JP2008285531A - Method for producing modified polyolefin particles - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a modified polyolefin particles in high yield, while keeping good physical properties and functions, by carrying out the purification and granulation at the same time without using an aromatic solvent. <P>SOLUTION: The method for producing modified polyolefin particles having an average particle diameter of 0.1-5 mm comprises mixing a molten carboxyl-modified polyolefin (A) having a neutralization degree of &le;0.3 equivalent with at least water to prepare a suspension of the modified polyolefin and the removal of water from the suspension. A suspension of particles having an average particle diameter of 0.1-5 mm can be produced according to the method of the present invention by mixing the modified polyolefin with water and stirring the mixture, and unreacted unsaturated carboxylic acid or a water-soluble by-product derived from unsaturated carboxylic acids and generated by the modification process can be removed by filtering the water from the suspension to obtain a modified polyolefin particle having improved color. Modified polyolefin particles keeping good physical properties and functions can be produced by the method of the present invention without using an aromatic solvent. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention relates to a novel production method for purifying and granulating a modified polyolefin resin obtained by adding an unsaturated carboxylic acid and / or its derivative to a polyolefin. More specifically, the present invention relates to a method for producing modified polyolefin particles, characterized in that a modified polyolefin resin is mixed and dispersed with water to form a suspension, and purified polyolefin particles are obtained by removing water from the suspension. .

  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”) Modified polyolefins obtained by graft reaction of ethylenically unsaturated compounds such as unsaturated carboxylic acids or their anhydrides are compatibilizers and adhesives between polyolefins and other resins, dispersants and adhesives for inorganic materials It is a useful material that can be used as an adhesive to metal, a primer such as a polyolefin substrate, an additive for ink or paint, and the like.

  However, the grafting reaction involves removing hydrogen from the polyolefin with an organic peroxide and adding unsaturated carboxylic acid, resulting in unreacted unsaturated carboxylic acid residue and by-product derived from unsaturated carboxylic acid that does not graft, There have been problems such as degradation of the performance of the modified polyolefin due to the mixture of unreacted products and by-products, and defects of the by-products as foreign matters.

  In addition, since the modified polyolefin is extremely viscous, it is very difficult to pulverize it, so that the shape to be handled may be a solidified state in a lump shape or a solidified state by a pelletizer. However, in the case of a massive modified polyolefin, since it must be melted in order to send it into a kneader or molding machine, it is necessary to install an apparatus capable of melting the massive polymer. Therefore, the modified polyolefin is generally handled with particles.

In order to obtain high-performance modified polyolefin particles, it is necessary to carry out purification by removing unreacted products and by-products after the production of modified polyolefin by grafting reaction of polyolefin, and further to form particles with a pelletizer. The removal of unreacted products and by-products involves refining the modified polyolefin obtained by refining it with a poor solvent after dissolving the modified polyolefin in a solvent (see, for example, Patent Document 1). Then, a method for reducing unreacted substances (for example, see Patent Document 2), a purification step performed by melt-kneading the modified polyolefin in the presence of water and volatilizing and removing water (for example, see Patent Document 3). There have been proposed post-treatment methods for modified polyolefins such as However, there are problems that a complicated process such as separation of a large amount of organic solvent by filtration is required, the molecular weight of polyolefin is reduced by reheating, and that moisture needs to be volatilized during melt kneading. Further, in order to obtain particles, it is necessary to pass the modified polyolefin after purification through a pelletizer, which is a complicated process. Therefore, a simple purification and particle formation method has been desired.
JP 54-099193 A JP-A-56-095914 JP 08-325322 A

There is also known a technique in which a modified polyolefin is dissolved in a high-temperature aromatic solvent, and this is dropped into the same solvent at a temperature lower than or equal to the precipitation start temperature to precipitate as fine crystals to simultaneously perform purification and particle formation to obtain a fine powder. (See, for example, Patent Document 4), since the modified polyolefin is precipitated in a solvent in which the modified polyolefin is easily dissolved, there is a problem such as a decrease in yield, and in recent years, due to environmental problems, production without using aromatic hydrocarbons such as toluene and xylene. There is a need for a process.
Japanese Patent Laid-Open No. 05-017585

  In view of the above circumstances, the present invention provides a method for producing modified polyolefin particles having a good yield that retains good physical properties and functions by performing purification and particle formation simultaneously without using an aromatic solvent. Let it be an issue.

  As a result of repeating many trial and error trial manufactures and experiments in order to solve the above problems, the present inventor added at least high-temperature water to the melted modified polyolefin and stirred the modified polyolefin particles. By solving the suspension and filtering the suspension, the modified polyolefin can be purified and granulated with high yield, thereby solving the problem.

  The technical problem can be solved by the present invention as follows.

That is, the present invention
(1) A melted carboxyl group-modified polyolefin (A) having a neutralization degree of 0.3 equivalent or less and at least water are mixed to form a suspension of the modified polyolefin, and then the water is removed to obtain an average particle size. A method for producing modified polyolefin particles to obtain a modified polyolefin of 0.1 to 5 mm,
(2) The modified polyolefin (A), at least water and the dispersant (B) are mixed, and the modified polyolefin (A): dispersant (B) = 100: 0.01-20 is used in the solid content ratio (1) ) Modified polyolefin particles,
(3) The method for producing modified polyolefin particles according to the above (1) or (2), which is mixed at a softening start temperature or higher in the flow tester of the modified polyolefin (A),
(4) Production of modified polyolefin particles according to any one of (1) to (3), wherein the modified polyolefin (A) is a resin obtained by modifying the polyolefin (a) with at least an unsaturated carboxylic acid (b). Method,
(5) The method for producing modified polyolefin particles according to (1) to (4), wherein the dispersant (B) is a polyvinyl alcohol.

  According to the production method of the present invention, the modified polyolefin can be mixed with water and stirred to obtain a particle suspension having an average particle size of 0.1 to 5 mm. The modified polyolefin particle which improved the coloring state by removing the unreacted unsaturated carboxylic acid in modified polyolefin and the water-soluble by-product derived from the unsaturated carboxylic acid which is not grafted can be provided by separating. Moreover, the modified polyolefin particle which maintained the favorable physical property and function without using an aromatic solvent by the manufacturing method of this invention can be provided.

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

  The modified polyolefin (A) that can be used in the present invention is a modified polyolefin having a carboxyl group, and is preferably a polyolefin obtained by modifying a polyolefin (a) with at least an unsaturated carboxylic acid (b). ) Polyolefin obtained by modification using acrylic acid alkyl ester (b1), unsaturated carboxylic acid (b2) and organic peroxide (c) is more preferred.

  The polyolefin (a) is an α-olefin copolymer, and the α-olefin is 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 can be mentioned. Examples of the copolymer include a random copolymer, a block copolymer, a graft copolymer, and a mixture thereof.

  Unsaturated carboxylic acids (b) are unsaturated carboxylic acids and derivatives thereof, preferably unsaturated monobasic acids such as acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, and unsaturated monobasic esters and unsaturated carboxylic acids. Saturated monobasic acid amides, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride and other unsaturated dibasic acids, unsaturated dibasic acid anhydrides and unsaturated dibasic acids Half ester, diester, unsaturated dibasic acid amide and unsaturated dibasic acid imide, aconitic acid, 3-butene-1,2,3-tricarboxylic acid, 4-pentene-1,2,4-tricarboxylic acid, etc. Unsaturated tribasic acid, unsaturated tribasic acid anhydride and unsaturated tribasic acid mono, di, triester, unsaturated tribasic amide and unsaturated tribasic imide, 1-pentene-1 Unsaturated tetrabasic acids such as 1,4,4-tetracarboxylic acid, 4-pentene-1,2,3,4-tetracarboxylic acid, 3-hexene-1,1,6,6-tetracarboxylic acid, It is at least one compound selected from the group consisting of saturated tetrabasic acid anhydrides and mono-, di-, tri-, tetra-esters of unsaturated tetrabasic acids, unsaturated tetrabasic amides and unsaturated tribasic imides. Maleic anhydride and / or its derivatives are particularly preferred because of poor homopolymerization and easy progress of the grafting reaction.

  When the unsaturated carboxylic acids (b) are used in combination with the (meth) acrylic acid alkyl ester (b1) and the unsaturated carboxylic acid (b2), the grafting reaction is facilitated to generate unreacted products and ungrafted oligomers. This is particularly preferable because the amount can be easily suppressed.

  The (meth) acrylic acid alkyl ester (b1) is an acrylic acid alkyl ester or 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. Alkyl esters and alkyl methacrylates, specifically, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, i-propyl acrylate, methacryl I-propyl acid, n-butyl acrylate, n-butyl methacrylate, i-butyl acrylate, i-butyl methacrylate, 2-butyl acrylate, 2-butyl methacrylate, t-butyl acrylate, t-methacrylic acid -Butyl, cyclohexyl acrylate, methacryl Cyclohexyl, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, n-octyl acrylate, n-octyl methacrylate, n-dodecyl acrylate, n-dodecyl methacrylate, n-octadecyl acrylate, n-octadecyl methacrylate, etc. Can be mentioned.

  The unsaturated carboxylic acid (b2) is a polyvalent compound such as an unsaturated monobasic acid or an unsaturated dibasic acid or a derivative thereof, and preferably an unsaturated monobasic acid such as acrylic acid, methacrylic acid, crotonic acid, or cinnamic acid. Basic acids, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, unsaturated dibasic acids such as citraconic anhydride, and unsaturated dibasic acids 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 monobutyl ether, Groups of monoesters with ethylene 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-propylamine, It is at least one compound selected from the group of amides with n-butylamine, cyclohexylamine, 2-ethylhexylamine, n-octylamine, n-dodecylamine, n-octadecylamine, aniline, benzylamine and the like. Of these, maleic anhydride and / or its derivatives are particularly preferred because of their poor homopolymerization and the ease of the grafting reaction.

  In this invention, ethylenically unsaturated compounds other than the said unsaturated carboxylic acids (b) can be used simultaneously with unsaturated carboxylic acids (b). 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 organic peroxide (c) 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. Specifically, ketone peroxide, peroxy Ketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxyesters, peroxydicarbonates, alkylperoxycarbonates, specifically, diisobutyryl peroxide, cumyl peroxyneodecanate, di-n -Propyl peroxydicarbonate, diisopropyl peroxydicarbonate, di-sec-butyl peroxydicarbonate, 1,1,3,3-tetramethylbutyl peroxyneodecanate, di (4-t-butylcyclohexyl) peroxydi -Bonate, 1-cyclohexyl-1-methylethyl peroxyneodecanate, di (2-ethoxyethyl) peroxydicarbonate, di (2-ethylhexyl) peroxydicarbonate, t-hexyl peroxyneodecanate, dimethoxybutyl Peroxydicarbonate, t-butyl peroxyneodecanate, t-hexyl peroxypivalate, t-butyl peroxypivalate, di (3,3,5-trimethylhexanoyl) peroxide, di-n-octanoyl par Oxide, dilauroyl peroxide, distearoyl peroxide, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanate, disuccinic acid peroxide, 2,5-dimethyl-2,5-di (2-ethylhexa) Neu Peroxy) 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- Butylperoxy) 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-butyl peroxyacetate, 2,2-di- (t -Butylperoxy) butane, t-butylperoxybenzoate, n-butyl 4,4-di- (t-butylperoxy) valerate, di (2-t-butylperoxyisopropyl) benzene, dicumyl peroxide, di -T-hexyl peroxide, 2,5-dimethyl-2,5-di (t -Butylperoxy) hexane, t-butyl cumyl peroxide, di-t-butyl peroxide, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, Examples include cumene hydroperoxide and t-butyl hydroperoxide. These may be used individually by 1 type, and may be used in combination of 2 or more types.

  In the modified polyolefin obtained as described above, a stabilizer for adjusting the stability can be added during production according to the purpose of use. Examples of the stabilizer include sorbitol, sorbitol alkylate, hydroquinone, benzoquinone, nitrosophenylhydroxy compound, phosphite compounds such as tris (2,4-di-t-butylphenyl) phosphite, pentaerythrityl-tetrakis [3- ( 3,5-di-t-butyl-4-hydroxyphenyl) propionate] and other compounds such as pentaerythritol esters. These may be used individually by 1 type, and may be used in combination of 2 or more types.

  The method for modifying the polyolefin (a) can be carried out by a known method. For example, the polyolefin (a) is dissolved in an organic solvent at a temperature higher than the softening point, and the unsaturated carboxylic acids (b) and Solution method in which the organic peroxide (c) is added and reacted, the polyolefin (a) is melted by setting it to a softening point or higher, and the unsaturated carboxylic acid (b) and the organic peroxide (c) are added and mixed to react. Melting method, mixing polyolefin (a), unsaturated carboxylic acids (b) and organic peroxide (c) at a temperature above the softening point of polyolefin (a) using a Banbury mixer, kneader, extruder, etc. The method of tempering etc. is mentioned. As addition method of unsaturated carboxylic acids (b) and organic peroxide (c), batch addition, addition after diluting into solution, divided addition, continuous addition method by dropping, etc. can be selected as appropriate, and the order of addition is also It can be selected as appropriate. The modification reaction may be performed in multiple stages, and in that case, the respective reactors and reaction types can be used in appropriate combinations. In addition, a decompression step can be provided at the end of the reaction to remove residual unsaturated carboxylic acids (b), organic peroxide (c), decomposition products of organic peroxide (c), and organic solvents.

  When the polyolefin (a) is modified with the unsaturated carboxylic acid (b) by the solution method, examples of the organic solvent include saturated aliphatic hydrocarbons such as hexane, heptane, and octane, cyclohexane, methylcyclohexane, ethylcyclohexane, Saturated alicyclic hydrocarbons such as cycloheptane and methylcycloheptane, alkylene glycol alkyl ether alkylates such as ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate and propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate , Dialkylene glycol alkyl ether alkylates such as diethylene glycol monobutyl ether acetate, ethyl acetate, propyl acetate, vinegar Esters that do not contain ethylenic double bonds such as butyl, ethyl propionate, propyl propionate, butyl propionate, ethyl butyrate, propyl butyrate, butyl butyrate, ethylenic esters such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone Examples include ketones not containing a double bond, ethers not containing an ethylenic double bond such as n-butyl ether, isobutyl ether, tetrahydrofuran, diethyl ether, ethylene glycol dialkyl ether, and dioxane. Aromatic hydrocarbons that do not contain ethylenic double bonds such as toluene, xylene, and ethylbenzene can also be used, but it is preferable not to use them as much as possible due to recent environmental problems. These organic solvents may be used alone or in combination.

  Although there is no restriction | limiting in particular in the reaction temperature which modifies | denatures polyolefin (a), 100-200 degreeC is preferable. The temperature is preferably higher than the temperature at which the polyolefin melts or dissolves in the organic solvent so that the unsaturated carboxylic acids (b) and the organic oxide (c) can be uniformly dispersed. Is preferred. Moreover, it is preferable that the temperature is not excessively high in order to suppress a decrease in the molecular weight of the polyolefin due to peroxide. Specifically, it is preferably performed at 200 ° C. or lower.

  In the present invention, the modified polyolefin (A) is granulated by mixing the melted modified polyolefin (A) with at least water and stirring, and by applying a shearing force by stirring. The modified polyolefin particles can be obtained by removing. The water to be added is preferably an aqueous solution in which the dispersant (B) is dissolved, and the average particle diameter of the resulting modified polyolefin particles is 0.1 to 5 mm, preferably 0.5 to 2 mm. Compared to the case where the average particle diameter is larger than 5 mm, the case where the average particle diameter is 5 mm or less is preferable because the non-grafted acidic water-soluble component derived from unsaturated carboxylic acids in the modified polyolefin is easily removed. In the following, it is more preferable because acidic water-soluble components are easily removed. Compared to the case where the average particle diameter is smaller than 0.1 mm, the case where the average particle diameter is 0.1 mm or more is preferable because the yield when separating the modified polyolefin particles by filtration is increased. Since the rate is improved, it is more preferable. The particle diameter of the modified polyolefin was determined by measuring the particle diameter of spherical particles, and the biaxial average diameter of irregular particles. The average particle diameter was determined from the number average diameter.

  In the present invention, the carboxyl group-modified polyolefin (A) having a neutralization degree of 0.3 equivalent or less is a modified polyolefin in which a basic compound such as an organic amine compound, an alkali metal hydroxide or an alkaline earth metal hydroxide is modified. It is preferable that it is 0.3 equivalent or less with respect to the carboxyl group in (A), and the case where a basic compound is not included is more preferable. When the amount is 0.3 equivalents or less, the modified polyolefin particles have a particle diameter of 0.1 mm or more, and the yield when separating the modified polyolefin particles by filtration is higher than when the amount is 0.3 equivalents or less. In the case where no basic substance is contained, that is, in the case of non-neutralization (neutralization degree is 0.0 equivalent), the yield is further increased, which is further preferable.

  The dispersant (B) that can be used in the present invention is a partially and / or wholly hydrolyzed polyvinyl acetate, polyvinyl alcohol such as polyvinyl alcohol, carboxy-modified polyvinyl alcohol, and cation-modified polyvinyl alcohol, cation-modified starch, Monomers capable of copolymerization based on (meth) acrylamide, including starches such as amphoteric starch, oxidized starch and enzyme-modified starch, celluloses such as carboxymethylcellulose, hydroxyethylcellulose and hydroxypropylcellulose, and (meth) acrylamide homopolymer Acrylamide polymer polymerized, acrylic acid polymer polymerized with copolymerizable monomer mainly composed of acrylic acid including (meth) acrylic acid homopolymer, polyvinylpyrrolidone, zera Emissions, gum arabic, compounds used as a dispersion stabilizer and casein. These dispersants may be used alone or in combination of two or more. Among these, since a fine particle can be obtained with a small amount of polyvinyl alcohol, it is more preferable.

  The amount of the dispersant (B) used is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the modified polyolefin (A). In addition, this is the mass per solid content. 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, the modified polyolefin (A) particles are preferable because the suspension state of finer particles can be easily stabilized. When the amount is 0.1 part by mass or more, it is preferable because the suspended state is easily stabilized. In addition, when the amount is 20 parts by mass or less, the modified polyolefin particles have a particle diameter of 0.1 mm or more, and the yield when separating the modified polyolefin particles by filtration is higher than when the amount is 20 parts by mass or more. Therefore, it is preferable that the amount is 5 parts by mass or less because the yield is further increased.

  Although there is no restriction | limiting in particular in the usage-amount of the water mixed with the molten modified polyolefin (A), It is preferable that it will be 100-500 mass parts with respect to 100 mass parts of modified polyolefin (A). Compared with the case where the content is less than 100 parts by mass, the content of 100 parts by mass or more is preferable because the suspended state of the modified polyolefin (A) particles is stabilized and re-fusion can be easily prevented. Moreover, compared with the case where there are more than 500 mass parts, when it is 500 mass parts or less, since the quantity of the water isolate | separated from a modified polyolefin particle decreases and a separation process becomes easy, it is preferable.

  In the present invention, as long as the effects of the present invention are not impaired, the water mixed with the molten modified polyolefin (A) may contain a water-soluble organic solvent. Examples of the water-soluble organic solvent herein include alcohols such as methanol, ethanol and isopropanol, alkylene glycols such as ethylene glycol and propylene glycol, ketones such as acetone, ethers such as tetrahydrofuran and diethyl ether, and the like. . These water-soluble organic solvents may be used alone or in combination of two or more.

The water temperature when the molten modified polyolefin (A) and at least water are mixed and stirred is preferably a temperature equal to or higher than the softening start temperature of the modified polyolefin (A) in the flow tester. The softening start temperature of the modified polyolefin (A) in the present invention is obtained by a flow tester (manufactured by Shimadzu Corporation: CFT-500D) with a load of 0.49 MPa, a die having an inner diameter × length = 1 mm × 10 mm. Value. A temperature higher than the softening start temperature is preferable because the modified polyolefin (A) is likely to be granulated by shearing force generated by stirring.

  The melted modified polyolefin (A) and at least water can be mixed and stirred under normal pressure or under pressure. Even if the modified polyolefin (A) has a softening start temperature of 100 ° C. or higher in the flow tester, the modified polyolefin (A) can be made into particles by setting the water temperature to be higher than the softening start temperature under pressure.

  The modified polyolefin particles can be obtained by removing water from the suspension of the modified polyolefin particles obtained in the present invention, preferably by washing. Known methods such as centrifugal dehydration, vibration sieve filtration, squeezing dehydration, vacuum drying, vacuum belt filter, hot air drying and the like can be used for removing water.

  The modified polyolefin particles thus obtained can be used as, for example, heat sealants, adhesives, and adhesive modifiers, and are particularly suitable for adhesion between polyolefin resins and composite materials and other resins, metals, glass, and the like. Excellent in properties. In addition, when making polyolefin resins and composite materials such as films, sheets, structural materials, building materials, automobile parts, electrical / electronic products, and packaging materials, compatibilizers for polyolefin resins and other resins It can be used as a modifier such as a dispersant that facilitates dispersion of the composite material into the polyolefin. Further, it can be used as a paint binder, a binder for ink, and a primer, and particularly has excellent adhesion and paintability when applied to polyolefin resins and composite materials. It can also be used as a sizing agent for glass fibers.

  The modified polyolefin particles of the present invention can function as adhesives, compatibilizers, dispersants, modifier paint binders, ink binders, and primers as they are, 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 particles of the present invention are also excellent in compatibility with other resins, urethane resins, epoxy resins, acrylic resins, phenol resins, alkyd resins, silicone resins, polyacetal resins, polyester resins, polyamide resins, Other resins such as polyimide resin and nitrified cotton may be blended.

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

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

<Softening point of modified polyolefin>
The softening start temperature of the modified polyolefin (A) is a value obtained by 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.

<Acid value of acidic water-soluble component contained in modified polyolefin>
2 g of the modified polyolefin (A) was dissolved in 50 g of hot xylene, 100 g of ion exchange water was added, and the mixture was stirred for 10 minutes or more under reflux and then cooled. It is separated into a xylene layer and an aqueous layer by standing for 24 hours, and an acid value that is an impurity derived from unsaturated carboxylic acids that are not grafted to the polyolefin contained in the modified polyolefin is measured by measuring the acid value of the aqueous layer. The acid value of the water-soluble component was measured. For this reason, it shows that there are many impurities, so that this value is large.

<Decrease rate of acidic water-soluble component due to particle formation of modified polyolefin>
By measuring the acidic water-soluble component before and after particle formation of the modified polyolefin, the decrease rate of the acidic water-soluble component due to particle formation (hereinafter sometimes referred to as the decrease rate) was measured. . The reduction rate was a value obtained by the equation (1). For this reason, a larger value indicates that impurities could be removed.
(Reduction rate) = {(acid value of water-soluble component before particle formation) − (acid value of water-soluble component after particle formation)} / (acid value of water-soluble component before particle formation) × 100 ... (1)

<Average particle diameter of modified polyolefin particles>
Modified Polyolefin Particles The particle diameter of the modified polyolefin was measured using the dimension measuring function of Digital Microscope VH-6200 (manufactured by Keyence Corporation). Spherical particles were obtained by measuring the particle diameter, and for irregular particles, the biaxial average diameter represented by the formula (2) was obtained. The average particle diameter was obtained from the number average diameter represented by the formula (3).
(Biaxial average diameter) = {(Long axis diameter) + (Short axis diameter)} / 2 (2)
(Number average diameter) = Σ (Measured particle diameter) / (Measured number) (3)

Modified polyolefin (A-1)
As the modified polyolefin (A-1), TP LICOCENE PP MA1332 (manufactured by Clariant Japan Co., Ltd.), which is a polyolefin modified with maleic anhydride, was used as it was. The modified polyolefin (A-1) had a yellow appearance, a softening start temperature of 72 ° C., and the acidic water-soluble component contained in the modified polyolefin (A-1) was 3.5 mgKOH / g. Table 1 shows the physical properties of the modified polyolefin (A-1). The acid value of the modified polyolefin (A-1) was 18 mgKOH / g.

Modified polyolefin (A-2)
As the modified polyolefin (A-2), TP LICOCENE PP MA6252 (manufactured by Clariant Japan Co., Ltd.), which is a polyolefin modified with maleic anhydride, was used as it was. The modified polyolefin (A-2) had a yellow appearance, a softening start temperature of 136 ° C., and the acidic water-soluble component contained in the modified polyolefin (A-2) was 19.3 mgKOH / g. Table 1 shows the physical properties of the modified polyolefin (A-2). The acid value of the modified polyolefin (A-2) was 40 mgKOH / g.

Production Example of Modified Polyolefin (A-3) In a 3000 ml Separa flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet tube, 1000 g of VESTOPLAST 708 (manufactured by Degussa Japan) as polyolefin and Irganox 1010 (Ciba Geigy) as antioxidant Product: 1 g of product name) and 1 g of Irgafos 168 (product name: Ciba Geigy): The temperature is adjusted to 170 ° C. with stirring in a nitrogen atmosphere, and the polyolefin melts and becomes a uniform state. Then, 6 g of maleic anhydride was added, and then 1.4 g of di-t-hexyl peroxide (manufactured by NOF Corporation: Perhexyl D) was added. The reaction was continued for 30 minutes while maintaining at 170 ° C., then 6 g of maleic anhydride was added, and then 1 g of di-t-hexyl peroxide was added. Similarly, the same amount of maleic anhydride and di-t-hexyl peroxide are repeatedly added every 30 minutes. The total amount of maleic anhydride added is 30 g, and the total amount of di-t-hexyl peroxide added is It was set to 7 g. After adding all of the di-t-hexyl peroxide and reacting at 170 ° C. for 1 hour, while reducing the pressure in the flask with an aspirator, unreacted maleic anhydride, di-t-hexyl peroxide and di- Removal of the low molecular weight compound in which t-hexyl peroxide was decomposed was performed for 1 hour. The reaction product was taken out and cooled to obtain a modified polyolefin (A-3). The resulting modified polyolefin (A-3) was yellow in appearance, had a softening start temperature of 88 ° C., and the acidic water-soluble component contained in the modified polyolefin (A-3) was 4.2 mgKOH / g. Table 1 shows the physical properties of the modified polyolefin (A-3).

Production Example of Modified Polyolefin (A-4) In a 3000 ml Separa flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen gas introduction tube, VESTOPLAST 7081000 g as a polyolefin, 50 g of propylene glycol methyl ether acetate, 1 g of Irganox 1010 as an antioxidant and 1 g of Irgafos 168 was added and the temperature was adjusted to 170 ° C. while stirring in a nitrogen atmosphere. After the polyolefin melted and became homogeneous, 90 g of 2-ethylhexyl acrylate, 30 g of maleic anhydride, di- A solution prepared by dissolving 5 g of t-hexyl peroxide in 150 g of propylene glycol methyl ether acetate was added dropwise over 2 hours.
After completion of the dropwise addition, the reaction was conducted under reflux for 2 hours, and then the pressure in the flask was reduced with an aspirator while propylene glycol methyl ether acetate, unreacted 2-ethylhexyl acrylate, maleic anhydride, di-t-hexyl peroxide and Removal of the low molecular weight compound in which di-t-hexyl peroxide was decomposed was performed for 1 hour. The reaction product was taken out and cooled to obtain a modified polyolefin (A-4).
The obtained modified polyolefin (A-4) was pale yellow in appearance, the softening start temperature was 83 ° C., and the acidic water-soluble component contained in the modified polyolefin (A-4) was 2.0 mgKOH / g. . Table 1 shows the physical properties of the modified polyolefin (A-4).

Production Example of Modified Polyolefin (A-5) In a 3000 ml Separa flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas introduction tube, 1000 g of LICOCENE PP 2602 (manufactured by Clariant) as polyolefin, 20 g of butyl propionate, sorbitol 0 After adding 0.5 g and adjusting the temperature to 170 ° C. while stirring in a nitrogen atmosphere, and after the polyolefin has melted and becomes uniform, 12 g of n-butyl methacrylate and 12 g of maleic anhydride are added. 2 g of di-t-butyl peroxide (manufactured by NOF Corporation: Perbutyl D) was dissolved in 6 g of butyl propionate and added. The reaction was continued for 30 minutes while maintaining the system at 170 ° C., 12 g of n-butyl methacrylate and 12 g of maleic anhydride were added, and 2 g of di-t-butyl peroxide was dissolved in 6 g of butyl propionate. Added. Similarly, n-butyl methacrylate, maleic anhydride and di-t-butyl peroxide are added five times every 30 minutes, and the total amount of n-butyl methacrylate added is 60 g. The total amount was 60 g, and the total amount of di-t-butyl peroxide added was 10 g.
After completion of the addition, the reaction was carried out at 170 ° C. for 1.5 hours, and then, while reducing the pressure in the flask with an aspirator, butyl propionate, unreacted n-butyl methacrylate, maleic anhydride and di-t-butyl peroxide were added. Removal of the decomposed low molecular weight compound was performed for 1 hour. The reaction product was taken out and cooled to obtain a modified polyolefin (A-5).
The resulting modified polyolefin (A-5) had a pale yellow appearance, a softening start temperature of 98 ° C., and the acidic water-soluble component contained in the modified polyolefin (A-5) was 4.6 mgKOH / g. . Table 1 shows the physical properties of the modified polyolefin (A-5).

Production Example of Modified Polyolefin (A-6) In a 3000 ml Separa flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas introduction tube, 1000 g of LICOCENE PP 1602 (manufactured by Clariant) as a polyolefin, 1 g of Irganox 1010 as an antioxidant, and 1 g of Irgafos 168 was added and the temperature was adjusted to 170 ° C. while stirring in a nitrogen atmosphere. After the polyolefin melted and became homogeneous, 60 g of n-butyl methacrylate, 60 g of lauryl acrylate, i-maleic acid A monomer solution in which 100 g of butanol half ester, 1 g of styrene, and 10 g of di-t-butyl peroxide were mixed was dropped over 2 hours.
After completion of the dropwise addition, the reaction was carried out under reflux for 2 hours. The reaction product was taken out and cooled to obtain a modified polyolefin (A-6).
The obtained modified polyolefin (A-6) had a milky white appearance, a softening start temperature of 86 ° C., and the acidic water-soluble component contained in the modified polyolefin (A-6) was 1.2 mgKOH / g. Table 1 shows the physical properties of the modified polyolefin (A-6).

Production Example of Modified Polyolefin (A-7) 1000 g of LICOCENE PP 1602 (manufactured by Clariant) as polyolefin, 50 g of butyl acetate, antioxidant in a 3000 ml Separa flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas introduction tube 1 g of Irganox 1010 and 1 g of Irgafos 168 were added, and the temperature was adjusted so that the system became 150 ° C. while stirring in a nitrogen atmosphere, and after the polyolefin was melted and homogenized, 60 g of 2-ethylhexyl acrylate, A solution prepared by dissolving 30 g of methacrylic acid and 5 g of t-butylperoxy 2-ethylhexyl monocarbonate (manufactured by NOF Corporation: Perbutyl E) in 150 g of butyl acetate was added dropwise over 2 hours.
After completion of the dropwise addition, the reaction was carried out under reflux for 3 hours, and then butyl acetate, unreacted 2-ethylhexyl acrylate, methacrylic acid, t-butylperoxy 2-ethylhexyl monocarbonate and t -Butylperoxy The low molecular weight compound in which 2-ethylhexyl monocarbonate was decomposed was removed for 1 hour. After completion of the decompression, the reaction product was taken out and cooled to obtain a modified polyolefin (A-7).
The obtained modified polyolefin (A-7) had a milky white appearance, a softening start temperature of 83 ° C., and the acidic water-soluble component contained in the modified polyolefin (A-7) was 0.5 mgKOH / g. Table 1 shows the physical properties of the modified polyolefin (A-7).

Production Example of Modified Polyolefin (A-8) In a 3000 ml Separa flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas introduction tube, 1000 g of LICOCENE PP 2602 (manufactured by Clariant) as polyolefin, 50 g of propylene glycol methyl ether acetate, Add 1 g of Irganox 1010 and 1 g of Irgafos 168 as antioxidants, adjust the temperature so that the temperature inside the system becomes 170 ° C. while stirring in a nitrogen atmosphere, melt the polyolefin and make 2-ethylhexyl homogeneous A solution prepared by dissolving 120 g of acrylate, 60 g of maleic anhydride and 10 g of di-t-butyl peroxide in 150 g of propylene glycol methyl ether acetate was added dropwise over 2 hours.
After completion of the dropwise addition, the reaction was performed under reflux for 2 hours, and then the pressure in the flask was reduced with an aspirator while propylene glycol methyl ether acetate, unreacted 2-ethylhexyl acrylate, maleic anhydride, di-t-butyl peroxide and The removal of the low molecular weight compound in which di-t-butyl peroxide was decomposed was performed for 1 hour. The reaction product was taken out and cooled to obtain a modified polyolefin (A-8). The resulting modified polyolefin (A-8) was pale yellow in appearance, the softening start temperature was 93 ° C., and the acidic water-soluble component contained in the modified polyolefin (A-8) was 4.5 mgKOH / g. . Table 1 shows the physical properties of the modified polyolefin (A-8).

Polyolefin (a-1)
VESTOPLAST 792 (manufactured by Degussa Japan Co., Ltd.) was used as it was as the polyolefin (a-1). The polyolefin (a-1) was unmodified, had a white appearance, a softening start temperature of 92 ° C., and the acidic water-soluble component contained in the polyolefin (a-1) was 0 mgKOH / g. Table 1 shows the physical properties of the polyolefin (a-1).

Polyolefin (a-2)
As the polyolefin (a-2), TP LICOCENE PP 2602 (manufactured by Clariant Japan Co., Ltd.) was used as it was. Polyolefin (a-2) was unmodified, had a white appearance, a softening start temperature of 95 ° C., and the acidic water-soluble component in the resin was 0 mgKOH / g. Table 1 shows the physical properties of the polyolefin (a-2).

Dispersants (B-1) to (B-5)
Dispersant (B-1) (Gosenol GH-20 (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.)), dispersant (B-2) (Kuraray Poval PVA-210 (manufactured by Kuraray Co., Ltd.)), polyacrylic as polyvinyl alcohols Dispersant (B-3) (40% polyacrylic acid aqueous solution, Aron A-10SL (Toagosei Co., Ltd.) as an acid polymer, 197.5 g of ion-exchanged water was added to 2.5 g, and 200 g of an aqueous solution of the dispersant ( Solid content 1 g)), dispersants (B-4) as celluloses (methylcellulose MEROLOSE SM (Shin-Etsu Chemical Co., Ltd.) with 20%, 2% aqueous solution viscosity of 100 mPa · s), dispersants as starches ( B-5) (cationized starch EXCEL DH (Nissho Kagaku Co., Ltd.)) was used.

Dispersant (B-6)
In a 1000 ml four-necked flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet tube, 335.7 parts of 50% aqueous acrylamide solution, 16.2 parts N, N-dimethylaminopropylacrylamide, 80% aqueous methacrylic acid solution 11.2 parts, 4.1 parts of sodium methallyl sulfonate, 2.6 parts of normal dodecyl mercaptan, 215.6 parts of ion-exchanged water and 199.8 parts of isopropyl alcohol were added, and the pH was adjusted to 4.5 with 20% sulfuric acid. Adjusted. The mixture was heated to 60 ° C. in a nitrogen gas atmosphere while stirring. As a polymerization initiator, 14.8 parts of a 2% aqueous solution of ammonium persulfate was added, and the temperature was raised to 80 ° C. and held for 3 hours. Next, isopropyl alcohol was distilled off, ion-exchanged water was added, and the mixture was cooled to room temperature to obtain a polyacrylamide polymer aqueous solution having a solid content concentration of 20%, a viscosity of 190 mPa · s, and a pH of 4.2. 200 g (solid content 1 g) of an aqueous solution obtained by adding 195 g of ion-exchanged water to 5 g of the obtained polymer aqueous solution was used as a dispersant (B-6).

(Example 1) Production example of modified polyolefin particles (C-1) To a 1000 ml Separa flask equipped with a stirrer with a paddle blade, a thermometer and a reflux condenser, 200 g of ion-exchanged water was added and heated to 90 ° C. . Next, 100 g of polyolefin (A-1) is melted, polyolefin (A-1) melted in 90 ° C. ion-exchanged water is added, and the resin particles are not neutralized by stirring while maintaining at 90 ° C. (0.0 equivalent weight), suspended, cooled, and after the water temperature reaches 30 ° C., the suspension is filtered through a 300 mesh nylon mesh to separate the modified polyolefin particles and the filtrate. did. The modified polyolefin particles were washed twice with ion-exchanged water, then dehydrated with a centrifugal dehydrator, and dried with hot air at 40 ° C. to obtain 98 g of milky white modified polyolefin particles (C-1).
The average particle diameter of the modified polyolefin particles (C-1) is 2.3 mm, the acidic water-soluble component in the modified polyolefin particles (C-1) is 2.8 mgKOH / g, and the acidic water-soluble component The rate of decrease was 20%. Table 1 shows the yield, average particle diameter, reduction rate of acidic water-soluble components and appearance of the modified polyolefin particles obtained.

(Example 2) Production Example of Modified Polyolefin Particles (C-2) Into a 1000 ml Separa flask equipped with a stirrer with an anchor blade, a thermometer and a reflux condenser, 100 g of polyolefin (A-1) was put and melted. The temperature was adjusted to 90 ° C. while stirring. Next, the aqueous solution which melt | dissolved 5 g of dispersing agents (B-1) in 195 g of ion-exchange water was heated to 90 degreeC. Add the heated dispersant (B-1) aqueous solution to the molten resin under stirring, and perform the resin particle formation in an unneutralized (0.0 equivalent) state by stirring while maintaining at 90 ° C. After making it into a suspended state, it was cooled, and after the water temperature reached 30 ° C., the suspension was filtered through a 300 mesh nylon mesh to separate it into modified polyolefin particles and filtrate. The modified polyolefin particles were washed twice with ion-exchanged water, then dehydrated with a centrifugal dehydrator, and dried with hot air at 40 ° C. to obtain 97 g of white modified polyolefin particles (C-2).
The average particle diameter of the modified polyolefin particles (C-2) is 0.6 mm, the acidic water-soluble component in the modified polyolefin particles (C-2) is 1.3 mgKOH / g, and the acidic water-soluble component The decrease rate was 63%. Table 1 shows the yield, average particle diameter, reduction rate of acidic water-soluble components and appearance of the modified polyolefin particles obtained.

(Example 3) Production Example of Modified Polyolefin Particles (C-3) In a 1000 ml Separa flask equipped with a stirrer, thermometer and reflux condenser with three retreating blades, 20 g of dispersant (B-1) and ion-exchanged water 280g was added and it heated, stirring, and produced 100 degreeC dispersing agent aqueous solution. Next, 100 g of the polyolefin (A-2) is melted, and the melted polyolefin (A-2) is added to the 100 ° C. aqueous dispersant solution, and the resin is granulated by stirring while maintaining the temperature at 100 ° C. After the suspension is cooled to a water temperature of 30 ° C., the suspension is filtered through a 300-mesh nylon mesh to obtain modified polyolefin particles and a filtrate. separated. The modified polyolefin particles were washed twice with ion-exchanged water, then dehydrated with a centrifugal dehydrator, and dried with hot air at 40 ° C. to obtain 95 g of pale yellow modified polyolefin particles (C-3).
The average particle size of the modified polyolefin particles (C-3) is 3.1 mm, the acidic water-soluble component in the modified polyolefin particles (C-3) is 11.0 mgKOH / g, and the acidic water-soluble component The rate of decrease was 43%. Table 1 shows the yield, average particle diameter, reduction rate of acidic water-soluble components and appearance of the modified polyolefin particles obtained.

(Example 4) Production example of modified polyolefin particles (C-4) In a 1000 ml Separa flask equipped with a stirrer, thermometer and reflux condenser with a Max blend blade, 1 g of dispersant (B-1) and 199 g of ion-exchanged water were used. And heated with stirring to prepare a 90 ° C. aqueous dispersant solution. Next, 100 g of polyolefin (A-3) is melted, and the melted polyolefin (A-3) is added to a 90 ° C. aqueous dispersant solution, and the resin is not dispersed by stirring while maintaining 90 ° C. After the suspension is cooled to a water temperature of 30 ° C., the suspension is filtered through a 300-mesh nylon mesh to obtain modified polyolefin particles and a filtrate. separated. The modified polyolefin particles were washed twice with ion-exchanged water, then dehydrated with a centrifugal dehydrator, and dried with hot air at 40 ° C. to obtain 98 g of pale yellow modified polyolefin particles (C-4).
The average particle diameter of the modified polyolefin particles (C-4) is 1.2 mm, the acidic water-soluble component in the modified polyolefin particles (C-4) is 2.2 mgKOH / g, and the acidic water-soluble component The rate of decrease was 48%. Table 1 shows the yield, average particle diameter, reduction rate of acidic water-soluble components and appearance of the modified polyolefin particles obtained.

Example 5 Production Example of Modified Polyolefin Particles (C-5) The modified polyolefin used was the modified polyolefin (A-4), 1 g of the dispersant (B-1) was 197.25 g of ion-exchanged water, 90% 2- Except having used the aqueous solution melt | dissolved in 1.75 g (equivalent neutralization degree 0.3 equivalent) of methylaminopropanol, it carried out similarly to Example 4 and obtained the modified polyolefin particle (C-5) 85g. The modified polyolefin particles (C-5) are white particles having an average particle diameter of 0.2 mm, the acidic water-soluble component in the modified polyolefin particles (C-5) is 0.3 mg KOH / g, and acidic water The decrease rate of the soluble component was 85%. Table 1 shows the yield, average particle diameter, reduction rate of acidic water-soluble components and appearance of the modified polyolefin particles obtained.

(Example 6) Production of modified polyolefin particles (C-6).
Except that the modified polyolefin used was modified polyolefin (A-4), it was carried out in an unneutralized (0.0 equivalent) state in the same manner as in Example 4 to obtain 98 g of modified polyolefin particles (C-6). The modified polyolefin particles (C-6) are white particles having an average particle diameter of 0.7 mm, and the acidic water-soluble component in the modified polyolefin particles (C-6) is 0.8 mgKOH / g, The decrease rate of the soluble component was 60%. Table 1 shows the yield, average particle diameter, reduction rate of acidic water-soluble components and appearance of the modified polyolefin particles obtained.

(Example 7) Production example of modified polyolefin particles (C-7) In a 1000 ml autoclave equipped with a stirrer and a thermometer, 100 g of polyolefin (A-5) was added and melted to melt the polyolefin (A-5). Thereafter, the temperature of the autoclave was adjusted to 120 ° C. while stirring. After the stirring is stopped, an aqueous solution in which 5 g of the dispersant (B-1) heated to 90 ° C. is dissolved in 195 g of ion-exchanged water is added, and the autoclave temperature is adjusted so that the water temperature in the system becomes 120 ° C. under pressure. did. At 120 ° C., the resin is granulated in an unneutralized (0.0 equivalent) state by stirring, and after being suspended, cooled, and after the water temperature reaches 30 ° C., the pressure is returned to normal pressure. The suspension was filtered through a 300-mesh nylon mesh and separated into modified polyolefin particles and a filtrate. The modified polyolefin particles were washed twice with ion-exchanged water, then dehydrated with a centrifugal dehydrator and dried with hot air at 40 ° C. to obtain 98 g of milky white modified polyolefin particles (C-7).
The average particle diameter of the modified polyolefin particles (C-7) is 1.6 mm, and the acidic water-soluble component in the modified polyolefin particles (C-7) is 2.3 mgKOH / g. The reduction rate was 50%. Table 1 shows the yield, average particle diameter, reduction rate of acidic water-soluble components and appearance of the modified polyolefin particles obtained.

(Example 8) Production Example of Modified Polyolefin Particles (C-8) Unneutralized (0) as in Example 6 except that the modified polyolefin used was modified polyolefin (A-5) and granulated at 95 ° C. 0.0 equivalents) to obtain 90 g of modified polyolefin particles (C-8). The modified polyolefin particles (C-8) are light yellow particles having an average particle diameter of 4.1 mm, and the acidic water-soluble component in the modified polyolefin particles (C-8) is 3.7 mgKOH / g, The reduction rate of the water-soluble component was 20%. Table 1 shows the yield, average particle diameter, reduction rate of acidic water-soluble components and appearance of the modified polyolefin particles obtained.

(Example 9) Production example of modified polyolefin particles (C-9) Unneutralized (0) except that 25 g of the used dispersant (B-1) was used and 275 g of ion-exchanged water was used. 0.0 equivalent) to obtain 77 g of modified polyolefin particles (C-9). The modified polyolefin particles (C-9) are white particles having an average particle diameter of 0.1 mm, the acidic water-soluble component in the modified polyolefin particles (C-9) is 1.0 mgKOH / g, and acidic water The rate of decrease in soluble components was 78%. Table 1 shows the yield, average particle diameter, reduction rate of acidic water-soluble components and appearance of the modified polyolefin particles obtained.

(Example 10) Production example of modified polyolefin particles (C-10) The modified polyolefin used was (A-6), and an aqueous solution in which 0.01 g of the dispersant (B-1) was dissolved in 199.99 g of ion-exchanged water was used. Then, in the same manner as in Example 6 except that the particles were formed at 95 ° C., the reaction was performed in an unneutralized (0.0 equivalent) state to obtain 97 g of modified polyolefin particles (C-10). The modified polyolefin particles (C-10) are milky white particles having an average particle diameter of 3.1 mm, and the acidic water-soluble component in the modified polyolefin particles (C-10) is 0.8 mgKOH / g, The rate of decrease in soluble components was 33%. Table 1 shows the yield, average particle diameter, reduction rate of acidic water-soluble components and appearance of the modified polyolefin particles obtained.

Example 11 Production Example of Modified Polyolefin Particles (C-11) In a 1000 ml Separa flask equipped with a stirrer, thermometer and reflux condenser with three retreating blades, 0.005 g of a dispersant (B-1), ions 199.995 g of exchange water was added and heated with stirring to prepare a 90 ° C. aqueous dispersant solution. Next, 100 g of the polyolefin (A-7) is melted, and the melted polyolefin (A-7) is added to the 90 ° C. aqueous dispersant, and the resin is not dispersed by stirring while maintaining the temperature at 90 ° C. After the suspension is cooled to a water temperature of 30 ° C., the suspension is filtered through a 300-mesh nylon mesh to obtain modified polyolefin particles and a filtrate. separated. The modified polyolefin particles were washed twice with ion-exchanged water, then dehydrated with a centrifugal dehydrator, and dried with hot air at 40 ° C. to obtain 96 g of milky white modified polyolefin particles (C-11).
The average particle diameter of the modified polyolefin particles (C-11) is 4.2 mm, the acidic water-soluble component in the modified polyolefin particles (C-11) is 0.4 mgKOH / g, and the acidic water-soluble component The rate of decrease was 20%. Table 1 shows the yield, average particle diameter, reduction rate of acidic water-soluble components and appearance of the modified polyolefin particles obtained.

(Example 12) Production example of modified polyolefin particles (C-12) An aqueous solution in which the modified polyolefin used was modified polyolefin (A-8), and 0.2 g of the dispersant (B-1) was dissolved in 199.8 g of ion-exchanged water. In the same manner as in Example 6 except that particles were formed at 95 ° C. in an unneutralized (0.0 equivalent) state, 99 g of modified polyolefin particles (C-12) were obtained. The modified polyolefin particles (C-12) are white particles having an average particle diameter of 0.8 mm, the acidic water-soluble component in the modified polyolefin particles (C-12) is 2.1 mgKOH / g, and acidic water The reduction rate of soluble components was 53%. Table 1 shows the yield, average particle diameter, reduction rate of acidic water-soluble components and appearance of the modified polyolefin particles obtained.

(Examples 13 to 17) Production Examples of Modified Polyolefin Particles (C-13) to (C-17) The modified polyolefin used was the modified polyolefin (A-8), and the type of dispersant was the dispersant (B-2) to (B-6) was changed to the type shown in Table 1 and was carried out in an unneutralized (0.0 equivalent) state in the same manner as in Example 6 except that the particles were formed at 95 ° C. In addition, the usage-amount of the dispersing agent (B) in Table 1 is shown by solid content. Table 1 shows the yield of the modified polyolefin particles (C-13) to (C-17) obtained, the average particle diameter, the decrease rate of the acidic water-soluble component, and the appearance.

(Example 18) Production example of modified polyolefin particles (C-18) In a 1000 ml Separa flask equipped with a stirrer, thermometer and reflux condenser with three retreating blades, 0.1 g of dispersant (B-1), ions 189.9 g of exchange water and 10 g of ethanol were added, and the mixture was heated with stirring to prepare a 95 ° C. aqueous dispersant solution. Next, 100 g of polyolefin (A-8) is melted, and the melted polyolefin (A-8) is added to a 95 ° C. aqueous dispersing agent solution. After the suspension is cooled to a water temperature of 30 ° C., the suspension is filtered through a 300-mesh nylon mesh to obtain modified polyolefin particles and a filtrate. separated. The modified polyolefin particles were washed twice with ion-exchanged water, then dehydrated with a centrifugal dehydrator, and dried with hot air at 40 ° C. to obtain 99 g of white modified polyolefin particles (C-18).
The average particle diameter of the modified polyolefin particles (C-18) is 0.9 mm, the acidic water-soluble component in the modified polyolefin particles (C-18) is 2.0 mgKOH / g, and the acidic water-soluble component The decrease rate was 56%. Table 1 shows the yield, average particle diameter, reduction rate of acidic water-soluble components and appearance of the modified polyolefin particles obtained.

(Comparative Examples 1 and 2) Production of polyolefin particles (D-1), production example of (D-2) The modified polyolefin used was an unmodified polyolefin (a-1) or (a-2) at 95 ° C. Except for the formation of particles, it was performed in an unneutralized (0.0 equivalent) state in the same manner as in Example 6, but in both cases of polyolefins (a-1) and (a-2), a molten polyolefin As a result, the polyolefin was not suspended in the particles.

(Comparative Example 3) Production Example of Modified Polyolefin Particles (D-3) In a 1000 ml Separa flask equipped with a stirrer, thermometer and reflux condenser with three retreating blades, 5 g of dispersant (B-1) and ion-exchanged water 191.5 g, 90% 2-methylaminopropanol 3.5 g (corresponding to a neutralization degree of 1.1 equivalent) was added, and the mixture was heated in an oil bath with stirring to prepare a 90 ° C. aqueous dispersant solution. Next, 100 g of polyolefin (A-1) was melted, and the polyolefin (A-1) melted in a 90 ° C. aqueous dispersant was added, and the resin was granulated by stirring while maintaining at 90 ° C., After making it into a suspended state, it was cooled, and after the water temperature reached 30 ° C., the suspension was filtered through a 300 mesh nylon mesh to separate it into modified polyolefin particles and filtrate. The modified polyolefin particles were washed twice with ion-exchanged water, then dehydrated with a centrifugal dehydrator, and dried with hot air at 40 ° C. to obtain 11 g of milky white modified polyolefin particles (D-3).
The average particle diameter of the modified polyolefin particles (D-3) is 0.04 mm, the acidic water-soluble component in the modified polyolefin particles (D-3) is 0.7 mgKOH / g, and the acidic water-soluble component The reduction rate of was 80%. Table 1 shows the yield, average particle diameter, reduction rate of acidic water-soluble components and appearance of the modified polyolefin particles obtained.

(Comparative Example 4) Production Example of Modified Polyolefin Particles (D-4) In a 1000 ml Separa flask equipped with a stirrer, thermometer and reflux condenser with three retreating blades, 25 g of dispersant (B-1) and ion-exchanged water 275 g was added and heated in an oil bath with stirring to prepare a 90 ° C. aqueous dispersant solution. Next, 100 g of polyolefin (A-1) is melted, and the melted polyolefin (A-1) is added to a 90 ° C. aqueous dispersing agent solution. After the suspension is cooled to a water temperature of 30 ° C., the suspension is filtered through a 300-mesh nylon mesh to obtain modified polyolefin particles and a filtrate. separated. The modified polyolefin particles were washed twice with ion-exchanged water, then dehydrated with a centrifugal dehydrator, and dried with hot air at 40 ° C. to obtain 36 g of white modified polyolefin particles (D-4).
The average particle diameter of the modified polyolefin particles (D-4) is 0.06 mm, the acidic water-soluble component in the modified polyolefin particles (C-3) is 1.0 mgKOH / g, and the acidic water-soluble component The rate of decrease was 71%. Table 1 shows the yield, average particle diameter, reduction rate of acidic water-soluble components and appearance of the modified polyolefin particles obtained.

(Comparative Example 5) Production Example of Modified Polyolefin Particles (D-5) In a 1000 ml Separa flask equipped with a stirrer, thermometer and reflux condenser with three retreating blades, 0.001 g of dispersant (B-1), ion 199.999 g of exchange water was added, and heating in an oil bath was performed while stirring to prepare a 95 ° C. aqueous dispersant solution. Next, 100 g of polyolefin (A-4) was melted, and the melted polyolefin (A-4) was added to a 95 ° C. aqueous dispersant solution, and the mixture was kept at 95 ° C. while not neutralized (0.0 equivalents). And stirred. A part of the melted modified polyolefin was wound around the stirring shaft, but a part was oval particles. After particle formation, cooling was performed, and after the water temperature reached 30 ° C., the suspension was filtered through a 300-mesh nylon mesh to separate into modified polyolefin particles and filtrate. The modified polyolefin particles were washed twice with ion-exchanged water, then dehydrated with a centrifugal dehydrator, and dried with hot air at 40 ° C. to obtain 72 g of yellow, oval modified polyolefin particles (D-5).
The modified polyolefin particle (D-5) is an oval particle having an average major axis of 30 mm, an average minor axis of 17 mm, and a thickness of about 5 mm. The acidic water-soluble component in the modified polyolefin particle (D-5) is 4 The reduction rate of acidic water-soluble components was 4%. Table 1 shows the yield, average particle diameter, reduction rate of acidic water-soluble components and appearance of the modified polyolefin particles obtained.

(Comparative Example 6) Production Example of Modified Polyolefin Particles (D-6) Unneutralized (0.0 equivalent) modified polyolefin (A-3) was granulated with a rotfoam granulator and modified polyolefin particles (D-6) ). Yellow particles having an average particle diameter of 5.0 mm, the acidic water-soluble component in the modified polyolefin particle (D-6) is 4.2 mgKOH / g, and the reduction rate of the acidic water-soluble component is 0%. Met. Table 2 shows the color, average particle diameter, and reduction rate of acidic water-soluble components of the modified polyolefin particles obtained.

(Comparative Example 7) Production Example of Modified Polyolefin Particles (D-7) Modified polyolefin particles (A-5) were made into particles by using an underwater hot cut granulator in an unneutralized (0.0 equivalent) state, and modified polyolefin particles ( D-7). The modified polyolefin particles (D-7) are light yellow particles having an average particle diameter of 3.1 mm, and the acidic water-soluble component in the modified polyolefin particles (D-7) is 4.6 mgKOH / g. The reduction rate of the water-soluble component was 0%. Table 2 shows the color, average particle diameter, and reduction rate of acidic water-soluble components of the modified polyolefin particles obtained.

Explanation of annotations in the table:
(* 1) Neutralization of 0.3 equivalent of carboxyl group derived from carboxylic acid and acid anhydride in modified polyolefin with 2-methylaminopropanol.
(* 2) Neutralization of 1.2 equivalents of carboxyl group derived from carboxylic acid and acid anhydride in modified polyolefin with 2-methylaminopropanol.
(* 3) Not dispersed: A state in which the polyolefin is fused to the stirring shaft and does not become particles.
(* 4) Oval shape: Oval particles having an average major axis of 30 mm, an average minor axis of 17 mm, and a thickness of 5 mm.

  As shown in Table 1, the modified polyolefin (A) could be formed into particles by stirring in water or an aqueous solution of the dispersant (B). In Comparative Example 1 and Comparative Example 2 in which the unmodified polyolefin (a) was used, there was no acid group on the polyolefin surface, and thus the resin could not be stably dispersed as particles. In the case of Comparative Example 3 in which the carboxyl group in the modified polyolefin was neutralized with 1 equivalent or more of an amine, the number of fine particles that could not be separated by a 300 mesh nylon mesh was extremely large, and the yield was greatly reduced to 11%. The average particle diameter of the collected particles was also as extremely small as 0.04 mm. As in Comparative Example 3, there are many fine particles that cannot be separated by a 300-mesh nylon mesh, as in Comparative Example 3, in which an excessive dispersant (B) was used and modified polyolefin particles having a particle diameter of 0.1 mm or less. Yield decreased. In Comparative Example 5 in which the particle diameter is 5 mm or more, the modified polyolefin particles have a large particle diameter, so it is difficult to reduce water-soluble acidic substances that are impurities in the modified polyolefin, and the melt has a large particle diameter. Since it floated in a lump shape, a part of it was wound around the stirring shaft and fused, and the yield of the modified polyolefin particles was lowered. Further, in the case of Comparative Example 6 and Comparative Example 7 which are made into particles by a funnel foam granulator or an underwater hot cut pelletizer, the water-soluble acidic substance which is an impurity in the modified polyolefin is not particularly reduced, and the resin coloring is also particularly improved. There wasn't. On the other hand, in the examples, in all cases, the resin is less colored, and the modified polyolefin particles in which the water-soluble acidic substance that is an impurity in the modified polyolefin is also reduced can be recovered with good yield. became.

  According to the method for producing modified polyolefin resin particles of the present invention, a purified modified polyolefin in which water-soluble acidic substances that are impurities in the modified polyolefin are reduced and the coloring of the resin is improved can be obtained. In addition, the modified polyolefin particles obtained by the production method of the present invention are improved in coloration by purification, and are useful for polyolefin resins and composite materials in which coloring of resins such as films, sheets, and packaging materials is a problem. It can be considered to be a modified polyolefin. In addition, the modified polyolefin particles obtained by the production method of the present invention have reduced water-soluble acidic substances as impurities, and can be used as, for example, heat sealants, adhesives, and adhesive modifiers. It can be considered that the adhesion is improved in the adhesion between the polyolefin-based resin or composite material and another resin or metal. 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. 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 (5)

  The melted carboxyl group-modified polyolefin (A) having a neutralization degree of 0.3 equivalent or less and at least water are mixed to form a suspension of the modified polyolefin, and then the water is removed to obtain an average particle size of 0.1. A method for producing modified polyolefin particles, characterized by obtaining a modified polyolefin of -5 mm.   The modified polyolefin (A), at least water and a dispersant (B) are mixed, and the modified polyolefin (A): dispersant (B) = 100: 0.01-20 is used in a solid content ratio. Item 2. A method for producing modified polyolefin particles according to Item 1.   The method for producing modified polyolefin particles according to claim 1 or 2, wherein the mixing is performed at a temperature at or above the softening start temperature in the flow tester of the modified polyolefin (A).   The modified polyolefin particles according to any one of claims 1 to 3, wherein the modified polyolefin (A) is a resin obtained by modifying a polyolefin (a) with at least an unsaturated carboxylic acid (b). Production method.   The method for producing modified polyolefin particles according to any one of claims 1 to 4, wherein the dispersant (B) is a polyvinyl alcohol.