JP6796969B2 - Thermoplastic polymer composition and molded article - Google Patents

Description

The present invention relates to a thermoplastic polymer composition and a molded product composed of an acrylic block copolymer and a heat-resistant transparent resin.

A resin composition having excellent transparency, flexibility and molding processability, in which a methacrylic resin is mixed with an acrylic block copolymer, has been proposed. Resin compositions in which a methacrylic resin is mixed with such an acrylic block copolymer have been used in various applications such as automobile members and miscellaneous goods members.

For example, in Patent Document 1, a resin composition in which a methacrylic resin is mixed with an acrylic thermoplastic elastomer and has an excellent balance of weather resistance, flexibility, and mechanical strength is studied. In Patent Document 2, a resin composition in which a plurality of types of acrylic block copolymers are mixed with an acrylic resin and which has a wide range of compositions and is excellent in transparency, moldability and the like is studied. In Patent Document 3, a resin composition having excellent transparency, moldability, and mechanical properties, in which an acrylic block copolymer is mixed with a methacrylic resin, has been studied.

In Patent Document 4, a methacrylic resin capable of improving heat resistance and obtaining a molded product having an excellent appearance by blending a predetermined amount with the methacrylic resin without impairing the excellent transparency of the methacrylic resin. Copolymers for improving heat resistance are being studied.

Japanese Unexamined Patent Publication No. 2003-277574 International Publication 2010/055798 Pamphlet International Publication 2012/057079 Pamphlet International Publication 2014/021264 Pamphlet

However, the resin composition obtained by mixing the acrylic resin and the acrylic block copolymer of Patent Documents 1 to 3 does not have a specific description regarding a method for improving heat resistance.
Further, the copolymer for improving the heat resistance of the methacrylic resin in Patent Document 4 is limited to the addition to the methacrylic resin, and there is no description of the addition to the acrylic block copolymer. Therefore, only a molded product in a region having a high elastic modulus can be obtained, and there is room for improvement.

In view of the above circumstances, an object to be solved by the present invention is to provide a thermoplastic polymer composition having excellent heat resistance, transparency, flexibility, and excellent appearance of a molded product. Another object of the present invention is to provide a molded product made of the above-mentioned thermoplastic polymer composition and having the above-mentioned characteristics.

As a result of diligent research to solve the above problems, the present inventors have found that the above problems can be solved by blending a heat-resistant transparent resin with a specific acrylic block copolymer in a specific ratio. The invention was completed.

That is, the present invention
[1] The molecule has at least one structure in which a polymer block (a2) mainly composed of a methacrylic acid ester unit is bonded to both ends of a polymer block (a1) mainly composed of an acrylic acid ester unit. Acrylic block copolymer (A) and heat-resistant transparent resin (B) having a weight average molecular weight of 10,000 to 150,000 and a polymer block (a2) content of 30% by mass or more and 60% by mass or less. , And the mass ratio [(A) / (B)] of the acrylic block copolymer (A) to the heat-resistant transparent resin (B) is 85/15 to 1/99;
[2] The thermoplastic polymer composition according to [1], wherein the content of the polymer block (a2) in the acrylic block copolymer (A) is 40% by mass or more and 55% by mass or less;
[3] The polymer block (a1) of the acrylic block copolymer (A) is a copolymer block of 50 to 90% by mass of an acrylic acid alkyl ester and 50 to 10% by mass of an acrylic acid aromatic ester. The thermoplastic polymer composition according to [1] or [2];
[4] The thermoplastic polymerization composition according to [3], wherein the acrylic acid aromatic ester is benzyl acrylate;
[5] The mass ratio [(A) / (B)] of the acrylic block copolymer (A) and the heat-resistant transparent resin (B) is 80/20 to 60/40, [1] to [4]. The thermoplastic polymer composition according to any one of the above;
[6] The heat-resistant transparent resin (B) is a copolymer composed of an aromatic vinyl compound monomer unit, a (meth) acrylic acid ester monomer unit, and an unsaturated dicarboxylic acid anhydride monomer unit. 1] The thermoplastic polymer composition according to any one of [5];
[7] The thermoplastic polymer composition according to any one of [1] to [6], wherein the heat-resistant transparent resin (B) has a Vicat softening temperature of 120 ° C. or higher at 50 N;
[8] A molded product made of the thermoplastic polymer composition according to any one of [1] to [7];
[9] An automobile interior member made of the molded body according to [8];
[10] A cover for an electronic device made of the molded product according to [8];
Regarding.

According to the present invention, it is possible to provide a thermoplastic polymer composition having excellent heat resistance, transparency, flexibility, and an excellent appearance of a molded product, and a molded product made of the same.

Hereinafter, the present invention will be described in detail.
The thermoplastic polymer composition of the present invention has a structure in which a polymer block (a2) mainly composed of a methacrylate ester unit is bonded to both ends of a polymer block (a1) mainly composed of an acrylic acid ester unit. Acrylic block copolymer (A) having at least one of them, having a weight average molecular weight of 10,000 to 150,000, and having a polymer block (a2) content of 30% by mass or more and 60% by mass or less. ) And the heat-resistant transparent resin (B), and the mass ratio [(A) / (B)] of the acrylic block copolymer (A) and the heat-resistant transparent resin (B) is 85/15 to 1/99. A thermoplastic polymer composition.

The acrylic block copolymer (A), which is the first component in the present invention, is a polymer block mainly composed of a methacrylic acid ester unit at both ends of the polymer block (a1) mainly composed of an acrylic acid ester unit. An acrylic block copolymer having at least one structure (a2) bonded, that is, a structure of (a2)-(a1)-(a2) (where "-" in the structure indicates a chemical bond) in the molecule. Is.

In the polymer block (a1) mainly composed of an acrylic acid ester unit in the acrylic block copolymer (A), the content of the acrylic acid ester unit is usually 60% by mass or more in the polymer block (a1). , 80% by mass or more, more preferably 90% by mass or more, and may be 100% by mass in the polymer block (a1). Examples of the acrylic acid ester for forming the polymer block (a1) include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, and sec acrylate. -Butyl, tert-butyl acrylate, amyl acrylate, isoamyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, pentadecyl acrylate, dodecyl acrylate, isobornyl acrylate, phenyl acrylate, acrylic Examples thereof include benzyl acid acid, phenoxyethyl acrylate, 2-hydroxyethyl acrylate, and 2-methoxyethyl acrylate. Among these acrylic acid esters, methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, phenoxyethyl acrylate, acrylic from the viewpoint of improving flexibility. Acrylic acid alkyl esters such as 2-methoxyethyl acid are preferable, and n-butyl acrylate and 2-ethylhexyl acrylate are more preferable. The polymer block (a1) may be composed of one kind of these acrylic acid esters, or may be composed of two or more kinds.

Further, as long as the object and effect of the present invention are not hindered, the polymer block (a1) may be other than an acrylic acid ester unit having a reactive group, for example, glycidyl acrylate, allyl acrylate; or an acrylic acid ester unit. The polymerizable monomer unit of the above, for example, the following monomers such as methacrylic acid ester, methacrylic acid, acrylic acid, aromatic vinyl compound, acrylonitrile, methacrylonitrile, olefin; and the like may be contained as a copolymerization component. The amount of the acrylic acid ester unit or other polymerizable monomer unit having these reactive groups is preferably small, preferably 10% by mass or less, more preferably 2% by mass or less, from the viewpoint of exhibiting the effects of the present invention. is there.

From the viewpoint of improving the transparency of the obtained thermoplastic polymer composition, the polymer block (a1) mainly composed of an acrylic acid ester unit has the same weight of the acrylic acid alkyl ester and the acrylic acid aromatic ester. It is preferably a coalesced block. Examples of the acrylic acid aromatic ester copolymerized with the acrylic acid alkyl ester include benzyl acrylate, phenyl acrylate, phenoxyethyl acrylate, phenoxydiethylene glycol acrylate, phenoxy-polyethylene glycol acrylate, and 2-hydroxy-3-phenoxy acrylate. Propyl and the like are preferable, and benzyl acrylate is more preferable.

When the polymer block (a1) mainly composed of the acrylic acid ester unit is a copolymer block of an acrylic acid alkyl ester and an acrylic acid aromatic ester, the acrylic acid alkyl ester 50 to 90% by mass and the acrylic acid aromatic ester. A copolymer block of 50 to 10% by mass of ester is preferable, and a copolymer block of 60 to 80% by mass of acrylic acid alkyl ester and 40 to 20% by mass of acrylic acid aromatic ester is more preferable.

In the acrylic block copolymer (A), the polymer block (a2) mainly composed of a methacrylic acid ester unit usually contains 60% by mass or more of the methacrylic acid ester unit in the polymer block (a2). It is preferably 80% by mass or more, more preferably 90% by mass or more, and may be 100% by mass in the polymer block (a2). Examples of the methacrylic acid ester for forming the polymer block (a2) include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, and sec methacrylate. -Butyl, tert-butyl methacrylate, amyl methacrylate, isoamyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, pentadecyl methacrylate, dodecyl methacrylate, isobornyl methacrylate, phenyl methacrylate, methacrylic Examples thereof include benzyl acetate, phenoxyethyl methacrylate, 2-hydroxyethyl methacrylate, 2-methoxyethyl methacrylate and the like. Among these methacrylic acid esters, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, and isobornyl methacrylate from the viewpoint of improving transparency and heat resistance. Such as methacrylic acid alkyl ester is preferable, and methyl methacrylate is more preferable. The polymer block (a2) may be composed of one type of these methacrylic acid esters, or may be composed of two or more types.

In addition, the polymer block (a2) is a methacrylic acid ester unit having a reactive group, for example, other than glycidyl methacrylate, allyl methacrylate, or methacrylic acid unit, as long as it does not interfere with the object and effect of the present invention. A small amount, preferably 10% by mass or less, of a polymerizable monomer unit, for example, a monomer such as the acrylic acid ester, methacrylic acid, acrylic acid, aromatic vinyl compound, acrylonitrile, methacrylic nitrile, or olefin as a copolymerization component. It may preferably contain 2% by mass or less.

The molecular chain form of the acrylic block copolymer (A) is not particularly limited, and may be, for example, linear, branched, radial, or the like, but mainly composed of two methacrylic acid ester units. It is preferable to have at least one (a2)-(a1)-(a2) structure in the molecule, which is composed of the polymer block (a2) to be used and the polymer block (a1) mainly composed of one acrylic acid ester unit. Among them, the triblock bodies represented by (a2)-(a1)-(a2) are more preferable. Here, the molecular weight, composition, etc. of (a2) at both ends of (a1) may be the same or may be different from each other. Further, a diblock body represented by (a2)-(a1) is also preferable.

As long as the object and effect of the present invention are not hindered, the acrylic block copolymer (A) can be used as a polymer block different from these polymer blocks (a1) and (a2) in a single amount of acrylic acid ester. It may have a polymer block (c) derived from a monomer other than the body and the methacrylic acid ester monomer. The form of bonding between the polymer block (c) and the polymer block (a1) mainly composed of the acrylic ester unit and the polymer block (a2) mainly composed of the methacrylic acid ester unit is not particularly limited, but for example. , (A2)-((a1)-(a2)) n- (c), (c)-(a2)-((a1)-(a2)) n- (c) and other structures (n is 1) (It is an integer of ~ 20).

Examples of the monomer constituting the polymer block (c) include olefins such as ethylene, propylene, 1-butene, isobutylene and 1-octene; conjugated diene compounds such as 1,3-butadiene, isoprene and milsen; styrene. , Α-Methylstyrene, p-methylstyrene, m-methylstyrene and other aromatic vinyl compounds; vinyl acetate, vinylpyridine, acrylonitrile, methacrylonitrile, vinyl ketone, vinyl chloride, vinylidene chloride, vinylidene fluoride, acrylamide, methacrylicamide , Ε-caprolactone, valerolactone and the like.

The acrylic block copolymer (A) used in the present invention may have a functional group such as a hydroxyl group, a carboxyl group, an acid anhydride, or an amino group in the molecular chain or at the terminal of the molecular chain, if necessary. ..

The weight average molecular weight of the acrylic block copolymer (A) is 10,000 from the viewpoint of heat resistance, transparency, flexibility, and appearance of the molded product of the thermoplastic polymer composition of the present invention and the molded product made from the same. ~ 150,000. From the above viewpoint, it is preferably 30,000 to 120,000, and more preferably 50,000 to 100,000. When the weight average molecular weight of the acrylic block copolymer (A) is 10,000 or more, sufficient melt tension can be maintained in melt extrusion molding, and a good molded body can be obtained. In addition, it is excellent in mechanical properties such as breaking strength of the obtained molded product. On the other hand, when it is 150,000 or less, fine grain-like unevenness and lumps due to unmelted matter (high molecular weight body) are less likely to occur on the surface of the molded product obtained by melt extrusion molding, and the molded product has an excellent appearance. Tends to be obtained.

Further, the ratio (Mw / Mn) of the number average molecular weight (Mn) and the weight average molecular weight (Mw) of the acrylic block copolymer (A) is often in the range of 1.01 or more and less than 1.50. , 1.01 or more and 1.35 or less, more preferably. By taking such a range, the content of the unmelted material that causes the generation of lumps in the molded product made of the thermoplastic polymer composition of the present invention can be made extremely small.

The content of the polymer block (a2) in the acrylic block copolymer (A) is 30% by mass or more and 60% by mass or less from the viewpoint of heat resistance, transparency, flexibility, and appearance of the molded product. More preferably, it is 40% by mass or more and 55% by mass or less. When the content of the polymer block (a2) in the acrylic block copolymer (A) is smaller than the above range, the transparency of the thermoplastic polymer composition of the present invention and the molded product made from the same is lowered, and molding is performed. It tends to be unsuitable as a material. When the content of the polymer block (a2) in the acrylic block copolymer (A) is larger than the above range, the heat resistance of the thermoplastic polymer composition of the present invention and the molded product made from the same is improved. It tends to be inflexible.

The refractive index of the acrylic block copolymer (A) is preferably 1.485 to 1.495. When the refractive index is in the above range, the transparency of the thermoplastic polymer composition of the present invention and the molded product made from the same is improved. Further, the refractive indexes of the polymer block (a2) mainly composed of a methacrylic acid ester unit and the polymer block (a1) mainly composed of an acrylic acid ester unit are in the range of 1.485 to 1.495, respectively. preferable.

The method for producing the acrylic block copolymer (A) is not particularly limited, and a method according to a known method can be adopted. For example, a method of living polymerization of the monomers constituting each block is generally used. As such a living polymerization method, for example, an organic alkali metal compound is used as a polymerization initiator and anion polymerization is carried out in the presence of a mineral acid such as an alkali metal or an alkaline earth metal salt (Japanese Patent Publication No. 7-25859). (See), a method of anion polymerization using an organic alkali metal compound as a polymerization initiator in the presence of an organic aluminum compound (see JP-A-11-335432), and a method of polymerizing an organic rare earth metal complex as a polymerization initiator (Japanese Patent Laid-Open No. 6). -Refer to No. 93060), Method of radical polymerization in the presence of a copper compound using an α-halogen ester compound as an initiator (Macromol. Chem. Phys.) Vol. 201, pp. 1108 to 1114 (2000). )) And so on. Further, a method of polymerizing the monomers constituting each block using a polyvalent radical polymerization initiator or a polyvalent radical chain transfer agent to produce a mixture containing the acrylic block copolymer (A) of the present invention, etc. Can also be mentioned. Among these methods, in particular, since an acrylic block copolymer can be obtained with high purity, the molecular weight and composition ratio can be easily controlled, and it is economical, an organic alkali metal compound is used as a polymerization initiator and is organic. A method of anionic polymerization in the presence of an aluminum compound is recommended.

The acrylic acid ester used in producing the polymer block (a1) mainly composed of the acrylic acid ester unit may be a mixed monomer in which two or more kinds are mixed in advance, and may be an acrylic acid alkyl ester and an acrylic acid aromatic ester. It is preferably a mixed monomer. In this case, it is preferable that the monomer is a mixture of 50 to 90% by mass of the acrylic acid alkyl ester and 50 to 10% by mass of the acrylic acid aromatic ester, and 60 to 80% by mass of the acrylic acid alkyl ester and 40 to 20% by mass of the acrylic acid aromatic ester. More preferably, it is a mixed monomer of mass%.

The heat-resistant transparent resin (B) used in the present invention is a copolymer composed of an aromatic vinyl compound monomer unit, a (meth) acrylic acid ester monomer unit, and an unsaturated dicarboxylic acid anhydride monomer unit. The one is preferable.

Examples of the aromatic vinyl compound monomer unit include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, ethylstyrene, p-tert-butylstyrene, and α-methylstyrene. , Α-Methyl-p-methylstyrene, and other units derived from each styrene-based monomer. Of these, the styrene unit is preferable. The aromatic vinyl compound monomer unit may be one kind or a combination of two or more kinds.

Examples of the (meth) acrylic acid ester monomer unit include each methacrylate ester monomer such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, dicyclopentanyl methacrylate, and isobornyl methacrylate. And units derived from each acrylic acid ester monomer such as methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-methylhexyl acrylate, 2-ethylhexyl acrylate, and decyl acrylate. Of these, the methyl methacrylate unit is preferable. These (meth) acrylic acid ester monomer units may be one kind or a combination of two or more kinds.

Examples of the unsaturated dicarboxylic acid anhydride monomer unit include units derived from each anhydride monomer such as maleic acid anhydride, itaconic acid anhydride, citraconic acid anhydride, and aconitic acid anhydride. Of these, the maleic anhydride unit is preferable. The unsaturated dicarboxylic acid anhydride monomer unit may be one kind or a combination of two or more kinds.

The content of each of the above components in the heat-resistant transparent resin (B) is not particularly limited, but the aromatic vinyl compound monomer unit is 45 to 85% by mass, and the (meth) acrylic acid ester monomer unit is 5 to 45% by mass, respectively. , The unsaturated dicarboxylic acid anhydride monomer unit containing 10 to 20% by mass is preferable from the viewpoint of improving the heat resistance of the thermoplastic polymer composition of the present invention and the molded product made from the same.

The heat-resistant transparent resin (B) preferably has a total light transmittance of 88% or more, more preferably 89% or more, and further preferably 90% or more, as measured based on ASTM D1003. When the total light transmittance of the 2 mm thickness is 88% or more, the transparency of the thermoplastic polymer composition of the present invention and the molded product made from the same is good.

The heat-resistant transparent resin (B) preferably has a weight average molecular weight (Mw) of 100,000 to 200,000, and has heat resistance, transparency, and flexibility of the thermoplastic polymer composition of the present invention and a molded product made from the same. From the viewpoint of the appearance of the molded product, the weight average molecular weight (Mw) is more preferably 120,000 to 180,000.

The Vicat softening temperature of the heat-resistant transparent resin (B) is not particularly limited, but from the viewpoint of improving the heat resistance of the thermoplastic polymer composition of the present invention and the molded product made from the thermoplastic polymer composition, the Vicut softening temperature at 50 N is 120. The temperature is preferably ℃ or higher, and more preferably 130 ℃ or higher. The upper limit of the Vicat softening temperature is not particularly limited, but if the value of the Vicat softening temperature is too large, the heat-resistant transparent resin (B) tends to have a strong yellowish tint. Therefore, the thermoplastic polymer composition of the present invention and a molding comprising the same. The optical performance of the body may deteriorate. Further, if the value of the Vicat softening temperature is too small, the effect of improving the heat resistance of the thermoplastic polymer composition of the present invention and the molded product made from the same may not be sufficiently obtained. Therefore, the range of the Vicat softening temperature at 50 N is more preferably 120 ° C. or higher and 150 ° C. or lower, and further preferably 130 ° C. or higher and 150 ° C. or lower.

A commercially available product may be used as the heat-resistant transparent resin (B). Examples of such commercially available heat-resistant transparent resins include "Regisphi R100" (Vicat softening temperature: 126 ° C. (50N)) and "Regisphi R200" (Vicat softening temperature: 132 ° C. (50N)) [both trade names and Denka. Made by Co., Ltd.] and so on.

The mass ratio [(A) / (B)] of the acrylic block copolymer (A) and the heat-resistant transparent resin (B) in the thermoplastic polymer composition of the present invention is heat resistance, transparency, flexibility, and so on. From the viewpoint of excellent appearance of the molded product, it is 85/15 to 1/99, more preferably 85/15 to 55/45, and even more preferably 80/20 to 60/40.

The thermoplastic polymer composition of the present invention may be used in addition to the above-mentioned acrylic block copolymer (A) and heat-resistant transparent resin (B), if necessary, as long as the effects of the present invention are not impaired. May contain a polymer of the above. Other polymers include, for example, olefin resins such as polyethylene, polypropylene, polybutene-1, poly-4-methylpentene-1, polynorbornene; ethylene ionomers; polystyrene, styrene-maleic anhydride copolymers, high Impact Polystyrene, AS resin, ABS resin, AES resin, AAS resin, ACS resin, MBS resin and other styrene resins; Acrylic resins such as polymethylmethacrylate; Methylmethacrylate-styrene copolymer; Polyethylene terephthalate, Polybutylene terephthalate, Polyethylene resins such as polylactic acid; polyamide resins such as nylon 6, nylon 66 and polyamide elastomers; polyurethane resins such as ester-based polyurethane elastomers, ether-based polyurethane elastomers, non-yellowing ester-based polyurethane elastomers and non-yellowing carbonate-based polyurethane elastomers; Examples thereof include polycarbonate, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyacetal, polyvinylidene fluoride, modified polyphenylene ether, polyphenylene sulfide, and silicone rubber modified resin. Among these, acrylic resin, AS resin, and polyvinylidene fluoride are preferable from the viewpoint of compatibility with the acrylic block copolymer (A) contained in the thermoplastic polymer composition of the present invention.

Further, the thermoplastic polymer composition of the present invention has various known additives (for example, rubber, lubricant, antioxidant, light stabilizer, colorant, antistatic agent) within a range that does not impair the effects of the present invention. , Flame retardant, etc.), fillers (for example, fiber reinforcing agents such as glass fibers, inorganic fillers, etc.) and the like may be contained. Examples of rubbers that can be contained as additives include acrylic rubbers; silicone rubbers; styrene-based thermoplastic elastomers such as SEPS, SEBS, and SIS; and olefin-based rubbers such as IR, EPR, and EPDM. One or more types can be used. Examples of other additives and fillers are mineral oil softeners such as paraffin oils and naphthenic oils for improving fluidity during molding; for the purpose of improving or increasing heat resistance, weather resistance, etc. Inorganic fillers such as calcium carbonate, talc, carbon black, titanium oxide, silica, clay, barium sulfate, magnesium carbonate; glass fiber for reinforcement, inorganic fiber or organic fiber such as carbon fiber; heat stabilizer; antioxidant Agents; light stabilizers; pressure-sensitive agents; pressure-imparting agents; plasticizing agents; antistatic agents; foaming agents; coloring agents; dyeing agents and the like. Among these additives, it is practically preferable to add a heat stabilizer, an antioxidant, or the like in order to further improve the heat resistance and weather resistance.

The method for preparing the thermoplastic polymer composition of the present invention is not particularly limited, but a method of melt-kneading and mixing is recommended in order to enhance the dispersibility of each component constituting the thermoplastic polymer composition. Examples of the preparation method include a method of melt-kneading an acrylic block copolymer (A) and a heat-resistant transparent resin (B), and if necessary, these can be combined with the other polymers and additives described above. May be mixed at the same time, or the acrylic block copolymer (A) may be mixed with the above-mentioned other polymers and additives, and then mixed with the heat-resistant transparent resin (B). The mixing operation can be performed using, for example, a known mixing or kneading device such as a kneader luder, an extruder, a mixing roll, a Banbury mixer. In particular, it is preferable to use a twin-screw extruder from the viewpoint of improving the kneadability and compatibility between the acrylic block copolymer (A) and the heat-resistant transparent resin (B). The temperature at the time of mixing and kneading should be appropriately adjusted according to the melting temperature of the acrylic block copolymer (A) and the heat-resistant transparent resin (B) to be used, and is usually in the range of 110 ° C to 300 ° C. Mix at temperature. In this way, the thermoplastic polymer composition of the present invention can be obtained in any form such as pellets and powders. Thermoplastic polymer compositions in the form of pellets, powders and the like are suitable for use as molding materials.

The thermoplastic polymer composition of the present invention can be molded by using a molding processing method or a molding processing apparatus generally used for the thermoplastic polymer, and is derived from the thermoplastic polymer composition of the present invention. A molded product can be obtained. For example, a molded product can be manufactured by a molding process such as extrusion molding, injection molding, compression molding, blow molding, calendar molding, vacuum molding, etc., which undergoes heat melting, a solution casting method, or the like. In particular, the thermoplastic polymer composition of the present invention is suitable for injection molding because it has excellent melt fluidity, whereby a layer composed of a mold, a pipe, a sheet, a film, a fibrous material, and the thermoplastic polymer composition. It is possible to obtain a molded product having an arbitrary shape such as a laminated body containing the above.

The use of the thermoplastic polymer composition of the present invention and the molded product made from the same is not particularly limited, but the optical field, the food field, and the medical field are excellent in heat resistance, transparency, flexibility, and the appearance of the molded product. , Consumer field, automobile field, electrical / electronic field, construction field, etc. For example, by using it as an automobile interior member for car audio panels, instrument panels, dashboards, etc., it has excellent heat resistance, so the molded body is less likely to be deformed even if the temperature inside the car rises, and the transparency is utilized. It is possible to add designs and designs that have never been seen before. In addition, as a cover for electronic devices, since it has excellent heat resistance, it is possible to suppress deformation of the smartphone cover due to heat generation of, for example, a smartphone terminal, and because it is excellent in transparency and flexibility, it is possible to impart design and design. It is easy to put on and take off. Other applications include various covers, various terminal boards, printed wiring boards, speakers, microscopes, binoculars, cameras, watches, VTRs, projection TVs and other finder, filters, prisms, Fresnel lenses, and various optical disks (VD, CD, DVD). , MD, LD, etc.) Substrate protective film, optical switch, optical connector, liquid crystal display, light guide film / sheet for liquid crystal display, flat panel display, light guide film / sheet for flat panel display, plasma display, light guide for plasma display Film sheet, retardation film sheet, polarizing film sheet, polarizing plate protective film sheet, wavelength plate, light diffusion film sheet, prism film sheet, reflective film sheet, antireflection film sheet, viewing angle expansion Suitable for film sheets, anti-glare film sheets, brightness-enhancing film sheets, display element substrates for liquid crystals and electroluminescence applications, touch panels, light guide film sheets for touch panels, spacers between various front plates and various modules, etc. It is possible. Furthermore, for various liquid crystal display elements such as mobile phones, digital information terminals, pocket bells, navigation systems, in-vehicle liquid crystal displays, liquid crystal monitors, dimming panels, OA device displays, AV device displays, electroluminescence display elements, touch panels, etc. Can also be used. In addition, because of its excellent heat resistance and flexibility, for example, building interior / exterior members, curtain walls, roofing members, roofing materials, window members, gutters, exteriors, wall materials, flooring materials, etc. It can also be used for building materials, road construction materials, retroreflective film sheets, agricultural film sheets, lighting covers, signboards, translucent sound insulation walls, etc.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited thereto. Various physical properties in Examples and Comparative Examples were measured or evaluated by the following methods.

(1) Weight average molecular weight (Mw)
The weight average molecular weight (Mw) of the acrylic block copolymer (A) and the heat-resistant transparent resin (B) was determined by gel permeation chromatography (hereinafter abbreviated as GPC) in terms of polystyrene.
・ Equipment: GPC equipment "HLC-8020" manufactured by Tosoh Corporation
-Separation column: "TSKgel GMHXL", "G4000HXL" and "G5000HXL" manufactured by Tosoh Corporation are connected in series.-Eluent: tetrahydrofuran-Eluent flow rate: 1.0 ml / min-Column temperature: 40 ° C.
-Detection method: Differential refractometer (RI)

(2) Composition ratio of each polymer block The composition ratio of each polymer block and the composition ratio of each polymer block in the acrylic block copolymer (A) are measured by ¹ H-NMR ( ¹ H-nuclear magnetic resonance). Asked by.
・ Equipment: Nuclear magnetic resonance equipment "JNM-LA400" manufactured by JEOL Ltd.
・ Deuterated solvent: Deuterated chloroform

(3) Transparency Using the thermoplastic polymer composition obtained in the following Examples or Comparative Examples, the following cylinder temperature and mold were used by an injection molding machine (“SE18DU” manufactured by Sumitomo Heavy Industries, Ltd.). A molded product having a temperature of 50 mm × 50 mm and a thickness of 3 mm was produced, and the haze value was measured according to ISO 14782 by a direct reading haze meter (manufactured by Nippon Denshoku), and all light transmission was performed according to ISO 13468-1. The rate was measured.
・ Cylinder temperature: 230 ℃
・ Mold temperature: 50 ℃

(4) Vicat softening temperature Using the thermoplastic polymer composition obtained in the following Examples or Comparative Examples, the following cylinder temperature and the following cylinder temperature and the following cylinder temperature and the following cylinder temperature were used by an injection molding machine (“UH1000-80” manufactured by Nissei Resin Industry Co., Ltd.). A molded product having a mold temperature of 50 mm × 50 mm and a thickness of 3 mm was prepared and measured by the 50 method (load 50 N, heating rate 50 ° C./hour) in accordance with ISO 306. The measuring machine is an HDT manufactured by Toyo Seiki Seisakusho Co., Ltd. VSPT. The TESTER S-3M test equipment was used.
・ Cylinder temperature: 230 ℃
・ Mold temperature: 50 ℃

(5) Flexibility (flexural modulus)
Using the thermoplastic polymer composition obtained in the following example or comparative example, 80 mm at the following cylinder temperature and mold temperature by an injection molding machine (“UH1000-80” manufactured by Nissei Resin Industry Co., Ltd.). A molded product having a thickness of × 10 mm and a thickness of 4 mm was prepared, and the flexural modulus was measured in accordance with ISO 178.
・ Cylinder temperature: 230 ℃
・ Mold temperature: 50 ℃

(6) Appearance of molded product Using the pellets of the thermoplastic polymer composition obtained in the following Example or Comparative Example, the following was performed by an injection molding machine (“UH1000-80” manufactured by Nissei Resin Industry Co., Ltd.). A molded body having a smartphone cover shape (I-phone4s shape, thickness 1 mm) was prepared at the cylinder temperature and the mold temperature, and the cracks at the time of removal from the mold and the appearance of the obtained molded body were visually evaluated. This was used as an index of the appearance of the molded product.
A: There is no crack when it is removed from the mold and it is transparent.
B: There is no crack when the mold is removed, but it is cloudy and not transparent.
C: There is a crack when removing from the mold, but it is transparent.
・ Cylinder temperature: 230 ℃
・ Mold temperature: 50 ℃

In the synthetic examples shown below, the compound was dried and purified by a conventional method and degassed with nitrogen. In addition, the transfer and supply of the compound were carried out in a nitrogen atmosphere.

[Synthesis Example 1] [Organoaluminium compound: Preparation of isobutylbis (2,6-di-t-butyl-4-methylphenoxy) aluminum]
After drying with sodium, 25 ml of dried toluene obtained by distillation under an argon atmosphere and 11 g of 2,6-di-t-butyl-4-methylphenol were placed in a flask having an internal volume of 200 ml in which the internal atmosphere was replaced with argon. It was added and dissolved with stirring at room temperature. By adding 6.8 ml of triisobutylaluminum to the obtained solution and stirring at 80 ° C. for about 18 hours, the corresponding organoaluminum compound [isobutylbis (2,6-di-t-butyl-4-methylphenoxy)). A toluene solution containing [aluminum] at a concentration of 0.6 mol / l was prepared.

[Synthesis Example 2] [Synthesis of acrylic block copolymer (A1)]
In the presence of the isobutylbis (2,6-di-tert-butyl-4-methylphenoxy) aluminum obtained in Synthesis Example 1, sec-butyllithium was used as the polymerization initiator, and the monomer corresponding to each block in toluene (2,6-di-tert-butyl-4-methylphenoxy). Methyl methacrylate, n-butyl acrylate, methyl methacrylate) are sequentially added and living anionic polymerization is performed to remove the aluminum and lithium components used, and then the acrylic block copolymer (A1) is subjected to a devolatile twin-screw extruder. ) Was obtained.
The structure of the obtained acrylic block copolymer (A1) is a triblock of methyl methacrylate polymer block (PMMA) -n-butyl polymer block (PnBA) -methyl methacrylate polymer block (PMMA). It was a copolymer and had a PMMA content of 50% by mass, a weight average molecular weight of 62,000, and a molecular weight distribution (weight average molecular weight / number average molecular weight) of 1.12.

[Synthesis Example 3] [Synthesis of acrylic block copolymer (A2)]
Living anionic polymerization was carried out in the same manner as in Synthesis Example 2 except that the monomer used was changed to obtain the following acrylic block copolymer.
The structure of the obtained acrylic block copolymer is a methyl methacrylate polymer block (PMMA) -n-butyl acrylate / benzyl acrylate copolymer block (P (nBA / BzA)) -methyl methacrylate polymer. It was a triblock copolymer of block (PMMA), and had a PMMA content of 50.5% by mass, a weight average molecular weight of 62,600, and a molecular weight distribution (weight average molecular weight / number average molecular weight) of 1.11.

[Synthesis Example 4] [Synthesis of acrylic block copolymer (A3)]
Living anionic polymerization was carried out in the same manner as in Synthesis Example 2 except that the ratio of the monomers used was changed to obtain the following acrylic block copolymer.
The structure of the obtained acrylic block copolymer is a triblock copolymer of PMMA-PnBA-PMMA, with a PMMA content of 29% by mass, a weight average molecular weight of 120,000, and a molecular weight distribution (weight average molecular weight / number average molecular weight). ) 1.15.

[Synthesis Example 5] [Synthesis of acrylic block copolymer (A4)]
Living anionic polymerization was carried out in the same manner as in Synthesis Example 2 except that the ratio of the monomers used was changed to obtain the following acrylic block copolymer.
The structure of the obtained acrylic block copolymer is a triblock copolymer of PMMA-PnBA-PMMA, with a PMMA content of 63% by mass, a weight average molecular weight of 70,000, and a molecular weight distribution (weight average molecular weight / number average molecular weight). ) 1.15.

[Examples 1 to 9 and Comparative Examples 1 to 5]
Using the acrylic block copolymers (A1) to (A4) prepared in Synthesis Examples 2 to 5 and each of the resins shown below, 230 by a twin-screw extruder at the blending ratios shown in Tables 1 and 2 below. Pellets of the thermoplastic polymer composition were produced by melt-kneading at ° C., extruding, and cutting. This pellet was evaluated according to (4) to (7) above. The results obtained are shown in Tables 1 and 2.
Heat-resistant transparent resin (B1): "Registfy R100 (manufactured by Denka Co., Ltd.)" (polymer of styrene / methyl methacrylate / maleic anhydride, Vicat softening temperature: 126 ° C. (50N), weight average molecular weight (Mw): 161000)
Heat-resistant transparent resin (B2): "Registfy R200 (manufactured by Denka Co., Ltd.)" (polymer of styrene / methyl methacrylate / maleic anhydride, Vicat softening temperature: 132 ° C. (50N), weight average molecular weight (Mw): 172000)
PMMA resin (C): Parapet GF (manufactured by Kuraray Co., Ltd.)

From the results in Tables 1 and 2 above, it can be seen that the thermoplastic polymer compositions obtained in Examples 1 to 9 of the present invention have high transparency and excellent heat resistance. Further, it can be seen that the thermoplastic polymer compositions of Examples 1 to 3 and 5 to 9 are further excellent in flexibility and appearance of the molded product. In Example 5, by changing the heat-resistant transparent resin (B1) to (B2), the heat resistance could be further improved while maintaining the transparency as compared with Example 2 having the same composition ratio. Further, in Examples 6 to 7, by using the acrylic block copolymer (A2), the transparency could be further improved while maintaining the heat resistance as compared with Examples 2 to 3 having the same composition ratio. Further, in Examples 8 to 9, by changing the heat-resistant transparent resin (B1) to (B2), the heat resistance could be further improved as compared with Examples 6 to 7 having the same composition ratio.
On the other hand, Comparative Example 1 is inferior in heat resistance because it does not contain the heat-resistant transparent resin (B1). In Comparative Example 2, a heat-resistant transparent resin (B1) is blended, but the heat resistance is inferior because the amount is small. Since Comparative Example 3 uses an acrylic block copolymer (A3) which is outside the scope of the present invention, it is inferior in transparency, heat resistance, and appearance of the molded product. Since Comparative Example 4 uses an acrylic block copolymer (A4) which is outside the scope of the present invention, it is inferior in flexibility and appearance of the molded product. In Comparative Example 5, since the acrylic block copolymer is not contained, the flexibility is inferior, so that it is difficult to remove from the mold, and the appearance of the molded product is inferior.

According to the present invention, it is possible to provide a thermoplastic polymer composition having excellent heat resistance, transparency, flexibility, and an excellent appearance of a molded product, and a molded product made of the same, in the fields of optics, food, medical care, and consumer products. , Automotive field, electrical / electronic field, construction field, etc.

Claims (9)

It has at least one structure in which a polymer block (a2) mainly composed of a methacrylic acid ester unit is bonded to both ends of a polymer block (a1) mainly composed of an acrylic acid ester unit, and has a weight average molecular weight. Acrylic block copolymer (A) having a polymer block (a2) content of 30% by mass or more and 60% by mass or less, and an aromatic vinyl compound monomer unit. , A heat-resistant transparent resin (B) which is a copolymer composed of a (meth) acrylic acid ester monomer unit and an unsaturated dicarboxylic acid anhydride monomer unit, and is heat-resistant with an acrylic block copolymer (A). A thermoplastic polymer composition having a mass ratio [(A) / (B)] with the transparent resin (B) of 85/15 to 60/40 . The thermoplastic polymer composition according to claim 1, wherein the content of the polymer block (a2) in the acrylic block copolymer (A) is 40% by mass or more and 55% by mass or less. Claim 1 of the acrylic block copolymer (A), wherein the polymer block (a1) is a copolymer block of 50 to 90% by mass of an acrylic acid alkyl ester and 50 to 10% by mass of an acrylic acid aromatic ester. Alternatively, the thermoplastic polymer composition according to 2. The thermoplastic polymerization composition according to claim 3, wherein the acrylic acid aromatic ester is benzyl acrylate. The invention according to any one of claims 1 to 4, wherein the mass ratio [(A) / (B)] of the acrylic block copolymer (A) and the heat-resistant transparent resin (B) is 70/30 to 60/40. Thermoplastic polymer composition. The thermoplastic polymer composition according to any one of claims 1 to 5 , wherein the heat-resistant transparent resin (B) has a Vicat softening temperature of 120 ° C. or higher at 50 N. A molded product made of the thermoplastic polymer composition according to any one of claims 1 to 6 . An automobile interior member made of the molded body according to claim 7 . A cover for an electronic device made of the molded product according to claim 7 .