JP7067133B2 - Polyester-based thermoplastic elastomer composition and its molded product - Google Patents

Description

The present invention relates to a polyester-based thermoplastic elastomer in which the obtained molded product has a soft texture and is excellent in moldability, oil resistance, and wear resistance, and the molded product thereof.

Polyester-based thermoplastic elastomers have excellent mechanical properties such as strength, impact resistance, elastic recovery, and flexibility, as well as low temperature and constant temperature characteristics, as well as oil resistance and abrasion resistance. In addition, polycarbonate, Since it can be heat-sealed to a hard resin such as an acrylonitrile-butadiene copolymer resin (ABS resin), it is widely used in fields such as automobiles, electric / electronic parts, and consumer materials.

In recent years, polyester-based thermoplastic elastomers have been softened with rubber polymers and plasticizers, and their soft touch, oil resistance, and wear resistance have been focused on and applied to grips or packings of cameras, electric tools, bicycles, etc. Has been studied and put into practical use.

Patent Document 1 discloses a polyester-based thermoplastic elastomer composition that can be thermally fused to a polyolefin-based resin by blending a styrene-based thermoplastic elastomer with the polyester elastomer.

In Patent Document 2, 100 parts by mass of polyester elastoma is blended with 0.1 to 5.0 parts by mass of an ester-based plasticizer, and Duro D has a hardness of 47 to 50 and is highly elastic and resistant to constant temperature. A polyester elastoma resin composition having excellent bending fatigue resistance is disclosed.

Japanese Unexamined Patent Publication No. 9-1248887 JP-A-2015-168815

According to the detailed examination by the present inventors, it was found that the above-mentioned conventional technique has the following problems.

Since the polyester-based thermoplastic elastomer composition described in Patent Document 1 uses a styrene-based thermoplastic elastomer in order to achieve softening, it has poor oil resistance, and non-polar oil such as machine oil, sweat, etc. When it comes into contact with the oil component of the above, there is a problem that it absorbs the oil component and swells and deforms. Further, the polyester elastomer resin composition described in Patent Document 2 is not sufficiently flexible due to the small amount of the plasticizer compounded, and is flexible such as grips and packings for cameras, power tools, bicycles and the like. Is not suitable for use in the required parts. It is easily considered that sufficient flexibility can be imparted by increasing the blending amount of the plasticizer, and it has been clarified by the present inventors, but in this case, the mold releasability from the mold is remarkable in injection molding. It is known to get worse.

An object of the present invention is a polyester-based thermoplastic elastomer composition capable of obtaining a molded product having excellent moldability, oil resistance, and abrasion resistance and having a soft texture in view of the above-mentioned problems of the prior art. And to provide the molded product thereof.

As a result of diligent studies to solve the above problems, the present inventors can solve the above problems by blending a specific rubber polymer and an ester compound with a polyester elastomer, and further, a carbodiimide compound can be obtained. It has been found that the abrasion resistance can be further improved by blending.
That is, the gist of the present invention lies in the following [1] to [10].

[1] A polyester-based thermoplastic elastomer composition comprising the following components (A) to (C).
Component (A): Polyester elastomer Component (B): At least one selected from the group consisting of an acrylic core-shell rubber polymer, a silicone core-shell rubber copolymer, and a butadiene / acrylonitrile copolymer rubber polymer. Rubber polymer component (C): ester-based compound

[2] The rubbery polymer of the component (B) is contained in an amount of 10 to 400 parts by mass and the ester compound of the component (C) is contained in an amount of 6 to 100 parts by mass with respect to 100 parts by mass of the polyester elastomer of the component (A). The polyester-based thermoplastic elastomer composition according to [1].

[3] The polyester-based thermoplastic elastomer according to [1] or [2], further containing 0.01 to 10 parts by mass of a carbodiimide compound as the component (D) with respect to 100 parts by mass of the polyester elastomer of the component (A). Composition.

[4] The polyester-based thermoplastic elastomer composition according to any one of [1] to [3], wherein the component (A) contains a polyalkylene glycol component and the polyalkylene glycol is polytetramethylene glycol.

[5] The polyester-based thermoplastic elastomer composition according to any one of [1] to [4], which contains the polyalkylene glycol component of the component (A) and has a content of the polyalkylene glycol component of 60% by mass or more. ..

[6] The polyester-based thermoplastic elastomer composition according to any one of [1] to [5], wherein the component (B) contains a unit derived from an alkyl methacrylate compound.

[7] The polyester-based thermoplastic elastomer composition according to any one of [1] to [6], wherein the component (C) is tri-2-ethylhexyl trimellitic acid.

[8] The polyester-based thermoplastic elastomer composition according to any one of [1] to [7], wherein the component (D) is a carbodiimide-modified isocyanate.

[9] The polyester-based thermoplastic elastomer composition according to any one of [1] to [8], which is a polyester-based thermoplastic elastomer composition for grips.

[10] A molded product made from the polyester-based thermoplastic elastomer composition according to any one of [1] to [9].

According to the present invention, by blending a specific rubber polymer and an ester compound, preferably a carbodiimide compound, in a polyester elastomer, a molded product having a soft texture and excellent oil resistance and wear resistance can be obtained. It can be provided with good formability.

Hereinafter, embodiments of the present invention will be described in detail. The present invention is not limited to the following description, and can be arbitrarily modified and carried out without departing from the gist of the present invention. In this specification, when a numerical value or a physical property value is inserted before and after using "-", it is used as including the values before and after that.

[Polyester-based thermoplastic elastomer composition]
The polyester-based thermoplastic elastomer composition of the present invention is characterized by containing the following components (A) to (C), and preferably further contains the following components (D).
Component (A): Polyester elastomer Component (B): At least one selected from the group consisting of an acrylic core-shell rubber polymer, a silicone core-shell rubber copolymer, and a butadiene / acrylonitrile copolymer rubber polymer. Rubber polymer component (C): ester compound component (D): carbodiimide compound

[Ingredient (A)]
The polyester elastomer of component A is usually a block copolymer having a hard segment having crystallinity and a soft segment having flexibility.

The polyester elastomer includes, for example, a cyclic polysell (in the present invention, the "cyclic polyester" means a dicarboxylic acid as a raw material or an alkyl ester thereof containing a dicarboxylic acid having a cyclic structure or an alkyl ester thereof). A block copolymer having a hard segment (hereinafter, may be referred to as "cyclic polyester unit") and a soft segment composed of polyalkylene glycol (hereinafter, may be referred to as "polyalkylene glycol unit") (hereinafter, may be referred to as "polyalkylene glycol unit"). , "Cyclic polyester-polyalkylene glycol block copolymer"), and a hard segment composed of cyclic polyester and a chain aliphatic polyester (in the present invention, the "chain aliphatic polyester" is a raw material. A soft segment consisting of a certain dicarboxylic acid or an alkyl ester thereof is a dicarboxylic acid or an alkyl ester thereof having only a chain structure (hereinafter, may be referred to as a "chain aliphatic polyester unit"). Examples thereof include a block copolymer having the above (hereinafter, may be referred to as “cyclic polyester-chain aliphatic polyester block copolymer”) and the like. Of these, cyclic polyester-polyalkylene glycol block copolymers are preferred because they are readily available.

As the cyclic polyester-polyalkylene glycol block copolymer, for example, a copolymer having a hard segment made of aromatic polyester (hereinafter, may be referred to as “aromatic polyester unit”) and a polyalkylene glycol unit (hereinafter, may be referred to as “aromatic polyester unit”). , "Aromatic polyester-polyalkylene glycol block copolymer") and a hard segment made of alicyclic polyester (hereinafter, may be referred to as "alicyclic polyester unit") and polyalkylene. Examples thereof include a block copolymer having a glycol unit (hereinafter, may be referred to as “aromatic polyester-polyalkylene glycol block copolymer”) and the like. Among these, aromatic polyester-polyalkylene glycol block copolymers are preferable in terms of heat resistance.

The aromatic polyester-polyalkylene glycol block copolymer is a known thermoplastic elastomer as described in Japanese Patent Application Laid-Open No. 10-130451, and any polymer containing a polyalkylene glycol unit can be used. The block may be a monopolymer or a copolymer.

The raw material of the aromatic polyester unit is described in detail below, but it is preferable to include polybutylene terephthalate as a hard segment. On the other hand, the raw material of the polyalkylene glycol unit will be described in detail below, but it is preferable to include a soft segment made of polytetramethylene ether glycol (hereinafter, may be referred to as “polytetramethylene glycol unit”). ..

As the polyester elastomer used in the present invention, a polybutylene terephthalate-polyalkylene glycol block copolymer is preferable, and a polybutylene terephthalate-polytetramethylene glycol block copolymer is particularly preferable.

Further, as the alicyclic polyester-polyalkylene glycol block copolymer, for example, an alicyclic dicarboxylic acid (in the present specification, the “aliphatic dicarboxylic acid” is a cyclic aliphatic hydrocarbon in which two carboxyl groups are directly present. (Meaning a bound compound), those obtained from alicyclic diols and polyalkylene glycols as raw materials are typical examples.

As long as it is a polymer containing a polyalkylene glycol unit, each block may be a monopolymer or a copolymer. The alicyclic polyester unit preferably contains a hard segment obtained from cyclohexanedicarboxylic acid and cyclohexanedimethanol as raw materials. Further, the polyalkylene glycol unit of the alicyclic polyester-polyalkylene glycol block copolymer preferably contains a soft segment (polytetramethylene glycol unit) obtained from polytetramethylene ether glycol as a raw material.

As the cyclic polyester-chain aliphatic polyester block copolymer, for example, a block copolymer having a hard segment made of aromatic polyester and a soft segment made of chain aliphatic polyester (hereinafter, “aromatic polyester-chain form”). It may be referred to as an "aliphatic polyester block copolymer"), and a block copolymer having a hard segment composed of an alicyclic polyester and a soft segment composed of a chain aliphatic polyester (hereinafter, "alicyclic polyester-". It may be referred to as "chain aliphatic polyester block copolymer").

Among these, aromatic polyester-chain aliphatic polyester block copolymers are preferable. Among the aromatic polyester-chain aliphatic polyester block copolymers, the polybutylene terephthalate-chain aliphatic polyester block copolymer in which the aromatic polyester unit is composed of polybutylene terephthalate is more preferable. Further, the chain aliphatic polyester unit is preferably obtained from a chain aliphatic dicarboxylic acid having 4 to 10 carbon atoms represented by sebacic acid and adipic acid and a chain aliphatic diol.

As the flexible soft segment, a polyalkylene ether glycol unit is preferable. Examples of the polyalkylene ether glycol include linear and branched fats such as polymethylene glycol, polyethylene glycol, poly (1,2- and 1,3-) propylene glycol, polytetramethylene glycol and polyhexamethylene glycol. In addition to group ethers, monopolymers or copolymers of alicyclic ethers such as condensates of cyclohexanediol and condensates of cyclohexanedimethanol can be mentioned. Further, a random copolymer in these ether units may be used. Further, a block copolymer having a polyalkylene glycol unit can also be used. These may be used alone or in combination of two or more.

The number average molecular weight of the polyalkylene glycol unit contained in the cyclic polyester-polyalkylene glycol block copolymer is preferably 600 to 4,000, more preferably 800 to 2,500, and more preferably 900 to 2. , 100 is more preferred. Here, the number average molecular weight of the polyalkylene glycol unit refers to a polystyrene-equivalent value measured by gel permeation chromatography (GPC).

As these polyalkylene glycol units, only one type may be contained in the cyclic polyester-polyalkylene glycol block copolymer, or two or more types having different number average molecular weights or constituent components may be contained.

The method for producing the polyester elastomer is not particularly limited. For example, among the cyclic polyester-polyalkylene glycol block copolymers, the aromatic polyester-polyalkylene glycol block copolymer using aromatic polyester and polyalkylene ether glycol is used. If this is the case, the raw materials are a chain aliphatic and / or alicyclic diol having 1 to 12 carbon atoms, an aromatic dicarboxylic acid or an alkyl ester thereof, and a polyalkylene ether glycol, and the esterification reaction or the ester exchange reaction is carried out. It can be obtained by condensing the obtained oligomer.

As the chain aliphatic and / or alicyclic diol having 1 to 12 carbon atoms, those usually used as a raw material for polyester can be used. Examples of the chain aliphatic diol include ethylene glycol, propylene glycol, trimethylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 1,6-hexene glycol and the like. Of these, 1,4-butylene glycol is preferable.
Examples of the alicyclic diol include 1,4-cyclohexene glycol and 1,4-cyclohexanedimethanol, and 1,4-cyclohexanedimethanol is preferable.
As these chain aliphatic and / or alicyclic diols having 2 to 12 carbon atoms, one type may be used alone, or a mixture of two or more types may be used.

As the aromatic dicarboxylic acid or an alkyl ester thereof, those generally used as a raw material for polyester can be used. For example, terephthalic acid and its lower grade (“lower grade” in the present specification means 4 or less carbon atoms). .) Alkyl esters, isophthalic acid, phthalic acid, 2,5-norbornenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid and their lower alkyl esters, etc. Can be mentioned. Among these, terephthalic acid and isophthalic acid are preferable, and terephthalic acid is more preferable.
As for these aromatic dicarboxylic acids or alkyl esters thereof, one kind may be used alone, or two or more kinds may be used in combination.

As the polyalkylene ether glycol, as described above, for example, linear and linear such as polymethylene glycol, polyethylene glycol, poly (1,2- and 1,3-) propylene glycol, polytetramethylene glycol and polyhexanemethylene glycol and the like. In addition to branched aliphatic ether glycols, monopolymers or copolymers of alicyclic ethers such as condensates of cyclohexanediol and condensates of cyclohexanedimethanol can be mentioned.
Further, a random copolymer in these ether units may be used.
Of these, linear and branched aliphatic ether glycols such as polymethylene glycol, polyethylene glycol, poly (1,2- and 1,3-) propylene glycol, polytetramethylene glycol and polyhexamethylene glycol are preferable. More preferably, polymethylene glycol, polyethylene glycol, poly (1,2- and 1,3-) propylene glycol and polytetramethylene glycol are preferable, and polytetramethylene glycol is particularly preferable.
These may be used alone or in combination of two or more.

Further, in the case of producing an alicyclic polyester-polyalkylene glycol block copolymer, an aromatic dicarboxylic acid or an alkyl ester thereof used as a raw material in producing the above aromatic polyester-polyalkylene glycol block copolymer. Instead, an alicyclic dicarboxylic acid or an alkyl ester thereof may be used.

That is, it is obtained by an esterification reaction or a transesterification reaction using a chain aliphatic and / or alicyclic diol having 2 to 12 carbon atoms, an alicyclic dicarboxylic acid or an alkyl ester thereof, and a polyalkylene ether glycol as raw materials. It can be obtained by polycondensing the obtained oligomer.

As the alicyclic dicarboxylic acid or an alkyl ester thereof, those generally used as a raw material for polyester can be used, and for example, cyclohexanedicarboxylic acid and its lower alkyl ester, cyclopentane dicarboxylic acid and its lower alkyl ester and the like can be used. Can be mentioned. Among these, cyclohexanedicarboxylic acid and its lower alkyl ester are preferable, and cyclohexanedicarboxylic acid is particularly preferable. As for these alicyclic dicarboxylic acids, one kind may be used alone, or two or more kinds may be used in combination.

The content of each of the cyclic polySL unit and the polyalkylene glycol unit in the cyclic polyester-polyalkylene glycol block copolymer is not limited, but is usually as follows from the balance between the crystallinity of the hard segment and the flexibility of the soft segment. Range.

That is, the lower limit of the content of the cyclic polyester unit in the cyclic polyester-polyalkylene glycol block copolymer is usually 10% by mass or more, preferably 20% by mass or more. The upper limit of the content of the cyclic polyester unit is usually 95% by mass or less, preferably 90% by mass or less, more preferably 80% by mass or less, and particularly preferably 40% by mass or less.

The lower limit of the content of the polyalkylene glycol unit in the cyclic polyester-polyalkylene glycol block copolymer is usually 5% by mass or more, preferably 10% by mass or more, more preferably 20% by mass or more, and particularly preferably 20% by mass or more. It is 60% by mass or more. The upper limit of the content of the polyalkylene glycol unit is usually 90% by mass or less, preferably 80% by mass or less.

The content of the cyclic polyester unit in the block copolymer having the cyclic polyester unit can be calculated based on the chemical shift of the hydrogen atom and its content by using nuclear magnetic resonance spectroscopy (NMR). can. Similarly, the content of a polyalkylene glycol unit in a block copolymer having a polyalkylene glycol unit is calculated based on the chemical shift of its hydrogen atom and its content using nuclear magnetic resonance spectroscopy (NMR). can do.

As the aromatic polyester-polyalkylene glycol block copolymer, a polybutylene terephthalate-polyalkylene glycol block copolymer is preferable because it has a particularly high crystallization rate and excellent moldability. The alkylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms, still more preferably 2 to 5 carbon atoms, and particularly preferably 4 carbon atoms.

In addition to the above components, the cyclic polyester-polyalkylene glycol block copolymer represented by the aromatic polyester-polyalkylene glycol block copolymer according to the present invention includes trifunctional alcohols, tricarboxylic acids and / or its components. One or more of the esters may be copolymerized in a small amount, and a chain aliphatic dicarboxylic acid such as adipic acid or a dialkyl ester thereof may be introduced as a copolymerization component.

The above cyclic polyester-polyalkylene glycol block copolymer can also be obtained as a commercially available product. Examples of such commercially available products include "KEYFLEX® (registered trademark)" (manufactured by LG Chem Co., Ltd.), "Primaloy (registered trademark)" (manufactured by Mitsubishi Chemical Corporation), and "Perprene (registered trademark)" (Toyo Spinning Co., Ltd.). (Manufactured by) and "Hitrel (registered trademark)" (manufactured by DuPont).

As the polyester-based thermoplastic elastomer such as a cyclic polyester-polyalkylene glycol block copolymer, one type may be used alone, or two or more types may be used in combination.

[Component (B)]
In the present invention, as the rubbery copolymer of the component (B), an acrylic core-shell type rubbery polymer such as an acrylate / styrene / acrylonitrile copolymer (ASA resin) and an acrylate / methyl methacrylate copolymer; silicone / acrylate / Silicone-based core-shell type rubber polymer such as methyl methacrylate copolymer, silicone / acrylate / acrylonitrile / styrene copolymer; butadiene / acrylonitrile copolymer rubber polymer (NBR) is used. In the present invention, by using these limited specific rubbery polymers as the rubbery polymer of the component (B), oil resistance can be enhanced because of its high polarity.
In addition, only one kind of these rubbery polymers may be used, or two or more kinds may be used in combination.

Among these rubbery polymers, those using alkyl methacrylate compounds as raw materials such as acrylate / methylmethacrylate copolymer rubbery polymer and silicone / acrylate / methylmethacrylate copolymer rubbery polymer from the viewpoint of oil resistance. , Silicone / acrylate / acrylonitrile / styrene copolymer rubber polymer, butadiene / acrylonitrile copolymer rubber polymer, preferably one or more, and silicone / acrylate / methyl methacrylate copolymer rubber polymer. It is more preferable to use one kind or two or more kinds.

In the polyester-based thermoplastic elastomer composition of the present invention, the blending amount of the rubbery polymer of the component (B) is preferably 10 to 400 parts by mass with respect to 100 parts by mass of the polyester elastomer of the component (A). It is preferably 20 to 200 parts by mass, more preferably 40 to 125 parts by mass. If the blending amount of the component (B) is less than the above lower limit, flexibility cannot be imparted to the polyester-based thermoplastic elastomer composition of the present invention, and if it exceeds the above upper limit, oil resistance and abrasion resistance tend to be insufficient. ..

[Component (C)]
The ester compound of the component (C) is not particularly limited, but is preferably a compound having at least two ester bonds in the molecule.

Further, the component (C) functions as a plasticizing agent, and for example, dioctylphthalate, dibutylphthalate, diethylphthalate, butylbenzylphthalate, di-2-ethylhexylphthalate, diisodecylphthalate, diundecylphthalate, diisononylphthalate and the like. Phthalate ester compounds; Phosphoric acid ester compounds such as tricresyl phosphate, triethyl phosphate, tributyl phosphate, tri-2-ethylhexyl phosphate, trimethyl phosphate, tris-dichloropropyl phosphate; trioctyl trimellitic acid, trimellitic acid Trimellitic acid ester compounds such as tri-2-ethylhexyl; dipentaerythritol ester compounds; dioctyl adipate, di-2-ethylhexyl adipate, diisobutyl adipate, dibutyl adipate, diisodecyl adipate, dibutyl diglycol adipate, di Fatty acid ester compounds such as -2-ethylhexyl azelate, dioctyl sebacate, methyl acetyl lithinolate; pyromellitic acid ester compounds such as pyromellitic octyl ester; epoxidized soybean oil, epoxidized flaxseed oil, epoxidation Epoxidized ester compounds such as fatty acid alkyl esters; and polyether ester compounds such as adipic acid ether esters and polyether esters; diethylene glycol dibenzoates, polypropylene glycol dibenzoates, tripropylene glycol dibenzoates, dipropylene glycol dibenzoates, propylenes. Benzoate ester compounds such as glycol dibenzoate, dibutylene glycol dibenzoate, neopentyl glycol dibenzoate, glycerin tribenzoate, pentaerythritol tetrabenzoate, triethylene glycol dibenzoate, polyethylene glycol dibenzoate, trimethylolethanetribenzoate; Examples of softeners for hydrocarbon-based rubbers such as mineral oil-based softeners and synthetic resin-based softeners include trimellitic acid ester-based compounds in that they have a high affinity with the polyester elastomer of the component (A). Is preferred, and tri-2-ethylhexyl trimellitic acid is particularly preferred.

In the present invention, only one of these ester compounds may be used, or two or more thereof may be used in any combination and ratio.

In the polyester-based thermoplastic elastomer composition of the present invention, the blending amount of the ester-based compound of the component (C) is preferably 6 to 100 parts by mass with respect to 100 parts by mass of the polyester elastomer of the component (A). It is preferably 10 to 80 parts by mass, more preferably 15 to 50 parts by mass. If the blending amount of the component (C) is less than the above lower limit, flexibility cannot be imparted, and if it exceeds the above upper limit, the ester compound tends to bleed out.

[Component (D)]
The polyester-based thermoplastic elastomer composition of the present invention preferably contains a carbodiimide compound, particularly a carbodiimide-modified isocyanate, as the component (D) in addition to the above components (A), (B) and (C).
By including the component (D), the abrasion resistance can be improved without impairing the flexibility, oil resistance and moldability of the polyester-based thermoplastic elastomer composition.

Examples of the carbodiimide compound include compounds having one or more carbodiimide groups in the molecule (including polycarbodiimide compounds), and specifically, examples of the monocarbodiimide compound include dicyclohexylcarbodiimide, diisopropylcarbodiimide, dimethylcarbodiimide, and diisobutylcarbodiimide. Examples thereof include dioctylcarbodiimide, t-butylisopropylcarbodiimide, diphenylcarbodiimide, di-t-butylcarbodiimide, di-β-naphthylcarbodiimide, N, N'-di-2,6-diisopropylphenylcarbodiimide and the like. As the polycarbodiimide compound, a compound having a degree of polymerization having a lower limit of usually 2 or more, preferably 4 or more, and an upper limit of usually 40 or less, preferably 30 or less is used. Publication No. 47-33279, J. Mol. Org. Chem. Vol. 28, p2069-2075 (1963), and Chemical Reviews 1981, Vol. 81, No. 4, p. Examples thereof include those manufactured by the method described in 619-621 and the like.

Examples of the organic diisocyanate which is a raw material for producing a polycarbodiimide compound include aromatic diisocyanate, aliphatic diisocyanate, alicyclic diisocyanate and a mixture thereof. , 4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 1,3-phenylenediisocyanate, 1,4-phenylenediocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,4 -Mixed of tolylene diisocyanate and 2,6-tolylene diisocyanate, hexamethylene diisocyanate, cyclohexane-1,4-diisocyanate, xylylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, methylcyclohexanediisocyanate, tetramethylxyl Examples thereof include range isocyanate, 2,6-diisopropylphenyl isocyanate, 1,3,5-triisopropylbenzene-2,4-diisocyanate and the like.

Specific industrially available carbodiimide compounds include Carbodilite HMV-8CA (manufactured by Nisshinbo Chemical Co., Ltd.), Carbodilite LA-1 (manufactured by Nisshinbo Chemical Co., Ltd.), Stavaxol P (manufactured by Rheinchemy), and Stavaxol P100 (manufactured by Rheinchemy). ) Etc. are exemplified.

Only one kind of these carbodiimide compounds may be used, or two or more kinds thereof may be mixed and used.

In the polyester-based thermoplastic elastomer composition of the present invention, the blending amount of the carbodiimide compound of the component (D) is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the polyester elastomer of the component (A). More preferably, it is 1 to 3 parts by mass. If the blending amount of the component (D) is less than the above lower limit, the wear resistance cannot be sufficiently improved, and if it exceeds the above upper limit, the manufacturing cost becomes high, which is not realistic.

[Other ingredients]
The polyester-based thermoplastic elastomer composition of the present invention is filled with other components other than the above components (A) to (D), for example, various additives, as necessary, as long as the object of the present invention is not impaired. Materials and the like can be appropriately blended.

Examples of the additive include antioxidants, acidic compounds and derivatives thereof, lubricants, ultraviolet absorbers, light stabilizers, nucleating agents, flame retardant agents, impact resistance improving agents, foaming agents, colorants, organic peroxides and the like. .. These may be used alone or in combination of two or more.

Fillers include talc, calcium carbonate, zinc carbonate, wallastnite, silica, alumina, magnesium oxide, calcium silicate, sodium aluminate, calcium aluminate, sodium aluminosilicate, magnesium silicate, glass balloons, glass cut fiber, Glass milled fiber, glass flakes, glass powder, silicon carbide, silicon nitride, gypsum, plaster whiskers, calcined kaolin, carbon black, zinc oxide, antimony trioxide, zeolite, hydrotalcite, metal fibers, metal whiskers, metal powder, ceramic Inorganic fillers such as whiskers, potassium titanate, boron nitride, graphite, carbon fibers; naturally derived polymers such as starch, cellulose fine particles, wood flour, okara, fir shells, and bran, and organic fillers such as modified products thereof. And so on. These may be used alone or in combination of two or more. The blending amount of the filler is usually 50% by mass or less, preferably 30% by mass or less of all the components.

[Manufacturing method of polyester-based thermoplastic elastomer]
In the polyester-based thermoplastic elastomer composition of the present invention, the components (A) to (C), preferably the components (A) to (D), and other components to be blended as necessary, are contained in a known method, for example. It can be produced by mechanically mixing with a Henschel mixer, V blender, tumbler blender or the like, and then mechanically melt-kneading by a known method. For the mechanical melt-kneading, a general melt-kneader such as a Banbury mixer, various kneaders, a single-screw or twin-screw extruder can be used.

In the polyester-based thermoplastic elastomer composition of the present invention, the ester-based compound of the component (C), which is a plasticizer, is impregnated into the rubbery polymer of the component (B) to form a composite, and then the component (A) and the component (A). (D) The other components to be blended as necessary are mechanically mixed by a known method, for example, a Henschel mixer, a V blender, a tumbler blender, or the like, and then mechanically melt-kneaded by a known method. It can also be manufactured by In this case as well, a general melt-kneader such as a Banbury mixer, various kneaders, a single-screw or twin-screw extruder can be used for the mechanical melt-kneading.

When the ester compound of the component (C) is impregnated into the rubber polymer of the component (B), the blending amount of the ester compound may be 66 parts by mass or less with respect to 100 parts by mass of the rubber polymer. preferable. If the amount of the ester compound exceeds 66 parts by mass, the rubbery polymer may not be impregnated with the entire amount of the blended ester compound.

[Physical characteristics of polyester-based thermoplastic elastomer composition]
Since the polyester-based thermoplastic elastomer composition of the present invention is required to have excellent injection moldability from the viewpoint of its application, the melt flow rate measured at 230 ° C. and a load of 2.16 kgf according to ISO 1133. (MFR) is preferably 100 g / 10 minutes or less, more preferably 90 g / 10 minutes or less, and even more preferably 80 g / 10 minutes. If the MFR exceeds the above upper limit, it is considered that burrs are generated during injection molding and the molded product cannot be obtained.

Since the polyester-based thermoplastic elastomer composition of the present invention is required to have a soft touch from the viewpoint of its application, the Duro A hardness is preferably 40 to 90, more preferably 50 to 80. It is preferably 60 to 70, and more preferably 60 to 70.

Further, the polyester-based thermoplastic elastomer composition of the present invention is easily expected to come into contact with oil components such as human oil and fat components and machine oil from the viewpoint of its application, and is resistant to oil components. Since property is required, the mass increase rate and volume increase rate after being immersed in the liquid resistance test oil "IRM903" of vulture rubber or thermoplastic rubber at room temperature for 24 hours are preferably 9% or less, 7 It is more preferably% or less, and even more preferably 5% or less.

Since the polyester-based thermoplastic elastomer composition of the present invention is required to have excellent wear resistance from the viewpoint of its application, the mass loss before and after wear in the Taber wear test is preferably 1000 mg or less. , 500 mg or less, more preferably 300 mg or less.

The method for evaluating the Duro A hardness, oil resistance, and wear resistance described above will be specifically described in the section of Examples.

[Molded product of polyester-based thermoplastic elastomer composition]
The molded product of the present invention is formed by using the polyester-based thermoplastic elastomer composition of the present invention.

Since the polyester-based thermoplastic elastomer composition of the present invention has excellent moldability by using a specific rubbery polymer, it can be molded by various molding methods such as injection molding, extrusion molding, and blow molding. It can also be applied to a molding method that combines a plurality of molding processing techniques such as injection blow molding that combines injection molding and blow molding.

The molded product produced by the polyester-based thermoplastic elastomer composition of the present invention has a soft texture and is excellent in oil resistance, abrasion resistance and the like. For this reason, stationery; toys; sports equipment; covers for mobile phones and smartphones; parts such as grips; school materials, home appliances, repair parts for OA equipment, various parts such as automobiles, motorcycles, bicycles; building materials, etc. It can be suitably used for various purposes such as members.

Hereinafter, the content of the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples as long as the gist of the present invention is not exceeded. The values of various production conditions and evaluation results in the following examples have meanings as preferable values of the upper limit or the lower limit in the embodiment of the present invention, and the preferable ranges are the above-mentioned upper limit or lower limit values and the following. It may be in the range specified by the value of Examples or the combination with the values of Examples.

〔material〕
<Ingredient (A)>
A-1: KEYFLEX® (registered trademark) BT1028D manufactured by LG Chem Co., Ltd.
Polybutylene terephthalate-polytetramethylene glycol block copolymer Number of units of polytetramethylene glycol Average molecular weight: 2000
Content of polybutylene terephthalate unit: 25% by mass
Content of polytetramethylene glycol unit: 75% by mass
A-2: KEYFLEX® (registered trademark) BT1030D manufactured by LG Chem Co., Ltd.
Polybutylene terephthalate-polytetramethylene glycol block copolymer Number of units of polytetramethylene glycol Average molecular weight: 2000
Content of polybutylene terephthalate unit: 30% by mass
Content of polytetramethylene glycol unit: 70% by mass
A-3: KEYFLEX® (registered trademark) BT1033D manufactured by LG Chem
Polybutylene terephthalate-polytetramethylene glycol block copolymer Number of units of polytetramethylene glycol Average molecular weight: 2000
Content of polybutylene terephthalate unit: 36% by mass
Content of polytetramethylene glycol unit: 64% by mass

<Ingredient (B)>
B-1: Kaneka Corporation Kaneka (registered trademark) FM-40
Butyl acrylate / Methyl methacrylate copolymer B-2: Metabrene (registered trademark) manufactured by Mitsubishi Rayon Co., Ltd. W-450
Alkyl methacrylate / Alkyl acrylate copolymer B-3: Metabrene (registered trademark) manufactured by Mitsubishi Rayon Co., Ltd. S-2001
Alkyl methacrylate / Alkyl acrylate / Dimethylsiloxane copolymer B-4: Nipol (registered trademark) 1411 manufactured by Zeon Corporation
Acrylonitrile / Butadiene Copolymer B-5: Omnova Chemigum® P-83
Acrylonitrile / Butadiene Copolymer B-6: Mitsubishi Rayon Metabrene® S-2501
Alkyl methacrylate / Alkyl acrylate / Didimethylsiloxane copolymer B-7: Clayton (registered trademark) G1641HU manufactured by Clayton.
Styrene-Ethylene / Butylene-Styrene Block Copolymer <Component (C)>
C-1: TOTM (registered trademark) manufactured by J-PLUS Co., Ltd.
Tri-2-ethylhexyl trimellitic acid C-2: Process oil manufactured by Idemitsu Kosan Co., Ltd. (registered trademark) PW-90
Petroleum hydrocarbons (mineral oil)

<Component (D)>
D-1: Nisshinbo Chemical Co., Ltd. Carbodilite (registered trademark) LA-1
Carbodiimide-modified isocyanate

[Examples 1 to 13, Comparative Examples 1 to 3]
[Manufacturing of polyester-based thermoplastic elastomer composition]
Each component shown in the compounding compositions of Tables 1 and 2 was melt-kneaded (cylinder temperature 200) by a twin-screw kneader to produce pellets of a polyester-based thermoplastic elastomer composition.

[Creation of molded product for physical property evaluation]
The pellets of the above polyester-based thermoplastic elastomer composition are injected using an injection molding machine ("J110AD" manufactured by Japan Steel Works, Ltd., mold clamping force 110T) at a mold temperature of 40 ° C. and a cylinder temperature of 200 to 230 ° C. Molding was performed to obtain a molded product having a thickness of 100 mm × 100 mm and a thickness of 2 mm.
Hereinafter, they are referred to as "molds for physical property evaluation".

〔Evaluation methods〕
The results of evaluating the pellets of the polyester-based thermoplastic elastomer compositions of Examples 1 to 13 and Comparative Examples 1 to 3 shown in Tables 1 and 2 and the molded article for physical property evaluation by the following methods are shown in Tables 1 and 2. Shown in 2.

<MFR>
MFR (ISO 1133 (230 ° C., load 2.16 kgf)) was measured for pellets of the polyester-based thermoplastic elastomer composition.

<Formability>
In injection molding, the ease of taking out the molded product from the mold was evaluated according to the following criteria.
+: When removing the molded product from the mold, it is necessary to pull it with a strong force using human power.
++: When removing the molded product from the mold, it is necessary to pull it with a light force using human power.
+++: It is not necessary to use human power when removing the molded product from the mold.

<Duro A hardness>
The Duro A hardness of the molded product for physical property evaluation prepared above was measured in accordance with ISO 7619-1.

<Oil resistance>
The molded body for physical property evaluation prepared above is immersed in the liquid resistance test oil "IRM903" for vulcanized rubber and thermoplastic rubber specified by JIS K6258 and ASTM D47 at room temperature for 24 hours, and the mass before and after immersion. Oil resistance was evaluated by measuring the rate of increase and the rate of volume increase. It is desirable that both the mass increase rate and the volume increase rate are close to zero.

<Abrasion resistance>
With respect to the molded body for physical property evaluation prepared above, the amount of mass loss and the appearance of wear marks before and after the wear test were evaluated using a Taber type wear tester manufactured by Toyo Seiki Co., Ltd. A "CS-17" was used as the wear ring, a load of 9.8 N was applied, and the product was rotated 1000 times. Regarding the amount of mass loss, it is preferable that the amount of mass loss before and after the wear test is small, and the appearance of the wear mark is relatively evaluated by "+", "++", and "++++", and the larger the "+", the more preferable.

[Discussion]
As shown in Table 2, Comparative Examples 1 and 2 use only polyester elastomers and ester compounds and do not use rubber polymers, and are excellent in oil resistance and wear resistance, but have excellent moldability. Inferior.

Comparative Example 3 uses a styrene-based thermoplastic elastomer as the rubber polymer and paraffin oil as the ester-based compound, and it was found that the moldability was not inferior, but the oil resistance and abrasion resistance were inferior. rice field.

On the other hand, in Examples 1 to 13, as the rubber polymer, an acrylic core-shell type rubber polymer such as an acrylate / methyl methacrylate copolymer, a silicone / acrylate / methyl methacrylate copolymer rubber polymer, and a silicone / A rubbery polymer selected from silicone-based core-shell type rubbery copolymers such as acrylate / acrylonitrile / styrene copolymer resin and butadiene / acrylonitrile copolymer rubbery polymers is used, and trimellitic acid tri-, which is an ester-based compound, is used. 2-Ethylhexyl is used, and the flexibility, oil resistance, abrasion resistance, and moldability are well-balanced and excellent as compared with Comparative Examples 1 to 3. In particular, in Example 6, the use of the carbodiimide compound dramatically improved the wear resistance.

From Tables 1 and 2, according to the present invention, a polyester elastomer is blended with a specific rubbery polymer and an ester compound to have a soft texture, oil resistance, abrasion resistance and molding. It can be seen that a polyester-based thermoplastic elastomer composition having excellent properties can be provided. It can be seen that the wear resistance can be further enhanced by further blending the carbodiimide compound.

According to the present invention, a polyester elastomer is blended with a specific rubber polymer and an ester compound, preferably a carbodiimide compound to provide a molded product having a soft texture and excellent oil resistance and wear resistance. can do. The molded body manufactured by the present invention is stationery; toys; sports equipment; covers for mobile phones and smartphones; parts such as grips; school teaching materials, home appliances, repair parts for OA equipment, and various parts such as automobiles, motorcycles, and bicycles. It can be suitably used for applications such as members such as building materials.

Claims (8)

A polyester-based thermoplastic elastomer composition containing the following components (A) to (C), further comprising a carbodiimide compound as the component (D), and an aromatic polyester-polyalkylene glycol block copolymer of the following component (A). A polyester-based thermoplastic elastomer composition comprising 0.01 to 10 parts by mass with respect to 100 parts by mass.
Component (A): Aromatic polyester-polyalkylene glycol block copolymer
Component (B): At least one rubber polymer component selected from the group consisting of an acrylic core-shell rubber polymer, a silicone core-shell rubber copolymer, and a butadiene / acrylonitrile copolymer rubber polymer (B). C): Tri-2-ethylhexyl trimellitic acid 10 to 400 parts by mass of the rubbery polymer of the component (B) and trimellitic acid tri of the component (C) with respect to 100 parts by mass of the aromatic polyester-polyalkylene glycol block copolymer of the component (A). The polyester-based thermoplastic elastomer composition according to claim 1, which contains 6 to 100 parts by mass of 2-ethylhexyl . The polyester-based thermoplastic elastomer composition according to claim 1 or 2 , wherein the polyalkylene glycol of the component (A) is polytetramethylene glycol. The polyester-based thermoplastic elastomer composition according to any one of claims 1 to 3 , wherein the content of the polyalkylene glycol component of the component (A) is 60% by mass or more. The polyester-based thermoplastic elastomer composition according to any one of claims 1 to 4 , wherein the component (B) contains a unit derived from an alkyl methacrylate compound. The polyester-based thermoplastic elastomer composition according to any one of claims 1 to 5 , wherein the component (D) is a carbodiimide-modified isocyanate. The polyester-based thermoplastic elastomer composition according to any one of claims 1 to 6 , which is a polyester-based thermoplastic elastomer composition for grips. A molded product made from the polyester-based thermoplastic elastomer composition according to any one of claims 1 to 7 .