JP5169290B2 - Method for producing polymer powder - Google Patents

Description

  The present invention relates to a method for producing a powder comprising a polymer such as a thermoplastic resin. More specifically, the present invention relates to a method for producing a polymer powder such as a thermoplastic resin powder used for producing a molded article by die molding such as powder slush molding.

  Polymer powder is industrially used as a material for producing a molded body by die molding such as powder slush molding. In the mold molding, a desired molded article can be obtained through a process of melting a resin and cooling and hardening the resin after filling a desired molding mold with a thermoplastic resin powder.

  In recent years, as a molded body manufactured by the above-described mold molding, there is an increase in one having a fine and complicated structure. In order to manufacture a compact having such a fine and complicated structure, it is necessary that the powder material reaches every corner of the complicatedly shaped mold and the powder is uniformly filled in the mold. Therefore, the powder material to be used is required to have excellent fluidity. In order to obtain such excellent fluidity, the size (particle size) of the particles in the powder is in a range that is not easily affected by the attractive force between particles and electrostatic force, and the shape of the particles is spherical rather than distorted. That is important in terms of quality.

  Conventionally, as a powder (powder) material for mold molding as described above, a vinyl chloride resin powder that is inexpensive, excellent in flexibility, and can be molded into a complicated shape has been widely used (for example, Patent Documents). 1). However, polyvinyl chloride resin has problems in terms of environmental pollution, safety, and the like in which harmful substances such as dioxin are generated during incineration. Therefore, thermoplastic elastomers such as polyolefin elastomers and styrene elastomers have been developed as substitutes for polyvinyl chloride resin powder (see, for example, Patent Documents 2 to 6). However, polyolefin-based elastomers and styrene-based elastomers have a problem of low wear resistance, flexibility, and oil resistance of molded products and coatings. A slush molding material made of thermoplastic polyurethane has also been proposed (see, for example, Patent Documents 7 and 8). However, thermoplastic polyurethane has problems such as poor moldability and high cost. Moreover, the manufacturing method of the resin particle body of an isobutylene type block copolymer is also disclosed (for example, refer patent document 9). However, since the isobutylene block copolymer has high resin adhesiveness and low hardness, it is difficult to obtain a powder composed of spherical particles having a uniform particle shape and a small particle size. There was a problem that the fluidity was not sufficient.

  As a material for solving the problems in the powder material for molding as described above, in recent years, an acrylic block having excellent safety, weather resistance, flexibility, rubber elasticity, low temperature characteristics, adhesion to a polar resin, etc. A powder made of a copolymer is disclosed (Patent Document 10). However, the powder composed of the acrylic block copolymer is finally obtained by physical pulverization at an extremely low temperature of −100 ° C., and only a distorted powder far from spherical is obtained. I couldn't. For this reason, the powder has a drawback such that the static electricity is easily generated between the particles and the particle shape is distorted, so that the fluidity of the powder is poor.

  As a method for solving the distortion of the particle shape of the powder material as described above, a polymer spherical powder is obtained by heating a polymer solution dissolved in a solvent, water and a water dispersion containing a dispersant while stirring. Is disclosed (for example, see Patent Document 11). According to this method, a powder composed of spherical particles having a small particle diameter can be obtained, and the problem of particle distortion can be solved. However, the disclosed method tends to generate a large amount of fine powder and coarse particles that are not suitable as a molding material. If such fine powder or coarse particles are contained, the fluidity of the powder deteriorates, the powder material does not reach every corner of the complicatedly shaped mold, and a good molded product cannot be obtained. Therefore, the obtained powder must be sieved and the fine powder and coarse particles must be excluded from the powder material, and the use efficiency of the raw material is lowered, resulting in an increase in the unit price of the molded product. There are drawbacks.

As described above, a high-quality molded article and skin preparation that is excellent in powder flowability and is safe and excellent in weather resistance, flexibility, rubber elasticity, low temperature characteristics, adhesion to polar resins, texture, appearance, etc. Thus, there has been a demand for a production method capable of obtaining a high efficiency of using raw materials for polymer powder made of spherical particles having a small particle diameter capable of forming a coating film.
JP-A-5-279485 JP 49-53991 A JP 50-90693 A Japanese Patent Laid-Open No. 50-89494 JP-A-7-82433 Japanese Patent Laid-Open No. 10-30036 JP 2000-103957 A JP-A-7-133423 JP 2004-155880 A International Publication No. 2004/041886 Pamphlet International Publication No. 2006/085596 Pamphlet

  In view of the present state of the powder material as described above, the present invention is excellent in fluidity and safe, yet weather resistance, flexibility, rubber elasticity, low temperature characteristics, adhesion to polar resin, texture, appearance, etc. To provide a production method capable of forming high-quality molded products, skin preparations, coating films, etc. that are excellent in the production of polymer powders composed of spherical particles with small particle diameters, and that can obtain high use efficiency of raw materials. Objective.

In the method for producing polymer powder according to the present invention, an aqueous dispersion containing water, a polymer solution and a dispersant is charged in an agitation tank of an agitator, and the aqueous dispersion is stirred with an agitating blade. The method includes heating the aqueous dispersion by directly blowing steam into a stirring tank and removing the solvent of the polymer solution by steam stripping, and is represented by the following formula (1). The ratio (R) of the volume (v2) through which the stirring blade passes by rotation in the stirring tank to the volume (v1) of the charged amount of the aqueous dispersion is 20% or more. A solvent larger than 1 is used, and the solvent is removed by heating the aqueous dispersion with stirring while rotating the stirring blade at a rotational speed at which the power P / V per unit volume of the liquid is greater than 2 kW / m ^3. And
R (%) = (v2 / v1) × 100 Formula (1)

  It is preferable that two or more baffle plates extending from the lower part to the upper part are provided on the inner wall part of the stirring tank.

As the stirring blade,
Large lattice blades are preferred,
A wing (H-shaped wing) arranged on two sides of the stirring shaft as a target line, and two flat plates that are long in the axial direction.
A paddle blade made of a wide flat plate disposed at the bottom of the agitation tank is attached to the lowermost stage, and comb-like blades are attached to the middle and upper stages, and adjacent to the paddle blade located at the lowermost stage. The middle comb-like wings are arranged in a rotational direction with an intersection angle of less than 90 degrees, and the lowermost paddle wing and the upper middle comb-like wing overlap in the axial direction, In addition, the upper comb-like wing adjacent to the upper comb-like wing is arranged in advance in the rotational direction at an intersecting angle of less than 90 degrees, and the middle comb-like wing is disposed. And the upper comb-like wing adjacent to the upper wing has an overlap in the axial direction,
The average diameter (d _ave ) of the stirring blades is 30 to 70% with respect to the tank diameter (D) of the stirring tank, and the upper blade diameter (d _high ) is lower than the lower blade diameter (d _low ). Trapezoidal wings smaller than 10%,
The trapezoidal blade, wherein a stirring blade having a portion (d _ex ) having no stirring blade in a portion of 30 to 60% in a central portion with respect to an average diameter (d _ave ) of the stirring blade,
Max blend wing,
Etc. are preferable.
A flat wing can also be used.

  Moreover, in the manufacturing method of the polymer powder concerning this invention, it is preferable that the average particle diameter of the powder consisting of the spherical particle manufactured is 10 micrometers or more and less than 1000 micrometers.

  In the above production method, the polymer solution is preferably composed of a thermoplastic resin and an organic solvent, the thermoplastic resin is more preferably a (meth) acrylic block copolymer, and the (meth) acrylic block It is particularly preferable that the copolymer is a (meth) acrylic block copolymer (A) comprising a methacrylic polymer block (a) and an acrylic polymer block (b).

  In the method for producing polymer powder according to the present invention, at least one of cellulose ester, polyvinyl alcohol, polyvinyl pyrrolidone, calcium phosphate, calcium carbonate, and a nonionic surfactant is used as the dispersant. preferable.

  Since the method for producing polymer powder according to the present invention has the above-described configuration, the particle shape is close to a true sphere, the particle size is small, and the fluidity is high. The polymer powder is suitable as a molding material. The body, in particular, (meth) acrylic copolymer powder can be produced with a high yield of raw materials with high efficiency in use of raw materials with little generation of fine powder and coarse particles.

  The present invention is described in detail below.

  In the method of the present invention, an aqueous dispersion containing water, a polymer solution and a dispersing agent is heated while stirring in a stirring tank of a stirring device to remove the solvent.

(Stirring tank)
The stirring tank of the stirring device used in the present invention is stirred in the stirring tank 1 by providing two or more baffle plates 6 extending from the lower part to the upper part on the inner wall part as shown in FIG. It is preferable that the structure is such that the mixed state of the aqueous dispersion can be improved. The agitation tank 1 may be provided with a jacket so that preliminary heating and cooling are possible.

(Stirring blade)
The greatest feature of the present invention is that, in the production of the polymer powder, a stirring blade having a power number larger than 1 is used, and P / V (power per unit volume of the liquid charged into the stirring tank) is 2 kW / m ^3. Rotating at a higher rotational speed to stir the aqueous dispersion. The power number here refers to a value given by P / (ρn ³ d ⁵ ) under stirring conditions in a turbulent region (where P: required power for stirring, ρ: liquid density, n: number of stirring rotations, d : Blade diameter of stirring blade).

Among known stirring blades, (multistage) inclined paddle blades, turbine blades, three-way swept blades, and the like have a power number smaller than 1 based on a normal design concept. With such a blade, it is not possible to reduce the fine powder and coarse particles in the produced powder, even if stirring is performed under any P / V condition, and it is not possible to increase the use efficiency of raw materials. It was. Therefore, as a result of extensive studies, a stirring blade having a power number greater than 1 was used, and the stirring blade was rotated at a rotational speed at which the power P / V per unit volume of liquid was greater than 2 kW / m ^3. When the solvent is removed by heating while mixing the dispersion, fine powder and coarse particles in the resulting powder can be reduced, and the volume ratio of the volume through which the stirring blade passes and the amount of charged liquid is 20%. It was found that fine powder and coarse particles can be further reduced when the above conditions are satisfied. The ratio of the volume that the stirring blade passes through by rotation and the volume of the charged liquid amount is a value represented by the following formula (1) (where, v1: of the charged liquid volume of the aqueous dispersion into the stirring tank) Volume, v2: Volume through which the stirring blade passes by rotation in the stirring tank).
R (%) = (v2 / v1) × 100 Formula (1)

  Specific examples of the agitating blade satisfying the conditions as described above are described in H-shaped blade, Max blend blade, full-zone blade, Sammerer blade, Hi-Fi mixer blade, Supermix blade, JP-A-10-24230. And large wings such as a three-stage lattice wing having a large bottom paddle (hereinafter referred to as “Kaneka wing”) and a trapezoid wing. Among these, large wings having a lattice portion, represented by H-shaped wings, Max blend wings, Kaneka wings, and trapezoid wings, are excellent in that they have a simple structure. The lattice portion of the blade is a comb-shaped or lattice-shaped blade portion composed of an arm portion extending horizontally from the stirring shaft and a strip portion extending substantially perpendicularly from the arm portion. The H-shaped blade is an arm portion extending horizontally from the stirring shaft, two flat plates that are long in the axial direction as strip portions, and the stirring shaft on both sides of the stirring shaft as a target line. Sometimes called a pincushion. In addition, when the two flat plates are not separated from each other and are united around the stirring shaft, they are separately referred to as “flat plate blades”. The Max Blend wing refers to a wing whose detailed shape is described in, for example, JP-A-61-200842. As described in the official gazette, this Max Blend blade is equipped with a bottom paddle disposed on the bottom of the stirring shaft with the lower end being slidably contacted to the bottom wall surface of the stirring tank, and the bottom of the stirring shaft. A lattice blade is constructed by mounting an arm paddle and a strip extending in the axial direction on the upper part of the paddle.

  The “Kaneka wing” refers to a wing whose detailed shape is described in JP-A-10-24230. In this Kaneka blade, for example, as shown in FIGS. 1 to 3, the paddle blade 3 made of a wide flat plate disposed at the bottom of the stirring tank 1 is at the lowermost stage, and the comb-shaped blades are at the middle stage 4 and the upper stage 5. At the same time, with respect to the paddle wing 3 positioned at the lowermost stage, a comb-like wing 4 of the middle stage adjacent to the paddle wing 3 is arranged in advance in the rotation direction at an intersecting angle of less than 90 degrees. The middle comb-like blade 4 adjacent to the paddle blade 3 has an overlap in the axial direction of the stirring shaft 2 and is adjacent to the upper blade adjacent to the comb-like blade 4 located in the middle stage. The comb-like wings 5 are arranged in advance in the rotational direction at an intersecting angle of less than 90 degrees, and the middle comb-like wings 4 and the upper comb-like wings 5 adjacent to each other overlap in the axial direction. The wing has

The trapezoidal blade has an average stirring blade diameter (d _ave ) of 30 to 70% with respect to the tank diameter (D), and the upper blade diameter (d _high ) is lower than the lower blade diameter (d _low ). The stirring blade is smaller than 10% and has no phase difference in the upper and lower portions.

  The details of the shape of the trapezoidal wing will be described below with reference to FIG. Taking the shape of the trapezoidal blade 13 as an example, two trapezoidal stirring blades that are long in the axial direction are provided as strip portions 13b on arm portions 13a and 13a extending horizontally from the stirring shaft 12 as shown in FIG. As 13b, the one in which the stirring shaft 12 is symmetrically mounted on both sides of the stirring shaft 12 is most preferable because it has few right-angle to acute-angle angles and is not easily subjected to local shearing. In FIG. 4, 11 is a stirring tank, and 14 is a baffle (baffle).

Here, the upper blade diameter (d _high ) of the stirring blade is the radial width (corresponding to the length of the upper base of the trapezoid) of the trapezoid blade 13 and the lower blade diameter. (D _low ) is the radial width of the lower edge of the trapezoidal wing 13 (corresponding to the length of the lower base of the trapezoid). Usually, the trapezoidal blade has an isosceles trapezoidal shape that is line-symmetric with respect to the stirring axis, and the average stirring blade diameter (d _ave ) is determined at both ends of the upper and lower sides of the trapezoid blade. This is the average distance between the two hypotenuses of the isosceles trapezoid connected by a straight line (the other pair of opposite sides), and is usually expressed as the average stirring blade diameter (d _ave ) = (d _high + d _low ) / 2 . The trapezoidal blade is more preferably a stirring blade in which a portion having no stirring blade (d _ex ) is present in a central portion of 30 to 60% of the average diameter (d _ave ) of the stirring blade diameter. . The trapezoidal wings can generate a pressure difference due to the difference between the upper and lower blade diameters, thereby creating a gentle up-down flow, and can improve the mixing property between the upper and lower sides.

As described above, the stirring blade average diameter (d _ave ) of the trapezoidal blade is preferably 30 to 70% with respect to the tank inner diameter (D). If the stirring blade diameter is too large, the gap between the inner wall of the stirring tank 11 and the baffle 14 is narrowed, and the aqueous dispersion of the polymer mixed in the tank is subjected to a shearing force to easily cause agglomeration. . If the stirring blade diameter is too small, the stirring energy is only locally applied, so that the mixing performance is lowered.

In the method of the present invention, water, a polymer containing a polymer solution and a dispersant dissolved in a solvent, an aqueous dispersion of polymer solution, the power number is greater than one stirring blade P / V than 2 kW / m ³ A polymer powder composed of spherical particles having a small particle diameter can be produced by using steam at a large stirring speed and directly blowing steam into the stirring tank while stirring to heat the dispersion. When the value of P / V is too small, the dispersed polymer solution droplets are likely to coalesce, the coarse particles increase, the particle size distribution becomes wide, and the size that can be used as a molding material The yield of particles decreases. The value of P / V is preferably 2 kW / m ³ or more, and more preferably 3 kW / m ³ or more. The upper limit of P / V is not particularly limited, but is preferably 20 kW / m ³ or less and more preferably 15 kW / m ³ or less from the viewpoint of economy.

The value of P / V is obtained by the following principle. Along with the stirring, a load torque is generated on the shaft of the stirring blade as a repulsive force that pushes the liquid. Torque (T) is the product of the distance (M) from the axis center and the tangential force (F). When the load torque (kgf · cm) is obtained, the stirring power P (kW) is obtained by P = NT / 95000. Here, N is the shaft rotation speed (rpm). In the present invention, the value of P / V is P / V (kW / m ³ ) = based on the stirring power (P) indicated in the stirrer and the charged amount (V) of the aqueous dispersion into the stirring tank. It is determined by calculating [(stirring power (kW) indicated by the stirrer) / (charge amount into the reaction tank (m ³ ))].

(Description of manufacturing method)
<Operation procedure>
Next, a specific operation procedure of the method of the present invention will be described. First, water, a polymer solution as a raw material for the polymer powder, a dispersing agent, and other auxiliary agents are provided in a stirring vessel having a stirring blade satisfying the conditions of the present invention and a baffle plate extending from the lower part to the upper part of the inner wall of the stirring tank. Prepare raw materials. These raw materials may be mixed in a separate container in advance and then charged into a stirring tank, or may be mixed separately in a stirring tank after being charged separately. It is preferable to prepare the dispersant in an aqueous solution in advance. There is no particular limitation as an auxiliary material, depending on the quality of the target powder, antioxidants, ultraviolet absorbers, flame retardants, fillers, pigments, tackifiers, dyes, plasticizers, lubricants, crosslinking agents, A crosslinking accelerator or the like can be appropriately added.

  In general, steam stripping refers to a method of gasifying a volatile component by direct contact with the volatile component to exclude it from the system. In the present invention, polymer particles are obtained by volatilizing the solvent from the aqueous dispersion of the polymer solution by steam stripping. In the present invention, the steam stripping operation is carried out by venting steam in the same tank together with the heating performed when stirring the aqueous dispersion of the polymer solution. Therefore, when the raw materials have been charged into the stirring tank, stirring and steam blowing into the tank are started. The steam blowing means may be connected so that the pipe for introducing the steam is inserted into the liquid phase of the stirring tank. Either stirring or steam blowing can be started first, but if you want to prevent the backflow of polymer or the like to the steam line, you can start stirring after you start blowing steam, if you place importance on mixing of various raw materials Steam may be blown after an appropriate time has elapsed since the start of stirring. Usually, stirring and steam blowing may be performed almost simultaneously or within one hour from the start of stirring.

  In the present invention, a polymer powder composed of spherical particles having a small particle diameter is obtained by removing the solvent from the aqueous dispersion of the polymer solution by steam stripping. The time required for the steam stripping is selected to be sufficient for the solvent to be almost completely distilled off. In addition, the steam flow rate can be selected in an arbitrary range, but if the flow rate is too low, the heating rate is slow, so it takes time to produce, while if the flow rate is too high, the aqueous dispersion of the polymer solution is blown out due to foaming. There are problems such as requiring a huge steam boiler.

  The solvent gas that volatilizes due to steam heating and steam that does not condense and liquefy must be continuously purged so as not to accumulate in the stirring tank, and is usually liquefied and recovered through a heat exchanger.

  When the solvent is sufficiently removed from the polymer by the steam stripping, the steam blowing is stopped, and the resin slurry containing the spherical particles is cooled and discharged. If the slurry is dehydrated and dried, a powder of spherical particles can be obtained. In order to improve the properties as a powder, it is preferable to add an antiblocking agent to the slurry and the resin after dehydration. As an antiblocking agent, particles of about 0.05 to 10 μm can be used. For example, silica, calcium carbonate, metal soap, fatty acid amide, acrylic particles, and the like are preferably used. A latex obtained by homopolymerizing or copolymerizing acrylic acid ester or methacrylic acid ester is also preferably used. A general method for producing latex is described in detail in, for example, JP-A-2-269755, JP-A-8-134316, and JP-A-8-217817.

<Warming conditions>
Although the final liquid temperature at the time of a heating is not specifically limited, It is preferable that it is more than the azeotropic point of water and a solvent. However, the solvent can be easily removed by reducing the pressure in the stirring tank even below the azeotropic point of the solvent. From the viewpoint of economy and prevention of alteration of the resin skeleton, the upper limit of the temperature is preferably less than 160 ° C, more preferably less than 150 ° C, and most preferably less than 125 ° C. When the temperature is 160 ° C. or higher, the spherical particles of the polymer are softened, so that aggregation or the like may occur and the fine particles may not be dispersed in a single spherical shape. On the other hand, if the final liquid temperature is too low, the diffusion rate of the solvent contained in the powder will decrease and the amount of residual solvent in the powder will increase, resulting in safety during powder drying, VOC problems, and solvent recovery. It is not preferable in that the rate is lowered. Therefore, the lower limit of the temperature is preferably 60 ° C. or higher and more preferably 80 ° C. or higher from the viewpoint of solvent removal.

<Cooling conditions>
If the stirring is stopped at a high temperature after the granulation is completed, the particles may precipitate, and the slightly softened particles may be consolidated and aggregated. For this reason, before stopping stirring, it is preferable to cool to less than 100 ° C, and it is more preferable to cool to less than 70 ° C.

(raw materials)
<Dispersant>
The dispersant used in the method of the present invention is not particularly limited. For example, cellulose esters such as methyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, carboxymethyl cellulose, polyvinyl alcohols, polyethylene glycol, polyvinyl pyrrolidone, polyacrylamide, polystyrene sulfonic acid Organic salts, inorganic solids such as calcium phosphate and calcium carbonate, glycerin fatty acid ester, sorbitan ester, propylene glycol fatty acid ester, sucrose fatty acid ester, citric acid mono (di or tri) stearate ester, pentaerythritol fatty acid ester, trimethylolpropane Fatty acid ester, polyglycerol fatty acid ester, polyoxyethylene glycerol fatty acid ester, polyester Ter, polyoxyethylene sorbitan fatty acid ester, polyethylene glycol fatty acid ester, polypropylene glycol fatty acid ester, polyoxyethylene glycol fatty alcohol ether, polyoxyethylene alkylphenyl ether, N, N-bis (2-hydroxyethylene) fatty amine, ethylene bis Examples thereof include stearamide, a condensation product of fatty acid and diethanol, a block polymer of polyoxyethylene and polyoxypropylene, and a nonionic surfactant such as polyethylene glycol and polypropylene glycol. These are appropriately selected according to the polymer to be used. Among these, since dispersibility and particle size controllability are good, one or more selected from the group consisting of cellulose ester, polyvinyl alcohol, polyvinyl pyrrolidone, calcium phosphate, calcium carbonate and nonionic surfactant is used. Is preferred. Only one dispersant can be used, or two or more dispersants can be used in combination. When two or more types are used in combination, the combination is not particularly limited, but a mixture of two or more types selected from cellulose ester, polyvinyl alcohol, polyvinyl pyrrolidone, calcium phosphate, calcium carbonate and a nonionic surfactant is used. Is preferred.

<Dispersant usage>
The amount of the dispersant used is appropriately set in consideration of the dispersion performance with respect to the polymer and the properties of the solvent. For example, it is preferable to add 0.01 to 5 parts by weight of the dispersant with respect to 100 parts by weight of the polymer. It is more preferable to add 0.05 to 3 parts by weight, and it is particularly preferable to add 0.1 to 3 parts by weight. If the amount is less than 0.01 part by weight, the polymer may not be sufficiently dispersed in water and particles may not be formed. And may adversely affect physical properties such as transparency and moldability of the polymer.

<Solvent type>
In the present invention, the solvent used for producing the polymer powder comprising spherical particles is not particularly limited, and a solvent in which the polymer to be used is dissolved may be appropriately selected. The (co) boiling point of the solvent is preferably 25 ° C. or higher, more preferably 30 ° C. or higher at normal pressure (1 atm) in consideration of handling at room temperature. In addition, since the solvent is finally almost completely removed by evaporation, the (co) boiling point of the solvent is preferably 130 ° C. or less, more preferably 120 ° C. or less at normal pressure (1 atm), 100 ° C. It is particularly preferred that

  Specific examples of the solvent include aliphatic hydrocarbons such as pentane, hexane, heptane, cyclohexane and cyclopentane, aromatic hydrocarbons such as benzene, toluene, ethylbenzene and xylene, methyl ethyl ether, diethyl ether and Examples include ethers such as tetrahydrofuran, esters such as ethyl acetate, and halogenated hydrocarbons such as dichloromethane and chloroform.

<Amount of solvent used>
The amount of the solvent used is appropriately selected in consideration of the concentration, viscosity and the like of the polymer solution, but it is preferable to use such an amount that the solid content concentration of the polymer solution is 5 to 70% by weight. If the solid content concentration of the polymer solution is less than 5% by weight, the yield is reduced and is not efficient. On the other hand, if it exceeds 70% by weight, the viscosity of the whole solution becomes too high, and the polymer solution is sufficiently dispersed by stirring. May not be done. More preferably, the solvent is used so that the solid content concentration of the polymer solution is 10 to 50% by weight.

<Water volume>
The amount of water to be used can be appropriately determined in consideration of the particle diameter of the desired polymer powder. When the volume of the polymer solution before heating is 100% by volume, the amount of water used is preferably 25 to 500% by volume, more preferably 40 to 400% by volume, and 50 to 300% by volume. % Is particularly preferred. In addition, when metal salts are contained in water, the effect of the dispersant may be diminished, so that it is preferable to use ion-exchanged water or distilled water.

<Particle size>
The average particle diameter of the spherical particles of the polymer powder produced by the method of the present invention is preferably 10 μm or more and less than 1000 μm. When the particle diameter of the spherical particles is larger than 1000 μm, molding using a finely structured mold is not preferable because molding abnormalities are likely to occur. On the other hand, when it is smaller than 10 μm, the fluidity is deteriorated because attractive force between particles or static electricity is likely to occur. In addition, the said particle diameter can be adjusted by adjusting the quantity of a dispersing agent, the ratio of a polymer solution and water, etc. according to the intended use.

  In the present invention, a powder having a smaller particle diameter can be obtained as the amount of the dispersant increases. For example, when manufacturing powder used for mold molding applications such as powder slush molding, 20 μm or more and less than 700 μm in consideration of powder fluidity, mold filling, and dust control during handling. Preferably, the thickness is 50 μm or more and less than 500 μm.

<Measurement method of particle size>
The average particle diameter of the polymer powder of the spherical particles in the present invention was obtained by sieving the spherical particles with a standard sieve, and individually weighing the fractions belonging to the respective particle size ranges to obtain an average value based on the weight. Value. Specifically, for example, it can be obtained using an electromagnetic sieve shaker (manufactured by Lecce Co., Ltd., AS200BASIC (60 Hz)).

<Polymer>
The starting polymer used in the method for producing the polymer powder of the present invention is not particularly limited as long as it can be dissolved in a solvent and does not cure by heating, and various thermoplastic resins can be used. . Examples of the thermoplastic resin include olefin resins such as polyethylene, polypropylene, polybutene, polymethylpentene and norbornene resins, vinyl polymers such as polystyrene and styrene maleic anhydride copolymers, acrylic polymers, and methacrylic resins. (Meth) acrylic polymers or copolymers such as polymers, acrylic copolymers, methacrylic copolymers and (meth) acrylate-styrene copolymers, acrylonitrile-styrene copolymer resins (AS resins), Polycarbonate, polyarylate, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, modified polyphenylene ether, polyamide, polyamideimide, polyacetal, polyester, isobutylene polymer, styrene- (ethylene-propylene) -styrene Styrene copolymers such as coalescence (SEPS), styrene- (ethylene-butylene) -styrene copolymer (SEBS) and styrene-isoprene-styrene copolymer (SIS), acrylic rubber, silicon rubber, Examples include uncrosslinked rubbers such as isoprene rubber (IR) and ethylene-propylene rubber (EPR, EPDM). Among the above thermoplastic resins, olefin resins, vinyl polymers, (meth) acrylic polymers or (meth) acrylic copolymers because of their good physical properties such as heat resistance, moldability, impact resistance, AS resin, polycarbonate, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, modified polyphenylene ether, isobutylene polymer, styrene copolymer, and uncrosslinked rubber are preferred, and (meth) acrylic is superior in physical properties after molding. A polymer, a (meth) acrylic copolymer, or an isobutylene polymer is particularly preferable. In the present specification, “(meth) acryl” means acryl and / or methacryl.

<(Meth) acrylic block copolymer>
The (meth) acrylic block copolymer used in the present invention is a block copolymer having a block formed by polymerizing a monomer mainly composed of an acrylic ester and / or a methacrylic ester. Here, “having acrylic acid ester and / or methacrylic acid ester as the main component” means that the ratio of acrylic acid ester and methacrylic acid ester is the largest among all the monomer components constituting the polymer block. Means that.

  The acrylic ester that can be used as a monomer as a raw material for the (meth) acrylic block copolymer is not particularly limited. For example, methyl acrylate, ethyl acrylate, n-propyl acrylate, acrylic acid n-butyl, isobutyl acrylate, n-pentyl acrylate, n-hexyl acrylate, n-heptyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate, dodecyl acrylate, Acrylic aliphatic hydrocarbon (eg, alkyl having 1 to 20 carbon atoms, preferably 1 to 10 alkyl) ester such as stearyl acrylate; Acrylic alicyclic hydrocarbon ester such as cyclohexyl acrylate and isobornyl acrylate; Phenyl acrylate , Acrylics such as tolyl acrylate Acid aromatic hydrocarbon ester; acrylic acid aralkyl ester such as benzyl acrylate; ester of acrylic acid such as 2-methoxyethyl acrylate and 3-methoxybutyl acrylate and functional group-containing alcohol having etheric oxygen; acrylic acid Trifluoromethylmethyl, 2-trifluoromethylethyl acrylate, 2-perfluoroethylethyl acrylate, 2-perfluoroethyl-2-perfluorobutylethyl acrylate, 2-perfluoroethyl acrylate, perfluoroacrylate Methyl, diperfluoromethyl methyl acrylate, 2-perfluoromethyl-2-perfluoroethyl methyl acrylate, 2-perfluorohexyl ethyl acrylate, 2-perfluorodecylethyl acrylate, 2-perfluoro acrylate And acrylic acid fluoroalkyl esters such as hexadecyl ethyl and the like.

  The methacrylic acid ester that can be used as a monomer as a raw material for the (meth) acrylic block copolymer is not particularly limited. For example, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, methacrylic acid n-butyl, isobutyl methacrylate, n-pentyl methacrylate, n-hexyl methacrylate, n-heptyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, decyl methacrylate, dodecyl methacrylate, Methacrylic acid aliphatic hydrocarbons such as stearyl methacrylate (for example, alkyl having 1 to 20 carbon atoms, preferably 1 to 10 alkyl) esters; methacrylic acid alicyclic hydrocarbon esters such as cyclohexyl methacrylate and isobornyl methacrylate; Methacrylic acid aralkyl esters such as benzyl; Methacrylic acid aromatic hydrocarbon esters such as phenyl methacrylate and tolyl methacrylate; Functional groups having methacrylic acid and etheric oxygen such as 2-methoxyethyl methacrylate and 3-methoxybutyl methacrylate Esters with alcohols contained: trifluoromethyl methacrylate, 2-trifluoroethyl methacrylate, 2-perfluoroethyl ethyl methacrylate, 2-perfluoroethyl-2-perfluorobutyl ethyl methacrylate, 2-perfluoro methacrylate Ethyl, perfluoromethyl methacrylate, diperfluoromethyl methyl methacrylate, 2-perfluoromethyl-2-perfluoroethyl methyl methacrylate, 2-perfluorohexyl ethyl methacrylate, meta 2-perfluorodecyl ethyl acrylic acid, methacrylic acid fluorinated alkyl esters such as methacrylic acid 2-perfluoroalkyl-hexadecyl ethyl and the like.

  Among the acrylic acid esters or methacrylic acid esters, acrylic acid aliphatic hydrocarbon esters or methacrylic acid aliphatic hydrocarbon esters are preferable, and acrylic acid alkyl esters or methacrylic acid alkyl esters are more preferable in terms of cost and availability. Preferably, methyl acrylate or methyl methacrylate is particularly preferable.

  The average molecular weight of the (meth) acrylic block copolymer is not particularly limited, but may be appropriately determined in consideration of required physical properties. The average molecular weight of the (meth) acrylic block copolymer is preferably 3,000 to 500,000 as the number average molecular weight, more preferably 4,000 to 400,000, and still more preferably 5,000 to 300,000. is there. Further, the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the (meth) acrylic block copolymer is preferably 1.8 or less, and is 1.5 or less. More preferably. When Mw / Mn exceeds 1.8, the uniformity of the polymer spherical powder may deteriorate.

  The structure of the (meth) acrylic block copolymer is not particularly limited, but a linear block copolymer, a branched (star) block copolymer, or a mixture thereof is preferable. The structure of such a block copolymer is appropriately selected according to the required physical properties of the (meth) acrylic block copolymer, but in terms of cost and ease of polymerization, linear block copolymer Coalescence is particularly preferred.

  The spherical powder of the present invention may be a mixture of two or more (meth) acrylic block copolymers. Furthermore, you may use the (meth) acrylic block copolymer containing composition containing not only a (meth) acrylic block copolymer but another compound. For example, since the heat resistance, weather resistance, chemical resistance, and the like can be improved, a (meth) acrylic block copolymer-containing composition that can be finally crosslinked can also be used. Such a composition comprises, for example, a methacrylic polymer block (a) and an acrylic polymer block (b) having the structure shown below, and a reactive functional group [hereinafter referred to as a (meth) acrylic block copolymer. The (meth) acrylic block copolymer (A) having the reactive functional group of the block (a) or (b) in the block (a) or (b) and the reactive functional group thereof is referred to as “reactive functional group (X)”. The reactive functional group that reacts with the group (X) [hereinafter, this reactive functional group of the (meth) acrylic block copolymer is referred to as “reactive functional group (Y)”] is at least average per molecule. It is preferable to use a composition containing 1.1 or more compounds (B).

  The (meth) acrylic block copolymer (A) has a structure composed of a methacrylic polymer block (a) as a hard segment and an acrylic polymer block (b) as a soft segment. The methacrylic polymer block (a) provides a shape-retaining property at the time of molding, and the acrylic polymer block (b) provides a molded product having a high elasticity, and the fluidity at the time of melting at the time of molding increases.

  The (meth) acrylic block copolymer (A) preferably contains 15 to 50% by weight of the methacrylic polymer block (a) and 85 to 50% by weight of the acrylic polymer block (b). If the proportion of the methacrylic polymer block (a) is smaller than 15% by weight and the proportion of the acrylic polymer block (b) is larger than 85% by weight, the shape retention at the time of molding may be inferior. If the proportion of the combined block (a) is larger than 50% by weight and the proportion of the acrylic polymer block (b) is smaller than 50% by weight, the elasticity of the molded product may be lowered, and the fluidity at the time of melting may be reduced. May be reduced.

  From the viewpoint of the hardness of the molded body, the hardness is low when the proportion of the methacrylic polymer block (a) is small, and the hardness is high when the proportion of the acrylic polymer block (b) is small. is there. For this reason, the composition ratio of the methacrylic polymer block (a) and the acrylic polymer block (b) needs to be appropriately set in consideration of the required hardness of the molded product. From the viewpoint of moldability, when the proportion of the methacrylic polymer block (a) is small, the viscosity at the time of melting is low, and when the proportion of the acrylic polymer block (b) is small, the viscosity at the time of melting. Tend to be higher. For this reason, the composition ratio of the methacrylic polymer block (a) and the acrylic polymer block (b) needs to be appropriately set in consideration of the required viscosity.

The linear block copolymer may have any structure. From the viewpoint of the physical properties of the linear block copolymer or the powder, the methacrylic polymer block (a) is a, acrylic type. When the polymer block (b) is expressed as b, (ab) _n type, b- (ab) _n type and (ab) _n -a type (n is an integer of 1 or more, for example, 1 It is preferable that it consists of an at least 1 sort (s) of acrylic block copolymer selected from the group which consists of -3. Among these, an ab type diblock copolymer, an abb type triblock copolymer, or a mixture thereof is preferable from the viewpoint of easy handling at the time of processing and physical properties of the spherical powder. .
The relationship between the glass transition temperature of the methacrylic polymer block (a) and the acrylic polymer block (b) constituting the (meth) acrylic block copolymer (A) is the glass of the methacrylic polymer block (a). When the transition temperature is T _ga and the glass transition temperature of the acrylic polymer block (b) is T _gb , it is preferable to satisfy the relationship of the following formula in terms of mechanical strength and rubber elasticity expression.
T _ga > T _gb

The glass transition temperature (T _g ) of the (meth) acrylic block copolymer (A) (methacrylic polymer block (a) and acrylic polymer block (b)) is set according to the following Fox equation. This can be done by setting the weight ratio of the monomer in the polymer portion.
1 / T _g = (W ₁ / T _g1 ) + (W ₂ / T _g2 ) +... + (W _m / T _gm )
W ₁ + W ₂ + ... + W _m = 1
(In the formula, T _g represents the glass transition temperature of the polymer portion, and T _g1 , T _g2 ,..., T _gm represent the glass transition temperature of each polymerization monomer. Also, W ₁ , W ₂ , ..., W _m represents the weight ratio of each polymerization monomer).

  As the glass transition temperature of each polymerization monomer in the Fox formula, for example, a value described in Polymer Handbook Third Edition (Wiley-Interscience 1989) may be used.

  The glass transition temperature can be measured by DSC (Differential Scanning Calorimetry) or tan δ peak of dynamic viscoelasticity, but the polarities of the methacrylic polymer block (a) and the acrylic polymer block (b). If they are too close, or if the number of monomer chains in the block is too small, the measured values may be misaligned with the calculation formula based on the Fox formula.

<Methacrylic polymer block (a)>
The methacrylic polymer block (a) is a block formed by polymerizing a monomer having a methacrylic acid ester as a main component. The methacrylic acid ester is 50 to 100% by weight and a vinyl monomer copolymerizable therewith. It is preferably composed of 0 to 50% by weight. When the proportion of the methacrylic acid ester is less than 50% by weight, the weather resistance, which is a characteristic of the methacrylic acid ester, may be impaired.

  As a methacrylic acid ester which comprises a methacrylic polymer block (a), the above-mentioned methacrylic acid ester is mentioned, for example. Among these, methyl methacrylate is preferable in terms of processability, cost, and availability.

  Examples of vinyl monomers that can be copolymerized with methacrylic acid esters constituting the methacrylic polymer block (a) include acrylic acid esters, aromatic alkenyl compounds, vinyl cyanide compounds, conjugated diene compounds, halogens, and the like. Examples thereof include an unsaturated compound, a vinyl ester compound, and a maleimide compound.

  As an acrylic ester, the thing mentioned above can be mentioned as an example of the vinyl monomer copolymerizable with the methacrylic ester which comprises a methacrylic polymer block (a), for example.

  Examples of the aromatic alkenyl compound include styrene, α-methyl styrene, p-methyl styrene, p-methoxy styrene and the like.

  Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile.

  Examples of the conjugated diene compound include butadiene and isoprene.

  Examples of the halogen-containing unsaturated compound include vinyl chloride, vinylidene chloride, perfluoroethylene, perfluoropropylene, and vinylidene fluoride.

  Examples of the vinyl ester compound include vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, vinyl cinnamate, and the like.

  Examples of the maleimide compound include maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide and the like.

  These compounds mentioned as vinyl monomers can be used alone or in combination of two or more. These vinyl monomers are appropriately selected in consideration of the glass transition temperature of the methacrylic polymer block (a) described later, the compatibility with the acrylic polymer block (b), and the like.

The glass transition temperature of the methacrylic polymer block (a) is preferably adjusted to 50 to 130 ° C. At the time of molding, the powder and the fluid in which the powder is melted must flow sufficiently so that the polymer reaches the end of the mold. However, when the cohesive force and the glass transition temperature _{Tga of} the methacrylic polymer block (a) are too high, the melt viscosity tends to increase and the fluidity tends to deteriorate. On the other hand, when the glass transition temperature _Tga is too low, the resin composition has fluidity even at room temperature of about 25 ° C., and the powder shape may change.

<Acrylic polymer block (b)>
The monomer constituting the acrylic polymer block (b) is 100 to 50% by weight of an acrylate ester from the viewpoint of easily obtaining a spherical powder having the desired physical properties, cost and availability. It preferably consists of 0 to 50% by weight of a polymerizable vinyl monomer, and consists of 100 to 75% by weight of an acrylate ester and 0 to 25% by weight of a vinyl monomer copolymerizable therewith. Is more preferable. When the proportion of the acrylic ester is less than 50% by weight, the physical properties, particularly the impact resistance, of the spherical powder, which is a characteristic when these acrylic esters are used, may be impaired.

  The molecular weight required for the acrylic polymer block (b) may be determined from the elastic modulus and rubber elasticity required for the acrylic polymer block (b), the time required for the polymerization, and the like.

The elastic modulus is closely related to the ease of movement of the molecular chain and its molecular weight, and the original elastic modulus is not shown unless the molecular weight exceeds a certain level. The same applies to rubber elasticity, but from the viewpoint of rubber elasticity, a higher molecular weight is desirable. That is, when the range is exemplified with the number average molecular weight required for the acrylic polymer block (b) as M _b , preferably M _b > 3,000, more preferably M _b > 5,000, more preferably M _b > 10,000, particularly preferably M _b > 20,000, most preferably M _b > 40,000. However, since the polymerization time tends to be long when the number average molecular weight is large, it may be set according to the required productivity, but is preferably 500,000 or less, more preferably 300,000 or less. .

  Examples of the acrylate ester constituting the acrylic polymer block (b) include those described above as examples of the monomer that is a raw material of the (meth) acrylic block copolymer. These can be used alone or in combination of two or more.

  Among these, acrylate aliphatic hydrocarbon esters are preferable, alkyl acrylate esters are more preferable, and n-butyl acrylate, ethyl acrylate, and 2-ethylhexyl acrylate are still more preferable. N-butyl acrylate is particularly preferable in terms of impact resistance, cost, and availability of the spherical powder. Moreover, when the spherical powder needs oil resistance, ethyl acrylate is preferable. When low temperature characteristics are required, 2-ethylhexyl acrylate is preferable. Furthermore, when it is desired to achieve both oil resistance and low temperature characteristics, a mixture of ethyl acrylate, n-butyl acrylate, and 2-methoxyethyl acrylate is preferable.

  As an acrylic ester different from ethyl acrylate, n-butyl acrylate and 2-methoxyethyl acrylate constituting the acrylic polymer block (b), for example, a methacrylic polymer block (a) is formed. The monomer similar to the acrylic ester illustrated as a monomer to perform can be mentioned. These can be used alone or in combination of two or more thereof.

  Examples of the vinyl monomer copolymerizable with the acrylic ester constituting the acrylic polymer block (b) include, for example, a methacrylic ester, an aromatic alkenyl compound, a vinyl cyanide compound, a conjugated diene compound, and a halogen-containing compound. An unsaturated compound, a silicon-containing unsaturated compound, an unsaturated carboxylic acid compound, an unsaturated dicarboxylic acid compound, a vinyl ester compound, a maleimide compound, and the like can be mentioned. Specific examples thereof include a methacrylic polymer block (a The same thing as the above-mentioned used for a) can be mentioned. These vinyl monomers can be used alone or in combination of two or more. These vinyl monomers are suitably used in consideration of the balance of the glass transition temperature and oil resistance required for the acrylic polymer block (b), compatibility with the methacrylic polymer block (a), and the like. Choose one. For example, acrylonitrile may be copolymerized for the purpose of improving the oil resistance of the spherical powder.

  The glass transition temperature of the acrylic polymer block (b) is preferably 25 ° C. or lower, more preferably 0 ° C. or lower, and −20 ° C. or lower in consideration of the elasticity of the molded body. Further preferred. When the glass transition temperature of the acrylic polymer block (b) is higher than the temperature of the environment in which the molded body is used, flexibility and rubber elasticity are hardly exhibited.

<Reactive functional group (X)>
As described above, the (meth) acrylic block copolymer (A) preferably used in the present invention preferably has a reactive functional group (X) in the block (a) or (b). The reactive functional group (X) is not particularly limited as long as it acts as a reaction point with the following compound (B), and the (meth) acrylic block copolymer (A) is increased in molecular weight or crosslinked. It preferably acts as a reaction point or a crosslinking point, the stability of the bond produced by the reaction, the balance between the reaction efficiency at low and high temperatures, and easy introduction into the (meth) acrylic block copolymer (A) From the viewpoint of cost and the like, it is preferably at least one selected from an acid anhydride group, a carboxyl group, and an epoxy group. Especially, it is more preferable that it is an acid anhydride group and / or a carboxyl group at the point of the ease of introduction | transduction to a (meth) acrylic-type block copolymer (A), cost, and the reaction balance of low temperature and high temperature.

  The reactive functional group (X) is introduced into the block copolymer in a form in which the reactive functional group (X) is protected with an appropriate protective group or a precursor of the reactive functional group (X). Thereafter, the reactive functional group (X) can also be generated by a known chemical reaction.

  These reactive functional groups (X) can be used in combination of two or more, but when two or more types are used in combination, it is preferable to select functional groups that do not react with each other.

  The reactive functional group (X) may be contained only in one of the methacrylic polymer block (a) and the acrylic polymer block (b), or may be contained in both blocks. The reaction point of the (meth) acrylic block copolymer (A) and the blocks constituting the (meth) acrylic block copolymer (A) (methacrylic polymer block (a) and acrylic heavy The condition for introducing the reactive functional group (X) depends on the purpose, such as the cohesive strength of the combined block (b)), the glass transition temperature, and the required physical properties of the (meth) acrylic block copolymer (A). It can be used as appropriate.

  For example, a compound (B) containing a reactive functional group (Y) having reactivity with a reactive functional group (X), a methacrylic polymer block (a), and an acrylic polymer block (b) are selected. When it is desired to react the reactive functional group (X), the reactive functional group (X) may be introduced into the block to be reacted.

  In terms of improving the heat resistance and heat decomposability of the (meth) acrylic block copolymer (A), the reactive functional group (X) may be introduced into the methacrylic polymer block (a). From the viewpoint of imparting oil resistance, further rubber elasticity and compression set characteristics to the acrylic block copolymer (A), if a reactive functional group (X) is introduced into the acrylic polymer block (b) as a crosslinking point, Good.

  The content of the reactive functional group (X) is the cohesive force and reactivity of the reactive functional group (X), the structure and composition of the (meth) acrylic block copolymer (A), and the (meth) acrylic block copolymer. In consideration of the number of blocks constituting the polymer (A), the glass transition temperature, and the like, it is necessary to appropriately set as necessary, but the average is 1.0 or more per molecule of the block copolymer. Preferably, the average number is 2.0 or more. This is because if the average number is less than 1.0, the block copolymer tends to be insufficient in improving the heat resistance by increasing the molecular weight or crosslinking.

When the reactive functional group (X) is introduced into the methacrylic polymer block (a), it is preferably introduced within a range where the moldability of the acrylic block copolymer (A) does not deteriorate. If case of a powder slush molding is required to be flowing at no pressure, cohesive force and glass transition temperature Tg _a reactive functional group (X) methacrylic polymer block by introducing (a) increases, the melt viscosity Tends to increase and the moldability tends to deteriorate. Therefore, 130 ° C. Glass transition temperature Tg _a of methacrylic polymer block after introduction of the reactive functional group (X) is specifically (a) or less, more preferably 110 ° C. or less, more preferably 100 ° C. or less It is preferable to introduce in such a range.

When the reactive functional group (X) is introduced into the acrylic polymer block (b), it should be introduced in such a range that the flexibility, rubber elasticity, and low temperature characteristics of the (meth) acrylic block copolymer (A) are not deteriorated. Is preferred. When the cohesive force and glass transition temperature Tg _b of the acrylic polymer block (b) the introduction of reactive functional groups (X) increases, there is a tendency that flexibility, rubber elasticity, low temperature characteristics deteriorate. Specifically, the glass transition temperature Tg _b of the acrylic polymer block (b) after the introduction of the reactive functional group (X) is preferably 25 ° C. or less, more preferably 0 ° C. or less, More preferably, the temperature is set to −20 ° C. or lower.

  Below, an acid anhydride group, a carboxyl group, and an epoxy group preferable as the reactive functional group (X) will be described.

<Acid anhydride group>
An acid anhydride group easily reacts with a hydroxyl group and an amino group. Further, when the composition contains a compound having an active proton, it easily reacts with an epoxy group.

  The acid anhydride group may be introduced into the main chain of the (meth) acrylic block copolymer (A) or may be introduced into the side chain, but the (meth) acrylic block copolymer It is preferable to introduce | transduce into a principal chain from the ease of the introduction | transduction to a unification | combination (A). The acid anhydride group is obtained by dehydration and condensation of two carboxyl groups. Specifically, the general formula (1):

（式中、Ｒ¹は水素又はメチル基で、互いに同一でも異なっていてもよい。ｎは０〜３の整数、ｍは０又は１の整数）

(In the formula, R ¹ is hydrogen or a methyl group and may be the same or different. N is an integer of 0 to 3, and m is an integer of 0 or 1.)

  It is more preferable to contain in the form represented by these. N in General formula (1) is an integer of 0-3, Preferably it is 0 or 1, More preferably, it is 1. When n is 4 or more, polymerization tends to be complicated, and cyclization of the acid anhydride group tends to be difficult.

  When the monomer having an acid anhydride group does not poison the catalyst under the polymerization conditions, it is preferable to introduce the acid anhydride group by direct polymerization, and the monomer having a reactive functional group. When the body deactivates the catalyst during polymerization, a method of introducing an acid anhydride group by functional group conversion is preferred. Although not particularly limited, it is preferable in terms of ease of introduction that it is introduced into a (meth) acrylic block copolymer in the form of a precursor of an acid anhydride group and then cyclized. ):

（式中、Ｒ²は水素又はメチル基を表す。Ｒ³は水素、メチル基、又はフェニル基を表し、式中の３つのＲ³基のうち少なくとも２つはメチル基及びフェニル基からなる群から選択され、これらは互いに同一でも異なっていてもよい。）

(In the formula, R ² represents hydrogen or a methyl group. R ³ represents hydrogen, a methyl group, or a phenyl group, and at least two of the three R ³ groups in the formula consist of a methyl group and a phenyl group. And these may be the same or different from each other.)

It is more preferable to introduce a desired acid anhydride group by melting and kneading the (meth) acrylic block copolymer having at least one unit represented by
The introduction of the unit represented by the general formula (2) into the (meth) acrylic block copolymer is obtained by copolymerizing an acrylate ester or a methacrylic acid ester monomer derived from the general formula (2). Can be done. Examples of the monomer include t-butyl (meth) acrylate, isopropyl (meth) acrylate, α, α-dimethylbenzyl (meth) acrylate, α-methylbenzyl (meth) acrylate, It is not limited to these. Among these, (meth) acrylic acid-t-butyl is preferable from the standpoints of availability, ease of polymerization, and ease of acid anhydride group formation.

  The step of forming an acid anhydride group by cyclization from the precursor is preferably performed by heating a (meth) acrylic block copolymer having a precursor of an acid anhydride group at a high temperature, 180 to It is preferable to carry out by heating at 300 ° C. When the heating temperature is lower than 180 ° C., there is a tendency that the generation of acid anhydride groups tends to be insufficient. When the heating temperature is higher than 300 ° C., the (meth) acrylic block copolymer itself having a precursor of acid anhydride groups is decomposed. Tend to.

<Carboxyl group>
Carboxyl groups easily react with epoxy groups and amino groups. The carboxyl group may be introduced into the main chain of the (meth) acrylic block copolymer (A) or may be introduced into the side chain. The carboxyl group is preferably introduced into the main chain from the viewpoint of ease of introduction into the (meth) acrylic block copolymer (A).

  Regarding the method for introducing a carboxyl group, when the monomer having a carboxyl group does not poison the catalyst under the polymerization conditions, it is preferably introduced by direct polymerization. When deactivating the catalyst, a method of introducing a carboxyl group by functional group conversion is preferred.

  In the method of introducing a carboxyl group by functional group conversion, a (meth) acrylic block copolymer (A) in a form in which the carboxyl group is protected with an appropriate protecting group, or in the form of a functional group to be a precursor of the carboxyl group Then, a carboxyl group can be generated by a known chemical reaction known in the art.

  Examples of the method for synthesizing the (meth) acrylic block copolymer (A) having a carboxyl group include tert-butyl methacrylate, tert-butyl acrylate, trimethylsilyl methacrylate, and trimethylsilyl acrylate. In addition, a (meth) acrylic block copolymer containing a monomer having a functional group to be a precursor of a carboxyl group is synthesized, and a carboxyl group is generated by a known chemical reaction such as hydrolysis or acid decomposition (special (Kaihei 10-298248, JP-A-2001-234146) and general formula (2):

（式中、Ｒ²は水素又はメチル基を表す。Ｒ³は水素、メチル基、又はフェニル基を表し、式中の３つのＲ³基のうち少なくとも２つはメチル基及びフェニル基からなる群から選択され、これらは互いに同一でも異なっていてもよい。）

(In the formula, R ² represents hydrogen or a methyl group. R ³ represents hydrogen, a methyl group, or a phenyl group, and at least two of the three R ³ groups in the formula consist of a methyl group and a phenyl group. And these may be the same or different from each other.)

  There is a method in which a (meth) acrylic block copolymer having at least one unit represented by is melt-kneaded and introduced. The unit represented by the general formula (2) has a part of a pathway in which an ester unit decomposes at a high temperature to generate a carboxyl group, followed by cyclization to generate an acid anhydride group. Utilizing this, the carboxyl group can be introduced by appropriately adjusting the heating temperature and time according to the type and content of the unit represented by the general formula (2). Moreover, a carboxyl group can also be introduce | transduced by hydrolysis of an acid anhydride group. The introduction of a carboxyl group by hydrolysis can be hydrolyzed by heating an acrylic block copolymer having a (carboxyl group) precursor in the presence of an acid catalyst. The reaction temperature at that time is preferably heated at 100 to 300 ° C. When the temperature is lower than 100 ° C., the carboxyl group tends to be insufficiently generated. When the temperature is higher than 300 ° C., the acrylic block copolymer itself having a carboxyl group precursor may be decomposed.

<Epoxy group>
Epoxy groups readily react with carboxyl groups, hydroxyl groups, and amino groups. The epoxy group is not particularly limited as long as it is an organic group containing an epoxy ring. For example, 1,2-epoxyethyl group, 2,3-epoxypropyl group (that is, glycidyl group), 2,3-epoxy-2- Examples thereof include aliphatic hydrocarbon (eg, alkyl) groups having an epoxy ring such as methylpropyl group; alicyclic hydrocarbon groups having an epoxy ring such as 3,4-epoxycyclohexyl group. These may be selected from the reactivity, reaction rate, availability, cost, etc. as necessary. Although it does not restrict | limit in particular, A glycidyl group is preferable in these in view of availability.

  It is preferable to introduce the epoxy group by directly polymerizing a monomer having an epoxy group. Examples of the monomer having an epoxy group include glycidyl (meth) acrylate, 2,3-epoxy-2-methylpropyl (meth) acrylate, and (3,4-epoxycyclohexyl) methyl (meth) acrylate ( Examples thereof include esters of (meth) acrylic acid and an organic group-containing alcohol containing an epoxy ring; and epoxy group-containing unsaturated compounds such as 4-vinyl-1-cyclohexene-1,2-epoxide. These may be selected as necessary from the reactivity, reaction rate, availability, cost, etc. Among these, glycidyl (meth) acrylate is preferred from the viewpoint of availability.

<Production method of (meth) acrylic block copolymer (A)>
The method for producing the (meth) acrylic block copolymer (A) is not particularly limited, but it is preferable to use controlled polymerization using an initiator. Examples of controlled polymerization include living anion polymerization, radical polymerization using a chain transfer agent, and recently developed living radical polymerization. Especially, it is preferable to manufacture by living radical polymerization from the point of control of the molecular weight and structure of an acryl-type block copolymer.

  Living radical polymerization is radical polymerization in which the activity at the polymerization terminal is maintained without loss. In the narrow sense, living polymerization refers to polymerization in which the terminal always has activity, but generally includes pseudo-living polymerization in which the terminal is inactivated and the terminal is in equilibrium. . The definition here is also the latter. Living radical polymerization has been actively researched by various groups in recent years.

  Examples thereof include those using a chain transfer agent such as polysulfide, cobalt porphyrin complex (J. Am. Chem. Soc., 1994, 116, 7943), Those using radical scavengers such as nitroxide compounds (Macromolecules, 1994, 27, 7228), atom transfer radical polymerization using organic halides as initiators and transition metal complexes as catalysts ( Atom Transfer Radical Polymerization (ATRP). In the present invention, which of these methods is used is not particularly limited, but atom transfer radical polymerization is preferable from the viewpoint of easy control.

  Atom transfer radical polymerization is polymerized using an organic halide or a sulfonyl halide compound as an initiator and a metal complex having a group 7 element, 8 group, 9 group, 10 group or 11 element as a central metal in the periodic table as a catalyst. (For example, Mattyjaszewski et al., Journal of American Chemical Society, J. Am. Chem. Soc., 1995, 117, 5614, Macromolecules (Macromolecules). ), 1995, 28, 7901, Science, 1996, 272, 866, or Sawamoto et al., Macromolecules, 1995, 28, 1721).

  According to these methods, in general, the polymerization proceeds in a living manner and the molecular weight distribution is narrow (Mw / M), although the polymerization rate is very high and a radical reaction such as coupling between radicals is likely to occur. Mn = 1.1 to 1.5) polymer is obtained, and the molecular weight can be freely controlled by the charging ratio of the monomer and the initiator.

  In the atom transfer radical polymerization method, a monofunctional, difunctional, or polyfunctional compound can be used as the organic halide or sulfonyl halide compound used as an initiator. These may be properly used depending on the purpose. However, in the case of producing a diblock copolymer, a monofunctional compound is preferable from the viewpoint of easy availability of an initiator, and an aba triblock In the case of producing a copolymer and a b-a-b type triblock copolymer, it is preferable to use a bifunctional compound from the viewpoint of the number of reaction steps and shortening of the time. In the case of production, it is preferable to use a polyfunctional compound in terms of the number of reaction steps and time reduction.

  Moreover, it is also possible to use a polymer initiator as the initiator. The polymer initiator is a compound composed of a polymer in which a halogen atom is bonded to the end of a molecular chain among organic halides or sulfonyl halide compounds. Since such a polymer initiator can be produced by a controlled polymerization method other than the living radical polymerization method, a block copolymer obtained by combining polymers obtained by different polymerization methods is obtained. .

Examples of monofunctional compounds include:
C ₆ H ₅ -CH ₂ X,
_{C 6 H 5 -C (H)} (X) -CH 3,
_{C 6 H 5 -C (X)} (CH 3) 2,
R ⁴ —C (H) (X) —COOR ⁵ ,
R ⁴ —C (CH ₃ ) (X) —COOR ⁵ ,
R ⁴ —C (H) (X) —CO—R ⁵ ,
R ⁴ —C (CH ₃ ) (X) —CO—R ⁵ ,
R ⁴ —C ₆ H ₄ —SO ₂ X,
And the like. In the above formulas, C ₆ H ₅ represents a phenyl group, and C ₆ H ₄ represents a phenylene group (which may be ortho-substituted, meta-substituted, or para-substituted). R ⁴ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. X represents chlorine, bromine or iodine. R ⁵ represents a monovalent organic group having 1 to 20 carbon atoms.

  As specific examples of the monofunctional compound, ethyl 2-bromide propionate and butyl 2-bromide propionate are preferable because they are similar to the structure of the acrylate monomer and can easily control polymerization. .

As a bifunctional compound, for example,
_{X-CH 2 -C 6 H 4} -CH 2 -X,
X—CH (CH ₃ ) —C ₆ H ₄ —CH (CH ₃ ) —X,
_{X-C (CH 3) 2} -C 6 H 4 -C (CH 3) 2 -X,
X—CH (COOR ⁶ ) — (CH ₂ ) _n —CH (COOR ⁶ ) —X,
_{X-C (CH 3) (} COOR 6) - (CH 2) n -C (CH 3) (COOR 6) -X
X—CH (COR ⁶ ) — (CH ₂ ) _n —CH (COR ⁶ ) —X,
_{X-C (CH 3) (} COR 6) - (CH 2) n -C (CH 3) (COR 6) -X,
_{X-CH 2 -CO-CH 2} -X,
_{X-CH (CH 3) -CO} -CH (CH 3) -X,
_{X-C (CH 3) 2} -CO-C (CH 3) 2 -X,
_{X-CH (C 6 H 5} ) -CO-CH (C 6 H 5) -X,
X—CH ₂ —COO— (CH ₂ ) _n —OCO—CH ₂ —X,
X—CH (CH ₃ ) —COO— (CH ₂ ) _n —OCO—CH (CH ₃ ) —X,
_{X-C (CH 3) 2} -COO- (CH 2) n -OCO-C (CH 3) 2 -X,
_{X-CH 2 -CO-CO-} CH 2 -X,
_{X-CH (CH 3) -CO} -CO-CH (CH 3) -X,
_{X-C (CH 3) 2} -CO-CO-C (CH 3) 2 -X,
X—CH ₂ —COO—C ₆ H ₄ —OCO—CH ₂ —X,
X—CH (CH ₃ ) —COO—C ₆ H ₄ —OCO—CH (CH ₃ ) —X,
_{X-C (CH 3) 2} -COO-C 6 H 4 -OCO-C (CH 3) 2 -X,
_{X-SO 2 -C 6 H 4} -SO 2 -X,
And the like. In the above formulas, R ⁶ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. n represents an integer of 0 to 20. C ₆ H ₅ , C ₆ H ₄ and X are the same as described above.

  As specific examples of the bifunctional compound, bis (bromomethyl) benzene, diethyl 2,5-dibromoadipate and diethyl 2,6-dibromopimelate are preferable from the viewpoint of availability of raw materials.

As the multifunctional compound, for example,
_{C 6 H 3 - (CH 2} -X) 3,
_{C 6 H 3 - (CH (} CH 3) -X) 3,
_{C 6 H 3 - (C (} CH 3) 2 -X) 3,
_{C 6 H 3 - (OCO-} CH 2 -X) 3,
_{C 6 H 3 - (OCO-} CH (CH 3) -X) 3,
_{C 6 H 3 - (OCO-} C (CH 3) 2 -X) 3,
_{C 6 H 3 - (SO 2} -X) 3,
And the like. In the above formulas, C ₆ H ₃ is a trisubstituted benzene ring (the positions of the three bonds may be any of the 1st to 6th positions, and the combination thereof can be selected as appropriate), and X is Same as above.

  Specific examples of the polyfunctional compound include, for example, tris (bromomethyl) benzene, tris (1-bromoethyl) benzene, tris (1-bromoisopropyl) benzene and the like. Of these, tris (bromomethyl) benzene is preferable from the viewpoint of availability of raw materials.

  In addition, when an organic halide or sulfonyl halide compound having a functional group is used in addition to the group for initiating polymerization, a polymer in which a functional group other than the group for initiating polymerization is easily introduced at the terminal or in the molecule is obtained. It is done. Examples of the functional group other than the group that initiates polymerization include an alkenyl group, a hydroxyl group, an epoxy group, an amino group, an amide group, and a silyl group.

The transition metal complex used as a catalyst for atom transfer radical polymerization is not particularly limited, but preferred are monovalent and zerovalent copper, divalent ruthenium, divalent iron, and divalent nickel. A complex.
Among these, a copper complex is preferable from the viewpoint of cost and reaction control. Examples of the monovalent copper compound include cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, cuprous oxide, and cuprous perchlorate. Of these, cuprous chloride and cuprous bromide are preferred from the viewpoint of polymerization control. When a monovalent copper compound is used, 2,2′-bipyridyl and its derivatives (for example, 4,4′-dinolyl-2,2′-bipyridyl, 4,4′-di (5- Noryl) -2,2′-bipyridyl and the like; 1,10-phenanthroline, derivatives thereof (eg, 4,7-dinolyl-1,10-phenanthroline, 5,6-dinolyl- 1,10-phenanthroline-based compounds such as 1,10-phenanthroline); polyamines such as tetramethylethylenediamine (TMEDA), pentamethyldiethylenetriamine, and hexamethyl (2-aminoethyl) amine may be added as a ligand. .

  The type of catalyst, ligand and activator to be used may be appropriately determined from the relationship between the initiator, monomer and solvent to be used, and the required reaction rate.

  Similarly, the amount of catalyst and ligand to be used may be determined from the relationship between the amount of initiator, monomer and solvent to be used, and the required reaction rate. For example, in order to obtain a polymer having a high molecular weight, the initiator / monomer ratio must be made smaller than in the case of obtaining a polymer having a low molecular weight. The reaction rate can be increased by increasing the number of catalysts and ligands. In addition, when a polymer having a glass transition point higher than room temperature is produced, the reaction rate tends to decrease when an appropriate organic solvent is added to lower the viscosity of the system and increase the stirring efficiency. In such a case, the reaction rate can be increased by increasing the number of catalysts and ligands.

  Atom transfer radical polymerization can be carried out in the absence of a solvent (bulk polymerization) or in various solvents. Further, in bulk polymerization and polymerization performed in various solvents, the polymerization can be stopped halfway.

  Examples of the solvent that can be used include hydrocarbon solvents, ether solvents, halogenated hydrocarbon solvents, ketone solvents, alcohol solvents, nitrile solvents, ester solvents, carbonate solvents, and the like.

  The polymerization can be performed in the range of 20 ° C to 200 ° C, and is preferably performed in the range of 50 to 150 ° C.

  As a method of polymerizing the (meth) acrylic block copolymer (A), a method of sequentially adding monomers, a method of polymerizing the next block using a polymer synthesized in advance as a polymer initiator, separately Examples thereof include a method of bonding polymerized polymers by reaction. Any of these methods may be used and is appropriately selected according to the purpose. In addition, the method by the sequential addition of a monomer is preferable from the point of the simplicity of a manufacturing process.

  The reaction solution obtained by polymerization contains a mixture of a polymer and a metal complex, and by removing these, a polymer solution containing the (meth) acrylic block copolymer (A) is obtained. be able to.

  The polymer solution thus obtained is subsequently subjected to an evaporation operation, whereby the polymerization solvent and unreacted monomers are removed. Thereby, the (meth) acrylic block copolymer (A) can be isolated.

<Compound (B)>
As the polymer used in the present invention, a (meth) acrylic block copolymer composition containing not only the block copolymer (A) but also other compounds (hereinafter referred to as “compound B”) is used. May be. The compound (B) is not particularly limited as long as it is a compound containing at least 1.1 or more reactive functional groups (Y) on average per molecule. In particular, it is preferable that the block copolymer (A) can react with the functional group (X) to increase the molecular weight or be crosslinked.

  The reactive functional group (Y) is not particularly limited as long as it reacts with the reactive functional group (X) in the block copolymer (A). The stability of the bond produced by the reaction, low and high temperatures In view of the balance of the reaction and the cost of the compound (B), at least one selected from an epoxy group, a carboxyl group, an acid anhydride group and an oxazoline group is preferable. These reactive functional groups (Y) can be used in combination of two or more, but when two or more types are used in combination, they react with each other so as not to interfere with the reaction with the reactive functional group (X). It is preferable to make it.

  The compound (B) preferably has a boiling point of 200 ° C. or higher, more preferably 230 ° C. or higher, and still more preferably 250 ° C. or higher. Since the resulting composition is molded at a high temperature, if the boiling point is less than 200 ° C., the compound (B) tends to volatilize during molding, and the molding method and conditions are limited.

  Furthermore, the compound (B) is preferably a polymer having a weight average molecular weight of 50,000 or less, and more preferably a polymer having a weight average molecular weight of 30,000 or less. When the weight average molecular weight exceeds 50,000, the effect of improving fluidity as a plasticizer tends to be low.

  0.1-100 weight part is preferable with respect to 100 weight part of (meth) acrylic block copolymers (A), and, as for the compounding quantity of a compound (B), 1-50 weight part is more preferable. When the compounding amount of the compound (B) is less than 0.1 parts by weight, the crosslinking reaction with the (meth) acrylic block copolymer (A) does not sufficiently proceed, and the effect of improving the heat resistance of the molded article becomes insufficient. In some cases, when the amount is more than 100 parts by weight, the crosslinking reaction proceeds excessively, and the elongation and flexibility of the molded product may be impaired.

  The content of the reactive functional group (Y) in the compound (B) varies depending on the reactivity of the reactive functional group (Y), the site and manner of the reactive functional group (Y). Therefore, it may be set as necessary, preferably 1.1 or more on average per molecule of compound (B), more preferably 1.5 or more on average, particularly preferably 2.0 or more on average. . When the number is less than 1.1, the effect of the acrylic block copolymer as a high molecular weight reaction agent or a crosslinking agent is lowered, and the effect of improving the heat resistance of the acrylic block copolymer (A) tends to be insufficient. There is.

  When the reactive functional group (Y) is an epoxy group, the compound (B) having an epoxy group is not particularly limited as long as it is a compound having an average of 1.1 or more epoxy groups per molecule, and bisphenol A Type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, bisphenol S type epoxy resin and epoxy resins hydrogenated with these, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, alicyclic epoxy resin, novolak type Epoxy resins, urethane-modified epoxy resins having urethane bonds, fluorinated epoxy resins, rubber-modified epoxy resins containing polybutadiene or NBR, epoxy resins such as flame retardant epoxy resins such as glycidyl ether of tetrabromobisphenol A, polyhydric alcohols Epoxy plasticizers such as epoxidized soybean oil, epoxidized linseed oil, and epoxidized fatty acid alkyl ester, which are glycidyl ethers and glycidyl esters of polybasic acids, and Bond First (trade name, manufactured by Sumitomo Chemical Co., Ltd.) And ARUFON (trade name, manufactured by Toagosei Co., Ltd.) and other epoxy group-containing polymers; unsaturated polymer epoxy groups such as olefin polymers, styrene polymers and acrylic polymers, etc. Although a polymer etc. are illustrated, it is not limited to these, The epoxy group containing compound generally used can be used. Specifically, ARUFON (registered trademark) XG4000, ARUFUON UG4000, ARUFON XG4010, ARUFON UG4010, ARUFON XD945, ARUFON XD950, ARUFON UG4030, ARUFON UG4070, etc., which are available from Toagosei Co., Ltd. can be suitably used. These are all acrylic polymers such as acrylic and acrylate / styrene, and contain 1.1 or more epoxy groups in one molecule. These epoxy group-containing compounds may be used alone or in combination of two or more.

  When the reactive functional group (Y) is a carboxyl group, the compound (B) having a carboxyl group is not particularly limited as long as it is a compound having an average of 1.1 or more carboxyl groups per molecule, and adipic acid , Itaconic acid, iminodiacetic acid, glutaric acid, succinic acid, citraconic acid, oxalic acid, tartaric acid, sebacic acid, azelaic acid, decanedicarboxylic acid, dodecanedicarboxylic acid, cyclohexanedicarboxylic acid, trans-1,2-cyclohexanediaminetetraacetic acid, Fumaric acid, brassic acid (n11), malonic acid (n1), citraconic acid, maleic acid, isophthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 5-hydroxyisophthalic acid, o -Phthalic acid, 3,3,4,4-benzophenonetetracarboxylic acid , Diphenoxyethane dicarboxylic acid, biphenyl dicarboxylic acid, diphenyl ether dicarboxylic acid, diphenyl sulfone dicarboxylic acid, diphenyl ketone dicarboxylic acid, anthracene dicarboxylic acid, α, β-bis (4-carboxyphenoxy) ethane, trimellitic acid, pyromellitic acid, Imidazole-4,5-dicarboxylic acid, keridamic acid, 2,3-pyrazinedicarboxylic acid, citric acid, glycyrrhizic acid, aspartic acid, glutamic acid, malic acid, ACPEC (trade name, manufactured by Sumitomo Seika Co., Ltd.) and Actflow Carboxyl group-containing polymers such as (trade name, manufactured by Soken Chemical Co., Ltd.) and ARUFON (trade name, manufactured by Toagosei Co., Ltd.); petroleum resins such as olefin polymers, styrene polymers and acrylic polymers Carboxyl group content of unsaturated polymers such as Examples thereof include, but are not limited to, polymers that are generally used and carboxyl group-containing compounds can be used. These carboxyl group-containing compounds may be used alone or in combination of two or more.

  When the reactive functional group (Y) is an acid anhydride group, the compound (B) having an acid anhydride group is particularly a compound having at least 1.1 acid anhydride groups on average per molecule. Without limitation, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, pyromellitic dianhydride, 3,3 Contains acid anhydride groups such as', 4,4'-diphenylsulfonetetracarboxylic dianhydride, maleated methylcyclohexene tetrabasic anhydride, isobutylene maleic anhydride copolymer, bondine (trade name, manufactured by Sumika Atofina) Examples of the polymer include polymers, but are not limited thereto. These acid anhydride group-containing compounds may be used alone or in combination of two or more.

  When the reactive functional group (Y) is an oxazoline group, the compound (B) having an oxazoline group is not particularly limited as long as the compound has an average of at least 1.1 oxazoline groups per molecule. 2'-bis- (2-oxazoline), 2,2'-methylene-bis- (2-oxazoline), 2,2'-ethylene-bis- (2-oxazoline), 2,2'-trimethylene-bis- (2-oxazoline), 2,2'-tetramethylene-bis- (2-oxazoline), 2,2'-hexamethylene-bis- (2-oxazoline), 2,2'-octamethylene-bis- (2 -Oxazoline), 2,2'-ethylene-bis- (4,4'-dimethyl-2-oxazoline), 2,2'-p-phenylene-bis- (2-oxazoline), 2,2'-m- Feni -Bis- (2-oxazoline), 2,2'-m-phenylene-bis- (4,4'-dimethyl-2-oxazoline), 1,3-phenylenebisoxazoline, 1,4-phenylenebisoxazoline, Polyfunctional oxazoline compounds such as bis- (2-oxazolinylcyclohexane) sulfide and bis- (2-oxazolinylnorbornane) sulfide, and oxazoline group-containing polymers such as Epocross (trade name, manufactured by Nippon Shokubai Co., Ltd.) However, the present invention is not limited to these examples. These oxazoline group-containing compounds may be used alone or in combination of two or more.

  Among the compounds having the epoxy group (B), compatibility with the (meth) acrylic block copolymer (A), availability, cost, low volatility at the time of molding, improvement effect of moldability and gain Bisphenol A type epoxy resin, polyglycol glycidyl ethers and polybasic glycidyl esters epoxidized soybean oil, epoxidized linseed oil, epoxidized fatty acid alkyl ester, etc. Preferred examples include epoxy group plasticizers and epoxy group-containing polymers such as ARUFON (registered trademark) manufactured by Toagosei Co., Ltd.

  Among the compounds having a carboxyl group, carboxyl group-containing polymers such as trimellitic acid, Actflow (trade name, manufactured by Soken Chemical Co., Ltd.) and ARUFON (trade name, manufactured by Toagosei Co., Ltd.) Preferred examples are listed. Among the compounds having an acid anhydride group, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and pyromellitic dianhydride are preferable examples. Of the compounds having an oxazoline group, 1,3-phenylenebisoxazoline is a preferred example.

  In addition, it is also possible to use a compound (B) that can improve fluidity as a plasticizer during molding of the composition and can react with the (meth) acrylic block copolymer (A) simultaneously with molding. it can. An example of such a compound is an acrylic polymer.

  An acrylic polymer is a polymer of one or more acrylic monomers, or one or two or more acrylic monomers and a monomer other than an acrylic monomer. It is preferable that it was obtained by making it.

  Examples of the acrylic monomer include the acrylic acid ester and methacrylic acid ester described above as examples of the monomer constituting the methacrylic polymer block (a). Among these, it is preferable to use any one of acrylic acid-n-butyl, ethyl acrylate and acrylic acid-2-methoxyethyl, or a combination of two or more thereof.

  The monomer other than the acrylic monomer is not particularly limited as long as it is a monomer copolymerizable with the acrylic monomer. For example, vinyl acetate, styrene or the like can be used.

  In addition, it is preferable that the ratio of the acryloyl group containing monomer component with respect to all the monomer components in the said compound (B) is 70 weight% or more. When the proportion is less than 70% by weight, the weather resistance is lowered and the compatibility with the (meth) acrylic block copolymer (A) tends to be lowered. Moreover, discoloration tends to occur in the molded product.

  The molecular weight of the acrylic polymer is not particularly limited, but is preferably a low molecular weight having an average weight molecular weight of 30,000 or less, more preferably 500 to 30,000, and more preferably 500 to 10,000. Particularly preferred. If the weight average molecular weight is less than 500, the molded product tends to be sticky. On the other hand, if the weight average molecular weight exceeds 30,000, plasticization of the molded product tends to be insufficient.

  The viscosity of the acrylic polymer is preferably 35,000 mPa · s or less, preferably 10,000 mPa · s or less, when measured with a cone-plate type rotational viscometer (E-type viscometer) at 25 ° C. More preferably, it is 5,000 mPa · s or less. When the viscosity is higher than 35,000 mPa · s, the plasticizing effect of the spherical powder tends to decrease. Although there is no particular lower limit of the preferred viscosity, the normal viscosity of the acrylic polymer is 10 mPa · s or more.

The glass transition temperature T _g of the above acrylic polymer is preferably at 100 ° C. or less when measured by differential scanning calorimetry (DSC), more preferably at 25 ° C. or less, is 0 ℃ or less Is more preferable, and it is especially preferable that it is -30 degrees C or less. When the glass transition temperature T _g is higher than 100 ° C., there is a tendency that the effect of improving the moldability as a plasticizer may be insufficient, also tends to the flexibility of the obtained molded article decreases.

  The acrylic polymer can be obtained by polymerizing by a known predetermined method. The polymerization method may be appropriately selected as necessary. For example, the polymerization may be performed by a method such as suspension polymerization, emulsion polymerization, bulk polymerization, living anion polymerization, polymerization using a chain transfer agent, and controlled polymerization such as living radical polymerization. However, controlled polymerization in which a polymer having good weather resistance and heat resistance and a relatively low molecular weight and a small molecular weight distribution is obtained is preferable, and the method using high-temperature continuous polymerization described below is more preferable in terms of cost.

  The acrylic polymer is preferably obtained by a polymerization reaction at a temperature of 180 to 350 ° C. At this polymerization temperature, an acrylic polymer having a relatively low molecular weight can be obtained without using a polymerization initiator or a chain transfer agent. For this reason, the acrylic polymer is an excellent plasticizer and has good weather resistance. Specifically, the method by high-temperature continuous polymerization described in JP-A-57-502171, JP-A-59-6207, JP-A-60-215007 and WO01 / 083619, An example is a method in which the monomer mixture is continuously supplied at a constant supply rate into a reactor set to a temperature and a pressure, and an amount of the reaction liquid corresponding to the supply amount is withdrawn.

  When cross-linking is required between the (meth) acrylic block copolymer (A) and the compound (B), there is no particular limitation on the cross-linking method. For example, the (meth) acrylic block copolymer (A) and the compound A cross-linked (meth) acrylic copolymer can be obtained by using a kneader or the like that can melt and knead the composition containing (B) while heating.

(Sub-material)
<Filler>
The filler is not particularly limited, but glass fiber, mica, graphite, diatomaceous earth, white clay, silica (fumed silica, precipitated silica, crystalline silica, fused silica, dolomite, silicic anhydride, hydrous silica Acid etc.), reinforcing fillers such as carbon black; calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite, ferric oxide, red pepper, aluminum fine powder, flint powder, zinc oxide Active zinc white, zinc dust, zinc carbonate and shirasu balloon, glass fiber and glass filament, and activated carbon. The addition amount is appropriately adjusted according to the required physical properties, but it is preferably 1.0 to 50 parts by weight, more preferably 5 to 40 parts by weight based on 100 parts by weight of the polymer. It is particularly preferable to add 10 to 30 parts by weight. If the amount is less than 1.0 part by weight, the effect is often not sufficient. If the amount is more than 50 parts by weight, the mechanical properties of the resulting molded product may be adversely affected.

<Other additives>
Specific examples of the cross-linking agent include ARUFON (registered trademark) XG4000, ARUFON UG4000, ARUFON XG4010, ARUFON UG4010, ARUFON XD945, ARUFON XD950, ARUFON UG4030, and ARUFON UG40, which are available from Toagosei Co., Ltd. These are acrylic polymers such as all acrylic and acrylate / styrene, and contain 1.1 or more epoxy groups in one molecule.

  Although it does not specifically limit as a plasticizer, For example, dimethyl phthalate, diethyl phthalate, di-n-butyl phthalate, di- (2-ethylhexyl) phthalate, diheptyl phthalate, diisodecyl phthalate, diphthalate -Phthalic acid derivatives such as n-octyl, diisononyl phthalate, ditridecyl phthalate, octyl decyl phthalate, butyl benzyl phthalate, dicyclohexyl phthalate; isophthalic acid derivatives such as dimethyl isophthalate; di- (2-ethylhexyl) tetrahydro Tetrahydrophthalic acid derivatives such as phthalic acid; dimethyl adipate, dibutyl adipate, di-n-hexyl adipate, di- (2-ethylhexyl) adipate, isononyl adipate, diisodecyl adipate, dibutyl diglycol adipate, etc. No Pinic acid derivatives; azelaic acid derivatives such as di-2-ethylhexyl azelate; sebacic acid derivatives such as dibutyl sebacate and dioctyl sebacate; dodecane-2-acid derivatives; dibutyl maleate and di-2-ethylhexyl maleate Maleic acid derivatives; fumaric acid derivatives such as dibutyl fumarate; trimellitic acid derivatives such as tris-2-ethylhexyl trimellitic acid and trioctyl trimellitic acid; pyromellitic acid derivatives such as tetraoctyl pyromellitic acid; citric acid derivatives such as tributyl acetylcitrate; Benzoic acid derivatives such as 2-ethylhexyl hydroxybenzoate, itaconic acid derivatives; oleic acid derivatives; ricinoleic acid derivatives; stearic acid derivatives; other fatty acid derivatives; sulfonic acid derivatives such as N-alkylbenzenesulfonamide; Phosphoric acid derivatives such as tylphosphate, tris (2-ethylhexyl) phosphate, 2-ethylhexyldiphenyl phosphate; glutaric acid derivatives; dibasic acids such as adipic acid, azelaic acid, phthalic acid, glycols and monohydric alcohols, etc. Polyester plasticizers, glycol derivatives, glycerin derivatives, paraffin derivatives such as chlorinated paraffins, epoxy derivatives polyester polymerized plasticizers, polyether polymerized plasticizers, carbonate derivatives such as ethylene carbonate and propylene carbonate, etc. Is mentioned. Examples of other high molecular weight plasticizers include acrylic polymers, polypropylene glycol polymers, polytetrahydrofuran polymers, polyisobutylene polymers, and the like. Moreover, oil fractions, such as oils, such as animal oil and vegetable oil, kerosene, light oil, heavy oil, and naphtha, etc. are mentioned. Examples of the softening agent include process oil, and more specifically, petroleum process oil such as naphthenic process oil and aromatic process oil. Examples of vegetable oils include castor oil, cottonseed oil, linseed oil, rapeseed oil, soybean oil, palm oil, palm oil, peanut oil, pine oil, tall oil and the like.

  The antioxidant (stabilizer) is preferably used in the range of 0.1 to 20 parts by weight and more preferably in the range of 0.2 to 10 parts by weight with respect to 100 parts by weight of the polymer. . When the blending amount is less than 0.1 parts by weight, the heat resistance and light resistance effect of the resulting composition may not be sufficient, and when it exceeds 20 parts by weight, the mechanical properties of the resulting molded article deteriorate. There is.

  Examples of the light stabilizer include benzotriazole such as Tinuvin (registered trademark) P, Tinuvin 234, Tinuvin 320, Tinuvin 326, Tinuvin 327, Tinuvin 329, Tinuvin 213 (all of which are manufactured by Ciba Specialty Chemicals Co., Ltd.). Absorption of triazine-based compounds, triazine-based compounds such as Tinuvin 1577, benzophenone-based compounds such as CHIMASSORB (registered trademark) 81, and benzoate-based compounds such as Tinuvin 120 (manufactured by Ciba Specialty Chemicals) An agent can be illustrated. Hindered amine compounds are also preferred, and such compounds are described below. Dimethyl-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate of succinate, poly [{6- (1,1,3,3-tetramethylbutyl) Amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino}], N, N′-bis (3aminopropyl) ethylenediamine- 2,4-bis [N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino] -6-chloro-1,3,5-triazine condensate, bis (2, 2,6,6-tetramethyl-4-piperidyl) sebacate, succinic acid-bis (2,2,6,6-tetramethyl-4-piperidinyl) ester and the like. Such products include Tinuvin 622LD, Tinuvin 144, CHIMASSORB 944LD, CHIMASSORB 119FL, Irgafos 168 (all of which are manufactured by Ciba Specialty Chemicals Co., Ltd.), MARK (registered trademark) LA-52, MARK LA-57, MARK LA -62, MARK LA-67, MARK LA-63, MARK LA-68, MARK LA-82, MARK LA-87 (all of which are manufactured by Adeka Argus Chemical Co., Ltd.), SANOL (registered trademark) LS-770, Examples include Sanol LS-765, Sanol LS-292, Sanol LS-2626, Sanol LS-1114, Sanol LS-744, Sanol LS-440 (all of which are manufactured by Sankyo Lifetech Co., Ltd.), but are not limited thereto. Is not something

  Moreover, by using it combining a ultraviolet absorber and a hindered amine type compound, a higher stabilization effect may be exhibited, and these can be used together.

  The anti-aging agent is not particularly limited, but thioether type anti-aging agents such as MARK PEP-36 and MARK AO-23 (all of which are manufactured by Adeka A-Gas Chemical), Irgafos 38, Irgafos 168, Irgafos P-EPQ (above) Examples thereof include phosphorus antioxidants such as Ciba Specialty Chemicals Co., Ltd., and hindered phenol compounds. Of these, hindered phenol compounds as shown below are preferred.

  Specific examples of the hindered phenol compound include the following. 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, mono (or di or tri) (α methylbenzyl) phenol, 2,2′-methylenebis (4 ethyl-6-tert-butylphenol), 2,2'-methylenebis (4methyl-6-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), 4,4 ' -Thiobis (3-methyl-6-tert-butylphenol), 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, triethylene glycol-bis- [3- (3-t- Butyl-5-methyl-4hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3 5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3 5-triazine, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylenebis [3- (3,5-di-t -Butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, N, N'-hexamethylenebis (3,5-di-t- Butyl-4-hydroxy-hydrocinnamamide), 3,5-di-t-butyl-4-hydroxy-benzylphosphonate-diethyl ester, 1,3,5-trimethyl -2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, bis (3,5-di-t-butyl-4-hydroxybenzylphosphonate ethyl) calcium, tris- (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 2,4-2,4-bis [(octylthio) methyl] o-cresol, N, N′-bis [3- (3 5-di-t-butyl-4-hydroxyphenyl) propionyl] hydrazine, tris (2,4-di-t-butylphenyl) phosphite, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- [2-Hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) Benzotriazole, 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-tert-butyl-2-hydroxyphenyl) -5-chloro Benzotriazole, 2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole, 2- (2′-hydroxy-5′-t-octylphenyl) -benzotriazole, methyl-3- [3 -T-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate-condensate with polyethylene glycol (molecular weight about 300), hydroxyphenylbenzotriazole derivative, 2- (3,5- Di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonate bis (1,2,2,6,6-pentamethyl) -4-piperidyl), 2,4-di -t- butyl-3,5-di -t- butyl-4-hydroxybenzoate, and the like.

  As products of the anti-aging agent, NOCRACK (registered trademark) 200, NOCRACK M-17, NOCLACK SP, NOCRACK SP-N, NOCRACK NS-5, NOCRACK NS-6, NOCRACK NS-30, NOCRACK 300, NOCRACK NS-7 , Nocrack DAH, Nocrack CD (all manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.), MARK AO-30, MARK AO-40, MARK AO-50, MARK AO-60, MARK AO-616, MARK AO-635 , MARK AO-658, MARK AO-80, MARK AO-15, MARK AO-18, MARK 328, MARK AO-37 (all are manufactured by Adeka Argus Chemical Co., Ltd.), IRGANOX-245, IRGANOX-259, IRGANOX-565, IRGA OX-1010, IRGANOX-1024, IRGANOX-1035, IRGANOX-1076, IRGANOX-1081, IRGANOX-1098, IRGANOX-1222, IRGANOX-1330, IRGANOX-1425WL (all manufactured by Ciba Specialty Chemicals Co., Ltd.) Examples include Sumilizer (registered trademark) GM and Sumilizer GA-80 (all of which are manufactured by Sumitomo Chemical Co., Ltd.), but are not limited thereto.

(Examples and Comparative Examples)
EXAMPLES Next, although this invention is demonstrated further in detail based on an Example, this invention is not limited only to these Examples. In the description of the following examples and comparative examples, “parts” means “parts by weight”.

<Molecular weight>
The molecular weight and molecular weight distribution of the block copolymer shown in this example were measured using a Waters GPC system (column: Shodex K-804 (polystyrene gel) manufactured by Showa Denko KK, mobile phase: chloroform). The number average molecular weight is expressed in terms of polystyrene.

<Particle size>
The particle diameter and the average particle diameter of each section of the powder composed of spherical particles were measured using an electromagnetic sieve shaker (AS200BASIC (60 Hz), manufactured by Lecce Co., Ltd.). The median diameter based on weight was defined as the average particle diameter.

(Production Example 1)
<Abbreviation>
The abbreviations used in the description of the following production examples are as follows.
MMA: methyl methacrylate,
EA: ethyl acrylate,
BA: acrylic acid-n-butyl,
TBA: acrylate-t-butyl
TBMA: methacrylate-t-butyl
b: Acrylic polymer block.

<Synthesis of (meth) acrylic block copolymer>
(MMA / EA)-(b)-(BA / TBA)-(b)-(MMA / EA) type,
[However, BA / TBA = 22.4 / 1 (mol ratio), MMA / EA = 7.8 / 1 (mol ratio), (BA + TBA) / (MMA + EA) = 6/4 (weight ratio))
Synthesis of (meth) acrylic block copolymer of No. 7716.8 g of BA77816.8 g was charged into a 500 L reactor that had been purged with nitrogen and then vacuum degassed while the pressure inside the reactor was reduced. Next, 692.1 g of cuprous bromide was charged and stirred at 30 ° C. for 15 minutes. Thereafter, a solution prepared by dissolving 965.1 g of diethyl 2,5-dibromoadipate in 7137.1 g of acetonitrile was charged, and the mixture was further stirred for 60 minutes while raising the temperature to 75 ° C. By adding 83.6 g of pentamethyldiethylenetriamine, polymerization of BA / TBA as the first block was started. When the BA conversion rate reached 98.9%, 106860.6 g of toluene, 477.7 g of cuprous chloride, MMA49593.7 g, and 8050.9 g of EA were charged, 83.6 g of pentamethyldiethylenetriamine was added, The polymerization of MMA / EA was started.

  Every 45 minutes, 83.6 g of pentamethyldiethylenetriamine was added, and when the MMA conversion rate reached 95.4%, 240,000 g of toluene was added to dilute the reaction solution and the reactor was cooled. When the GPC analysis of the obtained block copolymer was conducted, the number average molecular weight Mn was 79800, and molecular weight distribution Mw / Mn was 1.48.

  Toluene was added to the resulting block copolymer solution to adjust the polymer concentration to 25% by weight. To 1 kg of the obtained polymer solution, 5.5 g of p-toluenesulfonic acid and 1.0 g of TBMA were added, the inside of the reactor was replaced with nitrogen, and the jacket was heated. Sampling was performed 7 hours after the internal temperature reached 148 ° C., and it was confirmed that the conversion rate of TBMA added as an internal standard substance to a carboxyl group was 100%. That is, TBA which is a precursor of a carboxyl group in the polymer was 100% modified to a carboxyl group by acid decomposition. Moreover, in the sampling, it confirmed that the copper complex aggregated and became insoluble. Further, 30 minutes later, cooling was started. After completion of cooling, 5.0 g of Radiolite # 3000 (manufactured by Showa Chemical Industry Co., Ltd.) was added as a filter aid, and the mixture was stirred at 30 ° C. for 30 minutes. The solid content was separated using a pressure filter.

  Kyoward 500SH (13.1 g) was added to about 4.50 kg of the block copolymer solution after filtration, and the atmosphere in the reactor was replaced with nitrogen, followed by stirring at 30 ° C. for 1 hour. The reaction solution was sampled to confirm that the solution was neutral, and the reaction was completed. Thereafter, the reactor was pressurized to 0.1 to 0.4 MPaG with nitrogen, and the solid component was separated using the above-described pressure filter equipped with polyester felt as a filter medium, and a (meth) acrylic block copolymer. A polymer solution containing was obtained.

<Example 1>
Production Example after adding 3.94 g of pure water 7L and polyvinyl alcohol (trade name Gohsenol KH-17, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) to a 50 L stirring device (tank diameter D = 300 mm, 4 baffle plates) 1 (meth) acrylic block copolymer toluene solution 3500 g (400 parts, solid content concentration 25%), ARUFON (registered trademark) UG4010 (manufactured by Toagosei Co., Ltd.) which is an acrylic polymer having an epoxy group 10 parts, 10 parts RS700 (Asahi Denka Kogyo Co., Ltd.) which is a polyether ester plasticizer, 1 part beef fat extremely hardened oil (melting point 60 ° C .: Nippon Oil & Fats Co., Ltd.) which is an ester lubricant did. Steam was blown into the tank while stirring at 500 rpm using an H-shaped blade having a blade diameter (d) of 120 mm (d / D = 0.4) as the stirring blade. The power number at this time is 2.7, the power P / V per unit volume of the supplied liquid is 3.4 kW / m ³ , and the ratio of the volume (v2) through which the stirring blade passes by rotation and the volume of the supplied liquid (v1) ( R) is 22%. The solvent gas which volatilizes was continuously purged so as not to accumulate in the stirring device. After 5 minutes had passed since the internal temperature reached 100 ° C., the steam was stopped and cooling was started, and the stirring was stopped after the internal temperature decreased to 60 ° C. When the particle size distribution of the resin slurry produced in the stirring vessel was measured with a wet sieve, the particles having a particle size of 53 μm to 500 μm accounted for 93% by weight of the entire spherical particles, and the average particle size was 190 μm.

<Example 2>
The same operation as in Example 1 except that the addition amount of polyvinyl alcohol was 4.81 g, and the stirring blade was stirred at 400 rpm using a Max Blend blade having a blade diameter (d) of 160 mm (d / D = 0.53). Went. The power number at this time is 2.6, the power P / V per unit volume of the supplied liquid is 6.9 kW / m ³ , and the ratio of the volume (v2) through which the stirring blade passes by rotation and the volume of the supplied liquid (v1) ( R) is 39%. When the particle size distribution of the resin slurry produced in the stirring vessel was measured with a wet sieve, the particles having a particle size of 53 μm to 500 μm accounted for 93% by weight of the entire spherical particles, and the average particle size was 170 μm.

<Example 3>
The same operation as in Example 1 except that the addition amount of polyvinyl alcohol was 4.81 g, and the stirring blade was stirred at 300 rpm using a Max Blend blade having a blade diameter (d) of 160 mm (d / D = 0.53). Went. The power number at this time is 2.6, the power P / V per unit volume of the supplied liquid is 2.9 kW / m ³ , and the ratio of the volume (v2) through which the stirring blade passes by rotation and the volume of the supplied liquid (v1) ( R) is 39%. When the particle size distribution of the resin slurry produced in the stirring vessel was measured with a wet sieve, the particles having a particle size of 53 μm to 500 μm accounted for 85% by weight of the entire spherical particles, and the average particle size was 160 μm.

<Example 4>
The same operation as in Example 1 except that the addition amount of polyvinyl alcohol was 5.25 g, and the stirring blade was stirred at 280 rpm using an H-shaped blade having a blade diameter (d) of 180 mm (d / D = 0.6). Went. The power number at this time is 1.4, the power P / V per unit volume of the supplied liquid is 2.4 kW / m ³ , and the ratio of the volume (v2) through which the stirring blade passes by rotation and the volume of the supplied liquid (v1) ( R) is 36%. When the particle size distribution of the resin slurry generated in the stirring vessel was measured with a wet sieve, particles having a particle size of 53 μm to 500 μm accounted for 88% by weight of the entire spherical particles, and the average particle size was 160 μm.

<Example 5>
The same operation as in Example 1 except that the addition amount of polyvinyl alcohol was 5.25 g, and the stirring blade was stirred at 220 rpm using a Max Blend blade having a blade diameter (d) of 210 mm (d / D = 0.7). Went. The power number at this time is 1.4, the power P / V per unit volume of the charged liquid is 2.5 kW / m ³ , and the ratio of the volume (v2) through which the stirring blade passes by rotation and the volume of the charged liquid (v1) ( R) is 58%. When the particle size distribution of the resin slurry generated in the stirring vessel was measured with a wet sieve, particles having a particle size of 53 μm to 500 μm accounted for 85% by weight of the entire spherical particles, and the average particle size was 150 μm.

<Example 6>
The same operation as in Example 1 was performed except that the addition amount of polyvinyl alcohol was 5.25 g, and the stirring blade was stirred at 300 rpm using a flat blade having a blade diameter (d) of 180 mm (d / D = 0.6). went. The power number at this time is 1.3, the power P / V per unit volume of the charged liquid is 2.7 kW / m ³ , and the ratio of the volume (v2) through which the stirring blade passes by rotation to the volume of the charged liquid (v1) ( R) is 65%. When the particle size distribution of the resin slurry produced in the stirring vessel was measured with a wet sieve, the particles having a particle size of 53 μm to 500 μm accounted for 90% by weight of the entire spherical particles, and the average particle size was 170 μm.

<Comparative Example 1>
Example 1 except that the addition amount of polyvinyl alcohol was 5.25 g, and the stirring blade was stirred at 600 rpm using a two-stage four-blade inclined blade having a blade diameter (d) of 150 mm (d / D = 0.5). The same operation was performed. The power number at this time is 0.8, the power P / V per unit volume of the supplied liquid is 5.4 kW / m ³ , and the ratio of the volume (v2) through which the stirring blade passes by rotation and the volume of the supplied liquid (v1) ( R) is 10%. When the particle size distribution of the resin slurry generated in the stirring vessel was measured with a wet sieve, particles having a particle size of 53 μm to 500 μm accounted for 67% by weight of the entire spherical particles, and the average particle size was 210 μm.

<Comparative example 2>
Example 1 except that the addition amount of polyvinyl alcohol was 6.13 g, and the stirring blade was stirred at 600 rpm using a two-stage four-blade inclined blade having a blade diameter (d) of 150 mm (d / D = 0.5). The same operation was performed. The power number at this time is 0.8, the power P / V per unit volume of the supplied liquid is 5.4 kW / m ³ , and the ratio of the volume (v2) through which the stirring blade passes by rotation and the volume of the supplied liquid (v1) ( R) is 10%. When the particle size distribution of the resin slurry produced in the stirring vessel was measured with a wet sieve, particles having a particle size of 53 μm to 500 μm accounted for 68% by weight of the entire spherical particles, and the average particle size was 160 μm.

<Comparative Example 3>
The same operation as in Example 1 except that the addition amount of polyvinyl alcohol was 6.13 g, and the stirring blade was stirred at 90 rpm using a Max Blend blade (d / D = 0.7) having a blade diameter (d) of 210 mm. Went. The power number at this time is 1.4, the power P / V per unit volume of the supplied liquid is 0.2 kW / m ³ , and the ratio of the volume (v2) through which the stirring blade passes by rotation and the volume of the supplied liquid (v1) ( R) is 58%. When the particle size distribution of the resin slurry produced in the stirring vessel was measured with a wet sieve, the particles having a particle size of 53 μm to 500 μm accounted for 67% by weight of the entire spherical particles, and the average particle size was 130 μm.

  In Table 1, the characteristic of the stirring blade used in Examples 1-6 and Comparative Examples 1-3 and the particle size of the obtained powder are shown.

<Example 7>
After adding 66 g of pure water 105 L and polyvinyl alcohol (trade name Gohsenol KH-17, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) to an 800 L stirring device (tank diameter D = 800 mm, 4 baffle plates), Production Example 1 53 kg (400 parts, solid content concentration 25%) of toluene solution of (meth) acrylic block copolymer, 15 parts of ARUFON (registered trademark) UG4012 (manufactured by Toagosei Co., Ltd.) which is an acrylic polymer having an epoxy group 5 parts of RS700 (Asahi Denka Kogyo Co., Ltd.) which is a polyether ester plasticizer and 1 part of beef tallow extremely hardened oil (melting point: 60 ° C .: manufactured by Nippon Oil & Fats Co., Ltd.) which is an ester-based lubricant were added. Steam was blown into the tank while stirring at 224 rpm using an H-shaped blade having a blade diameter (d) of 320 mm (d / D = 0.4) as the stirring blade. The power number at this time is 2.7, the power P / V per unit volume of the supplied liquid is 2.8 kW / m ³ , and the ratio of the volume (v2) through which the stirring blade passes by rotation to the volume of the supplied liquid (v1) ( R) is 35%. The solvent gas which volatilizes was continuously purged so as not to accumulate in the stirring apparatus. After 5 minutes had passed since the internal temperature reached 100 ° C., the steam was stopped and cooling was started, and the stirring was stopped after the internal temperature decreased to 60 ° C. When the particle size distribution of the resin slurry produced in the stirring vessel was measured with a wet sieve, the particles having a particle size of 53 μm to 500 μm accounted for 91% by weight of the entire spherical particles, and the average particle size was 240 μm.

<Example 8>
Example 7 except that the amount of polyvinyl alcohol added was 59 g, and the stirring blade was stirred at 150 rpm using the Kaneka blade shown in FIG. 1 having a blade diameter (d) of 420 mm (d / D = 0.53). The operation was performed. The power number at this time is 2.6, the power P / V per unit volume of the supplied liquid is 3.3 kW / m ³ , and the ratio of the volume (v2) through which the stirring blade passes by rotation and the volume of the supplied liquid (v1) ( R) is 67%. When the particle size distribution of the resin slurry produced in the stirring vessel was measured with a wet sieve, the particles having a particle size of 53 μm to 500 μm accounted for 90% by weight of the entire spherical particles, and the average particle size was 250 μm.

<Comparative example 4>
The same as Example 7 except that the addition amount of polyvinyl alcohol was 92 g, and the stirring blade was stirred at 250 rpm using a two-stage four-blade inclined blade (d / D = 0.5) having a blade diameter (d) of 400 mm. The operation was performed. The power number at this time is 0.8, the power P / V per unit volume of the supplied liquid is 3.5 kW / m ³ , and the ratio of the volume (v2) through which the stirring blade passes by rotation and the volume of the supplied liquid (v1) ( R) is 13%. When the particle size distribution of the resin slurry produced in the stirring vessel was measured with a wet sieve, particles having a particle size of 53 μm to 500 μm accounted for 74% by weight of the entire spherical particles, and the average particle size was 200 μm.

  Table 2 shows the characteristics of the stirring blades used in Examples 7 to 8 and Comparative Example 4 and the particle diameters of the obtained powders.

<Example 9>
Production Example after adding 3.94 g of pure water 7L and polyvinyl alcohol (trade name Gohsenol KH-17, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) to a 50 L stirring device (tank diameter D = 300 mm, 4 baffle plates) 1, 500 parts of toluene solution of a (meth) acrylic block copolymer (solid content concentration 25%), 10 parts of ARUFON (registered trademark) UG4010 (manufactured by Toagosei Co., Ltd.), which is an acrylic polymer having an epoxy group, 10 parts of RS700 (manufactured by Asahi Denka Kogyo Co., Ltd.) which is a polyether ester plasticizer and 1 part of beef tallow extremely hardened oil (melting point 60 ° C .: manufactured by Nippon Oil & Fats Co., Ltd.) which is an ester-based lubricant were added. The stirring blade has a trapezoidal stirring blade having a blade diameter (d _ave ) of 120 mm (d _ave /D=0.4), an upper blade diameter (d _high ) of 105 mm, and a lower blade diameter (d _low ) of 135 mm. Steam was blown into the tank while stirring at 500 rpm. The power number at this time is 2.7, the power per unit volume of the charged liquid is 3.4 kW / m ³ , and the ratio (R) of the volume (v2) through which the stirring blade passes by rotation and the volume of the charged liquid (v1) is 22%. The solvent gas which volatilizes was continuously purged so as not to accumulate in the stirring device. After 5 minutes had passed since the internal temperature reached 100 ° C., the steam was stopped and cooling was started, and the stirring was stopped after the internal temperature decreased to 60 ° C. When the particle size distribution of the resin slurry generated in the stirring vessel was measured with a wet sieve, the particles having a particle size of 53 μm to 500 μm accounted for 96% by weight of the entire spherical particles, and the average particle size was 200 μm. In addition, the average (d _ave ) of the stirring blade diameter with respect to the tank diameter (D) is 40%, and the ratio of the lower blade diameter (d _high ) to the lower blade diameter (d _low ) is 22%, the average diameter ( The portion without the stirring blades (d _ex ) for d _ave ) is 50%.

As can be seen from the examples shown in Tables 1 to 3, the power number, the power P / V (kW / m ³ ) per unit volume of the charged liquid, the volume (v2) through which the stirring blade passes by rotation, and the volume of the charged liquid By setting the ratio (R) to (v1) within the range of the present invention, the obtained spherical particle powder has a smaller total of fine powder and coarse particles than the conventional method. Therefore, according to the manufacturing method of this invention, it turns out that the use efficiency of a raw material is high compared with the former, and a spherical particle can be obtained.

  The polymer powder produced by the method of the present invention is composed of spherical particles having a small particle diameter and is excellent in fluidity and moldability, and therefore can be suitably used as various molding materials.

The schematic perspective view which shows an example of the stirring tank and stirring blade used for this invention. FIG. FIG. The abbreviated vertical side view of the stirring tank and the stirring blade showing the shape of the trapezoidal stirring blade.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Stirrer tank 2 Stirrer shaft 3 Lower paddle blade 4 Middle comb blade 5 Upper comb blade 6 Baffle plate 11 Stirrer 12 Stirrer shaft 13 Trapezoid blade 13a Trapezoid blade arm portion 13b Trapezoid blade strip portion 14 Baffle plate D Stirring tank diameter d Stirring blade diameter d _High stirring blade diameter (upper part)
d _ave stirring blade diameter (average)
d _low stirring blade diameter (bottom)
d _Ex part without stirring blade

Claims (14)

A water dispersion containing water, a polymer solution and a dispersing agent is charged into a stirring tank of a stirring device, and the water dispersion is obtained by directly blowing steam into the stirring tank while stirring the water dispersion with a stirring blade. In the method for producing a polymer powder including the step of heating the liquid and removing the solvent of the polymer solution by steam stripping , the aqueous dispersion liquid in the stirring tank represented by the following formula (1) The ratio (R) of the volume (v2) through which the stirring blade passes by rotation in the stirring tank to the volume (v1) of the charged liquid is 20% or more, and the stirring blade has a power number greater than 1 And the solvent is removed by heating the aqueous dispersion while stirring and rotating the stirring blade at a rotational speed at which the power P / V per unit volume of the liquid is greater than 2 kW / m ^3. Heavy consisting of spherical particles Method of manufacturing a body powder.
R (%) = (v2 / v1) × 100 Formula (1) The method for producing polymer powder according to claim 1 , wherein the stirring tank is provided with two or more baffle plates extending from the lower part to the upper part on the inner wall part thereof. The method for producing polymer powder according to claim 1 or 2 , wherein the stirring blade is a large lattice blade. 4. The method for producing polymer powder according to claim 3 , wherein the large lattice blade is an H-shaped blade having a stirring shaft as a target line and two flat plates extending in the axial direction on both sides thereof. The large lattice blade is mounted with a paddle blade made of a wide flat plate disposed at the bottom of the stirring tank at the lowermost stage, and comb-shaped blades at the middle and upper stages, and with respect to the paddle blade positioned at the lowermost stage. A middle comb-like wing adjacent thereto is arranged in advance in the rotational direction at a crossing angle of less than 90 degrees, and the middle paddle wing adjacent to the lowermost paddle wing is axially And an upper comb-like wing adjacent to the comb-like wing located in the middle stage at the crossing angle of less than 90 degrees in advance in the rotational direction; and 4. The method for producing polymer powder according to claim 3 , wherein the upper comb-like wing adjacent to the middle wing is an wing having an overlap in the axial direction. In the large lattice blade, the average blade diameter (d _ave ) of the stirring blade is 30 to 70% with respect to the tank diameter (D) of the stirring tank, and the upper blade diameter (d _high ) is the lower blade diameter ( _{4. The} method for producing a polymer powder according to claim 3 , wherein the trapezoidal wing is 10% or more smaller than _dlow ). The trapezoid blade, relative to the average diameter of the stirring blade diameter (d _ave), according to claim 6, wherein the stirring blades 30% to 60% with no stirring blade piece by piece in the center (d _ex) is present A method for producing a polymer powder. The method for producing polymer powder according to claim 3 , wherein the large lattice blade is a Max Blend blade. The method for producing a polymer powder according to claim 1 or 2 , wherein the large stirring blade is a flat blade. The method for producing a polymer powder according to any one of claims 1 to 9 , wherein an average particle diameter of the obtained powder is 10 µm or more and less than 1000 µm. The method for producing a polymer powder according to any one of claims 1 to 10 , wherein the polymer solution comprises a thermoplastic resin and an organic solvent. The method for producing polymer powder according to claim 11 , wherein the thermoplastic resin is a (meth) acrylic block copolymer. The (meth) acrylic block copolymer, according to claim 12, which is a methacrylic polymer block (a) and the acrylic polymer block (b) (meth) acrylic block copolymer (A) A method for producing a polymer powder. The said dispersing agent is at least 1 sort (s) chosen from a cellulose ester, polyvinyl alcohol, polyvinyl pyrrolidone, a calcium phosphate, a calcium carbonate, and a nonionic surfactant, Manufacture of the polymer powder in any one of Claims 1-13 Method.

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