether acetate (C-5), unreacted n-butyl methacrylate (D-5), and anhydrous maleic acid. Removal of the low molecular weight compound in which acid (E-1), perbutyl E (F-5) and perbutyl E (F-5) were decomposed was performed for 1 hour, and after completion of the decompression, the reaction product was taken out and cooled, A solid product of modified polyolefin (G-5) modified with pale yellow (meth) acrylic acid alkyl ester and unsaturated carboxylic acids was obtained.
The obtained modified polyolefin (G-5) had a melt viscosity (190 ° C.) of 33.9 Pa · s, a softening point of 121 ° C., and a weight average molecular weight of 153,000. 94% by weight of n-butyl methacrylate (D-5) and 93% by weight of maleic anhydride (E-1) were graft-reacted, and one black foreign substance of 1 mm or less was observed. Table 3 shows the materials used, equivalence ratio, and reaction temperature. Graft ratio, melt viscosity, measured molecular weight, softening point, black foreign material of (meth) acrylic acid alkyl ester (D) and unsaturated carboxylic acids (E) Table 4 shows the size and number.

(Example 6) Production of modified polyolefin (G-6) for Examples.
A 3000 ml Separa flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas introduction tube was charged with 1000 g of polyolefin (A-3), 1 g of sorbitol (B-1), and 50 g of butyl butyrate (C-6), and a nitrogen atmosphere Then, melting was carried out in an oil bath maintained at 180 ° C., and the temperature of the oil bath was adjusted so that the inside of the system became 170 ° C. while stirring. After the inside of the system melts, while stirring to a uniform state, 160 g of cyclohexyl methacrylate (D-4), 60 g of maleic anhydride (E-1) and 10 g of perbutyl D (F-1) are added to butyl butyrate (C-6). ) A monomer solution dissolved in 150 g was added dropwise over 1.5 hours. After completion of dropping, 1 g of α-methylstyrene was added.
After completion of the addition, the reaction was carried out at 170 ° C. for 2 hours, and then the pressure inside the flask was reduced with an aspirator while butyl butyrate (C-6), unreacted cyclohexyl methacrylate (D-4), and maleic anhydride (E-1 ), Perbutyl D (F-1) and a low molecular weight compound in which perbutyl D (F-1) is decomposed for 1 hour, and after completion of the pressure reduction, the reaction product is taken out and cooled to give a pale yellow (meta ) A solid product of modified polyolefin (G-6) modified with alkyl acrylate and unsaturated carboxylic acids was obtained.
The obtained modified polyolefin (G-6) had a melt viscosity (190 ° C.) of 17.3 Pa · s, a softening point of 106 ° C., and a weight average molecular weight of 93,000. 92% by weight of cyclohexyl methacrylate (D-4) and 90% by weight of maleic anhydride (E-1) were graft-reacted, and two black foreign objects of 1 mm or less were observed. Table 3 shows the materials used, equivalence ratio, and reaction temperature. Graft ratio, melt viscosity, measured molecular weight, softening point, black foreign material of (meth) acrylic acid alkyl ester (D) and unsaturated carboxylic acids (E) Table 4 shows the size and number.

(Example 7) Production of modified polyolefin (G-7) for Examples.
1000 g of polyolefin (A-1) and 1 g of sorbitol (B-1) were placed in a 3000 ml Separa flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet tube, and the oil was maintained at 170 ° C. under a nitrogen atmosphere. The temperature of the oil bath was adjusted so that the temperature in the system was 160 ° C. while melting in the bath and stirring. After the inside of the system is melted, while stirring to obtain a uniform state, 500 g of 2-ethylhexyl acrylate (D-2), 350 g of maleic anhydride (E-1) and 120 g of perbutyl D (F-1) are added to propylene glycol monomethyl ether. A monomer solution dissolved in 200 g of acetate (C-1) was added dropwise over 1.5 hours.
After completion of the dropping, the reaction was carried out at 160 ° C. for 3 hours, and then the pressure in the flask was reduced with an aspirator while propylene glycol monomethyl ether acetate (C-1), unreacted 2-ethylhexyl acrylate (D-2), and anhydrous maleic acid. The removal of the low molecular weight compound in which acid (E-1), perbutyl D (F-1) and perbutyl D (F-1) were decomposed was performed for 1 hour, and after completion of the decompression, the reaction product was taken out and cooled, A solid product of modified polyolefin (G-7) modified with brown alkyl (meth) acrylate and unsaturated carboxylic acids was obtained.
The resulting modified polyolefin (G-7) has a melt viscosity (190 ° C.) of 142.3 Pa · s, a softening point of 153 ° C., and a weight average molecular weight of 146,000 peaks (80%) and 500 peaks (20% The molecular weight was bimodal. 70% by weight of 2-ethylhexyl acrylate (D-2) and 62% by weight of maleic anhydride (E-1) were graft-reacted, and 12 black foreign objects having a size of 1 mm or less were observed. Table 3 shows the materials used, equivalence ratio, and reaction temperature. Graft ratio, melt viscosity, measured molecular weight, softening point, black foreign material of (meth) acrylic acid alkyl ester (D) and unsaturated carboxylic acids (E) Table 4 shows the size and number.

(Example 8) Production of modified polyolefin (G-8) for Examples.
In a 3000 ml Separa flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet tube, 1000 g of polyolefin (A-2), 1 g of sorbitol (B-1), and 200 g of propylene glycol monomethyl ether acetate (C-1) are placed. Then, melting was performed in an oil bath maintained at 170 ° C. in a nitrogen atmosphere, and the temperature of the oil bath was adjusted so that the temperature in the system was 160 ° C. while stirring. After the system melted, 4 g of lauryl methacrylate (D-1), 3 g of maleic anhydride (E-1), and 0.5 g of perbutyl D (F-1) were added while stirring to obtain a uniform state.
After the addition, the reaction was performed at 160 ° C. for 2 hours, and then the inside of the flask was decompressed with an aspirator while propylene glycol monomethyl ether acetate (C-1), unreacted lauryl methacrylate (D-1), and maleic anhydride (E -1), perbutyl D (F-1), and low molecular weight compounds in which perbutyl D (F-1) is decomposed are removed for 1 hour. After completion of the decompression, the reaction product is taken out and cooled to obtain milky white ( A solid product of modified polyolefin (G-8) modified with (meth) acrylic acid alkyl ester and unsaturated carboxylic acids was obtained.
The obtained modified polyolefin (G-8) had a melt viscosity (190 ° C.) of 48.1 Pa · s, a softening point of 108 ° C., and a weight average molecular weight of 118,000. 80% by weight of lauryl methacrylate (D-1) and 75% by weight of maleic anhydride (E-1) were graft-reacted, and no black foreign matter was observed. Table 3 shows the materials used, equivalence ratio, and reaction temperature. Graft ratio, melt viscosity, measured molecular weight, softening point, black foreign material of (meth) acrylic acid alkyl ester (D) and unsaturated carboxylic acids (E) Table 4 shows the size and number.

(Example 9) Production of modified polyolefin (G-9) for Examples.
In a 3000 ml Separa flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet tube, 1000 g of polyolefin (A-3), 1 g of sorbitol (B-1) and 50 g of propylene glycol monomethyl ether acetate (C-1) are placed. Then, melting was performed in an oil bath maintained at 170 ° C. in a nitrogen atmosphere, and the temperature of the oil bath was adjusted so that the temperature in the system was 160 ° C. while stirring. After the inside of the system melts, while stirring to obtain a uniform state, 120 g of cyclohexyl methacrylate (D-4), 30 g of maleic anhydride (E-1) and 5 g of perbutyl D (F-1) are added to propylene glycol monomethyl ether acetate ( C-1) A monomer solution dissolved in 150 g was added dropwise over 1.5 hours.
After completion of the dropwise addition, the reaction was performed at 160 ° C. for 2 hours, and then the pressure in the flask was reduced with an aspirator while propylene glycol monomethyl ether acetate (C-1), unreacted cyclohexyl methacrylate (D-4), and maleic anhydride ( E-1), perbutyl D (F-1), and low molecular weight compound in which perbutyl D (F-1) is decomposed are removed for 1 hour. After completion of the decompression, the reaction product is taken out and cooled to give milky white A solid product of modified polyolefin (G-9) modified with (meth) acrylic acid alkyl ester and unsaturated carboxylic acids was obtained.
The obtained modified polyolefin (G-9) had a melt viscosity (190 ° C.) of 17.1 Pa · s, a softening point of 106 ° C., and a weight average molecular weight of 93,000. 73% by weight of cyclohexyl methacrylate (D-4) and 75% by weight of maleic anhydride (E-1) were graft-reacted, and three black foreign objects of 1 mm or less were observed. Table 3 shows the materials used, equivalence ratio, and reaction temperature. Graft ratio, melt viscosity, measured molecular weight, softening point, black foreign material of (meth) acrylic acid alkyl ester (D) and unsaturated carboxylic acids (E) Table 4 shows the size and number.

(Example 10) Production of modified polyolefin (G-10) for Examples.
In a 3000 ml Separa flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet tube, 1000 g of polyolefin (A-4), 1 g of sorbitol (B-1) and 50 g of propylene glycol monomethyl ether acetate (C-1) are placed. Then, melting was performed in an oil bath maintained at 170 ° C. in a nitrogen atmosphere, and the temperature of the oil bath was adjusted so that the temperature in the system was 160 ° C. while stirring. After the system is melted, stirring is performed to obtain a uniform state, and 30 g of n-butyl methacrylate (D-5), 60 g of maleic anhydride (E-1) and 10 g of perbutyl D (F-1) are added to propylene glycol monomethyl ether. A monomer solution dissolved in 150 g of acetate (C-1) was added dropwise over 1.5 hours.
After completion of the dropwise addition, the reaction was carried out at 160 ° C. for 2 hours, and then the pressure in the flask was reduced with an aspirator while propylene glycol monomethyl ether acetate (C-1), unreacted n-butyl methacrylate (D-5), and anhydrous maleic acid were added. The removal of the low molecular weight compound in which acid (E-1), perbutyl D (F-1) and perbutyl D (F-1) were decomposed was performed for 1 hour, and after completion of the decompression, the reaction product was taken out and cooled, A solid product of a modified polyolefin (G-10) modified with yellow alkyl (meth) acrylate and unsaturated carboxylic acids was obtained.
The obtained modified polyolefin (G-10) had a melt viscosity (190 ° C.) of 6.1 Pa · s, a softening point of 101 ° C., and a weight average molecular weight of 63,000. 86% by weight of n-butyl methacrylate (D-5) and 75% by weight of maleic anhydride (E-1) were graft-reacted, and 10 black foreign objects of 1 mm or less were observed. Table 3 shows the materials used, equivalence ratio, and reaction temperature. Graft ratio, melt viscosity, measured molecular weight, softening point, black foreign material of (meth) acrylic acid alkyl ester (D) and unsaturated carboxylic acids (E) Table 4 shows the size and number.

(Example 11) Production of modified polyolefin (G-11) for Examples.
In a 3000 ml Separa flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet tube, 1000 g of polyolefin (A-2), 0.1 g of sorbitol (B-1) and 200 g of butyl propionate (C-4) are placed. The mixture was melted in an oil bath maintained at 160 ° C. in a nitrogen atmosphere, and the temperature of the oil bath was adjusted so that the temperature in the system was 150 ° C. while stirring. After the inside of the system is melted, while stirring to obtain a uniform state, 5 g of cyclohexyl methacrylate (D-4), 5 g of itaconic acid (E-2), and 1 g of perbutyl E (F-5) are mixed with butyl propionate (C-4). ) A monomer solution dissolved in 250 g was added dropwise over 1.5 hours.
After completion of the dropwise addition, the reaction was performed at 150 ° C. for 2 hours, and then the pressure in the flask was reduced with an aspirator while butyl propionate (C-4) and unreacted cyclohexyl methacrylate (D-4) and perbutyl E (F-5). ) And perbutyl E (F-5) decomposed low molecular weight compounds for 1 hour, and after completion of the pressure reduction, the reaction product is taken out and cooled to give pale brown (meth) acrylic acid alkyl ester and unsaturated A solid product of modified polyolefin (G-11) modified with carboxylic acids was obtained.
The obtained modified polyolefin (G-11) had a melt viscosity (190 ° C.) of 24.3 Pa · s, a softening point of 104 ° C., and a weight average molecular weight of 92,000. 65% by weight of cyclohexyl methacrylate (D-4) and 59% by weight of itaconic acid (E-2) were graft-reacted, and three black foreign objects of 1 mm or less were observed. Table 3 shows the materials used, equivalence ratio, and reaction temperature. Graft ratio, melt viscosity, measured molecular weight, softening point, black foreign material of (meth) acrylic acid alkyl ester (D) and unsaturated carboxylic acids (E) Table 4 shows the size and number.

(Example 12) Production of modified polyolefin (G-12) for Examples.
In a 3000 ml Separa flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet tube, 1000 g of polyolefin (A-2), 2 g of sorbitol (B-1), and 100 g of butyl propionate (C-4) were added, and nitrogen was added. Melting was carried out in an oil bath maintained at 160 ° C. under an atmosphere, and the temperature of the oil bath was adjusted so that the inside of the system became 150 ° C. while stirring. After the inside of the system melts, 15 g of 2-ethylhexyl acrylate (D-2), 10 g of methacrylic acid (E-3) and 2 g of perbutyl E (F-5) are mixed with butyl propionate (C -4) A monomer solution dissolved in 200 g was dropped over 1.5 hours.
After completion of the dropwise addition, the reaction was carried out at 150 ° C. for 2 hours, and then the pressure inside the flask was reduced with an aspirator while butyl propionate (C-4), unreacted 2-ethylhexyl acrylate (D-2), and methacrylic acid (E -3), removal of low molecular weight compounds in which perbutyl E (F-5) and perbutyl E (F-5) were decomposed for 1 hour, and after completion of the decompression, the reaction product was taken out and cooled to give milky white ( A solid product of modified polyolefin (G-12) modified with (meth) acrylic acid alkyl ester and unsaturated carboxylic acids was obtained.
The obtained modified polyolefin (G-12) had a melt viscosity (190 ° C.) of 67.6 Pa · s, a softening point of 119 ° C., and a weight average molecular weight of 124,000. 75% by weight of 2-ethylhexyl acrylate (D-2) and 78% by weight of methacrylic acid (E-3) were graft-reacted, and no black foreign matter was observed. Table 3 shows the materials used, equivalence ratio, and reaction temperature. Graft ratio, melt viscosity, measured molecular weight, softening point, black foreign material of (meth) acrylic acid alkyl ester (D) and unsaturated carboxylic acids (E) Table 4 shows the size and number.

(Example 13) Production of modified polyolefin (G-13) for Examples.
In a 3000 ml Separa flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet tube, 1000 g of polyolefin (A-3), 0.5 g of sorbitol (B-1), Irganox 1010 manufactured by Ciba Geigy as an antioxidant (product) Name) 1 g and Irgafos 168 (trade name) 1 g, melt in an oil bath maintained at 190 ° C. in a nitrogen atmosphere, and adjust the temperature of the oil bath to 180 ° C. while stirring. did. After the inside of the system melts, while stirring to a uniform state, 30 g of 2-ethylhexyl acrylate (D-2), 30 g of phenylmaleimide (E-4) and 2.5 g of perbutyl D (F-1) are added to butyl propionate. (C-4) A monomer solution dissolved in 100 g was added dropwise over 1.5 hours.
After completion of the dropwise addition, the reaction was carried out at 180 ° C. for 2 hours, and then the inside of the flask was decompressed with an aspirator while butyl propionate (C-4) and unreacted 2-ethylhexyl acrylate (D-2), perbutyl D (F -1) and low molecular weight compounds in which perbutyl D (F-1) was decomposed for 1 hour, and after completion of the decompression, the reaction product was taken out and cooled, so that milky white (meth) acrylic acid alkyl ester and A solid product of modified polyolefin (G-13) modified with saturated carboxylic acids was obtained.
The obtained modified polyolefin (G-13) had a melt viscosity (190 ° C.) of 12.1 Pa · s, a softening point of 98 ° C., and a weight average molecular weight of 88,000. 91% by weight of 2-ethylhexyl acrylate (D-2) and 88% by weight of phenylmaleimide (E-4) were graft-reacted, and no black foreign matter was observed. Table 3 shows the materials used, equivalence ratio, and reaction temperature. Graft ratio, melt viscosity, measured molecular weight, softening point, black foreign material of (meth) acrylic acid alkyl ester (D) and unsaturated carboxylic acids (E) Table 4 shows the size and number.

(Example 14) Production of modified polyolefin (G-14) for Examples.
A 3000 ml Separa flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen gas introduction tube was charged with 1000 g of polyolefin (A-4), 1 g of sorbitol (B-1), and 50 g of butyl propionate (C-4). Melting was carried out in an oil bath maintained at 180 ° C. under an atmosphere, and the temperature of the oil bath was adjusted so that the temperature in the system was 170 ° C. while stirring. After the inside of the system melts, stirring is performed to obtain a uniform state, while 60 g of n-butyl methacrylate (D-5), 100 g of maleic acid i-butanol half ester (E-5), and 10 g of perbutyl D (F-1). The mixture was added dropwise over 1.5 hours.
After completion of the dropwise addition, the reaction was carried out at 170 ° C. for 2 hours, and then the inside of the flask was decompressed with an aspirator while butyl propionate (C-4), unreacted n-butyl methacrylate (D-5), perbutyl D (F -1) and the removal of the low molecular weight compound in which perbutyl D (F-1) was decomposed for 1 hour, and after completion of the decompression, the reaction product was taken out and cooled to obtain a pale yellow (meth) acrylic acid alkyl ester and A solid product of modified polyolefin (G-14) modified with unsaturated carboxylic acids was obtained.
The obtained modified polyolefin (G-14) had a melt viscosity (190 ° C.) of 5.2 Pa · s, a softening point of 97 ° C., and a weight average molecular weight of 70,000. 90% by weight of n-butyl methacrylate (D-5) and 88% by weight of maleic acid i-butanol half ester (E-5) were graft-reacted, and three black foreign matters having a size of 1 mm or less were observed. Table 3 shows the materials used, equivalence ratio, and reaction temperature. Graft ratio, melt viscosity, measured molecular weight, softening point, black foreign material of (meth) acrylic acid alkyl ester (D) and unsaturated carboxylic acids (E) Table 4 shows the size and number. The molecular weight is measured using gel permeation chromatography (supra), and the melt viscosity and softening point are measured using a flow tester (supra).

(Example 15) Production of modified polyolefin (G-15) for Examples.
In a 5000 ml Separa flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet tube, 1000 g of polyolefin (A-4), 5 g of sorbitol (B-1), and 50 g of propylene glycol monomethyl ether acetate (C-1) are placed. The mixture was melted in an oil bath maintained at 160 ° C. in a nitrogen atmosphere, and the temperature of the oil bath was adjusted so that the temperature in the system was 150 ° C. while stirring. After the inside of the system melts, while stirring to obtain a uniform state, 300 g of 2-ethylhexyl acrylate (D-2), 300 g of maleic acid i-butanol half ester (E-5), and 60 g of perbutyl E (F-5) are added. A monomer solution dissolved in 450 g of propylene glycol monomethyl ether acetate (C-1) was added dropwise over 3 hours.
After completion of the dropwise addition, the reaction was carried out at 150 ° C. for 3 hours, and then the pressure in the flask was reduced with an aspirator while propylene glycol monomethyl ether acetate (C-1) and unreacted 2-ethylhexyl acrylate (D-2) and maleic acid were used. i-Butanol half ester (E-5), perbutyl E (F-5), and low molecular weight compounds decomposed by perbutyl E (F-5) are removed for 1 hour. After completion of the decompression, the reaction product is taken out and cooled. As a result, a solid product of modified polyolefin (G-15) modified with dark yellow (meth) acrylic acid alkyl ester and unsaturated carboxylic acids was obtained.
The resulting modified polyolefin (G-15) has a melt viscosity (190 ° C.) of 84.5 Pa · s, a softening point of 148 ° C., and a weight average molecular weight of 182,000 (95%) and 2300 peaks (5% The molecular weight was bimodal. 74 wt% of 2-ethylhexyl acrylate (D-2) and 70 wt% of maleic acid i-butanol half ester (E-5) were graft-reacted, and 8 black foreign objects having a size of 1 mm or less were observed. Table 3 shows the materials used, equivalence ratio, and reaction temperature. Graft ratio, melt viscosity, measured molecular weight, softening point, black foreign material of (meth) acrylic acid alkyl ester (D) and unsaturated carboxylic acids (E) Table 4 shows the size and number.

(Example 16) Production of a modified polyolefin (G-16) for Examples.
A 3000 ml Separa flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet tube is charged with 1000 g of polyolefin (A-5), 1 g of sorbitol (B-1), and 50 g of propylene glycol monomethyl ether acetate (C-1). Then, melting was performed in an oil bath maintained at 170 ° C. in a nitrogen atmosphere, and the temperature of the oil bath was adjusted so that the temperature in the system was 160 ° C. while stirring. After the system is melted, stirring is performed to obtain a uniform state, and 60 g of n-butyl methacrylate (D-5), 60 g of maleic anhydride (E-1) and 10 g of perbutyl D (F-1) are added to propylene glycol monomethyl ether. A monomer solution dissolved in 150 g of acetate (C-1) was added dropwise over 1.5 hours.
After completion of the dropwise addition, the reaction was carried out at 160 ° C. for 2 hours, and then the pressure in the flask was reduced with an aspirator while propylene glycol monomethyl ether acetate (C-1), unreacted n-butyl methacrylate (D-5), and anhydrous maleic acid were added. The removal of the low molecular weight compound in which acid (E-1), perbutyl D (F-1) and perbutyl D (F-1) were decomposed was performed for 1 hour, and after completion of the decompression, the reaction product was taken out and cooled, A solid product of modified polyolefin (G-16) modified with pale yellow (meth) acrylic acid alkyl ester and unsaturated carboxylic acids was obtained.
Since the melt viscosity at 190 ° C. of the resulting modified polyolefin (G-16) was out of the measurement range, the melt viscosity at 140 ° C., which is a temperature above the softening point, was measurable. The melt viscosity at 140 ° C. was 0.3 Pa · s, the softening point was 126 ° C., and the weight average molecular weight was 10,000. 92% by weight of n-butyl methacrylate (D-5) and 89% by weight of maleic anhydride (E-1) were graft-reacted, and one black foreign substance of 1 mm or less was observed. Table 3 shows the materials used, equivalence ratio, and reaction temperature. Graft ratio, melt viscosity, measured molecular weight, softening point, black foreign material of (meth) acrylic acid alkyl ester (D) and unsaturated carboxylic acids (E) Table 4 shows the size and number.

Comparative Example 1 Production of a modified polyolefin (H-1) for a comparative example.
In a 3000 ml Separa flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet tube, 1000 g of polyolefin (A-1), 50 g of propylene glycol monomethyl ether acetate (C-1), and Irganox 1010 manufactured by Ciba Geigy as an antioxidant (Product name) 1 g and Irgafos 168 (product name) 1 g were added, melted in an oil bath maintained at 170 ° C. in a nitrogen atmosphere, and the temperature of the oil bath was adjusted to 160 ° C. while stirring. Adjusted. After the system is melted, stirring is performed to obtain a uniform state, and 60 g of n-butyl methacrylate (D-5), 60 g of maleic anhydride (E-1) and 10 g of perhexyl D (F-4) are added to propylene glycol monomethyl ether. A monomer solution dissolved in 150 g of acetate (C-1) was added dropwise over 1.5 hours.
After completion of the addition, the reaction was carried out at 160 ° C. for 2 hours, and then the pressure in the flask was reduced with an aspirator while propylene glycol monomethyl ether acetate (C-1), unreacted n-butyl methacrylate (D-5), and anhydrous maleic acid. Removal of the low molecular weight compound in which acid (E-1), perhexyl D (F-4) and perhexyl D (F-4) were decomposed was performed for 1 hour, and after completion of the decompression, the reaction product was taken out and cooled, A solid product of modified polyolefin (H-1) modified with yellow alkyl (meth) acrylate and unsaturated carboxylic acids was obtained.
The obtained modified polyolefin (H-1) had a melt viscosity (190 ° C.) of 17.8 Pa · s, a softening point of 108 ° C., and a weight average molecular weight of 92,000. 86% by weight of n-butyl methacrylate (D-4) and 82% by weight of maleic anhydride (E-1) were graft-reacted, and 25 black foreign substances having a size of 1 mm or less were observed. Table 3 shows the materials used, equivalence ratio, and reaction temperature. Graft ratio, melt viscosity, measured molecular weight, softening point, black foreign material of (meth) acrylic acid alkyl ester (D) and unsaturated carboxylic acids (E) Table 4 shows the size and number.

Comparative Example 2 Production of a modified polyolefin (H-2) for a comparative example.
In a 3000 ml Separa flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet tube, 1000 g of polyolefin (A-2), 1 g of sorbitol (B-1) and 200 g of xylene were placed, and kept at 170 ° C. under a nitrogen atmosphere. The temperature of the oil bath was adjusted so that the inside of the system became 160 ° C. while stirring while being melted in a dripping oil bath. After the inside of the system is melted, 12 g of n-butyl methacrylate (D-5) and 12 g of maleic anhydride (E-1) are added while stirring to obtain a uniform state, followed by perhexyl D (manufactured by NOF Corporation). F-4) 2 g was added. The reaction was continued for 30 minutes while maintaining the temperature at 160 ° C., 12 g of n-butyl methacrylate (D-5) and 12 g of maleic anhydride (E-1) were added, and 2 g of perhexyl D (F-4) was added. Was added. In the same manner, n-butyl methacrylate (D-4), maleic anhydride (E-1), and perhexyl D (F-4) were added five times every 30 minutes to obtain n-butyl methacrylate (D-5). The total addition amount of 60 g, the total addition amount of maleic anhydride (E-1) was 60 g, and the total addition amount of perhexyl D (F-4) was 10 g.
After completion of the addition, the reaction was performed at 160 ° C. for 2 hours, and then the unreacted n-butyl methacrylate (D-5), maleic anhydride (E-1), perhexyl D (F -4) and a low molecular weight compound in which perhexyl D (F-4) is decomposed for 1 hour, and after completion of the decompression, the reaction product is taken out and cooled, so that the yellow (meth) acrylic acid alkyl ester and the A solid product of modified polyolefin (H-2) modified with saturated carboxylic acids was obtained.
The obtained modified polyolefin (H-2) had a melt viscosity (190 ° C.) of 20.2 Pa · s, a softening point of 109 ° C., and a weight average molecular weight of 93,000. 78% by weight of n-butyl methacrylate (D-5) and 70% by weight of maleic anhydride (E-1) had undergone a graft reaction, and 25 black foreign substances having a size of 1 mm or less were observed. Table 3 shows the materials used, equivalence ratio, and reaction temperature. Graft ratio, melt viscosity, measured molecular weight, softening point, black foreign material of (meth) acrylic acid alkyl ester (D) and unsaturated carboxylic acids (E) Table 4 shows the size and number.

(Comparative Example 3) Production of a modified polyolefin (H-3) for a comparative example.
1000 g of polyolefin (A-1) and 1 g of sorbitol (B-1) were placed in a 3000 ml Separa flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet tube, and the oil was maintained at 170 ° C. under a nitrogen atmosphere. The temperature of the oil bath was adjusted so that the temperature in the system was 160 ° C. while melting in the bath and stirring. After the inside of the system is melted, 12 g of n-butyl methacrylate (D-5) and 12 g of maleic anhydride (E-1) are added while stirring to obtain a uniform state, followed by perhexyl D (manufactured by NOF Corporation). F-4) 2 g was added. The reaction was continued for 30 minutes while maintaining the temperature at 160 ° C., 12 g of n-butyl methacrylate (D-5) and 12 g of maleic anhydride (E-1) were added, and 2 g of perhexyl D (F-4) was added. Was added. In the same manner, n-butyl methacrylate (D-4), maleic anhydride (E-1), and perhexyl D (F-4) were added five times every 30 minutes to obtain n-butyl methacrylate (D-5). The total addition amount of 60 g, the total addition amount of maleic anhydride (E-1) was 60 g, and the total addition amount of perhexyl D (F-4) was 10 g.
After completion of the addition, the reaction was performed at 160 ° C. for 2 hours, and then the unreacted n-butyl methacrylate (D-5), maleic anhydride (E-1), perhexyl D (F -4) and the removal of the low molecular weight compound in which perhexyl D (F-4) was decomposed for 1 hour, and after completion of the decompression, the reaction product was taken out and cooled to obtain a dark yellow (meth) acrylic acid alkyl ester and A solid product of modified polyolefin (H-3) modified with unsaturated carboxylic acids was obtained.
The obtained modified polyolefin (H-3) had a melt viscosity (190 ° C.) of 14.6 Pa · s, a softening point of 105 ° C., and a weight average molecular weight of 84,000. 63% by weight of n-butyl methacrylate (D-5) and 57% by weight of maleic anhydride (E-1) were graft-reacted, and 50 or more black foreign matters having a size of 1 mm or less were observed. Table 3 shows the materials used, equivalence ratio, and reaction temperature. Graft ratio, melt viscosity, measured molecular weight, softening point, black foreign material of (meth) acrylic acid alkyl ester (D) and unsaturated carboxylic acids (E) Table 4 shows the size and number.

Comparative Example 4 Production of a modified polyolefin (H-4) for a comparative example.
In a 5000 ml Separa flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet tube, 1000 g of polyolefin (A-1), 1 g of sorbitol (B-1), 50 g of propylene glycol monomethyl ether acetate (C-1), oxidation 1 g of Irganox 1010 (trade name) and 1 g of Irgafos 168 (trade name) manufactured by Ciba-Geigy Co., Ltd. are added as an inhibitor, melted in an oil bath maintained at 170 ° C. in a nitrogen atmosphere, and the system is refluxed while stirring. The temperature was adjusted to 160 ° C. After the system melts, a monomer solution in which 60 g of maleic anhydride (E-1) and 10 g of perhexyl D (F-4) are dissolved in 150 g of propylene glycol monomethyl ether acetate (C-1) is stirred. The solution was added dropwise over 1.5 hours.
After completion of the addition, the reaction was carried out at 160 ° C. for 2 hours, and then the inside of the flask was decompressed with an aspirator while propylene glycol monomethyl ether acetate (C-1), unreacted maleic anhydride (E-1), and perhexyl D ( F-4) and low molecular weight compounds in which perhexyl D (F-4) was decomposed were removed for 1 hour, and after completion of the decompression, the reaction product was taken out and cooled to be modified with dark yellow unsaturated carboxylic acids. A solid product of modified polyolefin (H-4) was obtained.
The obtained modified polyolefin (H-4) had a melt viscosity (190 ° C.) of 6.6 Pa · s, a softening point of 103 ° C., and a weight average molecular weight of 58,000. 43% by weight of maleic anhydride (E-1) had undergone a graft reaction, and 20 black foreign substances having a size of 1 to 3 mm were observed. Table 3 shows the materials used, equivalence ratio, and reaction temperature. Graft ratio, melt viscosity, measured molecular weight, softening point, black foreign material of (meth) acrylic acid alkyl ester (D) and unsaturated carboxylic acids (E) Table 4 shows the size and number.

Comparative Example 5 Production of a modified polyolefin (H-5) for a comparative example.
In a 3000 ml Separa flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet tube, polyolefin (A-3) 1000 g, sorbitan laurate (B-2) 1 g, propylene glycol monomethyl ether acetate (C-1) 50 g The mixture was melted in an oil bath maintained at 170 ° C. under a nitrogen atmosphere, and the temperature of the oil bath was adjusted so that the temperature in the system was 160 ° C. while stirring. After the inside of the system is melted, while stirring to obtain a uniform state, 60 g of n-butyl methacrylate (D-5) and 10 g of perhexyl D (F-4) are dissolved in 150 g of propylene glycol monomethyl ether acetate (C-1). The monomer solution was added dropwise over 1.5 hours.
After completion of the dropwise addition, the reaction was performed at 160 ° C. for 2 hours, and then the pressure in the flask was reduced with an aspirator while propylene glycol monomethyl ether acetate (C-1), unreacted n-butyl methacrylate (D-4), and perhexyl D The removal of the low molecular weight compound in which (F-4) and perhexyl D (F-4) were decomposed was performed for 1 hour, and after completion of the decompression, the reaction product was taken out and cooled to give milky white (meth) acrylic acid alkyl ester. A solid product of modified polyolefin (H-5) modified with 1 was obtained.
The obtained modified polyolefin (H-5) had a melt viscosity (190 ° C.) of 3.4 Pa · s, a softening point of 99 ° C., and a weight average molecular weight of 60,000. 23% by weight of n-butyl methacrylate (D-5) had undergone a graft reaction, and no black foreign matter was observed. Table 3 shows the materials used, equivalence ratio, and reaction temperature. Graft ratio, melt viscosity, measured molecular weight, softening point, black foreign material of (meth) acrylic acid alkyl ester (D) and unsaturated carboxylic acids (E) Table 4 shows the size and number.

Comparative Example 6 Production of a modified polyolefin (H-6) for a comparative example.
Into a 3000 ml Separ flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet tube, 1000 g of polyolefin (A-6), 1 g of sorbitol (B-1), and 50 g of propylene glycol monomethyl ether acetate (C-1) are placed. Then, melting was performed in an oil bath maintained at 170 ° C. in a nitrogen atmosphere, and the temperature of the oil bath was adjusted so that the temperature in the system was 160 ° C. while stirring. After the system is melted, stirring is performed to obtain a uniform state, and 60 g of n-butyl methacrylate (D-5), 60 g of maleic anhydride (E-1) and 10 g of perhexyl D (F-4) are added to propylene glycol monomethyl ether. A monomer solution dissolved in 150 g of acetate (C-1) was added dropwise over 1 hour.
After completion of the dropwise addition, the reaction was carried out at 160 ° C. for 2 hours, and then the pressure in the flask was reduced with an aspirator while propylene glycol monomethyl ether acetate (C-1), unreacted n-butyl methacrylate (D-5), and anhydrous maleic acid were added. Removal of the low molecular weight compound in which acid (E-1), perhexyl D (F-4) and perhexyl D (F-4) were decomposed was performed for 1 hour, and after completion of the decompression, the reaction product was taken out and cooled, A solid product of modified polyolefin (H-6) modified with (meth) acrylic acid alkyl ester and unsaturated carboxylic acids was obtained.
However, in the case of modified polyolefin (H-6), dropping about 50% (about 130 g) of the monomer solution drastically increases the viscosity of the modified polyolefin, resulting in insufficient stirring, and therefore the resin is in a non-uniform state. Thus, a modified polyolefin (H-6) was obtained in a state where yellow and milky white resins were mixed and black portions were also scattered. Regarding the properties of the obtained modified polyolefin (H-6), the yellow part resin was examined.
The melt viscosity (190 ° C.) of the yellow part of the modified polyolefin (H-6) obtained was 142.2 Pa · s, the softening point was 148 ° C., and the weight average molecular weight was 9,500. 43% by weight of n-butyl methacrylate (D-5) and 36% by weight of maleic anhydride (E-1) were graft-reacted. In 1000 g of the modified polyolefin (H-6), milky white wax-like and yellow wax-like portions were mixed, and black foreign matter was about 3 to 5 mm in size and 50 points or more were observed. Table 3 shows the materials used, equivalence ratio, and reaction temperature. Graft ratio, melt viscosity, measured molecular weight, softening point, black foreign material of (meth) acrylic acid alkyl ester (D) and unsaturated carboxylic acids (E) Table 4 shows the size and number.

Explanation of annotations in the table:
> 1 mm: less than 1 mm,> 50 points: more than 50 points.
(* 1) Bimodal peak consisting of 80% high molecular weight component with Mw = 146,000, 20% low molecular weight component with Mw = 500 (* 2) 95% high molecular weight component with Mw = 182,000, Mw = 2300 The bimodal peak (* 3) melting temperature consisting of 5% of the low molecular weight component was a value measured at 140 ° C. only in Example 16.
(* 4) Milky white waxy part and yellow waxy part were mixed.

(Example 17) Modified polyolefin resin aqueous dispersion composition (G-17).
To a 1000 ml Separa flask equipped with a stirrer, a thermometer, and a reflux condenser, 100 g of the modified polyolefin (G-4) obtained in Example 4 and 10 g of AS1540 (alkenyl succinic anhydride, manufactured by Seiko PMC Co., Ltd.) were added, and 130 It melt | dissolved in the oil bath kept at 0 degreeC, and it stirred and mixed. After melt mixing, 10 g of a 90% aqueous solution of 2-methyl-2-aminopropanol was added, and then ion exchange water at 80 ° C. was added little by little with vigorous stirring. Although the viscosity increased, the viscosity decreased when water was continuously added. When 250 g of water was added, the contents were taken out to obtain a milky white modified polyolefin resin aqueous dispersion composition (G-17).
The obtained modified polyolefin resin aqueous dispersion composition (G-17) had a solid content of 32.0%, a viscosity of 180 mPa · s (25 ° C.), a pH of 7.3, and a particle diameter (median diameter) of 0.16 μm. Table 5 shows the materials used, the equivalent ratio, and the properties. The particle size is a value measured by a particle size distribution measuring apparatus by dynamic light scattering method / laser Doppler method (Nikkiso Co., Ltd .: Microtrac UPA150), and the viscosity is Brookfield rotational viscometer (Tokimec Co., Ltd .: VISCOMETER). The measured value at 25 ° C.

(Crosscut test) Adhesiveness of modified polyolefins of Examples and Comparative Examples.
15% by weight toluene solution of the modified polyolefins obtained in Examples 1 to 16 and Comparative Example 5 in which the number of black foreign matters that cause defects in the resin is 15 points or less and the black foreign matters can be easily removed by a strainer or the like. Adjusted. Moreover, the modified polyolefin resin aqueous dispersion composition obtained in Example 17 was diluted with ion-exchanged water to a solid content of 15% by weight. The obtained toluene solution and aqueous dispersion were applied to an ultra-high rigidity polypropylene plate with No. It was applied with a 20 bar coater and dried at 90 ° C. for 30 minutes. After leaving the test piece to stand at room temperature for 3 days, the surface of the coating film was cut with a cutter, and 100 grids were made at intervals of 2 mm, on which cellotape (registered trademark) (manufactured by Nichiban Co., Ltd., The cellophane adhesive tape for packaging (24 mm width) is adhered and peeled off in the direction of 180 degrees, the number of remaining grids (X) is counted, and the remaining number per 100 grids produced (X / 100) is shown in Table 5 displayed. The greater the number of remaining grids (X), the better the adhesion. Since the modified polyolefins (H-1) to (H-4) obtained in Comparative Examples 1 to 4 have more than 15 black foreign substances, it is estimated that it is difficult to separate the black foreign substances using a strainer or the like. Further, the modified polyolefin (H-6) obtained in Comparative Example 6 was non-uniform, and only a part of the resin was dissolved in toluene. Therefore, the cross cut test was not performed for the modified polyolefins (H-1) to (H-4) and (H-6).

  As shown in Table 3, the molecular weight of the polyolefin (A) and the added amount of the unsaturated carboxylic acids (E) can be set to various values depending on the intended use of the modified polyolefin to be produced.

  The graft ratio of (meth) acrylic acid alkyl ester (D) and unsaturated carboxylic acids (E) shown in Table 4 and the size and number of black foreign matters can be viewed as indicators of the amount of by-products generated. As a result, in Comparative Example 1 in which sorbitols (B) are not used and in Comparative Example 2 in which xylene is used without using the organic solvent (C), the black foreign matter is less in comparison with the Examples although the adhesiveness is sufficient. In many cases, the number of defects in the resin increases. In Comparative Example 3 in which no organic solvent (C) was used, the number of black foreign matters was extremely large as compared with the Examples, resulting in a large number of defects in the resin. The comparative example 4 which does not use a (meth) acrylic-acid alkylester (D) was a result that adhesiveness deteriorated and black foreign materials also increased compared with an Example. In Comparative Example 5 in which the unsaturated carboxylic acids (E) were not used, no black foreign matter was generated, but the adhesion of the resin to the polypropylene base material was very low. In Comparative Example 6, polyethylene that does not contain propylene was grafted, but a uniform modified polyolefin could not be produced. However, in the examples, only a very small amount of black foreign matter was generated, and the adhesiveness was good, both of which were good results.

  As shown in Example 17, the modified polyolefin resin obtained in the Example could be obtained as an aqueous dispersion composition and exhibited good adhesion as shown in Table 5.

  By the method for producing a modified polyolefin resin of the present invention, it is possible to obtain a modified polyolefin that suppresses the decrease in the molecular weight of the polyolefin and suppresses the generation of by-products. The obtained modified polyolefin can be dispersed in water to obtain a modified polyolefin resin aqueous dispersion composition. In addition, the modified polyolefin obtained by the production method of the present invention is excellent in adhesiveness, so that it can be used, for example, as a heat sealant, an adhesive, and an adhesive modifier. It can be considered that the adhesiveness is excellent in bonding with a resin, metal, or the like. It can also be considered as a modifier for polyolefin resins and composite materials such as films, sheets, structural materials, building materials, automobile parts, electrical / electronic products, and packaging materials. It can also be used for paints, ink binders, paint binders, primers, and the like, and particularly when coated on polyolefin resins and composite materials, it can be considered that adhesion and paintability are excellent. In addition, the modified polyolefin resin aqueous dispersion composition obtained by the production method of the present invention is excellent in adhesiveness, so it can be used for paints, ink binders, paint binders, primers, and the like, especially polyolefin resins and composite materials. It can be considered that adhesion, paintability, etc. are excellent when painting against. It can also be used for adhesives, heat sealing agents, glass fiber sizing agents, and the like. It can be considered that it can be used for various purposes in a wide range where the general-purpose polyolefin-based resin as described above is used.

Claims (4)

100 parts by mass of polyolefin (A) having at least ethylene and propylene as structural units, 0.01 part by mass or more and 2 parts by mass or less of sorbitols (B), alkyl alkylate, alkylene glycol alkyl ether alkylate, dialkylene glycol alkyl (Meth) acrylic acid alkyl ester (D) in the presence of 5 parts by mass or more and 50 parts by mass or less of organic solvent (C) having at least one selected from ether alkylates and having a boiling point of 250 ° C. or less 0.5 to 30 parts by mass and unsaturated carboxylic acids (E) (excluding (meth) acrylic acid alkyl ester (D)) 0.5 to 30 parts by mass of organic peroxide (F ) to characterized in that it is obtained by adding with 0.1 part by mass 10 parts by weight Method for producing a modified polyolefin resin. The molar ratio of the (meth) acrylic acid alkyl ester (D) and the unsaturated carboxylic acid (E) is (meth) acrylic acid alkyl ester (D) / unsaturated carboxylic acid (E) = 0.5 to 2.0. The method for producing a modified polyolefin resin according to claim 1 . The method for producing a modified polyolefin resin according to claim 1 or 2, wherein the polyolefin (A) has a weight average molecular weight of 10,000 to 200,000 and a density of 0.85 g / cm ^{3 to} 0.89 g / cm ^3. . A modified polyolefin resin aqueous dispersion composition obtained by dispersing a modified polyolefin obtained by the method for producing a modified polyolefin resin according to any one of claims 1 to 3 in water.