Resin composition and molded article

Abstract

The purpose of the present invention is to provide a polymer with which compatibility is improved when a polyester resin such as a poly(butylene terephthalate) resin is compounded with another resin and with which the tensile elongation of a molded body can be improved. This polymer has a first polymer portion and a second polymer portion. The first polymer portion is a polyester-based polymer. The second polymer portion has a constituent unit that is different from a constituent unit that constitutes the first polymer portion. The proportion of the first polymer is more than 20 parts by mass and not more than 90 parts by mass relative to a total of 100 parts by mass of the first polymer portion and the second polymer portion. The second polymer portion has a constituent unit derived from a (meth)acrylate monomer.

Description

Technical Field

[0001] The present invention relates to a polymer, a resin additive, a resin composition, and a molded body.

Background Art

[0002] Conventionally, attempts have been made to mix multiple resins to achieve the expression of functions or the improvement of performance that cannot be obtained with a single resin. However, since many combinations of resin types are incompatible, the performance or functions achieved by compounding often deteriorate compared to those of a single resin. Therefore, in order to improve the compatibility of multiple resin types, a compatibilizer is added.

[0003] Patent Document 1 discloses that a polybutylene terephthalate resin, a polystyrene resin, and carbon fiber have good flatness and mechanical properties by using polycarbonate as a compatibilizer.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] However, according to the study by the present inventors, it has been found that the compatibilizer described in Patent Document 1 may not sufficiently improve the compatibility between the polybutylene terephthalate resin and the polystyrene resin. Therefore, one aspect of the present invention aims to provide a polymer or the like that can improve the compatibility when a polyester resin typified by a polybutylene terephthalate resin is compounded with other resins, and further has excellent tensile elongation of the molded body.

Means for Solving the Problems

[0006] One aspect of the present invention is a polymer having a first polymer portion and a second polymer portion, wherein the first polymer portion is a polyester polymer, and the second polymer portion has different structural units from the structural units constituting the first polymer portion, and the first polymer is present in a total of 100 parts by mass of the first polymer portion and the second polymer portion. portion The proportion of is greater than 20 parts by mass and less than or equal to 90 parts by mass, and the second polymer portion has constituent units derived from (meth)acrylate monomers. [Effects of the Invention]

[0007] According to one aspect of the present invention, when two or more resins are mixed, it is possible to provide a polymer or the like that can improve the compatibility of the resins and reduce phase separation, and also exhibit excellent tensile elongation of the molded article. [Brief explanation of the drawing]

[0008] [Figure 1] This is a cross-sectional photograph of the molded body of Example 1, observed with a transmission electron microscope. [Figure 2] This is a cross-sectional image of the molded product of Comparative Example 1, observed with a transmission electron microscope. [Modes for carrying out the invention]

[0009] The following describes this embodiment in detail. Note that the following description is one embodiment of the present invention, and the present invention is not limited to the configuration described below. The polymer according to this embodiment is a polymer (hereinafter sometimes referred to as polymer A) having a first polymer portion which is a polyester polymer, and a second polymer portion which has different structural units from the structural units constituting the first polymer portion. By using polymer A as a resin additive to two or more matrix resins including a polyester resin, the first matrix resin and Compatibility with the second matrix resin can be improved. Therefore, phase separation between the first matrix resin and the second matrix resin can be reduced.

[0010] <1. Modulation A> Polymer A according to this embodiment is a polymer having a first polymer portion and a second polymer portion, wherein the first polymer portion is a polyester polymer, and the second polymer portion has different structural units from the structural units constituting the first polymer portion, and in a total of 100 parts by mass of the first polymer portion and the second polymer portion, the first polymer portion The proportion of is greater than 20 parts by mass and less than or equal to 90 parts by mass, and the second polymer portion has constituent units derived from (meth)acrylate monomers. In one embodiment of the present invention, the polymer having the first polymer portion and the second polymer portion may be a polymer in which the first polymer portion and the second polymer portion are covalently bonded. In another embodiment of the present invention, even when the first polymer portion and the second polymer portion are not covalently bonded, the first polymer portion The second polymer portion This also includes polymers that are encapsulated or ex-encapsulated by the same entity.

[0011] Examples of polymers in which a first polymer portion and a second polymer portion are covalently bonded include block copolymers having a first polymer portion and a second polymer portion. portion The second polymer portion Polymers encapsulated or encapsulated by include polymers having a core-shell structure, in which the core portion contains one of the polymer portions of the first and second polymer portions, and the shell portion contains the other polymer portion of the first and second polymer portions. A core-shell structure is a structure in which a portion called the core is encapsulated within a portion called the shell.

[0012] In particular, polymer A is preferably a polymer having a core-shell structure, in which the first polymer portion constitutes the shell portion of the core-shell structure. That is, polymer A is preferably a polymer in which the first polymer portion, which is a polyester polymer, constitutes the shell portion of the core-shell structure, and the second polymer portion, which has different structural units from those constituting the first polymer portion, constitutes the core portion. The following describes in detail a preferred form of polymer A having the core-shell structure as a representative example.

[0013] <1-1. First Polymerized Portion> As described above, the first polymer portion is composed of a polyester polymer. In one embodiment of the present invention, a polyester polymer refers to a polymer composed of structural units containing ester bonds as repeating units, and polyester is synthesized by a polycondensation reaction between a dicarboxylic acid component and a diol component. By composing the first polymer portion of a polyester polymer, the affinity with the first matrix resin, which is a polyester resin, is improved, and as a result, the compatibility between the first matrix resin and the second matrix resin is improved.

[0014] There are no particular restrictions on the dicarboxylic acid, and examples include aromatic dicarboxylic acids, aliphatic dicarboxylic acids, and alicyclic dicarboxylic acids. Examples of such aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, phthalic acid, and 2,5-norbo Ru Nandicarboxylic acid, 1,4-naphthalic acid, 1,5-naphthalic acid, 4,4-oxybenzoic acid, fumaric acid, maleic anhydride, succinic acid, glutaric acid, adipic acid, sebacic acid, dodecanedicarboxylic acid, tetrahydrophthalic anhydride, tetrahydroterephthalic acid, 5-sodium sulfisophthalic acid, 5-lithium sulfisophthalic acid, (anhydride) trimellitic acid, (anhydride) pi B Examples include melitic acid.

[0015] There are no particular restrictions on the diol component, and examples include ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, triethylene glycol, dipropylene glycol, 2,2,4-trimethyl-1,3-pentanediol, cyclohexanedimethanol, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, ethylene oxide and propylene oxide adduct of bisphenol A, ethylene oxide adduct and propylene oxide adduct of hydrogenated bisphenol A, polytetramethylene glycol, polyethylene glycol, polypropylene glycol and their modified products, sodium sulfobutanediol, and the like.

[0016] In addition, two or more dicarboxylic acid components may be used, and similarly, two or more diol components can also be used.

[0017] In addition, the first polymer portion may be composed of a plurality of polymers having a plurality of different constitutional units. The constitutional units in this case can be those exemplified as the constitutional units of the first polymer portion and can be used.

[0018] The mass average molecular weight of the first polymer portion is not particularly restricted, but for the handling property of the powder, it is preferably 3000 or more, more preferably 5000 or more, and particularly preferably 7000 or more. On the other hand, for suppressing the increase in viscosity during the addition of the matrix resin, the mass average molecular weight is preferably 200000 or less, more preferably 100000 or less, and particularly preferably 50000 or less. The mass average molecular weight can be measured by gel permeation chromatography (GPC).

[0019] The glass transition temperature of the first polymer portion is not particularly limited, but is preferably 40°C or higher, more preferably 45°C or higher, and particularly preferably 50°C or higher in order to ensure powder recoverability. On the other hand, in order to avoid pulverization of the powder, the glass transition temperature is preferably 150°C or lower, more preferably 130°C or lower, and particularly preferably 100°C or lower.

[0020] <1-2. The second polymer portion> The second polymer portion has a constitutional unit different from the constitutional unit constituting the first polymer portion. The second polymer portion has a constitutional unit derived from a (meth)acrylate monomer. By having a constitutional unit derived from a (meth)acrylate monomer, the tensile elongation of the molded body is improved. Further, the second polymer portion preferably has a constitutional unit other than the constitutional unit derived from the (meth)acrylate monomer, and such a constitutional unit is preferably a component having excellent affinity with the second matrix resin. Specifically, it is preferable that at least a part of the constitutional units of the second polymer portion and at least a part of the constitutional units of the second matrix resin are the same.

[0021] Regarding the constitutional unit derived from the (meth)acrylate monomer constituting the second polymer portion, examples of the (meth)acrylate monomer include methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, butyl methacrylate, propyl acrylate, 2-ethylhexyl acrylate, glycidyl acrylate, propyl methacrylate, 2-ethylhexyl methacrylate, glycidyl methacrylate, phenyl acrylate, phenyl methacrylate, hydroxyethyl acrylate, 4-hydroxybutyl acrylate, benzyl acrylate, benzyl methacrylate, polyalkylene glycol monoacrylate or polyalkylene glycol monomethacrylate. Among them, from the viewpoint of the tensile elongation of the molded body, methyl methacrylate, butyl acrylate, glycidyl methacrylate or polyalkylene glycol monomethacrylate is preferable.

[0022] All constituent units that make up the second polymer portion A total of 100 parts by mass In this mixture, there are no particular restrictions on the proportion of constituent units derived from (meth)acrylate monomers, but in order to further improve the compatibility between the first matrix resin and the second matrix resin, and to further improve the tensile elongation of the molded article, it is preferably 5 parts by mass or more, and on the other hand, 80 parts by mass or less. More preferably, it is 8 parts by mass or more, and on the other hand, 60 parts by mass or less.

[0023] The constituent units that make up the second polymer portion, other than those derived from (meth)acrylate monomers, are preferably set in accordance with the structure of the second matrix resin used, but examples include constituent units derived from aromatic vinyl monomers. vinyl monomer When the polymer contains constituent units derived from polystyrene, for example, when a polystyrene-containing resin is used as the second matrix resin, the affinity between the second polymer portion and the polystyrene-containing resin is good, and as a result, the compatibility between the first matrix resin and the second matrix resin is expected to be better. In particular, the constituent units constituting the second polymer portion are more preferably constituent units derived from an aromatic vinyl monomer having a six-membered monocyclic structure, and even more preferably constituent units derived from styrene, which may have substituents. Examples of styrene-derived constituent units, which may have substituents, include styrene-derived constituent units or α-methylstyrene-derived constituent units, and among these, styrene-derived constituent units are particularly preferred.

[0024] All constituent units of the second polymerization section A total of 100 parts by mass There are no particular restrictions on the proportion of constituent units derived from aromatic vinyl monomers in the mixture, but in order to further improve the compatibility between the first matrix resin and the second matrix resin, it is preferably 30 parts by mass or more, more preferably 50 parts by mass or more, even more preferably 60 parts by mass or more, and particularly preferably 70 parts by mass or more, while it is preferably 95 parts by mass or less, and less than 100 parts by mass. You can .

[0025] The second morning section ,So It may further have other constituent units. All constituent units of the second polymer portion A total of 100 parts by mass There are no particular restrictions on the proportion of other constituent units in the mixture, but it is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, and particularly preferably 20 parts by mass or less, in order to further improve the compatibility between the first matrix resin and the second matrix resin, while it is 0 parts by mass or more.

[0026] The second polymer portion may be composed of multiple polymers, each having multiple different constituent units. In this case, the constituent units are the second polymer. portion The examples provided can be used as constituent units.

[0027] In a total of 100 parts by mass of the first polymer portion and the second polymer portion, the first polymer portion The proportion of polymer A is preferably more than 20 parts by mass and 90 parts by mass or less in order to further improve the compatibility between the first matrix resin and the second matrix resin when polymer A is added to the first matrix resin and the second matrix resin as a resin additive. More preferably more than 20 parts by mass and 80 parts by mass or less, even more preferably more than 20 parts by mass and 70 parts by mass or less, even more preferably more than 20 parts by mass and 60 parts by mass or less, even more preferably more than 20 parts by mass and 50 parts by mass or less, even more preferably more than 20 parts by mass and 45 parts by mass or less, and particularly preferably more than 20 parts by mass and 40 parts by mass or less.

[0028] <1-3. Method for producing polymer A> There are no particular limitations on the method for producing polymer A when it has a core-shell structure, and it can be produced by known methods such as suspension polymerization, solution polymerization, or emulsion polymerization. Among these, emulsion polymerization is preferred from the viewpoint of ease of production. That is, polymer A is preferably a polymer obtained by emulsion polymerization of monomer components constituting the second polymer portion in the presence of the polymer constituting the first polymer portion that is ultimately obtained. When performing emulsion polymerization, it may be carried out by batch polymerization in which the monomer components are added all at once and polymerized, or by dropwise polymerization in which they are added stepwise.

[0029] More specifically, the second polymer is added to a solution in which the polymer that will constitute the first polymer portion is dispersed in any solvent. portion The monomer components that make up the mixture can be added, emulsified using various mixers, and then polymerized by adding a polymerization initiator.

[0030] First Polymer The polymer that will make up the part A solution in which the polymer is dispersed in any solvent can be obtained, for example, by adding the polymer constituting the first polymer portion to one or more solvents such as water, isopropyl alcohol, ethanol, methanol, acetone, methyl ethyl ketone, or diethyl ether, and stirring while applying shear. The polymer that will make up the part The proportion of is preferably 10% by mass or more due to its excellent dispersibility, and preferably 50% by mass or less from the viewpoint of handling ease considering the viscosity of the dispersion solution.

[0031] When adding monomer components constituting the second polymer portion to a solution in which the polymer constituting the first polymer portion is dispersed in any solvent, a surfactant may be added further. Examples of surfactants include anionic surfactants, cationic surfactants, or neutral surfactants. One or more of these may be used.

[0032] Polymerization initiators generally used in radical polymerization can be used, and specific examples include persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate; oil-soluble azo compounds such as azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), and 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile; and 2,2'-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)-2-Hyd 2,2'-Azobis{2-methyl-N-[2-(1-hydroxyethyl)]propionamide}, 2,2'-Azobis{2-methyl-N-[2-(1-hydroxybutyl)]propionamide}, 2,2'-Azobis[2-(5-methyl-2-imidazolin-2-yl)propane] and its salts, 2,2'-Azobis[2-(2-imidazolin-2-yl)propane] and its salts, 2,2'-Azobis{2-[1-(2-hydroxyethyl)-2-imidazolin-2-yl]propane} and its salts, 2,2'-Azobis(2-methylprop O Examples include water-soluble azo compounds such as 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine] and its salts, benzoyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, t-butyl peroxy-2-ethylhexanoate, and t-butyl peroxyisobutyrate. The polymerization initiator may be used alone or in combination of two or more types.

[0033] Preferred radical polymerization methods in one aspect of the present invention include, for example, a method of polymerization using a water-soluble polymerization initiator, and a method of polymerization using a redox reaction with an organic peroxide and a reducing agent such as ferrous sulfate or isoascorbic acid.

[0034] The amount of polymerization initiator used is the second polymer portionThe amount of the reducing agent is preferably 0.05 to 1.0 parts by mass per 100 parts by mass of the total monomers constituting the second polymer, with a lower limit of 0.1 parts by mass or more and a higher limit of 0.3 parts by mass or less. When a peroxide-based polymerization initiator is used, it can be used as a redox polymerization initiator in combination with a reducing agent. The amount of the reducing agent used is the amount of the second polymer portion Preferably, the amount is 0.0001 to 1 part by mass per 100 parts by mass of the total amount of monomers constituting the compound.

[0035] Furthermore, monomers may be polymerized using known chain transfer agents such as n-dodecyl mercaptan, t-dodecyl mercaptan, and α-methylstyrene dimer as molecular weight modifiers.

[0036] There are no specific restrictions on the reaction temperature, but it is usually between 45°C and 80°C. Similarly, there are no specific restrictions on the reaction time, but it is usually between 30 minutes and 300 minutes.

[0037] The latex of polymer A obtained by emulsion polymerization can be recovered as polymer powder by drying by spray drying or freeze-drying, or by coagulation. Of these methods, drying by spray drying or coagulation is preferred.

[0038] When drying by spray drying, it is preferable to spray the latex of polymer A onto fine droplets and dry them by applying hot air. Any of the following devices may be used to generate the droplets: a rotating disc type, a pressure nozzle type, a two-fluid nozzle type, etc.

[0039] Hot air is blown onto the latex of polymer A. of When drying by applying hot air, the temperature of the hot air is preferably between 100°C and 200°C. If the hot air temperature is 100°C or higher, the latex can be dried sufficiently, and if it is 200°C or lower, the thermal decomposition of the resulting powder can be suppressed.

[0040] When performing coagulation, the latex of polymer A is added to hot water in which a coagulant is dissolved, polymer A is separated and purified by salting out, and the resulting wet material is dehydrated and dried. Examples of coagulants include inorganic salts such as aluminum chloride, aluminum sulfate, sodium sulfate, magnesium sulfate, sodium nitrate, and calcium acetate, or acids such as sulfuric acid, with calcium acetate being particularly preferred. These coagulants may be used individually or in combination of two or more, but when used in combination, it is preferable to select a combination that does not form a water-insoluble salt. For example, using calcium acetate in combination with sulfuric acid or its sodium salt is undesirable because it forms a water-insoluble calcium salt.

[0041] It is common technical knowledge that the polymerization mode of the first polymer portion and the second polymer portion of polymer A changes depending on the manufacturing method, but it is difficult to specify what the polymerization mode is. For example, polymer A obtained by emulsion polymerization of monomer components constituting the second polymer portion in the presence of the polymer constituting the first polymer portion is thought to have a different polymerization mode and therefore a difference in structure or properties compared to polymer A obtained by other methods. However, it is technically impossible or impractical to specify the structure or properties in a way that clearly reveals such differences.

[0042] [Resin additives] Polymer A can be used as a resin additive, such as a compatibilizer. The resin additive may be polymer A as is, or it may be compounded with any auxiliary agent. Examples of known auxiliary agents include flame retardants, anti-dripping agents, antioxidants, ultraviolet absorbers, light stabilizers, mold release agents, lubricants, sliding agents, colorants, fluorescent whitening agents, phosphorescent pigments, fluorescent dyes, and antistatic agents.

[0043] <2.Resin composition> The resin composition according to this embodiment comprises polymer A and a first matrix resin. The resin composition may further contain a second matrix resin which is different from the first matrix resin. There are no particular restrictions on the ratio of polymer A to 100 parts by mass of the total of the first matrix resin and the second matrix resin, but it is preferably 0.1 to 30 parts by mass, and more preferably 5 to 20 parts by mass. If the ratio of the resin additive is 0.1 parts by mass or more, the compatibility of the first matrix resin and the second matrix resin is further improved, and if it is 30 parts by mass or less, the processability during the manufacture of the resin composition is excellent.

[0044] The resin composition according to this embodiment may further contain other components. For example, known auxiliary agents may be added as needed to impart functionality or improve properties. Examples of such auxiliary agents include flame retardants, anti-dripping agents, antioxidants, ultraviolet absorbers, light stabilizers, mold release agents, lubricants, sliding agents, colorants, fluorescent whitening agents, phosphorescent pigments, fluorescent dyes, and antistatic agents.

[0045] <2-1. First Matrix Resin> The first matrix resin is not particularly limited, but is preferably a polyester resin, and may be a resin consisting of at least one of the following: polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), polybutylene succinate (PBS), polyhydroxyalkanoic acid (PHA), and polylactic acid (PLA). Recycled materials may also be used.

[0046] <2-2. Second Matrix Resin> The second matrix resin is not particularly limited as long as it is a different resin from the first matrix resin, but for example, it is a polystyrene-containing resin, and polystyrene-containing resins such as polystyrene, high-impact polystyrene (HIPS), and acrylonitrile-butadiene-styrene copolymer (ABS) can be used. Recycled materials may also be used. From the viewpoint of improving compatibility, it is preferable that at least some of the constituent units of the second matrix resin are the same as at least some of the constituent units of the second polymer portion in polymer A.

[0047] There are no particular restrictions on the proportion of the first matrix resin in a total of 100 parts by mass of the first and second matrix resins, but it is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, even more preferably 20 parts by mass or more, and particularly preferably 25 parts by mass or more. On the other hand, the proportion of the first matrix resin is preferably 95 parts by mass or less, more preferably 90 parts by mass or less, even more preferably 80 parts by mass or less, and particularly preferably 75 parts by mass or less.

[0048] <2-3. Method for producing resin compositions> There are no particular limitations on the method for producing the resin composition, but it can be produced by mixing polymer A, a first matrix resin, and a second matrix resin in powder form, or by melt-kneading them together. For mixing or melt-kneading, for example, a Henschel mixer, a Banbury mixer, a single-screw extruder, a twin-screw extruder, a two-roll machine, a kneader, or a Brabender can be used. mixer These are used.

[0049] <3. Molded body> The resin composition according to this embodiment can be molded into a molded article. Alternatively, the resin composition according to this embodiment may be mixed with other materials before being molded into a molded article. In other words, the molded article may contain the resin composition. Known molding methods can be used, such as compression molding, transfer molding, injection molding, blow molding, vacuum molding, extrusion molding, lamination molding, and calendering.

[0050] <4. Summary> As described above, the present invention has the following aspects.

[0051] [1] A polymer having a first polymer portion and a second polymer portion, wherein the first polymer portion is a polyester polymer, and the second polymer portion has different structural units from the structural units constituting the first polymer portion, and the first polymer in a total of 100 parts by mass of the first polymer portion and the second polymer portion portion A polymer in which the proportion of exceeds 20 parts by mass and is 90 parts by mass or less, and the second polymer portion has constituent units derived from (meth)acrylate monomers.

[0052] [2] All constituent units that make up the second polymer portion A total of 100 parts by mass The polymer according to [1], wherein the proportion of constituent units derived from the (meth)acrylate monomer is 5 parts by mass or more.

[0053] [3] The second polymer portion further comprises structural units derived from aromatic vinyl monomers 、[ The polymer described in [1] or [2].

[0054] [4] All constituent units that make up the second polymer portion A total of 100 parts by mass The polymer according to [3], wherein the proportion of constituent units derived from the aromatic vinyl monomer is 30 parts by mass or more and 95 parts by mass or less.

[0055] [5] A polymer according to any one of [1] to [4], having a core-shell structure, wherein the first polymer portion constitutes the shell portion of the core-shell structure, and the second polymer portion constitutes the core portion of the core-shell structure.

[0056] [6] The polymer according to any one of [1] to [5], obtained by emulsion polymerization of monomer components constituting the second polymer portion in the presence of the polymer constituting the first polymer portion.

[0057] A resin additive comprising any one of the polymers described in [7], [1], through [6].

[0058] A resin composition comprising a polymer described in any one of [8], [1] to [6], and a polyester resin as a first matrix resin.

[0059] [9] The resin composition according to [8], further comprising a second matrix resin, wherein the second matrix resin is a resin different from the first matrix resin.

[0060]

[10] The resin composition according to [9], wherein the second matrix resin is a polystyrene-containing resin.

[0061] A resin composition comprising a polymer described in

[11] [1], [5] or [6], a polyester resin as a first matrix resin, and a second matrix resin which is a different resin from the first matrix resin, wherein at least a portion of the constituent units of the second polymer portion and at least a portion of the constituent units of the second matrix resin are identical.

[0062] A molded article comprising the resin composition described in any one of

[12] , [8], to

[11] . [Examples]

[0063] One aspect of the present invention will be described below with reference to an example. In the example, "part" refers to "mass part".

[0064] <Tensile modulus of elasticity, tensile elongation> Tensile tests were conducted using a Tensilon universal testing machine (model name "RTC-1250A-PL", manufactured by Orientec Co., Ltd.) in accordance with JIS K7139, and the tensile modulus and tensile elongation of the molded articles were measured.

[0065] <Size> Using a transmission electron microscope (TEM) (model "H-7600", Hitachi), the phase size of some molded bodies was observed. Test specimens were stained with osmium tetroxide for 12 hours, then stained with ruthenium tetroxide for 5 hours, and observation sections were prepared. The average diameter of the major axis portion of 30 arbitrary dispersed phases in the TEM images was determined and defined as the phase size.

[0066] (Manufacturing Example 1) As an aqueous dispersion solution of the polymer constituting the first polymer portion, 240 parts of Nichigo Polyester WR-905 (manufactured by Mitsubishi Chemical Corporation: solid content 20%) were added, along with 90 parts of styrene (St) and 10 parts of glycidyl methacrylate (GMA) as radical polymerizable monomers. These were emulsified using a homomixer to obtain a preemulsion solution of radical polymerizable monomers.

[0067] 222 parts of pre-emulsion solution and deionized water were added to a flask equipped with a stirrer, reflux condenser, and temperature control device. The mixture was heated to 50°C and held for 1 hour while nitrogen bubbling was performed at a flow rate of 200 ml / min. 0.7 parts of Perkmill P (manufactured by NOF Corporation) was added as a polymerization initiator, and 0.002 parts of ferrous sulfate, 0.006 parts of sodium ethylenediaminetetraacetate (EDTA), 0.3 parts of sodium formaldehyde sulfoxylate, and 10 parts of deionized water were added as reducing agents. The mixture was then switched to nitrogen flow and polymerization was started. After 1 hour, the temperature was raised to 60°C and held for 2 hours, then cooled to obtain the latex of polymer A1 according to one embodiment of the present invention. of Latex was added to 460 parts of deionized water containing 5 parts by mass of calcium acetate to coagulate, and polymer A1 was obtained in powder form by washing, dehydrating, and drying.

[0068] (Manufacturing Examples 2-9) Polymers A2 to A6 according to one aspect of the present invention and polymers B1 to B3 according to comparative examples were obtained by the same manufacturing method as in Manufacturing Example 1, except that the amount of the first polymer portion used, the type of radically polymerizable monomer, and the copolymerization amount were changed as shown in Table 1 below. One or two types of (meth)acrylate were used as the radically polymerizable monomer. In Table 1, the two types of (meth)acrylate are denoted as "a1" and "a2," respectively. In Manufacturing Examples 2 to 7, at least one of glycidyl methacrylate (GMA), butyl acrylate (BA), methyl methacrylate (MMA), and polypropylene glycol monomethacrylate (Bremmer PP-800, manufactured by NOF Corporation) was used as the radically polymerizable monomer.

[0069] <Polymerization stability> The polymerization stability of each polymer was evaluated as follows: if the radical polymerizable monomer remained emulsified by the first polymer throughout the polymerization process, it was considered "suitable"; if it separated, it was considered "unsuitable."

[0070] (Example 1) 70 parts of polybutylene terephthalate (PBT, manufactured by Mitsubishi Engineering Plastics Corporation: Novaduran 5010R) as the first matrix resin, 30 parts of polystyrene (PS, manufactured by Toyo Styrene Co., Ltd.: Toyo Styrofoam GP200) as the second matrix resin, and 10 parts of polymer A1 produced in Production Example 1 were placed in a polyethylene bag. The polyethylene bag was shaken well by hand to hand blend the mixture, and then melt-kneaded at 250°C using a twin-screw extruder (manufactured by Toshiba Machine Co., Ltd., product name: TEM35B). The extruded strands were cut to obtain pellets. The obtained pellets were molded using an injection molding machine (manufactured by Toshiba Machine Co., Ltd., product name: IS100EN) at a molding temperature of 250°C and a mold temperature of 60°C to produce a dumbbell-shaped molded body in accordance with JIS K7139, obtaining the molded body according to Example 1. Cross-sectional observation and tensile testing were performed on the molded body using a transmission electron microscope (TEM). A TEM image of the cross-section of the molded body is shown in Figure 1. The average diameter of the major axis portion of any 30 dispersed phases in the TEM image was 0.58 μm. Furthermore, the tensile modulus of the molded article was 2.2 GPa and the tensile elongation was 3.1%.

[0071] (Examples 2-8) Except for changing the second matrix resin to high-impact polystyrene (HIPS, manufactured by Toyo Styrene: Toyo Styrofoam H350), or changing the ratio of the first and second matrix resins, the type of polymer used, and the amount added as shown in Table 2 below, molded articles were obtained and evaluated in the same manner as in Example 1.

[0072] (Comparative Example 1) A resin composition and molded article were prepared in the same manner as in Example 1, except that polymer A1 obtained in Production Example 1 was not added, to obtain a molded article according to Comparative Example 1. The molded article was subjected to cross-sectional observation by TEM and tensile testing. A TEM image of the cross-section of the molded article is shown in Figure 2. The average diameter of the major axis portion of any 30 dispersed phases in the TEM image was 1.01 μm. Furthermore, the tensile modulus of the molded article obtained by tensile testing was 2.1 GPa, and the tensile elongation was 2.9%.

[0073] (Comparative Examples 2-7) Except for changing the second matrix resin to high-impact polystyrene (HIPS, manufactured by Toyo Styrene: Toyo Styrofoam H350), or changing the presence or absence of polymer addition, the type of polymer used, and the amount added as shown in Table 2 below, molded articles were obtained and evaluated in the same manner as in Example 1.

[0074] [Table 1]

[0075] [Table 2]

[0076] From the above results, it can be seen that when the ratio of the first matrix resin to the second matrix resin is 70 / 30 (first matrix resin / second matrix resin), the average diameter of the dispersed phase is significantly smaller in Example 1, which uses the polymer according to one aspect of the present invention, compared to Comparative Example 1, which does not use the polymer according to one aspect of the present invention, and the tensile elongation of the molded article is improved by 7% when Comparative Example 1 is set to 100%. Similarly, in Examples 4 and 6, which use the polymer according to one aspect of the present invention, the average diameter of the dispersed phase and the tensile elongation of the molded article are improved compared to Comparative Example 1. From the above results, it can be seen that using the polymer according to one aspect of the present invention as a resin additive improves the compatibility between the first matrix resin and the second matrix resin and the tensile elongation of the molded article. The improved tensile elongation results in good toughness of the molded article, making it highly valuable for industrial use.

[0077] Furthermore, compared to Comparative Example 5, which used a polymer with a small proportion of the first polymer portion, Example 2, which had a sufficient proportion of the first polymer portion, showed a smaller average diameter of the dispersed phase, and the tensile elongation of the molded article also improved by 3% when Comparative Example 5 was set to 100%. Similarly, in Comparative Example 4, which used a polymer with a small proportion of the first polymer portion, and Example 7, which had a sufficient proportion of the first polymer portion, improvements were observed in both the average diameter of the dispersed phase and the tensile elongation of the molded article. From these results, it can be seen that using a polymer according to one aspect of the present invention as a resin additive improves the compatibility between the first matrix resin and the second matrix resin, as well as the tensile elongation of the molded article. The improved tensile elongation results in better toughness of the molded article, thus having high industrial value.

[0078] Furthermore, compared to Comparative Example 6, which used a polymer that did not contain (meth)acrylate monomers in the second polymer portion, Examples 2, 5, and 7, which contained (meth)acrylate monomers in the second polymer portion, showed a smaller average diameter of the dispersed phase and improved tensile elongation of the molded article. Examples 2, 5, and 7 showed improvements of 20%, 44%, and 96% respectively in tensile elongation compared to Comparative Example 6 (with the tensile elongation set at 100%). These results indicate that using a polymer according to one aspect of the present invention as a resin additive improves the compatibility between the first matrix resin and the second matrix resin, as well as the tensile elongation of the molded article. Improved tensile elongation increases the toughness of the molded article, thus giving it high industrial value.

[0079] In Example 3, where the ratio of the first matrix resin to the second matrix resin is 90 / 10 (first matrix resin / second matrix resin), the average diameter of the dispersed phase is significantly smaller compared to Comparative Example 2, which does not use the polymer according to one aspect of the present invention. Furthermore, the tensile elongation of the molded article is improved by 29% when Comparative Example 2 is set to 100%. From these results, it can be seen that using the polymer according to one aspect of the present invention as a resin additive improves the compatibility between the first matrix resin and the second matrix resin, as well as the tensile elongation of the molded article. The improved tensile elongation increases the toughness of the molded article, thus giving it high industrial value.

[0080] In Example 8, where HIPS was used as the second matrix resin, the average diameter of the dispersed phase was significantly smaller compared to Comparative Example 3, which did not use the polymer according to one aspect of the present invention. Furthermore, the tensile elongation of the molded article was improved by 14% when Comparative Example 3 was set to 100%. From these results, it can be seen that using the polymer according to one aspect of the present invention as a resin additive improves the compatibility between the first matrix resin and the second matrix resin, as well as the tensile elongation of the molded article. The improved tensile elongation increases the toughness of the molded article, thus giving it high industrial value.

[0081] In Comparative Example 7, which used a polymer that did not have a second polymeric portion, the weight of the polymer Aisan Because the qualitative properties are poor and the tensile elongation of the molded article is inferior to that of Comparative Example 1, which does not contain a polymer, it has low industrial value. [Industrial applicability]

[0082] A polymer according to one aspect of the present invention can reduce phase separation of resins when two or more types of resins are mixed, and can be suitably used as a compatibilizer that exhibits excellent tensile elongation when a resin composition containing the polymer is made into a molded article.

Claims

1. A resin composition comprising a polymer having a first polymer portion and a second polymer portion, and a first matrix resin, The polymer has a core-shell structure, The first polymer portion constitutes the shell portion of the core-shell structure, The second polymer portion constitutes the core portion of the core-shell structure. The first polymer portion is a polyester polymer, and the second polymer portion has different structural units from the structural units constituting the first polymer portion. The proportion of the first polymer portion in a total of 100 parts by mass of the first polymer portion and the second polymer portion is greater than 20 parts by mass and less than or equal to 90 parts by mass. The second polymer portion has constituent units derived from (meth)acrylate monomers, A resin composition in which the first matrix resin is a polyester resin.

2. The resin composition according to claim 1, wherein the proportion of constituent units derived from the (meth)acrylate monomer in a total of 100 parts by mass of all constituent units constituting the second polymer portion is 5 parts by mass or more.

3. The resin composition according to claim 1, wherein the second polymer portion further comprises structural units derived from aromatic vinyl monomers.

4. The resin composition according to claim 3, wherein the proportion of constituent units derived from the aromatic vinyl monomer in a total of 100 parts by mass of all constituent units constituting the second polymer portion is 30 parts by mass or more and 95 parts by mass or less.

5. The resin composition according to claim 1, wherein the polymer is obtained by emulsion polymerization of monomer components constituting the second polymer portion in the presence of the polymer constituting the first polymer portion.

6. The resin composition according to claim 1, comprising the polymer as a resin additive.

7. The resin composition according to claim 1, further comprising a second matrix resin, wherein the second matrix resin is a resin different from the first matrix resin.

8. The resin composition according to claim 7, wherein the second matrix resin is a polystyrene-containing resin.

9. The resin composition according to claim 7, wherein at least a portion of the constituent units of the second polymer portion and at least a portion of the constituent units of the second matrix resin are the same.

10. A molded article comprising the resin composition according to any one of claims 1 to 9.

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