Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J3/00—Processes of treating or compounding macromolecular substances

Definitions

• the present invention relates to a method for producing a (meth)acrylic polymer coagulated product excellent in warm water whitening resistance from a polymer latex obtained by emulsion polymerization, and more specifically, used for building materials and the like.
• the present invention relates to an optimal method for producing a (meth)acrylic polymer solidified product.
• the present invention also relates to a molded product of the (meth)acrylic polymer solidified product obtained by the above-mentioned production method.
• Acrylic-based multi-layered polymer particles have been conventionally called a core-shell (0 ⁇ "6-3 61 1) type polymer, which has a layer made of a cross-linked elastic body inside and a thermal layer in the outermost layer. It is a structure having a layer composed of a plastic resin component, and is used for modifying thermoplastic resins such as acrylic resin, and is known to be particularly useful as a modifier for imparting impact resistance.
• the addition of the multi-layer structure polymer particles improves the impact resistance, it causes a decrease in heat resistance, a decrease in surface hardness, a whitening in bending, a whitening in hot water, and further improvement is desired.
• Patent Document 1 As an attempt to improve hot water whitening resistance, a method of setting the content of the water-soluble substance to 200 111 or less (Patent Document 1) and the residual amount of cations derived from the coagulant are 180 g The following method (Patent Document 2) is being studied. However, these do not have the expected effect on hot water of 100 °.
• Patent Document 4 A method of atomizing or dropping an emulsion-polymerized latex containing a thickening agent composed of a nonionic water-soluble polymer in a gas phase contained in the form of a particle (Patent Document 4) is being studied.
• Patent Document 1 Japanese Patent Laid-Open No. 20 0 3— 2 7 7 5 2 8
• Patent Document 2 Patent No. 4 0 8 0 0 7 6
• Patent Document 3 Japanese Patent Laid-Open No. 20 17-6 1 6 4 6
• Patent Document 4 Japanese Patent Laid-Open No. 20 17-6 1 6 4 5
• An object of the present invention is to improve the effect of whitening of emulsion-polymerized resins by warm water.
• Step 1 A latex containing (meth)acrylic multilayer structure particles (8) obtained by emulsion polymerization in coagulation tank (1)) and an aqueous coagulant solution are continuously supplied and mixed to form a (meth)acrylic multilayer.
• Step 2 Granulation step in which the salting-out slurry obtained in step 1 and the washing water are supplied to the flocculation tank (2) and hard flocculation is performed at an internal liquid temperature higher than that of the flocculation tank (1) (where, The washing water is supplied so that the solid content concentration in the flocculation tank (2) is less than 2/3 of the solid content concentration in the flocculation tank (1));
• Step 3 The (meth)acrylic multilayer structure particle (8) aggregate obtained in Step 2 is treated with water. 20/175516 3 ⁇ (: 170? 2020 /007611
• a method for producing a (meth)acrylic polymer solidified product comprising:
• (Meth)acrylic multi-layered structure particles (8) are the innermost layer ⁇ , intermediate layer!
• the (meth)acrylic multilayer structure particles (8) are the innermost layer composed of a hard polymer ⁇ having methacrylic acid ester units of 50 to 100% by mass, acrylic acid ester units 40 to 999.
• the internal liquid temperature of the coagulation tank (2) is less than the glass transition temperature of the outermost layer ⁇ of the (meth)acrylic multilayer structure particle (8) + 1 ° ° ⁇ [3] or [4] ]
• the coagulant is at least one selected from the group consisting of magnesium sulfate, calcium chloride, aluminum sulfate and calcium acetate.
• the solid content concentration in the salting-out slurry obtained in step 1 is relatively high and the temperature of the flocculation tank (1) is lower than the temperature of the flocculation tank (2).
• (Meth) acrylic multi-layered structure particles (8) are softly agglomerated by a weak cohesive force, and impurities (for example, emulsifier, polymerization initiator residue, coagulant, etc.) other than the above-mentioned particles are dispersed into the soft aggregate. Uptake is suppressed.
• step 2 the salting-out slurry is diluted with washing water to reduce the solid content concentration, and the internal liquid temperature of the aggregating tank (2) is raised above that of the aggregating tank (1).
• step 2 the particles are aggregated more strongly (hard aggregation).
• the impurity concentration is lowered, the amount of impurities taken into the hard agglomerate (granulated material) is suppressed, and as a result, whitening of hot water is suppressed.
• the internal liquid of the coagulation tank (1) contains latex), a coagulant and water, and the mixture is mixed in the coagulation tank (1) to obtain a (meth)acrylic multilayer structure.
• Soft agglomerates of particles (eight) are deposited to form salting-out slurry.
• This salting-out slurry is sent to the aggregating tank (2), and the soft agglomerates are fused together to obtain hard agglomerates (granulated or solidified).
• the aggregating tank (1) and the aggregating tank (2) are connected in series, and aggregates of the acrylic multi-layered structure particles (8) are collected from the aggregating tank (1) to the aggregating tank (2).
• a salting-out slurry containing is supplied.
• the aggregating tank (1) and the aggregating tank (2) are each provided with a mixing device so that the internal liquid can be stirred.
• the mixing device is, for example, ⁇ 2020/175516 5 (: 170? 2020 /007611
• Examples thereof include a stirring blade and a stirring blade.
• the precipitation of aggregates of (meth)acrylic multilayer structure particles (8) is likely due to the high coagulant concentration and high solids concentration.
• the present inventor believes that a large number of small aggregates having a small particle size are generated in the salting-out slurry and that the small particles are loosely bound to form particles having a small bulk specific gravity and a large size. It is desirable that the internal liquid temperature of the coagulation tank (1) is lower than the outermost layer 9 (glass transition temperature) of the particles (8) above. The particles (8) softly aggregate.
• the internal liquid temperature is higher than that in the coagulation tank (1), especially higher than the outermost layer 9 of the particles (8), and the coagulant and emulsification are made by the washing water.
• impurities such as agents and polymerization initiator residues
• the method for producing a (meth)acrylic polymer solidified product of the present invention includes the following steps 1 to 3.
• Step 1 A latex containing (meth)acrylic multilayer structure particles (8) obtained by emulsion polymerization in coagulation tank (1)) and an aqueous coagulant solution are continuously supplied and mixed to form a (meth)acrylic multilayer.
• Step 2 Granulation step in which the salting-out slurry obtained in step 1 and the washing water are supplied to the flocculation tank (2) and hard flocculation is performed at an internal liquid temperature higher than that of the flocculation tank (1) (where, The washing water is supplied so that the solid content concentration in the flocculation tank (2) is less than 2/3 of the solid content concentration in the flocculation tank (1));
• Step 3 A step of washing, dehydrating and drying the aggregate of the (meth)acrylic multilayer structure particles (8) obtained in Step 2.
• step 1 a salting-out slurry containing a soft aggregate of the (meth)acrylic multilayer structure particles (8) is obtained.
• the coagulant destroys the electric double layer generated on the surface of the latex particles by the emulsifier and creates an aggregate.
• a large number of agglomerates with a high concentration of coagulation liquid in the agglomeration tank (1) and a small particle size are generated, and at the same time, multiple agglomerates are formed due to the low internal liquid temperature. ⁇ 2020/175 516 6 boxes (: 170? 2020 /007611
• step 2 the salting-out slurry is diluted with washing water to reduce the concentration of components other than particles (8) such as emulsifiers, polymerization initiator residues, and coagulants.
• the production method of the present invention uses a combination of soft coagulation due to a low internal liquid temperature and a high coagulant concentration in step 1, and hard coagulation due to a high internal liquid temperature and a low impurity concentration in step 2 to solidify a (meth)acrylic polymer. It is possible to effectively suppress the incorporation of impurities into the object. Since this impurity causes hot water whitening, as a result, the present invention can significantly improve the hot water whitening resistance of the coagulum.
• the washing water and the salting-out slurry are mixed to reduce the solid content concentration and the coagulant concentration.
• the solid content concentration of the liquid inside the coagulation tank (2) is less than 2/3 of the solid content concentration of the coagulation tank (1), preferably 7/11 or less, 5/8 or less, 3/5. Below, 7/12 or less, 6/11 or less, or 1/2 or less.
• washing and dehydration in step 3 water-soluble components such as coagulant, emulsifier, and residue of polymerization initiator can be removed.
• Washing and dehydration can be performed with, for example, a filter press, a belt press, a gina-type centrifuge, a screw decanter-type centrifuge, or the like. From the viewpoint of productivity and cleaning efficiency, it is preferable to use a screw decanter type centrifugal separator.
• the washing and dehydration of the granulated product are preferably performed at least twice. The greater the number of washings and dehydrations, the lower the residual amount of water-soluble components. However, from the viewpoint of productivity, the number of times of washing and dehydration is preferably 3 times or less.
• step 2 The washing of the granules obtained in step 2 and the drying after dehydration are carried out so that the moisture content is preferably less than 0.2% by mass, more preferably less than 0.1% by mass.
• the coagulant used in step 1 includes an inorganic acid or a salt thereof having a property of coagulating and coagulating latex) or an organic acid or a salt thereof.
• an aqueous solution of these coagulants is used.
• Specific examples of the inorganic acid, organic acid salt, organic acid or organic acid salt include sodium chloride, potassium chloride, lithium chloride, sodium bromide, potassium bromide, lithium bromide, potassium iodide, and iodine.
• Alkali metal halides such as sodium chloride; Potassium sulfate, alkali metal sulfates such as sodium sulfate; Ammonium sulfate; Ammonium chloride; Sodium nitrate, potassium nitrate and other alkali metal nitrates; Calcium ferrous chloride, magnesium sulfate, calcium acetate , Zinc sulphate, copper sulphate, barium chloride, ferrous chloride, ferric chloride, magnesium chloride, ferric sulphate, aluminum sulphate, potassium myoban, iron myoban etc. Used alone or in combination of two or more.
• an aqueous solution of a salt of a monovalent or divalent inorganic acid such as sodium chloride, potassium chloride, sodium sulfate, ammonium chloride, calcium chloride, magnesium chloride, magnesium sulfate, barium chloride or calcium acetate can be preferably used.
• a salt of a monovalent or divalent inorganic acid such as sodium chloride, potassium chloride, sodium sulfate, ammonium chloride, calcium chloride, magnesium chloride, magnesium sulfate, barium chloride or calcium acetate
• the concentration of the coagulant aqueous solution supplied to the flocculation tank (1) is preferably 5 to 20% by mass, and more preferably 10 to 15% by mass.
• the concentration of the coagulant in the mixture containing the coagulant (the latex in the coagulation tank (1)) and the coagulant is preferably 0.2 to 5.0% by mass, more preferably 0.3 to 2.0% by mass.
• the solid content concentration of the latex supplied to the coagulation tank (1) is preferably 10 to 60 mass%, more preferably 30 to 50 mass%.
• Latex and the solid content concentration of the inner liquid in the coagulation tank (1) for supplying the coagulant aqueous solution are preferably 5 to 30% by mass, and more preferably 7 to 20% by mass, in a desired amount. Add water.
• the mixture (internal liquid) containing the coagulant (latex of the coagulation tank (1)) is mixed by a mixing device equipped with a stirring blade, a stirring blade and the like. ⁇ 2020/175 516 8 ⁇ (: 170? 2020 /007611
• internal solution temperature of coagulation tank (1) is preferably 70 to 1 00 ° ⁇ , more preferably 75 ⁇ 95 ° ⁇ , more preferably 75 to 85 ° ⁇ . Internal solution temperature of coagulation tank (1) is preferably lower than the outermost layer of the sheets 9 grain child (eight).
• the average particle size of the aggregate of the (meth)acrylic multilayer structure particles (8) in the salting-out slurry in the aggregating tank (1) is preferably 10 to 400, more preferably 50 to 400.
• the bulk specific gravity is 300, preferably from 0.1 to ⁇ .69/ ⁇ , and more preferably from 0.2 to ⁇ . Is.
• the residence time of the mixture in the flocculation tank (1) is not particularly limited, but is preferably 0.3 to 2 hours, more preferably 0.5 to 1.5 hours.
• the solid content concentration in the mixture (internal liquid) in the flocculation tank (2) is preferably 3 to 20 mass%, more preferably 4.5 to 13.5 mass%.
• the mixture of the slurry in the flocculation tank (2) and the wash water is stirred by a stirring blade or a mixing device equipped with a stirring blade.
• the temperature of the liquid inside the coagulation tank (2) is preferably 80 to 110°, more preferably 85 to 100°, and further preferably 90 to 98°.
• the internal liquid temperature of the flocculation tank (2) is preferably 5 to 20° higher than the internal liquid temperature of the flocculation tank (1), more preferably 7 to 15°. ⁇ High.
• the average particle size of the solidified product of the (meth)acrylic multilayer structure particles (8) produced in the coagulation tank (2) is preferably 50 to 400, more preferably 100 to 30.
• the average particle size of the aggregate and the cumulative particle size distribution of the aggregate can be measured by a light scattering method (laser diffraction/scattering method, dynamic light scattering method), For example, it can be measured by using a laser diffraction/scattering particle size distribution measuring device !_8-920 2 manufactured by Horiba Ltd. ⁇ 2020/175 516 9 (: 170? 2020/007611
• the bulk specific gravity of the solidified product of the (meth)acrylic multi-layer structure particles (8) produced in the coagulation tank (2) is preferably 0.2 to 0.669 / ⁇ ⁇ ⁇ , more preferably ⁇ . 3 to ⁇ . Is.
• the bulk specific gravity of the solidification product of the (meth)acrylic multi-layer structure particles (8) produced in the coagulation tank (2) depends on the (meth)acrylic multi-layer structure particles in the salting-out slurry of the coagulation tank (1). (eight) ⁇ than the bulk density of the agglomerates. 05 to 0.3 9
• the residence time of the mixture in the flocculation tank (2) is preferably 0.3 to 2 hours ().
• the thickness of the (meth)acrylic polymer solidified product obtained in the present invention is 1 When the plate-shaped molded product is soaked in warm water of 98° ⁇ for 4 hours, the difference in aze ( ⁇ !) before and after the crushing is preferably less than 1.0%, and more preferably less than 1.0%. Is less than 0.9%.
• the haze is Optical path length according to 36 1 Measure with the test piece of.
• the (meth)acrylic polymer granules obtained in step 2 can be washed with water, dehydrated and dried according to a conventional method to obtain a (meth)acrylic polymer coagulated product as a powder. ..
• the water content of the obtained coagulated product powder is 0.01 to 0.3% by mass.
• (meth) acrylic multilayer structure particles (eight) obtained by an emulsion polymerization method are particles having a three-layer structure of an innermost layer ⁇ , an intermediate layer _1 and an outermost layer ⁇ .
• the temperature of the liquid inside the coagulation tank (2) is less than the glass transition temperature of the outermost layer ⁇ 9 + 10° ⁇ . More preferably, the internal liquid temperature of the flocculation tank (2) is from 9 to 1° ⁇ to 9 + 9 ° .
• the temperature of the liquid inside the flocculation tank (1) is preferably the glass transition temperature of the outermost layer ⁇ from 9 to -20° ⁇ to 9-0. It is ⁇ , and more preferably Ding 9-15° 0 to Ding 9 _ 5° ⁇ .
• the number of layers of the (meth)acrylic multilayer structure particles (8) is 2 to 5, preferably 2 to
• the hard polymer ⁇ , the mixture ⁇ , and the latex ⁇ are the innermost layer ( ⁇ “6). ⁇ 2020/175 516 10 boxes (: 170? 2020 /007611
• Hard polymer, mixture, latex means hard polymer _1, mixture _1, latex _1 means hard polymer, mixture, latex of intermediate layer (_1 6 "1116 ⁇ 1 _13 6), hard polymer ⁇ , mixture ⁇ , latex ⁇ means the hard polymer, mixture, and latex of the outermost layer ( ⁇ 1 ⁇ 6 “111031;).
• the layer structure of the (meth)acrylic multilayer structure particles (8) for example, a core shell multilayer structure is preferable.
• the core-shell multi-layer (meth)acrylic multi-layer structure particles ( ⁇ ) can be obtained, for example, by melt-kneading a three-layer granule consisting of the innermost layer 0, the intermediate layer and the outermost layer ⁇ .
• the innermost layer and the intermediate layer, and the intermediate layer and the outermost layer are composed of different polymers. It is preferable that the innermost layer and the intermediate layer are in contact with each other and the intermediate layer and the outermost layer are in contact with each other without any gap.
• the polymer forming the intermediate layer is preferably softer than the polymer forming the innermost layer and the polymer forming the outermost layer.
• the hard polymer constitutes the innermost layer O
• the soft polymer constitutes the intermediate layer
• the hard polymer constitutes the outermost layer O.
• the glass transition temperature of the hard polymer ⁇ constituting the outermost layer is preferably 60 to 105°°, more preferably 70 to 100°°.
• the glass transition temperature of the soft polymer that constitutes the intermediate layer is preferably from 60 to 0 ° , more preferably from -40 to 110 ° .
• the hard polymer ⁇ may be composed of a structural unit derived from a methacrylic acid ester (hereinafter referred to as a methacrylic acid ester unit), and a methacrylic acid ester unit and a structural unit derived from an acrylate ester (hereinafter , An acrylic acid ester unit) and, if necessary, a structural unit derived from a polyfunctional monomer (hereinafter referred to as a polyfunctional monomer unit).
• the polyfunctional monomer unit includes a structural unit derived from a grafting agent (hereinafter referred to as a grafting agent unit or a structural unit derived from a crosslinking agent (hereinafter referred to as a crosslinking agent unit)).
• the amount of methacrylic acid ester units in the hard polymer ⁇ is preferably 50 to 100% by mass, and more preferably 50 to 80% by mass, based on the total units of the hard polymer ⁇ . .. ⁇ 2020/175 516 1 1 ⁇ (: 170? 2020 /007611
• the amount of the structural unit derived from an acrylate ester in the hard polymer ⁇ is preferably ⁇ to 50 mass%, more preferably 10 to 50 mass% with respect to the total units of the hard polymer ⁇ . Is. It is preferable that the ester portion (01 [3 ⁇ 4)) of the acrylic acid ester has a carbon number of 1 to 8. The smaller the amount of acrylate ester units, the lower the thermal decomposition resistance of the (meth)acrylic polymer coagulum, and the larger the amount of acrylate ester units, the more the (meth)acrylic polymer coagulate is used. The hot water whitening resistance of the film produced by the method tends to decrease.
• the amount of the grafting agent unit in the hard polymer ⁇ is preferably 0.01 to 1% by mass, and more preferably 0.1 to 00.5% by mass, based on all the units of the hard polymer ⁇ . %.
• the impact resistance of the film produced by the method tends to decrease.
• the soft polymer _1 comprises: an acrylate ester unit, and a grafting agent unit, and optionally a methacrylic acid ester unit, a crosslinking agent unit, and other monomer. It is a polymer composed of body units.
• flexible polymer 'the amount of acrylic acid ester units in I is soft polymer' relative to the total units of the I, preferably 1 ⁇ _ ⁇ 1 0 0 wt%, more preferably 2 0-9 0 Quality The amount is %. It is preferable that the ester portion (01 [3 ⁇ 4)) of the acrylic ester has 1 to 8 carbon atoms. The smaller the amount of acrylic acid ester units, the lower the impact resistance of the film produced by using the (meth)acrylic polymer coagulum, and the larger the amount of acrylic acid ester units, the more the (meth)acrylic type. There is a tendency that stress whitening resistance and transparency of a film produced by using a polymer solidified product are lowered.
• the amount of the grafting agent unit in the soft polymer I is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass, based on the total units of the soft polymer. ..
• flexible polymer 'amount of methacrylic acid ester units in I is soft polymer' with respect to the total units of I, preferably ⁇ _ ⁇ 5 0 wt%, more preferably ⁇ _ ⁇ 2 0% by weight.
• the hard polymer ⁇ is a polymer composed of a methacrylic acid ester unit and an acrylic acid ester unit.
• the rigid polymer ⁇ preferably does not contain a polyfunctional monomer unit. By not containing a polyfunctional monomer unit, the rigid polymer ⁇ dissolves in acetone.
• the amount of the methacrylic acid ester unit in the hard polymer ⁇ is preferably 50 to 100 mass%, more preferably 70 to 100 mass% with respect to the total units of the hard polymer ⁇ . is there.
• the stress whitening resistance of the film tends to decrease as the amount of methacrylic acid ester units decreases, and the thermal decomposition resistance of the coagulated (meth)acrylic polymer decreases as the amount of structural units derived from methyl methacrylate increases. There is a tendency to
• the amount of acrylic acid ester units in the hard polymer O is preferably 0 to 50% by mass, more preferably 0 to 30% by mass, based on all units of the hard polymer O. It is preferable that the ester portion (01[3 ⁇ 4)) in the acrylic ester has 1 to 8 carbon atoms. The smaller the amount of acrylic acid ester units, the lower the thermal decomposition resistance of the multi-layered acrylic polymer, and the larger the amount of acrylic acid ester units, the (meth)acrylic polymer coagulation product The stress whitening resistance of the formed film tends to decrease.
• hard polymer ⁇ has a glass transition temperature of preferably 8 0 ° ⁇ As, more preferably 8 5 ° ⁇ As. The higher the glass transition temperature of the hard polymer ⁇ , the more the hot water resistance or boiling water whitening resistance of the film tends to improve.
• Acrylic multilayer structure particles (8) are: the innermost layer consisting of a hard polymer ⁇ having methacrylic acid ester units of 50 to 100 mass%, acrylic acid ester units of 40 to 99.9 mass. % And polyfunctional monomer units 0.01 to 5% by mass, and an intermediate layer consisting of a soft polymer I having a glass transition temperature of less than 25°, and a methacrylic acid ester unit 80 to 1 It has a three-layer structure consisting of the outermost layer of a hard polymer ⁇ having a glass transition temperature of 80° C. or higher and a glass transition temperature of 0.
• Examples of the acrylic acid ester used for the hard polymer ⁇ , the soft polymer _1 and the hard polymer ⁇ include, for example, methyl acrylate, ethyl acrylate, and polypropylene acrylate.
• _Butyl acrylate, 3 _Butyl acrylate, 1:-Putyl acrylate, Butyl methyl acrylate Mention may be made of acrylate alkyl esters such as heptyl acrylate, 2-ethylhexyl acrylate, and _octyl acrylate. These acrylic esters may be used alone or in combination of two or more. Among these, methyl acrylate and/or 1 ⁇ !_butyl acrylate are preferable.
• the grafting agent used for the hard polymer ⁇ and the soft polymer I mainly has a role of chemically bonding the hard polymer ⁇ and the soft polymer 1 and the soft polymer 1 and the hard polymer ⁇ . In addition, it is a monomer considered to have a role of assisting the formation of a crosslinked structure in the hard polymer ⁇ or the soft polymer 1.
• the grafting agent is a monomer having two or more different kinds of polymerizable groups.
• examples of the grafting agent include allyl methacrylate, allyl acrylate, mono- or diallyl maleate, mono- or diallyl fumarate, crotyl acrylate, crotyl methacrylate and the like. These grafting agents can be used alone or in combination of two or more.
• allyl methacrylate improves the binding ability between the hard polymer ⁇ and the soft polymer or between the soft polymer and the hard polymer ⁇ , and the stress whitening resistance and transparency of the film are improved. Because it is excellent in improving ⁇ 2020/175 516 14 ⁇ (: 170? 2020 /007611
• the cross-linking agent used for the hard polymer ⁇ and the soft polymer _1 is a monomer that is considered to mainly have a role of forming a cross-linked structure in the hard polymer ⁇ or the soft polymer.
• the cross-linking agent is a monomer having two or more polymerizable groups of the same kind, and examples thereof include diacryl compounds, dimethacryl compounds, diallyl compounds, divinyl compounds, diene compounds, trivinyl compounds and the like.
• Examples of the cross-linking agent include ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, divinylbenzene, trivinylbenzene, Examples thereof include ethylene glycol diallyl ether, propylene glycol diallyl ether, and butadiene. These cross-linking agents can be used alone or in combination of two or more.
• the other polymerizable monomer used in the hard polymer ⁇ and the soft polymer _1 may be any vinyl-based monomer copolymerizable with a methacrylic acid ester or an acrylic acid ester,
• aromatic vinyl monomers such as styrene, _methylstyrene, ⁇ -methylstyrene, vinylnaphthalene, unsaturated nitrile-based monomers such as acrylonitrile, olefin-based monomers such as ethylene and propylene, and chlorides.
• Vinyl halides such as vinyl, vinylidene chloride, vinylidene fluoride, unsaturated carboxylic acid monomers such as acrylic acid, methacrylic acid, maleic anhydride, vinyl acetate, 1 ⁇ 1-propylmaleimide, Examples include maleimide-based monomers such as —cyclohexylmaleimide and 1 ⁇ 1 _ ⁇ —chlorophenylmaleimide. These compounds can be used alone or in combination of two or more kinds.
• solidified product obtained by the process of the present invention 2 3 0 ° ⁇ 3.
• 81 ⁇ 9 melt flow rate under a load, preferably ⁇ . 5-2 0 9/1 0 min, and more favorable Mashiku a ⁇ . 8-1 0 9/1 0 minutes.
• the moldability of the rubber tends to decrease.
• the method for producing the (meth) latex containing the acrylic multilayer structure particles (8) is not particularly limited.
• a latex can be obtained by sequentially forming a hard polymer O, a soft polymer I, and a hard polymer O by emulsion polymerization, for example, a seed emulsion polymerization method.
• the coagulated product of the present invention may be mixed with another thermoplastic resin and extruded.
• Other thermoplastic resins include polycarbonate-based polymers, vinyl chloride-based polymers, vinylidene fluoride-based polymers, vinyl acetate-based polymers, maleic acid-based copolymers, acrylic resins, Mitsumi 3 resin, 3 resin a day, 3 Resin etc. can be mentioned.
• the weight ratio of the other thermoplastic resin/solidified product is preferably 0/100 to 35/65, more preferably 0/100 to 20/80.
• the solidified product of the present invention may be mixed with an acrylic resin and extruded.
• the mass ratio of the acrylic resin/solidified product is preferably 0/100 to 35/65, more preferably 0/100 to 20/80. Within this range, the film formability will be good.
• the acrylic resin that can be used as necessary in the extrusion molding is a resin having a structural unit derived from methyl methacrylate and, if necessary, a structural unit derived from an acrylate ester.
• the amount of structural units derived from methyl methacrylate in the acrylic resin is preferably 85 to 100 mass%, more preferably 92 to 100 mass% with respect to the mass of all structural units of the acrylic resin. Is.
• the amount of the structural unit derived from the acrylate ester in the acrylic resin is preferably 0 to 15 mass%, more preferably 0 to 8 mass% with respect to the mass of all structural units of the acrylic resin.
• acrylic acid ester in the acrylic resin examples include methyl acrylate, ethyl acrylate, _propyl acrylate, isopropyl acrylate, 1 ⁇ _butyl acrylate, isoptyl acrylate, 3 _butyl acrylate. ⁇ 2020/175 516 16 ⁇ (: 170? 2020 /007611
• Extrusion acrylic resin optionally used in the molding, the glass transition temperature, preferably 9 5 ° ⁇ As, more preferably 1 0 0 ° ⁇ As, more preferably at 1 0 5 ° ⁇ As is there.
• the acrylic resin is 2300° ⁇ , 3.
• Melt flow rate under a load is preferably ⁇ . 5-2 0 9/1 0 minutes, more rather preferably is from 0.8 to 1 0 9/1 0 minutes.
• the acrylic resin is not particularly limited depending on its manufacturing method.
• it can be produced by a known polymerization method such as a radical polymerization method or an anionic polymerization method.
• the adjustment of the above-mentioned characteristic values of the acrylic resin is performed by adjusting the polymerization conditions, specifically, the polymerization temperature, the polymerization time, the type and amount of the chain transfer agent, the type and amount of the polymerization initiator, etc. It can be done by adjusting.
• the adjustment of resin properties by adjusting such polymerization conditions is a technique well known to those skilled in the art.
• the coagulated product and acrylic resin obtained by the production method of the present invention are preferably pelletized in order to facilitate transportation, storage, molding and the like.
• Multilayer Structure The extruder used for pelletizing the acrylic polymer preferably has a vent.
• the vent is preferably a vacuum vent or an open vent. It is preferable to provide at least one vent downstream of the resin melting start portion.
• the pressure at the vacuum vent is preferably 30 or less "" or less, more preferably less than or equal to 157, rr, more preferably 9 or less "", or less, more preferably 6 or less ", most preferably or less.
• the pressure at the vent is within the above range. ⁇ 2020/175 516 17 ⁇ (: 170? 2020/007611
• the devolatilization efficiency is good, and the residual water content and the monomer can be reduced.
• the extruder used for pelletization is preferably a single screw type.
• the single-screw extruder has a small shearing energy applied to a multi-layered acrylic polymer or the like, and can suppress thermal decomposition of the polymer.
• the screen configuration is preferably full frying.
• the cylinder heating temperature of the extruder used for pelletization is preferably 2
• the residence time in the extruder is preferably 7 minutes or less, more preferably 5 minutes or less, and further preferably 3 minutes or less. Cylinder heating The higher the heating temperature or the longer the residence time, the greater the shearing energy applied to the multi-layered acrylic polymer, etc., and the thermal decomposition of the polymer tends to proceed, tending to reduce the warm water whitening resistance of the film. ..
• the water content of the multi-layered acrylic polymer and the acrylic resin before being subjected to extrusion molding is preferably less than 0.2% by mass, more preferably less than 0.1% by mass. The higher the water content, the more likely it is that silver streaks will occur and that the hot water whitening resistance will decrease.
• the coagulated product and the acrylic resin known agents such as an ultraviolet absorber, an antioxidant, a light stabilizer, an antiaging agent, a plasticizer, a polymer processing aid, a lubricant, a dye and a pigment may be used, if necessary.
• Resin additives may be included.
• the total content of the resin additive is preferably 20% by mass or less with respect to 100% by mass of the total amount of the solidified product and the acrylic resin.
• the resin additive may be added to, for example, the solidified product and the acrylic resin melted in the film forming machine, or may be dry blended with the pelletized solidified product or the acrylic resin. It may be added when pelletizing a solidified product or acrylic resin (masterbatch method).
• the coagulated product and the acrylic resin contain an ultraviolet absorber.
• an ultraviolet absorber for example, 2-[ 2-hydroxy _ 5- (2-me ⁇ 2020/175 516 18 ⁇ (: 170? 2020 /007611
• Tacryloyloxyethyl)phenyl Mention may be made of reactive UV absorbers such as 2,3-benzotriazole.
• the content of the ultraviolet absorber is preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the total amount of the solidified product and the acrylic resin.
• the solidified product of the present invention when used as a molded product, it can be molded into a plate shape, a film shape or the like by a general molding method such as heat-melting, extrusion molding, and injection molding.
• the extruder used for film formation preferably comprises a vent.
• the vent is preferably a vacuum vent or an open vent. At least one vent is preferably provided on the downstream side of the resin melting start portion.
• the pressure in the vacuum vent is preferably 30 or less "" or less, more preferably 15 or less "", more preferably less than or equal to 9 T ° rr, most preferably less than or equal to 6 T ° rr.
• the extruder used for this purpose is preferably a single-screw system or a co-rotating twin-screw system.
• the cylinder heating temperature of the extruder used for film formation is preferably
• the residence time in the extruder used for film formation is preferably 7 minutes or less, more preferably 5 minutes or less, and further preferably 3 minutes or less.
• the higher the cylinder heating temperature or the longer the residence time the greater the shearing energy applied to the multi-layered acrylic polymer, etc., and the thermal decomposition of the polymer is likely to proceed, and the hot water whitening resistance of the film tends to decrease. Therefore, it is preferable that the extrusion molding for forming the film is carried out with the residence time in the extruder being 5 minutes or less and the resin temperature being 280 ° C. or less.
• the resin film obtained from the solidified product of the present invention is excellent in impact resistance, excellent in stress whitening resistance, does not cause whitening even when bent, and is excellent in hot water whitening resistance and boiling water whitening resistance. No bleaching occurs when exposed to hot and boiling water.
• the resin film obtained from the solidified product of the present invention is also excellent in adhesiveness to other polymers, especially thermoplastic polymers. ⁇ 2020/175 516 19 ⁇ (: 170? 2020 /007611
• the resin film obtained from the solidified product of the present invention preferably has a thickness of 10 to
• a laminate using the coagulated product obtained by the production method of the present invention has at least one layer using the coagulated product of the present invention and at least one layer made of another thermoplastic polymer.
• thermoplastic polymer used in the laminate of the present invention is not particularly limited.
• thermoplastic polymers include polycarbonate-based polymers, vinyl chloride-based polymers, vinylidene fluoride-based polymers, vinyl acetate-based polymers, maleic acid-based copolymers, methacrylic resins, Mitsumi 3 resins, Mitsumi 3 resins, Alternatively, 3 resin is preferable because it has good adhesiveness to the resin film of the present invention.
• the thermoplastic polymer molded article may be a planar molded article such as a film, a sheet, a plate, etc., a linear molded article such as a tube, a rod, etc., a lens, a prism, a container, etc. Molded products of various shapes such as
• the laminate of the present invention is not particularly limited by its manufacturing method.
• the laminate may be formed, for example, by coextrusion of the above-mentioned multilayer acrylic polymer and another thermoplastic polymer onto another thermoplastic polymer molded article to form the above-mentioned multilayer acrylic polymer.
• Other thermoplastic polymer moldings are placed in the desired mold by coating and extruding the resin to melt the multi-layered acrylic polymer and injecting or injecting it into the other thermoplastic polymer.
• the above-mentioned multi-layered acrylic resin is placed on a polymer molded article and press-molded, or another thermoplastic polymer molded article contains a resin powder containing the solidified product obtained by the production method of the present invention. It can be obtained by heat-sealing or gluing the film.
• the glass transition temperature (end 9 ) of the hard polymer is the same as that in the process of forming the hard polymer in the process of producing the polymer particles, and only the hard polymer is produced. It is an intermediate glass transition temperature measured by.
• the glass transition temperature (end 9 ) of the soft polymer is the same as that in the process of forming the soft polymer in the process of producing the polymer particles, and only the soft polymer is produced. It is an intermediate glass transition temperature measured according to 121.
• Thickness of hot-pressed solidified material Of the flat plate was prepared, and the haze of the flat plate was measured.
• the flat plate was immersed in warm water at 98° for 4 hours, and the haze before and after immersion was measured.
• the difference between the haze after immersing in warm water and the haze before immersing in warm water was defined as ⁇ haze.
• a volume average particle size (in the present specification, “average particle size” is measured by a light scattering method using a laser diffraction/scattering particle size distribution measuring device 1 ⁇ -9202 manufactured by Horiba Ltd. )), the proportion of particles below 20 was determined.
• the solidified product was filled into a 100 000 graduated cylinder while tapping, and the mass was measured to determine the bulk specific gravity.
• the latex was further mixed with methyl methacrylate 0/1/8) 56.9 parts, butyl acrylate 8) 8.1 parts and a door-octyl mercaptan (011/1) 0.19.
• the mixture ⁇ consisting of parts was continuously added dropwise over 100 minutes. After the addition of the mixture ⁇ was maintained for 60 minutes, seed emulsion polymerization was carried out to obtain a latex 1-1 containing (meth)acrylic multilayer structure particles (8).
• the hardness 9 of the hard polymer constituting the outermost layer of the (meth)acrylic multilayer structure particles (8) was 87°.
• Table 1 shows the composition of the (meth)acrylic multilayer structure particles (8) contained in the latex 1-1.
• the latex 1-1 1 was added to the flocculation tank (1) equipped with a Max Blend blade agitator ⁇ 2020/175 516 22 ⁇ (: 170? 2020 /007611
• the solid content concentration, stirring speed, heating temperature, and magnesium sulfate aqueous solution addition concentration in the flocculation tank (1) were changed as shown in Table 2, and the mixture was stirred for 60 minutes to obtain salting-out slurry N0.2.
• the slurry and ion-exchanged water were charged into a flocculation tank (2) equipped with another Max-blend blade agitator so that the solid content concentration of the above-mentioned slurry N0.1 was 7.5% by mass, and the agitation speed was changed.
• the mixture was stirred at 400 ", heated to 90° and stirred for 60 minutes. After that, washing with water twice, dehydration and drying were performed to obtain a (meth)acrylic polymer coagulated product.
• a (meth)acrylic polymer coagulated product was obtained in the same manner as in Example 1 except that the solid content concentration at the time of aggregation was changed to 5% by mass and the rotation speed of stirring was changed to 300!
• a (meth)acrylic polymer coagulated product was obtained in the same manner as in Example 1 except that the temperature at the time of aggregation was changed to 97°.
• a (meth)acrylic polymer coagulum was prepared in the same manner as in Example 1 except that the solid content concentration of the slurry at the time of aggregation was changed to 10% by mass and the stirring time at the time of aggregation was changed to 20 minutes. ⁇ 2020/175 516 23 ⁇ (: 170? 2020 /007611
• a (meth)acrylic polymer coagulated product was obtained in the same manner as in Example 1 except that the temperature at the time of aggregation of Example 1 was changed to 85 ° and the solid content concentration of the slurry was changed to 15% by mass.
• a (meth)acrylic polymer coagulated product was obtained in the same manner as in Example 1 except that the temperature at the time of aggregation in Example 1 was changed to 80 ° and the solid content concentration of the slurry was changed to 15% by mass.
• a (meth)acrylic polymer coagulated product was obtained in the same manner as in Example 1 except that the salting-out slurry N0.2 was used.

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